CN109573991B - Method for preparing graphene arrays with different lattice point thicknesses by using composite metal template - Google Patents
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
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Abstract
The invention relates to a method for preparing graphene arrays with different array point thicknesses by using a composite metal template, which comprises the steps of plating a nickel array on a copper foil by using a mask (or plating a copper array on a nickel foil), heating at high temperature to change the surface of the copper array into a copper-nickel alloy array, introducing a carbon source at the growth temperature of a CVD (chemical vapor deposition) process, growing the graphene array on the surface of a composite metal film during cooling, controlling the number of layers of graphene in different areas by using the composite metal film, preparing a high-quality graphene array with a thick middle edge and a thin middle edge or a graphene array with a thick middle edge, solving the problem that the thickness of each array point of the graphene array is uniform by using the conventional method, meeting the special requirements of applications such as an acceleration sensor and a pressure sensor on the graphene, and obtaining the high-quality graphene array.
Description
Technical Field
The invention relates to a method for preparing graphene arrays with different lattice point thicknesses by using a composite metal template, and belongs to the technical field of graphene array preparation.
Background
Graphene is a new carbonaceous material with a two-dimensional honeycomb lattice structure formed by tightly stacking carbon atoms, has excellent electrical, optical, thermal and mechanical properties, is expected to be widely applied to the fields of high-performance nano electronic devices, composite materials, field emission materials, photoelectric detectors, gas sensors, energy storage and the like, and has wide application prospects in the industries, the power industries and the electronic industries.
At present, the preparation methods commonly used for graphene single crystals mainly comprise two main types, one is a Chemical Vapor Deposition (CVD) method, and the other is a high-temperature SiC pyrolysis method. The Chemical Vapor Deposition (CVD) method mainly uses metal as a substrate, and carbon-containing compounds such as methane as a carbon source, and grows graphene by decomposing the carbon source at high temperature on the surface of a substrate. The CVD method has the advantages of simple process and low cost, and is one of the common methods for preparing graphene. The Tang military et al report a method for growing graphene on a 6H-SiC silicon surface, the adopted equipment is molecular beam epitaxy equipment, and the method is that a layer of silicon is deposited at 750 ℃ in vacuum, and then the temperature is raised to 1300 ℃ to epitaxially generate graphene (see the Tang military et al, the influence of annealing time on the appearance and structure of the epitaxial graphene on the 6H-SiC (0001) surface, the report on physical chemistry, 2010, 26(1), 253-ion 258).
However, most of the graphene prepared by the chemical vapor deposition method is randomly nucleated and grown, the controllability of the spatial distribution of the graphene is poor, large-size single-layer and uniform multi-layer graphene is obtained, and the specific arrayed graphene is difficult to prepare. However, graphene-based electronic devices typically require graphene to be arrayed.
Chinese patent document 201210008150.8 discloses a method for preparing a controllable graphene array, which includes performing small-angle bonding on two silicon substrates with the same crystal orientation to form square grid-shaped screw dislocation, etching a vertically corresponding region affected by dislocation lines by utilizing stress selective corrosion due to uneven stress distribution on the silicon surface caused by dislocation to form square grid-shaped patterned silicon islands, forming metal nanoparticles with segregation characteristics by epitaxy using electron technology, and finally preparing a graphene array by using a chemical vapor deposition method and a segregation method. However, each lattice point of the graphene array prepared by the method is uniform in thickness, and the requirements of applications such as novel acceleration sensors, pressure sensors and vector sensors cannot be met: the acceleration sensor and the pressure sensor are widely applied in military, the sensing film of the acceleration sensor and the pressure sensor needs a graphene film which is airtight, transparent and thin in the middle and thick at the edge, and the vector sensor needs a graphene film which is thick in the middle and thin at the edge and is not a graphene film material with uniform thickness.
Therefore, there is a need to establish a scientific and high-quality method for preparing graphene arrays with controllable number of layers in the center and the edges.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing graphene arrays with different lattice point thicknesses by using a composite metal template.
