CN117364054A - Method for preparing few-layer large-area graphene by chemical vapor deposition and transfer method thereof - Google Patents
Method for preparing few-layer large-area graphene by chemical vapor deposition and transfer method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 172
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000011889 copper foil Substances 0.000 claims abstract description 77
- 239000000758 substrate Substances 0.000 claims abstract description 62
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 38
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 239000010937 tungsten Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 21
- 239000010949 copper Substances 0.000 abstract description 21
- 230000007547 defect Effects 0.000 abstract description 9
- 238000001237 Raman spectrum Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
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- 239000010410 layer Substances 0.000 description 33
- 239000010408 film Substances 0.000 description 22
- 239000007788 liquid Substances 0.000 description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
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- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/003—Coating on a liquid substrate
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
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Abstract
The invention relates to a method for preparing few-layer large-area graphene and transferring the graphene by a chemical vapor deposition method. The method comprises the following steps: placing copper foil in a tube furnace, annealing the copper foil in a mixed atmosphere at a temperature of 1100-1200 ℃ and keeping the temperature for annealing for 30-40 min to enable the copper foil to be in a molten state; introducing CH into a tube furnace under the condition of keeping atmosphere and temperature 4 The gas is kept for 10 to 90 minutes; then CH is carried out 4 Closing gas, naturally cooling to room temperature, and forming a copper foilA few graphene films are available on the substrate. The graphene monocrystal prepared by the method has almost no defect peak as measured by Raman spectrum, and the grown graphene has higher crystallization quality and higher application value.
Description
Technical Field
The invention belongs to the field of graphene material growth. Relates to a method for preparing few-layer large-area graphene and transferring the same by a chemical vapor deposition method under normal pressure.
Background
Graphene is a hexagonal honeycomb lattice structure composed of single-layer carbon atoms, the electronic structure of the graphene is quite unique, a Brillouin zone has six peaks (namely Dirac points, also called K points), a conduction band and a valence band of the graphene take the Dirac points as symmetry centers, and the energy band structure and a wave vector of the graphene are in a linear relationship at the K points. The unique lattice structure and electronic structure of the graphene enable the graphene to have very excellent physical and electrical properties, including high mobility, high transmittance, high mechanical strength, large specific surface area and the like. Graphene is thus an excellent material for the preparation of flexible displays and photovoltaic devices. The current preparation methods of graphene comprise a mechanical stripping method, a redox method, a silicon carbide epitaxial growth method, a chemical vapor deposition method, a redox method and the like, wherein the graphene prepared by the chemical vapor deposition method has uniform layer number, low cost and good quality.
In recent years, graphene is prepared on various metal substrates, particularly on copper substrates, by adopting a chemical vapor deposition method. Graphene is readily available on copper foil substrates due to the unique "self-limiting growth" mechanism of copper foil substrates. The conventional chemical vapor deposition method is to grow graphene on solid copper, the carrier gas is hydrogen-argon mixed gas, the growing carbon source is methane and other schemes, but the problems still exist, and the defects of uneven nucleation and uncontrollable carbon precipitation at the copper grain boundary result in low grain quality and uneven graphene layer number, and the prepared graphene is a polycrystalline film generally, and the grain boundaries among the grains reduce the excellent physical and chemical properties of the graphene. Therefore, the surface treatment of solid copper is quite strict with the growth of graphene on solid copper. However, our research objective was to produce high quality, uniform, large area graphene single crystals. The use of single crystal metal substrates can achieve uniform monolayer graphene growth but is expensive and limited in yield. Unlike solid substrates, which are rich in surface topography, the quasi-smooth and rheological surfaces of liquid substrates provide an alternative, simpler method to produce high quality uniform graphene layers. Therefore, how to grow a large-sized, small-layer and high-quality graphene film on a liquid copper foil substrate has become one of the important points in the field of graphene materials at present.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a method for preparing few-layer large-area graphene and transferring the graphene by a chemical vapor deposition method. The method adopts a Chemical Vapor Deposition (CVD) method, takes copper foil as a substrate, takes methane as a carbon source, takes hydrogen-argon mixed gas as carrier gas, and solves the problems of low quality, small size, uneven layer number and the like of graphene crystal grains caused by uneven nucleation and uncontrollable carbon precipitation at a copper crystal boundary by enabling the growth temperature to be higher than the melting temperature of the copper foil, the melting temperature of the copper foil to be 1084 ℃ and utilizing the quasi-smooth and rheological surface of liquid copper. And a method for growing small-layer, large-area and high-quality graphene on a liquid copper foil substrate by adjusting the growth time and hydrogen-argon gas flow, and transferring the graphene from the copper foil surface to Si/SiO by wet transfer 2 A substrate surface. Finally preparing graphene monocrystal, and measuring almost no defect peak by Raman spectrum, thus proving that the grown graphene has higher crystallization quality and higher application value.
