CN115433920B - Process method for growing single-layer graphene - Google Patents
Process method for growing single-layer graphene Download PDFInfo
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- CN115433920B CN115433920B CN202110622642.5A CN202110622642A CN115433920B CN 115433920 B CN115433920 B CN 115433920B CN 202110622642 A CN202110622642 A CN 202110622642A CN 115433920 B CN115433920 B CN 115433920B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 83
- 239000002356 single layer Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 58
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 165
- 239000011889 copper foil Substances 0.000 claims abstract description 161
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 73
- 239000010439 graphite Substances 0.000 claims abstract description 73
- 239000010410 layer Substances 0.000 claims abstract description 27
- 238000004140 cleaning Methods 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 60
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 40
- 239000001257 hydrogen Substances 0.000 claims description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims description 40
- 229910052786 argon Inorganic materials 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 14
- 230000002829 reductive effect Effects 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C23C16/22—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
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
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- General Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
The invention relates to the technical field of material preparation, in particular to a process method for growing single-layer graphene, which comprises the following steps: step 1, fixing a copper foil on a cathode, placing the copper foil in an acidic electrolyte, applying a voltage V 0 between a working electrode and a counter electrode, and treating the copper foil for a duration t 0; step 2, the copper foil obtained in the step 1 is sequentially placed in deionized water and alcohol for cleaning, and the copper foil is dried by nitrogen; step 3, placing the copper foil obtained in the step 2 between two layers of graphite sheets, and growing single-layer graphene on two sides of the copper foil by adopting a chemical vapor deposition method; according to the process method disclosed by the invention, the prepared monolayer graphene is high in purity.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a process method for growing monolayer graphene.
Background
Graphene has been attracting attention because of its excellent physical properties and chemical inertness, and its properties are changed by its own structural changes: for example, different stacking modes of graphenes and different offset included angles between layers can cause the electrical performance of the graphenes to be switched between conductors and semiconductors; and the performance of the composite material is more and more similar to that of graphite along with the increase of the layer number, and the electrical performance and the mechanical performance of the composite material are obviously changed. Therefore, in order to obtain a stable graphene material with high electric conductivity and thermal conductivity, a method for preparing single-layer graphene is particularly critical.
The preparation of the single-layer graphene is subjected to various technical constraints, such as the quality, technological parameters, growth impurities and the like of the copper foil, so that the existing preparation method of the single-layer graphene has the following two main problems:
First, copper foil pretreatment techniques now have a number of ways: electrochemical etching, polishing, chemical treatments, etc., for example, anodic etching is typically used in electrochemical etching to reduce roughness, and conditions are controlled to metal etch electrochemical windows to avoid oxidation of the solution.
Secondly, when the CVD graphene grows, white particle impurities appear on the surface of the grown graphene, the impurities mainly originate from SiOx generated by the reaction of reactive gas and quartz equipment, the growth mechanism of the graphene is changed, and the conductivity is reduced due to the non-conductivity of the impurities.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a process method for growing single-layer graphene, wherein the prepared single-layer graphene has high purity.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A process for growing single-layer graphene, comprising the steps of:
step 1, fixing a copper foil on a cathode, placing the copper foil in an acidic electrolyte, applying a voltage V 0 between a working electrode and a counter electrode, and treating the copper foil for a duration t 0;
step 2, the copper foil obtained in the step 1 is sequentially placed in deionized water and alcohol for cleaning, and the copper foil is dried by nitrogen;
And 3, placing the copper foil obtained in the step 2 between two layers of graphite sheets, and growing single-layer graphene on two sides of the copper foil by adopting a chemical vapor deposition method.
Preferably, in the step 1, the acid electrolyte is an aqueous solution of sulfuric acid with the mass concentration of 3.0% -5.0%, the voltage V 0 is less than or equal to 2.5V, the time t 0 is less than or equal to 5.0min, and the voltage V 0 is less than or equal to 2.5V.
Preferably, in step 1, the acid electrolyte is an aqueous solution of sulfuric acid with a mass concentration of 4.0%, the voltage V 0 is 2.0V, and the time t 0 is 10.0min;
Or in the step 1, the acid electrolyte is sulfuric acid aqueous solution with the mass concentration of 4.0%, the voltage V 0 is 2.3V, and the time t 0 is 20.0min.