Brief description of the invention:
according to the invention, a metal nickel array is plated on a copper foil (or a metal copper array is plated on a nickel foil) by using a mask, then the surface of the copper foil is heated at a high temperature to be changed into a copper-nickel alloy array, then a carbon source is introduced at the growth temperature of a CVD (chemical vapor deposition) process, a graphene array grows on the surface of a composite metal film when the temperature is reduced, the number of layers of graphene in different areas is controlled by using the composite metal film, and a high-quality graphene array with thick middle edges or a graphene array with thick middle thin edges is prepared.
Interpretation of terms:
optical mask: various functional patterns are made and precisely positioned on a film, plastic or glass substrate material for a structure for selective exposure of a photoresist coating.
Electroplating: the process of plating a thin layer of other metal on the metal surface by using the principle of electrolysis.
Electron beam evaporation: the evaporation material is placed in a water-cooled crucible, and is directly heated by electron beams to be vaporized and condensed on the substrate to form a thin film.
Plasma sputtering: the rare gas is ionized into plasma by a direct current or radio frequency method, and then the target material is bombarded by a bias method and the like, so that atoms on the target have enough capacity to be separated out and fall on the substrate to form a film.
Detailed description of the invention:
the invention is realized by the following technical scheme:
a method for preparing graphene arrays with different lattice point thicknesses by using a composite metal template comprises the following steps:
(1) providing a metal foil, cleaning, and removing surface impurities to obtain an impurity-removed metal foil;
(2) electroplating or depositing other metal arrays on the metal foil after impurity removal in an electroplating or depositing mode to obtain a metal array substrate;
(3) placing the metal array substrate on a quartz boat sample table of a CVD growth furnace, vacuumizing, heating to 200-; then heating to 550-650 ℃, introducing high-purity hydrogen, controlling the pressure at 100-300mbar, preserving the heat for 10-60min, and annealing to obtain a composite metal array substrate;
(4) the obtained composite metal array substrate is continuously heated to 1000-1100 ℃, and the temperature is kept for 10-60 min; then introducing high-purity carbon source gas, controlling the pressure at 300mbar for 100-;
(5) and (4) removing composite metal from the composite metal substrate of the graphene array obtained in the step (4) or separating the graphene from the substrate, and cleaning and drying to obtain the graphene array with different lattice point thicknesses.
Preferably, in the step (1), the metal foil is nickel foil, copper foil, platinum foil, iron foil or cobalt foil; the thickness of the metal foil is 0.010mm-0.10mm, and the purity is more than 99.9%; the cleaning is to perform ultrasonic cleaning on the metal foil by using deionized water and absolute ethyl alcohol in sequence.
Preferably, in the step (2), the other metal array is a copper array or a nickel array, and is different from the metal of the metal foil in the step (1), when the metal foil in the step (1) is a nickel foil, the other metal array in the step (2) is a copper array; and (3) when the metal foil in the step (1) is copper foil, and the other metal arrays in the step (2) are nickel arrays.
Preferably, in step (2), the metal array substrate is obtained in one of the following two ways:
a. covering a metal foil with a metal porous mask plate, wherein the holes on the metal porous mask plate are circular holes, electroplating or depositing a layer of other metal on the metal porous mask plate by adopting an electroplating or depositing mode, removing the metal porous mask plate, and obtaining a metal array of other metals on the metal foil, wherein the diameter of a metal array point is 10-500 mu m;
b. adhering an optical mask plate on the upper surface of the metal foil, exposing the optical mask plate, wherein holes on the optical mask plate are circular holes, removing glue at exposure points, electroplating or depositing a layer of other metal on the metal porous mask plate at the exposure points in an electroplating or depositing mode, removing the rest glue, and obtaining a metal array of the other metal on the metal foil, wherein the diameter of the metal array points is 10-500 mu m.