The technical scheme of the invention is as follows:
a method for preparing few-layer large-area graphene by a chemical vapor deposition method comprises the following steps:
s1, respectively ultrasonically cleaning copper foil and tungsten foil in acetone, ethanol and deionized water for 10-20 min, and then drying by nitrogen;
s2, placing the copper foil on a tungsten foil, taking the tungsten foil as a support when copper is melted, placing the tungsten foil and the copper foil into a quartz boat, pushing the quartz boat into a heating area in a tube furnace, and vacuumizing to 9-8.5E-1 Pa;
s3, in the mixed atmosphere, the temperature is raised to 1100-1200 ℃ for annealing, and the temperature is kept for annealing for 30-40 min, so that the copper foil is in a molten state;
the mixed atmosphere is hydrogen and argon, and the volume ratio of the hydrogen to the argon is 5-50: 100-200.
The heating time is 55-65 min;
s4, introducing CH into the tubular furnace while maintaining the atmosphere and the temperature of the previous step 4 The gas is kept for 10 to 90 minutes; then CH is carried out 4 Closing gas, naturally cooling to room temperature, and obtaining a few-layer graphene film on the copper foil substrate;
CH 4 the flow is 1-5 sccm;
the few layers are 1-3 layers. Preferably 2 layers.
The area of the graphene film is 0.25cm 2 ～1cm 2 ；
The thickness of the copper foil substrate in S1 is 250-300 mu m.
The transfer method of the graphene film prepared by the method comprises the following steps:
(1) Spin-coating PMMA on the copper foil substrate deposited with the graphene film by a spin-coating instrument;
wherein the rotation Tu Yi parameter is 1000-1500 r/min for 1-5 s, and then 2500-3000 r/min for 55-60 s;
(2) Drying the graphene/copper foil spin-coated with PMMA;
(3) Removing the area of the copper foil substrate, which is not spin-coated with PMMA, to obtain PMMA/graphene/copper foil;
(4) Soaking PMMA/graphene/copper foil in FeCl 3 In the solution, until the copper foil is completely etched, PMMA/graphene is completely separated, and PMMA/graphene is obtained;
the FeCl 3 The concentration of the solution is 0.1-0.5 mol/L; etching time is 24-72 h;
(5) Soaking PMMA/graphene in deionized water for cleaning;
(6) Spreading the cleaned PMMA/graphene on a second substrate, and naturally drying;
(7) Heating the second substrate paved with PMMA/graphene obtained in the previous step at 55-65 ℃ for 20-30 minutes, and attaching the PMMA/graphene to the second substrate;
(8) Naturally cooling the product obtained in the previous step, soaking the product in acetone, and cleaning PMMA;
(9) And after the acetone soaking is finished, soaking the substrate in isopropanol, and finally taking out the substrate and drying the substrate by nitrogen to obtain the graphene film on the transferred second substrate.
The second substrate is made of Si/SiO 2 A TPU or PET.
The invention has the substantial characteristics that:
in the invention, firstly, the copper foil is melted at 1100-1200 ℃, and then graphene is grown on the liquid copper foil substrate by a chemical vapor deposition method.