Preferably, in the step 2, the copper foil obtained in the step 1 is placed in deionized water, ultrasonic cleaning is carried out to obtain t 1min,3.0≤t1 which is less than or equal to 7.0, then the copper foil is placed in alcohol, and ultrasonic cleaning is carried out to obtain t 2min,8.0≤t2 which is less than or equal to 12.0.
Preferably, in step 2, the copper foil obtained in step 1 is placed in deionized water, and then the copper foil is ultrasonically cleaned t 1 min,t1 =5.0, and then the copper foil is placed in alcohol, and then the copper foil is ultrasonically cleaned t 2 min,t2 =10.0.
Preferably, step 3 comprises the following operative steps:
step 31, placing the copper foil obtained in the step 2 on one layer of graphite sheet, and covering the copper foil with another layer of graphite sheet to obtain a copper foil graphite sheet composite structure;
step 32, placing the copper foil graphite sheet composite structure in a crucible, and integrally placing the crucible in a CVD furnace;
step 33, vacuumizing a CVD furnace to 10.0-30.0Pa, then introducing argon with n 1 sccm into the CVD furnace and keeping the argon at 120.0-n 1 -280, then heating the CVD furnace to T 0 ℃ and keeping the temperature of the CVD furnace, 1050.0-T 0 -1070.0, then introducing hydrogen with n 2 sccm into the CVD furnace and keeping the hydrogen at 10.0-n 2 -30.0, and annealing for 5.0-15.0min;
Step 34, cooling the CVD furnace to T 1 ℃ and keeping the temperature, wherein T 1 is less than or equal to 950.0 and less than or equal to 1050.0, then introducing n 3 sccm of methane into the CVD furnace and keeping the temperature, n 3 is less than or equal to 2.0 and less than or equal to 5.0, adjusting the flow of hydrogen to n 4 sccm and keeping the temperature, n 4 is less than or equal to 12 and less than or equal to 30, adjusting the flow of argon to n 5 sccm and keeping the temperature, and n 5 is less than or equal to 120 and less than or equal to 280, so that single-layer graphene grows for 1.0-1.5h;
and 35, after the growth of the single-layer graphene is completed, stopping introducing hydrogen and methane into the CVD furnace, and cooling the CVD furnace to room temperature.
Preferably, in step 33, the CVD furnace is evacuated to 20.0Pa, then n 1 sccm of argon is introduced into the CVD furnace and kept, n 1 =120.0, then the CVD furnace is heated to T 0 ℃ and kept, T 0 = 1070.0, then n 2 sccm of hydrogen is introduced into the CVD furnace and kept, n 2 =20.0, and annealing is performed for 10.0min;
In step 34, the CVD furnace is cooled to T 1 ℃ and kept, T 1 =1000.0, then n 3 sccm of methane is introduced into the CVD furnace and kept, n 3 =2.0, the flow rate of hydrogen is adjusted to n 4 sccm and kept, n 4 =12.0, and the flow rate of argon is adjusted to n 5sccm,n5 =120.0, so that single-layer graphene grows for 1.5h;
in step 35, the CVD furnace is rapidly cooled to room temperature.
Preferably, in step 33, the CVD furnace is evacuated to 20.0Pa, then n 1 sccm of argon is introduced into the CVD furnace and kept, n 1 =280.0, then the CVD furnace is heated to T 0 ℃ and kept, T 0 = 1070.0, then n 2 sccm of hydrogen is introduced into the CVD furnace and kept, n 2 =20.0, and annealing is performed for 10min;
In step 34, the CVD furnace is cooled to T 1 ℃ and kept, T 1 =1000.0, then n 3 sccm of methane is introduced into the CVD furnace and kept, n 3 =5.0, n 4 sccm of hydrogen is adjusted and kept, n 4 =30.0, the flow rate of argon is adjusted and kept, n 5 sccm and n 5 =120.0, and single-layer graphene is grown for 1.0h;
In the step 35, the temperature of the CVD furnace is reduced to the room temperature within the time t 3, and t 3 is more than 0 and less than or equal to 2.0 hours.
Preferably, the graphite sheets and the copper foil are stacked together by self gravity, and the specification and the size of the graphite sheets are larger than those of the copper foil.
Preferably, the graphite flake is sized to exceed the copper foil by 1.5-2.5cm in all directions; the thickness of the graphite flake is d nm, and d is 150-300 nm.