Further preferably, in the step (2), the diameter of the hole on the mask plate is 100-500 μm, the thickness of the array point of the metal array is 10nm-800nm, and the mass ratio of the total mass of the array point to the metal foil is 1:10-1: 5000.
Preferably, the diameter of the hole on the mask plate is 200-500 μm, the thickness of the array point of the metal array is 200-400 nm, and the mass ratio of the total mass of the array point to the metal foil is 1:500-1: 2000.
The distance between the holes on the porous mask plate is determined according to requirements, and the distance adopted by the invention is 1-5 mm.
Preferably, in the step (2), the electroplating is to use an anode of an electrochemical workstation for the metal foil, put the metal foil into other metal salt solution, use a copper sheet as a cathode, and electroplate a layer of other metal arrays on the metal foil.
Preferably, in step (2), the deposition is performed by electron beam evaporation or plasma sputtering.
Preferably, in step (3), the vacuum degree is 10-4～10-6Pa, the heating rate of heating to 200-300 ℃ is 5-20 ℃/min, and the flow of the high-purity argon is 10-100 sccm; the temperature rise rate is 5-20 ℃/min when the temperature rises to 550-650 ℃, and the flow of the high-purity hydrogen is 4-20 sccm; the high-purity argon and the high-purity hydrogen are argon with the purity of more than or equal to 5N and hydrogen with the purity of more than or equal to 5N.
Preferably, in the step (4), the heating rate of the temperature rise to 1000-1100 ℃ is 1-10 ℃/min, the flow of the high-purity carbon source gas is 1-20sccm, and the high-purity carbon source gas is methane or propane gas which is more than or equal to the flow of the high-purity carbon source gas; after the growth is finished, high-purity argon is introduced with the flow rate of 10-100sccm, and the rapid cooling rate is 120-240 ℃/min.
Preferably, in the present invention, the removing of the composite metal or the separating of the graphene from the substrate in the step (5) is performed by one of the following methods:
e. dripping 1% polymethyl methacrylate solution on the composite metal with the graphene array grown, whirl coating and drying, and then putting the sample into 1mol/L FeCl3With nitric acid (FeCl)3Soaking the mixture in a mixed solution with the mass ratio of nitric acid being 1:1) for 2-10 h to remove the composite metal; fishing out the graphene array by using a glass slide, putting the graphene array into deionized water, cleaning the graphene array, fishing out the graphene array by using a silicon wafer, and drying the graphene array; and (3) repeatedly using hot acetone to remove PMMA, finally respectively cleaning with deionized water and ethanol, and finally drying with a nitrogen gun.
f. Dripping 1% polymethyl methacrylate solution on the composite metal with the graphene array grown, spinning and drying, putting the composite metal foil as an anode of an electrochemical workstation into a salt solution, taking a copper sheet as a cathode, and separating the composite metal from the graphene array by a bubbling method; fishing out the graphene array into deionized water by using a glass slide, cleaning the graphene array, fishing out the graphene array by using a silicon wafer, and drying the graphene array; and (3) repeatedly using hot acetone to remove PMMA, finally respectively cleaning with deionized water and ethanol, and finally drying with a nitrogen gun.
g. Putting the composite metal of the grown graphene array into 1mol/L FeCl3With nitric acid (FeCl)3Soaking the mixture in a mixed solution with the mass ratio of nitric acid being 1:1) for 2-10 h to remove the composite metal; fishing out the graphene array into deionized water by using a glass slide, cleaning, fishing out by using a pressure and acceleration sensor substrate, and drying; and finally, respectively cleaning with deionized water and alcohol, and finally drying with a nitrogen gun.
In the preparation method, the step (4) is vacuumized and heated to 200 ℃ and 300 ℃, the composite metal and the interior of the reaction cavity are pre-baked, so that the gas adsorbed on the surface of the composite metal and the interior of the cavity is desorbed and discharged out of the cavity, and the residual oxygen content in the cavity is reduced and the vacuum degree is further improved.
All the raw materials in the method are commercial products. The prior art can be referred to for any part not specifically defined.