The invention is kept for a period of time in high-temperature annealing, because the copper foil is just melted into liquid copper, at the moment, if methane is directly introduced to carry out graphene growth, the graphene lattice has a plurality of defects due to the fact that a large number of areas with larger roughness such as grain boundaries and steps exist in the copper foil, the growth temperature is kept unchanged, annealing treatment is carried out firstly, the copper foil is completely melted into liquid copper, and then the defect number of the graphene lattice is greatly reduced when methane is introduced to carry out graphene growth. In addition, the annealing treatment can promote interaction and combination between the graphene and the liquid copper bottom layer, so that the adhesion and stability of the graphene on the surface of the liquid copper are improved, the quality and performance of the graphene can be effectively improved, and the graphene is more suitable for being applied to actual scenes.
Large area graphene is readily available on copper foil substrates due to the unique "self-limiting growth" mechanism of copper foil substrates. By adjusting the gas flow, the growth temperature and the growth time, a large-area graphene film with fewer layers and high quality can be obtained on the surface of the liquid copper foil, and the graphene film can be prepared in a short time and can reach atomic level flatness, so that a method premise is provided for producing the high-quality graphene film;
second, the unique lattice structure and unique energy band structure of graphene impart many excellent properties thereto, such as high carrier mobility, ultra-high conductivity, excellent thermal properties and optical properties, and thus, graphene can be designed into various stable optoelectronic devices and manufacture various van der waals heterojunctions. According to the invention, the graphene film is peeled off from the substrate by a graphene wet transfer technology and transferred to the substrate which is more suitable for specific application.
The beneficial effects of the invention are as follows:
excellent crystal quality: the chemical vapor deposition method can be used for growing graphene on liquid copper to obtain high-quality crystals. The liquid copper serving as the bottom substrate can provide uniform heat transfer and stable environment, and is favorable for forming larger crystal particles and fewer defects in the growth process of the graphene, so that the crystal quality of the graphene is improved.
Good mechanical stability: the whole structure of the small-layer and large-area graphene prepared on the liquid copper foil substrate is relatively stable, which is favorable for improving the mechanical property and long-term stability of the graphene, so that the graphene is more suitable for the fields of flexible electronic devices and the like.
The adjustability is strong: the shape, thickness, crystal shape and the like of the graphene are regulated and controlled by regulating growth conditions such as growth temperature, growth time, flow rate of hydrogen-argon mixed gas and the like.
Reducing the substrate surface treatment process: when graphene is grown on solid copper, in order to make the quality of the grown graphene better, electrochemical polishing treatment is needed to achieve surface smoothing treatment in addition to removing surface impurities through acetone and isopropanol. By increasing the temperature, the copper foil is melted into liquid copper, the complicated step of electrochemical polishing is omitted by utilizing the quasi-smooth and rheological surface of the liquid copper, and the quality of the grown graphene is better.
Drawings
FIG. 1 is a schematic diagram of chemical vapor deposition of graphene used in an embodiment of the present invention;
FIG. 2 is a diagram showing the growth process of the chemical vapor deposition graphene used in example 1;
fig. 3 is an optical microscope image of a liquid copper foil substrate for growing few-layer graphene, wherein fig. 3 (a) is an optical microscope image of the few-layer graphene grown in example 1, fig. 3 (b) is an optical microscope image of the multi-layer graphene grown in comparative example 3, and fig. 3 (c) is an optical microscope image of the graphene after oxidation in comparative example 1;
FIG. 4 is an optical microscope image of graphene grown on a solid copper substrate in comparative example 2;
FIG. 5 is a Raman diagram of a few-layer graphene grown on a copper foil substrate in example 1;
FIG. 6 is a representation of the transferred graphene in example 1, wherein FIG. 6 (a) is an optical microscopy image of the transferred graphene on the copper foil, FIG. 6 (b) is a scanning electron microscopy image of the transferred graphene on the copper foil, and FIG. 6 (c) is a Raman image of the transferred graphene on the copper foil;
FIG. 7 is a schematic diagram of graphene thin film wet transfer;
Detailed Description
For a better understanding of the present invention, the chemical vapor deposition of the present invention is further described in detail with reference to examples, but the scope of the present invention is not limited to the scope of the examples.