According to the process method for growing the single-layer graphene, the copper foil is fixed on the cathode to perform electrochemical treatment, so that generated hydrogen bubbles and reduction on the surface of the copper foil can effectively remove surface impurities, microscopic cleaning and reduction on the surface of the copper foil are realized, nucleation sites are reduced, oxidation or corrosion pit formation on the surface of the copper foil is reduced, and obvious roughening phenomenon on the surface of the copper foil is avoided; and the copper foil is arranged between two layers of graphite sheets, and single-layer graphene grows on two sides of the copper foil through a chemical deposition method, so that direct deposition of S iOx compounds on the surface of the single-layer graphene is obviously reduced or avoided, the flow mode of gas is improved, and the small-flow single-layer graphene growth is realized.
Drawings
FIG. 1 is an SEM low-magnification view of single-layer graphene of example 1 of the present invention;
Fig. 2 is a SEM high-magnification view of single-layer graphene of example 1 of the present invention;
Fig. 3 is a raman diagram of monolayer graphene of example 1 of the present invention;
fig. 4 is a TEM image of single-layer graphene of example 1 of the present invention.
Detailed Description
The process for growing single-layer graphene of the present invention is not limited to the description of the following examples.
The invention relates to a process method for growing single-layer graphene, which comprises the following operation steps:
step 1, fixing a copper foil in an acid electrolyte, applying a voltage V 0 between a working electrode and a counter electrode, and processing the copper foil for a duration of T 0;
Step 2, the copper foil obtained in the step 1 is sequentially placed in deionized water and alcohol for cleaning, and the copper foil is dried by nitrogen;
And 3, placing the copper foil obtained in the step 2 between two layers of graphite sheets, and growing single-layer graphene on two sides of the copper foil by adopting a chemical vapor deposition method.
According to the process method for growing the single-layer graphene, the copper foil is fixed on the cathode to perform electrochemical treatment, so that generated hydrogen bubbles and reduction on the surface of the copper foil can effectively remove surface impurities, microscopic cleaning and reduction on the surface of the copper foil are realized, nucleation sites are reduced, oxidation or corrosion pit formation on the surface of the copper foil is reduced, and obvious roughening phenomenon on the surface of the copper foil is avoided; and the copper foil is arranged between two layers of graphite sheets, and single-layer graphene grows on two sides of the copper foil through a chemical deposition method, so that direct deposition of S iOx compounds on the surface of the single-layer graphene is obviously reduced or avoided, the flow mode of gas is improved, and the small-flow single-layer graphene growth is realized.
The following is one embodiment of the process for growing single-layer graphene according to the present invention.
The process method for growing single-layer graphene of the embodiment comprises the following operation steps:
Step 1, a copper foil is fixed on a cathode and placed in an acidic electrolyte, a voltage V 0 is applied between a working electrode and a counter electrode, and the copper foil is treated for a duration t 0.
Preferably, the acidic electrolyte is an aqueous sulfuric acid solution. It should be noted that the acidic electrolyte may also be an aqueous solution of other acids, such as an aqueous solution of H 3PO4; because the electrochemical window, acid solution concentration and acid strength of different acid solutions are different, when the copper foil is treated by using the aqueous solutions of different acids, the concentration, voltage, treatment time and the like of the aqueous solutions need to be correspondingly adjusted.
Preferably, in step 1, the acid electrolyte is an aqueous solution of sulfuric acid with a mass concentration of 3.0-5.0%, V 0 is less than or equal to 2.0V, V 0 is less than or equal to 5.0min, and the voltage V 0 is constant, for example, 2.5V or 2.2V is maintained all the time in step 1.
In the method for growing single-layer graphene in the prior art, anodic etching is adopted for copper foil treatment (electrochemical polishing), copper is controlled to react in an electrochemical window so as to avoid electrolyte reaction, and the surface current distribution is influenced by the uneven plane state of the surface of the copper. The corrosion speed is high at the raised position because of current concentration, the corrosion speed is low at the recessed position, so that the surface tends to be flattened, the concave-convex difference is reduced, namely the mechanism and the aim of electrochemical polishing are achieved, and the surface roughness of the copper foil is reduced. In the method, one key point is to fix the copper foil on a cathode for treatment, and the other key point is to decompose the acid electrolyte outside an electrochemical window so as to assist the cleaning treatment of the surface of the copper foil; therefore, the roughness of the copper foil is reduced, and meanwhile, more importantly, the surface of the copper foil is subjected to cleaning, reduction and activation, so that the growth of single-layer graphene by a subsequent CVD process is facilitated.