The invention adopts nickel/copper foil as the substrate, so the production cost is very low, and the nickel/copper foil is sold in various specifications.
The nickel/copper foil adopted by the invention is subjected to ultrasonic cleaning and annealing treatment, so that the layer is not damaged; and the surface is smooth after hydrogen etching treatment in the heating process of the step (4).
The invention has the technical characteristics and excellent effects that:
1. according to the preparation method, a metal nickel array is plated on a copper foil (or a metal copper array is plated on a nickel foil) by using a mask, then the surface of the copper foil is heated at high temperature to be changed into a copper-nickel alloy array, the growth of the graphene array can be catalyzed, then a carbon source is introduced at the growth temperature of a CVD (chemical vapor deposition) process, the graphene array grows on the surface of a composite metal film when the temperature is reduced, the number of layers of graphene in different areas is controlled by using the composite metal film, and a high-quality graphene array with thick middle edges or a high-quality graphene array with thick middle edges is prepared.
2. Compared with the traditional graphene array preparation method, the graphene coverage rate of each array point is high, the graphene array is more controllable, and the number of layers in different areas is more controllable; the method can also solve the problem that the number of layers in different areas is difficult to control in the traditional graphene preparation method, meets the special requirements of applications such as acceleration sensors and pressure sensors on graphene, and can obtain high-quality graphene arrays.
3. According to the invention, a high-quality graphene array with thick middle edge or a graphene array with thin middle edge is obtained by combining the hole diameter on the mask plate and the thickness of the array points of the metal array with a growth method.
4. According to the method, the number of layers of graphene is controlled by accurately controlling the temperature and the temperature rise and fall rate and adjusting the components of the composite metal array by using the intelligent composite metal array (different thicknesses of the copper array and the nickel array) on the surface of the metal foil alloy; the problem that the number of layers of different areas of graphene is difficult to control is solved.
Drawings
FIG. 1 is a schematic diagram of the present invention of preparing a graphene array with thin middle edge and thick edge by plating a copper array on a nickel foil.
FIG. 2 is a schematic diagram of a method for preparing a graphene array with a thin middle edge and a thick edge by plating a nickel array on a copper foil according to the present invention.
Fig. 3 is an SEM image of the graphene arrays grown in examples 1 and 2. a is an SEM image of the graphene array of example 1, and b is an SEM image of the graphene array of example 2.
Fig. 4 is an XRD pattern of graphene array obtained by growth in example 1. The test point is area 3 in fig. 3 a.
Fig. 5 is a raman spectrum of different positions of the graphene array obtained by growth in example 1. The abscissa is the Raman shift (cm)-1) And the ordinate is intensity (a.u.). The areas one, two and three are areas 1, 2 and 3 in fig. 3 a.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
The slide rail tube type CVD growth furnace used in the embodiment is a combined fertilizer and crystal OTF-1200 type CVD furnace, the heating rate can reach 30 ℃/min, and the cooling rate can reach 300 ℃/min at the fastest speed.
The adopted copper foil and nickel foil are commercial products, and the thickness is as follows: 0.010mm-0.1mm, and the purity is more than 99.9%.