Example 1
The embodiment discloses a method for preparing a few-layer large-area graphene film, which specifically comprises the following steps:
s1, cutting copper foil (250 mu m) and tungsten foil into square shapes with the size of 1 multiplied by 1cm, and flattening. Respectively ultrasonically cleaning in acetone, ethanol and deionized water for 10min to remove pollutants on the surface of the substrate, and then drying by nitrogen;
s2, placing the copper foil on the tungsten foil, placing the tungsten foil and the copper foil into a quartz boat, pushing the quartz boat into a heating area in a tube furnace, and vacuumizing to 8.5E-1Pa;
s3, controlling the temperature rise time to be 65min, growing to 1100 ℃, keeping the temperature at 1100 ℃ in the annealing stage unchanged, and annealing for 30min, and introducing two gases during the annealing processIn (H) 2 Ar (volume ratio of the two is 1:1) flow is 50sccm, and single argon flow is 150sccm;
s4, maintaining the temperature at 1100 ℃ in the growth process, and starting to introduce CH 4 Gas, CH 4 The flow rate is 5sccm;
s5, maintaining the temperature and the growth time to be 40min. The method comprises the steps of carrying out a first treatment on the surface of the
S6, closing methane gas after the growth is finished, naturally cooling the system to room temperature, and obtaining a few-layer large-area graphene film on the copper foil substrate;
example 2
This embodiment differs from embodiment 1 in that: and changing the growth time in the step S5 into 60 minutes to obtain a sample to be detected.
Example 3
This embodiment differs from embodiment 1 in that: CH in S4 4 The flow rate was changed to 1sccm to obtain a sample to be detected.
Example 4
This embodiment differs from embodiment 1 in that: and (3) changing the flow of CH4 in the step S4 to 1sccm, and changing the growth time in the step S5 to 20 minutes to obtain a sample to be detected.
Example 5
The embodiment discloses a graphene film transfer method:
s1, fixing four edges of the upper surface of the copper foil substrate, on which the graphene grows, in the embodiment 1 on a cover glass by using an adhesive tape.
S2, placing the sample in a spin coater and fixing the sample by using an adhesive tape, dripping PMMA solution on the surface of the sample, and then rotating the spin coater to uniformly throw PMMA. Spin coater parameters were 1500r/min for 5s followed by 2500r/min for 55s.
S3, taking down the sample, removing the adhesive tape, and naturally airing the graphene/copper foil sample spin-coated with PMMA in a fume hood.
S4, after the sample is dried, the periphery of the copper foil substrate is covered by the adhesive tape, and the area which is not coated with PMMA in a spin-coating mode is cut off.
S5, configuring FeCl of 0.1mol/L 3 Solution, PMMA/graphene/copper foil sample was immersed in the solution for 50 hours until the copper foil was immersedCompletely etching, and floating the PMMA/graphene film on the surface of the solution.
S6, lightly picking up the PMMA/graphene sample by using a cover glass, putting the PMMA/graphene sample into deionized water, and transferring the PMMA/graphene sample into the deionized water for multiple times to sufficiently clean residual FeCl 3 A solution.
S7, using new cleaned Si/SiO 2 The substrate takes the clean PMMA/graphene sample out of the deionized water and naturally dries the PMMA/graphene sample in the sun.
And S8, placing the sample on a heating table, and heating at 60 ℃ for 30 minutes to enable the PMMA/graphene film to be tightly attached to the substrate.
And S9, after the sample is cooled, placing the sample in acetone, soaking the sample for 90 minutes to remove PMMA, replacing the acetone every 30 minutes, and cleaning the PMMA. Note that when the acetone liquid is replaced, a small portion of the acetone liquid is kept so as to be over the surface of the sample, and the acetone liquid is prevented from completely volatilizing to leave organic matters or other impurities on the surface of the sample.
And S10, after the acetone soaking is finished, soaking the sample in isopropanol for 45 minutes to remove the acetone, replacing the isopropanol every 15 minutes, and finally taking out the sample, and drying the sample by nitrogen to obtain a transferred clean graphene film sample.
Comparative example 1
The difference between this comparative example and example 1 is that: the graphene obtained by growth in example 1 was placed on a glue baking machine, set at 200 ℃, and baked for 30min.