And 2, cleaning the copper foil obtained in the step 1 in deionized water and alcohol in sequence, and blow-drying the copper foil by using nitrogen.
Preferably, in the step 2, the copper foil obtained in the step 1 is placed in deionized water, ultrasonic cleaning is carried out to obtain t 1min,3.0≤t1 which is less than or equal to 7.0, then the copper foil is placed in alcohol, and ultrasonic cleaning is carried out to obtain t 2min,8.0≤t2 which is less than or equal to 12.0.
And 3, placing the copper foil obtained in the step 2 between two layers of graphite sheets, and growing single-layer graphene on two sides of the copper foil by adopting a chemical vapor deposition method.
Preferably, step 3 comprises the following operative steps:
And 31, placing the copper foil obtained in the step 2 on one layer of graphite sheet, and covering the copper foil with the other layer of graphite sheet to obtain the copper foil graphite sheet composite structure. Further, the graphite sheets and the copper foil are stacked together by self gravity, and the specification size of the graphite sheets is larger than that of the copper foil. Further, the specification and the size of the graphene exceed 1.5-2.5cm of the copper foil in all directions; the thickness of the graphite flake is d nm, and d is 150-300 nm. It should be noted that the thickness of the graphite sheet must not be too thin, otherwise it cannot maintain its own stability and shape, and it is easily blown away or destroyed by the air flow; the thickness of the graphite sheet must not be too thick as it would affect the gap between the graphite sheet and the copper foil and affect the air flow in the gap; therefore, the thickness of the graphite flake is preferably 150nm, 200nm, 250nm or 300nm, and the graphite flake can maintain its shape and stability, and also can form a reasonable gap between the graphite flake and the copper foil.
Specifically, the graphite sheets and the copper foil are loosely stacked together by self gravity, and the space between the graphite sheets and the copper foil is naturally formed; for example: if the copper foil is rectangular, the length of the graphite sheet exceeds the length of the copper foil by 1.5-2.5cm, and the width of the graphite sheet exceeds the width of the copper foil by 1.5-2.5cm; if the copper foil is circular in shape, the minimum width of the graphite sheet also exceeds the radius of the copper foil by 1.5-2.5cm.
And step 32, placing the copper foil graphite sheet composite structure in a crucible, and integrally placing the crucible in a CVD furnace.
Step 33, vacuumizing the CVD furnace to 10.0-30.0Pa, introducing argon with n 1 sccm into the CVD furnace and keeping the argon at 120.0-n 1 -280, heating the CVD furnace to T 0 ℃ and keeping the temperature, 1050.0-T 0 -1070.0, introducing hydrogen with n 2 sccm into the CVD furnace and keeping the hydrogen at 10.0-n 2 -30.0, and annealing for 5.0-15.0min.
And 34, cooling the CVD furnace to T 1 ℃ and keeping the temperature, wherein T 1 is less than or equal to 950.0 and less than or equal to 1050.0, then introducing methane with n 3 sccm into the CVD furnace and keeping the temperature, n 3 is less than or equal to 2.0 and less than or equal to 5.0, adjusting the flow of hydrogen to n 4sccm,12.0≤n4 and less than or equal to 30.0sccm and keeping the flow of argon to n 5 sccm and keeping the flow of argon to 120.0 and less than or equal to n 5 and less than or equal to 280.0, and enabling the single-layer graphene to grow for 1.0-1.5 hours.
And 35, after the growth of the single-layer graphene is completed, stopping introducing hydrogen and methane into the CVD furnace, and cooling the CVD furnace to room temperature within the time t 3, wherein t 3 is more than 0 and less than or equal to 2.0 hours. Furthermore, the intermediate sample area can not be insulated in the hearth by pulling the hearth of the CVD to one side, so that the intermediate sample area is connected with the atmosphere for rapid cooling, and the cooling can be assisted by adopting a fan for accelerating cooling. In the steps, the temperature of the CVD furnace is reduced to the room temperature within 2 hours, so that the phenomenon that the residual gas is separated at a high temperature to produce opposite amorphous carbon to deposit on the single-layer graphene is avoided, copper atoms can escape and carbon atoms on the surface are taken away to damage the graphene structure if the temperature of the CVD furnace is excessively long, and free carbon can grow at the damage positions to reduce the quality of the single-layer graphene.
Preferably, t 3 may be 0.2h, 0.5h, 0.8h, 1.0h, 1.2h, 1.5h, 1.8h or 2.0h, and the specific value of t 3 is related to the CVD furnace specifications and their contents.