Example 1:
a method for preparing graphene arrays with different lattice point thicknesses by using a composite metal template comprises the following steps:
(1) sequentially ultrasonically cleaning a nickel foil with the size of 1 square centimeter by using deionized water and absolute ethyl alcohol to remove impurities on the surface of the nickel foil;
(2) coating glue on the nickel foil cleaned in the step (1), exposing under an optical mask and washing off the glue at the exposure point to serve as electrochemical workAnode of the station, 1mol/L CuCl is put in2In the solution, a copper sheet is used as a cathode, the reaction is carried out for 20min at normal temperature, a layer of copper array is electroplated on a nickel foil, redundant glue is removed, and a copper metal array substrate is obtained, wherein the diameter of a metal array point is about 200 mu m, the thickness is 200nm, and the distance is 2 mm;
(3) placing the nickel-copper composite metal array substrate in the step (2) on a quartz boat sample table of a slide rail tube type CVD growth furnace; the mechanical pump and the molecular pump for the tubular CVD growth furnace are pumped to the vacuum degree of 10-4Pa, heating to 200 ℃, heating at a rate of 20 ℃/min, introducing high-purity argon at a flow rate of 20sccm and a pressure of 100-300mbar, and keeping the temperature for 5 min; then heating to 550 ℃, wherein the heating rate is 20 ℃/min, introducing hydrogen, controlling the flow rate to 10sccm, controlling the pressure to be 100-; then heating to 1100 deg.C, heating rate 10 deg.C/min, and keeping the temperature for 20 min; introducing methane gas with the flow rate of 5sccm and the pressure of 100-;
after the growth is finished, closing the carbon source gas, continuously introducing argon gas with the flow rate of 30sccm and the pressure controlled at 300mbar, pulling the heating area to the other side, rapidly cooling to 600 ℃, wherein the cooling rate can reach 240 ℃/min in case of 120 sccm; then naturally cooling to room temperature, and growing a graphene array with a thin middle and a thick edge on the surface of the nickel-copper composite metal array substrate;
(4) dripping 1% PMMA solution on the composite metal with the graphene array grown in the step (3), whirl coating and drying, and then putting the sample into 1mol/L FeCl3Treating the mixture with a mixed solution of nitric acid (1:1) for more than 2 hours to remove the composite metal; fishing out the graphene array into deionized water by using a glass slide, cleaning the graphene array, fishing out the graphene array by using a silicon wafer, and drying the graphene array; repeatedly removing PMMA with hot acetone, finally respectively cleaning with deionized water and alcohol, and finally drying with a nitrogen gun; and obtaining the graphene array with thin middle and thick edges.
Example 2:
a method for preparing graphene arrays with different lattice point thicknesses by using a composite metal template comprises the following steps:
(1) sequentially ultrasonically cleaning a copper foil with the size of 1 square centimeter by using deionized water and absolute ethyl alcohol to remove impurities on the surface of the copper foil;
(2) coating glue on the copper foil cleaned in the step (1), exposing under an optical mask, washing off glue at an exposure point, evaporating and depositing 200nm nickel by using an electron beam, and removing redundant glue to obtain a nickel metal array substrate, wherein the diameter of a metal array point is about 300 mu m, the thickness of the metal array point is 300nm, and the distance between the metal array points is 2 mm;
(3) horizontally placing the copper-nickel composite metal array substrate in the step (2) on a quartz boat sample table of a slide rail tube type CVD growth furnace; the mechanical pump and the molecular pump for the tubular CVD growth furnace are pumped to the vacuum degree of 10-4Pa, heating to 200 ℃, heating at a rate of 20 ℃/min, introducing high-purity argon at a flow rate of 20sccm and a pressure of 100-300mbar, and keeping the temperature for 10 min; then heating to 550 ℃, wherein the heating rate is 20 ℃/min, introducing hydrogen, controlling the flow rate to 10sccm, controlling the pressure to be 100-; then heating to 1050 ℃, wherein the heating rate is 10 ℃/min, and keeping the temperature for 20 min; introducing methane gas with the flow rate of 10sccm and the pressure of 100-;
after the growth is finished, closing the carbon source gas, continuously introducing argon gas with the flow rate of 30sccm and the pressure controlled at 300mbar, pulling the heating area to the other side, rapidly cooling to 600 ℃, wherein the cooling rate can reach 240 ℃/min in case of 120 sccm; then naturally cooling to room temperature, and growing a graphene array with thick middle and thin edge on the surface of the copper-nickel composite metal array substrate;
(4) dripping 1% PMMA solution on the composite metal of the graphene array grown in the step (3), spinning and drying, taking a composite metal foil as an anode of an electrochemical workstation, putting the composite metal foil into a salt solution, taking a copper sheet as a cathode, and separating the composite metal from the graphene array by a bubbling method; fishing out the graphene array into deionized water by using a glass slide, cleaning the graphene array, fishing out the graphene array by using a silicon wafer, and drying the graphene array; repeatedly removing PMMA with hot acetone, finally respectively cleaning with deionized water and alcohol, and finally drying with a nitrogen gun; and obtaining the graphene array with thick middle and thin edge.