Comparative example 2
The difference between this comparative example and example 1 is that: and changing the temperature in S3 and S4 to 900 ℃ to obtain a sample to be detected.
Comparative example 3
This embodiment differs from embodiment 1 in that: CH in S4 4 The flow rate was changed to 10sccm to obtain a sample to be detected.
For the 6 examples and 2 comparative examples, the samples were placed under an optical microscope for observation, the surface morphology features were preliminarily judged, the morphology was further characterized by a scanning electron microscope, and the number of layers and the quality of graphene were characterized by using a raman spectrum.
Fig. 1 is a schematic diagram of chemical vapor deposition for growing graphene, wherein a copper foil is a growth substrate, a tungsten foil is used as a support substrate, a carrier gas is hydrogen-argon mixture and pure argon, a growth carbon source is methane, and the temperature is raised to the melting temperature of the copper foil, so that graphene is prepared on liquid copper.
Fig. 2 is a graph of the growth process of the chemical vapor deposition graphene used in example 1, and it can be seen from fig. 2 that the temperature of the growth of the graphene is 1100 ℃, and since the melting point of the copper foil is 1084 ℃, the copper foil has been melted into a liquid when the graphene is grown at 1100 ℃, and the quasi-smooth and rheological surface of the liquid copper makes the number of layers of the prepared graphene uniform and the quality of the graphene higher.
Fig. 3 is an optical microscopic view showing that few graphene layers are grown on the copper foil substrate in example 1, and it can be seen from fig. 3 (a) that the copper foil surface is even and smooth, which means that the growth of graphene is positively facilitated after the liquefaction of the copper foil, but that the island shape of graphene, in which the graphene layers are transparent in color and the few graphene layers are not multi-layered, is as shown in fig. 3 (b), so that the surface of the copper foil cannot be intuitively illustrated as being covered with graphene under light, in comparative example 1, the graphene grown in example 1 is oxidized for 30 minutes at 200 ℃, and then observed under an optical microscope, as shown in fig. 3 (c), fine light red cracks are found, which are generated because the thin film is torn by the thermal expansion generated when the copper foil is heated, the torn portion is not covered with the copper foil, fine light red oxidized portion is generated after the oxidation, and the small crack also indirectly indicates that the grown graphene is relatively thin, and the portion where the color is not changed is indirectly illustrated as being covered with graphene. Comparative example 1 reflects that example 1 grows graphene with a large area and a small layer.
Fig. 4 is an optical microscopic image of comparative example 2 after graphene oxidation is grown on the surface of a solid copper foil at 900 c, and it can be seen from the light-induced image that the surface of the copper foil is severely oxidized with little graphene coverage. This is because the surface of the solid copper foil has a large number of regions with large roughness such as grain boundaries and steps, which results in low quality of graphene crystal grains, small size and uneven layer number.
FIG. 5 is a diagram showing the growth of few graphene layers on a copper foil substrate in example 1Raman diagrams, from which the spectrum at 1580cm is also evident -1 And 2687cm -1 G peak and 2D peak of graphene are arranged nearby, the intensities of the G peak and the 2D peak are equivalent, and the grown graphene can be obtained to be double-layer graphene according to related data or literature and is 1350cm in length -1 No obvious D peak of graphene (defect peak of graphene) was found nearby, indicating that the graphene grown on the copper foil substrate was structurally complete and good in performance. In addition to the characteristic peaks of graphene, the characteristic peaks of graphene are found to be very weak in the raman plot, and there are many hetero peaks in addition to the characteristic peaks, because the copper foil surface has an interfering effect on its measurement, not because the grown graphene is defective.