The following is a specific example of the process method for growing single-layer graphene according to the present invention.
Example 1:
the process method for growing the single-layer graphene in the embodiment comprises the following operation steps:
And step 1, fixing a copper foil on a cathode, placing the copper foil in a sulfuric acid aqueous solution with the mass concentration of 4.0%, applying a voltage V 0 of 2.0V between a working electrode and a counter electrode, treating the copper foil, and keeping the time t 0 of 10.0min.
And 2, placing the copper foil obtained in the step 1 in deionized water, ultrasonically cleaning t 1min,t1 =5.0, and then placing the copper foil in alcohol, and ultrasonically cleaning t 2min,t2 =10.0.
Step 3, comprising the following operation steps:
And 31, placing the copper foil obtained in the step 2 on one layer of graphite sheet, and covering the copper foil with the other layer of graphite sheet to obtain the copper foil graphite sheet composite structure. Further, the specification and the size of the graphite flake exceed 2.0cm of the copper foil in all directions.
And step 32, placing the copper foil graphite sheet composite structure in a crucible, and integrally placing the crucible in a CVD furnace.
Step 33, vacuuming the CVD furnace to 20.0Pa, introducing argon with n 1 sccm into the CVD furnace and keeping, wherein n 1 =120.0, then heating the CVD furnace to T 0 ℃ and keeping, T 0 = 1070.0, then introducing hydrogen with n 2 sccm into the CVD furnace and keeping, and n 2 =20.0, and annealing for 10.0min.
Step 34, cooling the CVD furnace to T 1 ℃ and keeping the temperature, T 1 =1000.0, then introducing n 3 sccm of methane into the CVD furnace and keeping the temperature, n 3 =2.0, adjusting the flow rate of hydrogen to n 4 sccm and keeping the temperature, n 4 =12.0, and adjusting the flow rate of argon to n 5 sccm,n5 =120.0, so that the single-layer graphene grows for 1.5h.
And 35, after the growth of the single-layer graphene is completed, stopping introducing hydrogen and methane into the CVD furnace, and cooling the CVD furnace to room temperature within the time t 3.
As shown in fig. 1 to 4, the copper crystal grains grown in example 1 were several hundred micrometers to millimeter-sized, well-clad, and had no significant white SiOx impurity particles at the grain boundaries even under the SEM low-power and high-power fields of view.
Example 2:
the process method for growing the single-layer graphene in the embodiment comprises the following operation steps:
And step 1, fixing the copper foil on a cathode, placing the copper foil in a sulfuric acid aqueous solution with the mass concentration of 4.0%, applying a voltage V 0 of 2.3V between a working electrode and a counter electrode, and treating the copper foil, wherein the holding time t 0 is 20.0min.
And 2, placing the copper foil obtained in the step 1 in deionized water, ultrasonically cleaning t 1 min,t1 =5.0, and then placing the copper foil in alcohol, and ultrasonically cleaning t 2 min,t2 =10.0.
Step 3, comprising the following operation steps:
And 31, placing the copper foil obtained in the step 2 on one layer of graphite sheet, and covering the copper foil with the other layer of graphite sheet to obtain the copper foil graphite sheet composite structure. Further, the specification and the size of the graphite flake exceed 2.0cm of the copper foil in all directions.
And step 32, placing the copper foil graphite sheet composite structure in a crucible, and integrally placing the crucible in a CVD furnace.
Step 33, vacuuming the CVD furnace to 20.0Pa, introducing argon with n 1 sccm into the CVD furnace and keeping, wherein n 1 =280.0, then heating the CVD furnace to T 0 ℃ and keeping, T 0 = 1070.0, then introducing hydrogen with n 2 sccm into the CVD furnace and keeping, and n 2 =20.0, and annealing for 10.0min.
Step 34, cooling the CVD furnace to T 1 ℃ and keeping, T 1 =1000.0, then introducing n 3 sccm of methane into the CVD furnace and keeping, n 3 =5.0, adjusting the flow rate of hydrogen to n 4 sccm and keeping, n 4 =30.0, adjusting the flow rate of argon to n 5 sccm and keeping, and n 5 =120.0, so that the single-layer graphene grows for 1.0h.
And 35, after the growth of the single-layer graphene is completed, stopping introducing hydrogen and methane into the CVD furnace, and cooling the CVD furnace to room temperature within the time t 3.