Example 3:
a method for preparing graphene arrays with different lattice point thicknesses by using a composite metal template comprises the following steps:
(1) sequentially ultrasonically cleaning a copper foil with the size of 1 square centimeter by using deionized water and absolute ethyl alcohol to remove impurities on the surface of the copper foil;
(2) pasting a metal porous mask plate on the copper foil cleaned in the step (1), and depositing 300nm nickel by using electron beam evaporation or plasma sputtering to obtain a nickel metal array substrate, wherein the diameter of a metal array point is about 500 mu m, the thickness is 300nm, and the distance is 2 mm;
(3) horizontally placing the copper-nickel composite metal array substrate in the step (2) on a quartz boat sample table of a slide rail tube type CVD growth furnace; the mechanical pump and the molecular pump for the tubular CVD growth furnace are pumped to the vacuum degree of 10-4Pa, heating to 200 ℃, heating at a rate of 20 ℃/min, introducing high-purity argon at a flow rate of 20sccm and a pressure of 100-300mbar, and keeping the temperature for 10 min; then heating to 550 ℃, wherein the heating rate is 20 ℃/min, introducing hydrogen, controlling the flow rate to 10sccm, controlling the pressure to be 100-; then heating to 1030 ℃, wherein the heating rate is 10 ℃/min, and keeping the temperature for 20 min; introducing methane gas with the flow rate of 10sccm and the pressure of 100-;
after the growth is finished, closing the carbon source gas, continuously introducing argon gas with the flow rate of 30sccm and the pressure controlled at 300mbar, pulling the heating area to the other side, rapidly cooling to 600 ℃, wherein the cooling rate can reach 240 ℃/min in case of 120 sccm; then naturally cooling to room temperature, and growing a graphene array with thick middle and thin edge on the surface of the copper-nickel composite metal array substrate;
(4) putting the composite metal of the graphene array grown in the step (3) into 1mol/L FeCl3Treating the mixture with a mixed solution of nitric acid (1:1) for more than 2 hours to remove the composite metal; fishing out the graphene array into deionized water by using a glass slide, cleaning the graphene array, fishing out the graphene array by using a pressure sensor substrate, an acceleration sensor substrate and the like, and drying the graphene array; finally, respectively cleaning with deionized water and alcohol, and finally drying with a nitrogen gun; and obtaining the graphene array with thick middle and thin edge.
Experimental example:
the products of examples 1-3 above were tested.
SEM images of graphene arrays grown in examples 1 and 2 are shown in fig. 3: in fig. 3, a is an SEM image of the graphene array of example 1, and b is an SEM image of the graphene array of example 2. From the SEM image of example 1, it can be seen that the first region is a copper foil substrate made of single-layer graphene, the second region is a graphene array, the number of layers is increased, and the third region is the thickest (the raman image of fig. 5 also proves that the first region is a copper foil substrate made of single-layer graphene, and the third region is the thickest), so that the present invention successfully forms a graphene array with thick middle and thin edge, and the size of the single array can reach 200-; in the SEM image 3b of example 2, it can be seen that the peripheral region is the nickel foil substrate and is multi-layer graphene, the central region is the graphene array, the number of layers is reduced, the graphene array with thin middle and thick edges is formed, and the size of the single array can reach 300 μm. The graphene array has good quality.
The XRD pattern of the graphene array grown according to the procedure described in example 1 is shown in fig. 4. From the above fig. 4, the XRD pattern of the graphene array sample grown in example 1 has a distinct protrusion at 25o to 30o compared to the nickel foil, which is a diffraction peak of the aggregated carbon, indicating the formation of graphene; examples 2-3 are also similar.