FIG. 6 is a representation of the transferred graphene in example 1, wherein FIG. 6 (a) is an optical microscopy image of the transferred graphene on a copper foil, FIG. 6 (b) is a scanning electron microscopy image of the transferred graphene on a copper foil, FIG. 6 (c) is a Raman image of the transferred graphene on a copper foil, and from FIG. 6 (a) it can be seen that the transferred graphene film compares Si/SiO 2 The substrate was a little darker in color, indicating that the film was indeed visually transferred to Si/SiO 2 On the substrate, but some colored impurities on the graphene film were also found, due to FeCl during transfer 3 The solution was not cleaned and the film fragments after transfer were more clearly seen from fig. 6 (b) and raman characterization was performed. As apparent from the Raman diagram in FIG. 6 (c), the region at 1580cm -1 And 2687cm -1 G peak and 2D peak of graphene are arranged nearby, the intensities of the G peak and the 2D peak are equivalent, and the grown graphene can be obtained to be double-layer graphene according to related data or literature and is 1350cm in length -1 No obvious D peak of graphene (defect peak of graphene) was found nearby, indicating that the transferred graphene is structurally complete and good in performance.
Fig. 7 is a schematic diagram of graphene wet transfer. According to the invention, the graphene film is peeled off from the substrate by a graphene wet transfer technology and transferred to the substrate which is more suitable for specific application, such as TPU, PET and the like.
The invention is not a matter of the known technology.
Claims (7)
1. A method for preparing few-layer large-area graphene by a chemical vapor deposition method is characterized by comprising the following steps:
s1, respectively ultrasonically cleaning copper foil and tungsten foil in acetone, ethanol and deionized water for 10-20 min, and then drying by nitrogen;
s2, placing the copper foil on the tungsten foil, placing the tungsten foil and the copper foil into a quartz boat, pushing the quartz boat into a heating area in a tube furnace, and vacuumizing to 9-8.5E-1 Pa;
s3, annealing at the temperature of 1100-1200 ℃ under the mixed atmosphere, and keeping the temperature for 30-40 min;
s4, introducing CH into the tubular furnace while maintaining the atmosphere and the temperature of the previous step 4 The gas is kept for 10 to 90 minutes; then CH is carried out 4 And closing the gas, naturally cooling to room temperature, and obtaining the few-layer graphene film on the copper foil substrate.
2. The method for preparing the few-layer large-area graphene by using the chemical vapor deposition method as claimed in claim 1, wherein the heating time is 55-65 min.
3. The method for preparing the few-layer large-area graphene by using the chemical vapor deposition method as claimed in claim 1, wherein the mixed atmosphere is hydrogen and argon, and the volume ratio of the hydrogen to the argon is 5-50: 100-200.
4. The method for preparing few-layer large-area graphene by using a chemical vapor deposition method according to claim 1, wherein the few layers are 1-3 layers.
5. The method for preparing a few-layer large-area graphene by using a chemical vapor deposition method according to claim 1, wherein the area of the graphene film is 0.25cm 2 ～1cm 2 。
The thickness of the copper foil substrate in S1 is 250-300 mu m.
6. The transfer method of the graphene film prepared by the method of claim 1, which is characterized by comprising the following steps:
(1) Spin-coating PMMA on the copper foil substrate deposited with the graphene film by a spin-coating instrument;
wherein the rotation Tu Yi parameter is 1000-1500 r/min for 1-5 s, and then 2500-3000 r/min for 55-60 s;
(2) Drying the graphene/copper foil spin-coated with PMMA;
(3) Removing the area of the copper foil substrate, which is not spin-coated with PMMA, to obtain PMMA/graphene/copper foil;
(4) Soaking PMMA/graphene/copper foil in FeCl 3 In the solution, until the copper foil is completely etched, PMMA/graphene is completely separated, and PMMA/graphene is obtained;
the FeCl 3 The concentration of the solution is 0.1-0.5 mol/L; etching time is 24-72 h;
(5) Soaking PMMA/graphene in deionized water for cleaning;
(6) Spreading the cleaned PMMA/graphene on a second substrate, and naturally drying;
(7) Heating the second substrate paved with PMMA/graphene obtained in the previous step at 55-65 ℃ for 20-30 minutes, and attaching the PMMA/graphene to the second substrate;
(8) Naturally cooling the product obtained in the previous step, soaking the product in acetone, and cleaning PMMA;
(9) And after the acetone soaking is finished, soaking the substrate in isopropanol, and finally taking out the substrate and drying the substrate by nitrogen to obtain the graphene film on the transferred second substrate.
7. The transfer method of claim 6, wherein the second substrate is Si/SiO 2 A TPU or PET.
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