The raman spectra of different positions of the graphene array obtained by the growth in the steps described in example 1 are shown in fig. 5.
From the graph of fig. 5, the raman characteristic peaks 2D and G of the three regions of the graphene array obtained by growth in example 1 are obvious, and the ratio (I) of the D peak to the G peak in the raman spectrogram is comprehensively analyzedG/I2D0.35-2) and 2D peak full width at half maximum FWHM, obtaining the number of layers of the three areas growing graphene, which is 1, 3 and 5, and forming a graphene array with thick middle and thin edge and high quality. The half-peak width and the number of layers correspond to the formula: FWHM (-45 × (1/n)) +88(n is the number of graphene layers).
And (3) comparison test:
by the process of the invention, with CH4Or C3H8Similar results were obtained for graphene arrays prepared with different ratios of external carbon source and mixed gas (results of 4 and 5 in table 1 are similar). Table 1 shows the results of graphene array preparation under different conditions, and comparison shows that graphite is prepared by using traditional CVD method under the same conditionsThe number of the layers of the graphene is single-layer or even multiple layers, and the thin graphene array with the thin middle edge and the thick middle edge is prepared by adopting the novel method for preparing the graphene array by adopting the composite metal template, so that the growth of the graphene is easier to control by using the copper-nickel composite metal to assist in controlling an external carbon source. Therefore, the problem that the graphene array is difficult to control when the traditional CVD method is adopted for preparing the graphene array is expected to be obviously improved, and the performance of the corresponding graphene array is expected to be obviously improved.
Table 1, comparison of the results of graphene array growth under different conditions.
In conclusion, by using the novel method for preparing the graphene array by using the composite metal template, high-quality graphene arrays with thin middle edges and thin middle edges can be prepared on commercially available nickel foils (copper foils).
Claims (4)
1. A method for preparing graphene arrays with different lattice point thicknesses by using a composite metal template comprises the following steps:
(1) providing a metal foil, cleaning, and removing surface impurities to obtain an impurity-removed metal foil;
(2) electroplating or depositing other metal arrays on the metal foil after impurity removal in an electroplating or depositing mode to obtain a metal array substrate; the other metal arrays are copper arrays or nickel arrays, and are different from the metal of the metal foil in the step (1), when the metal foil in the step (1) is nickel foil, the other metal arrays in the step (2) are copper arrays; when the metal foil in the step (1) is copper foil, the other metal arrays in the step (2) are nickel arrays;
the metal array substrate is specifically obtained in one of two ways:
a. covering a metal foil with a metal porous mask plate, wherein the holes on the metal porous mask plate are circular holes, electroplating or depositing a layer of other metal on the metal porous mask plate by adopting an electroplating or depositing mode, removing the metal porous mask plate, and obtaining a metal array of other metals on the metal foil, wherein the diameter of a metal array point is 10-500 mu m; the diameter of the hole on the mask plate is 200-500 mu m, the thickness of the array point of the metal array is 200-400 nm, and the mass ratio of the total mass of the array point to the metal foil is 1:500-1: 2000;
b. adhering an optical mask plate on the upper surface of the metal foil, exposing the optical mask plate, wherein holes on the optical mask plate are circular holes, removing glue at exposure points, electroplating or depositing a layer of other metal on the metal porous mask plate at the exposure points in an electroplating or depositing mode, removing the rest glue, and obtaining a metal array of the other metal on the metal foil, wherein the diameter of the metal array points is 10-500 mu m; the diameter of the hole on the mask plate is 200-500 mu m, the thickness of the array point of the metal array is 200-400 nm, and the mass ratio of the total mass of the array point to the metal foil is 1:500-1: 2000;
(3) placing the metal array substrate on a quartz boat sample table of a CVD growth furnace, vacuumizing, heating to 200-; then heating to 550-650 ℃, introducing high-purity hydrogen, controlling the pressure at 100-300mbar, preserving the heat for 10-60min, and annealing to obtain a composite metal array substrate; the vacuum degree of the vacuum pumping is 10-4～10-6Pa, the heating rate of heating to 200-300 ℃ is 5-20 ℃/min, and the flow of the high-purity argon is 10-100 sccm; the temperature rise rate is 5-20 ℃/min when the temperature rises to 550-650 ℃, and the flow of the high-purity hydrogen is 4-20 sccm; the high-purity argon and the high-purity hydrogen are argon with the purity of more than or equal to 5N and hydrogen with the purity of more than or equal to 5N;
(4) the obtained composite metal array substrate is continuously heated to 1000-1100 ℃, and the temperature is kept for 10-60 min; then introducing high-purity carbon source gas, controlling the pressure at 300mbar for 100-; the heating rate is 1-10 ℃/min when the temperature is increased to 1000-1100 ℃, the flow of the high-purity carbon source gas is 1-20sccm, and the high-purity carbon source gas is methane or propane gas; after the growth is finished, introducing high-purity argon at a flow rate of 10-100sccm, and rapidly cooling at a rate of 120-;
(5) and (4) removing composite metal from the composite metal substrate of the graphene array obtained in the step (4) or separating the graphene from the substrate, and cleaning and drying to obtain the graphene array with different lattice point thicknesses.
2. The method for preparing graphene arrays with different lattice thicknesses by using a composite metal template according to claim 1, wherein in the step (1), the thickness of the metal foil is 0.010mm-0.10mm, and the purity is more than 99.9%; the cleaning is to perform ultrasonic cleaning on the metal foil by using deionized water and absolute ethyl alcohol in sequence.
3. The method for preparing graphene arrays with different lattice point thicknesses by using the composite metal template as claimed in claim 1, wherein in the step (2), the electroplating is to use an anode of an electrochemical workstation for the metal foil, put the metal foil into other metal salt solution, use a copper sheet as a cathode, and electroplate a layer of other metal arrays on the metal foil; the deposition is electron beam evaporation or plasma sputtering deposition.
4. The method for preparing graphene arrays with different lattice thicknesses by using a composite metal template as claimed in claim 1, wherein the step (5) of removing the composite metal or separating the graphene from the substrate is performed by using one of the following methods:
e. dripping 1% polymethyl methacrylate solution on the composite metal with the graphene array grown, whirl coating and drying, and then putting the sample into 1mol/L FeCl3Soaking in mixed solution of nitric acid for 2-10 h, and adding FeCl in the mixed solution3Removing the composite metal with the mass ratio of nitric acid being 1: 1; fishing out the graphene array into deionized water by using a glass slide, cleaning the graphene array, fishing out the graphene array by using a silicon wafer, and drying the graphene array; removing PMMA by using hot acetone repeatedly, and finally respectively removing ionsWashing with water and ethanol, and blow-drying with a nitrogen gun;
f. dripping 1% polymethyl methacrylate solution on the composite metal with the graphene array grown, spinning and drying, putting the composite metal foil as an anode of an electrochemical workstation into a salt solution, taking a copper sheet as a cathode, and separating the composite metal from the graphene array by a bubbling method; fishing out the graphene array into deionized water by using a glass slide, cleaning the graphene array, fishing out the graphene array by using a silicon wafer, and drying the graphene array; repeatedly using hot acetone to remove PMMA, finally respectively cleaning with deionized water and ethanol, and finally drying with a nitrogen gun;
g. putting the composite metal of the grown graphene array into 1mol/L FeCl3Soaking in mixed solution of nitric acid for 2-10 h, and adding FeCl in the mixed solution3Removing the composite metal with the mass ratio of nitric acid being 1: 1; fishing out the graphene array into deionized water by using a glass slide, cleaning, fishing out by using a pressure and acceleration sensor substrate, and drying; and finally, respectively cleaning with deionized water and alcohol, and finally drying with a nitrogen gun.
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