Example 3:
the process method for growing the single-layer graphene in the embodiment comprises the following operation steps:
And step 1, fixing a copper foil on a cathode, placing the copper foil in a sulfuric acid aqueous solution with the mass concentration of 5.0%, applying a voltage V 0 to be 2.0V between a working electrode and a counter electrode, treating the copper foil, and keeping the time t 0 to be 5.0min.
And 2, placing the copper foil obtained in the step 1 in deionized water, ultrasonically cleaning t 1 min,t1 =7.0, and then placing the copper foil in alcohol, and ultrasonically cleaning t 2 min,t2 =12.0.
Step 3, comprising the following operation steps:
and 31, placing the copper foil obtained in the step 2 on one layer of graphite sheet, and covering the copper foil with the other layer of graphite sheet to obtain the copper foil graphite sheet composite structure. Further, the specification and the size of the graphite flake exceed 1.5cm of the copper foil in all directions.
And step 32, placing the copper foil graphite sheet composite structure in a crucible, and integrally placing the crucible in a CVD furnace.
Step 33, vacuuming the CVD furnace to 10.0Pa, introducing argon with n 1 sccm into the CVD furnace and keeping, wherein n 1 =200.0, then heating the CVD furnace to T 0 ℃ and keeping, T 0 = 1050.0, then introducing hydrogen with n 2 sccm into the CVD furnace and keeping, and n 2 =30.0, and annealing for 5.0min.
Step 34, cooling the CVD furnace to T 1 ℃ and keeping, T 1 =950.0, then introducing n 3 sccm of methane into the CVD furnace and keeping, n 3 =3.5, adjusting the flow rate of hydrogen to n 4 sccm and keeping, n 4 =21.0, adjusting the flow rate of argon to n 5 sccm and keeping, and n 5 =200.0, so that the single-layer graphene grows for 1.2h.
And 35, after the growth of the single-layer graphene is completed, stopping introducing hydrogen and methane into the CVD furnace, and cooling the CVD furnace to room temperature within the time t 3.
Example 4:
the process method for growing the single-layer graphene in the embodiment comprises the following operation steps:
And step 1, fixing the copper foil on a cathode, placing the copper foil in a sulfuric acid aqueous solution with the mass concentration of 3.0%, applying a voltage V 0 of 2.5V between a working electrode and a counter electrode, and treating the copper foil, wherein the holding time t 0 is 15.0min.
And 2, placing the copper foil obtained in the step 1 in deionized water, ultrasonically cleaning t 1 min,t1 =3.0, and then placing the copper foil in alcohol, and ultrasonically cleaning t 2 min,t2 =8.0.
Step 3, comprising the following operation steps:
And 31, placing the copper foil obtained in the step 2 on one layer of graphite sheet, and covering the copper foil with the other layer of graphite sheet to obtain the copper foil graphite sheet composite structure. Further, the specification and size of the graphite flake exceeds 2.5cm of the copper foil in all directions.
And step 32, placing the copper foil graphite sheet composite structure in a crucible, and integrally placing the crucible in a CVD furnace.
Step 33, vacuuming the CVD furnace to 30.0Pa, introducing argon with n 1 sccm into the CVD furnace and keeping, wherein n 1 =160.0, then heating the CVD furnace to T 0 ℃ and keeping, T 0 = 1060.0, then introducing hydrogen with n 2 sccm into the CVD furnace and keeping, and n 2 =10.0, and annealing for 15.0min.
Step 34, cooling the CVD furnace to T 1 ℃ and keeping, T 1 = 1050.0, then introducing n 3 sccm of methane into the CVD furnace and keeping, n 3 =4.0, adjusting the flow rate of hydrogen to n 4 sccm and keeping, n 4 =16.0, adjusting the flow rate of argon to n 5 sccm and keeping, and n 5 =160.0, so that the single-layer graphene grows for 1.4h.
And 35, after the growth of the single-layer graphene is completed, stopping introducing hydrogen and methane into the CVD furnace, and cooling the CVD furnace to room temperature within the time t 3.
Example 5:
the process method for growing the single-layer graphene in the embodiment comprises the following operation steps:
And step 1, fixing the copper foil on a cathode, placing the copper foil in a sulfuric acid aqueous solution with the mass concentration of 3.5%, applying voltage V 0 to be 2.4V between a working electrode and a counter electrode, treating the copper foil, and keeping the time t 0 to be 18.0min.
And 2, placing the copper foil obtained in the step 1 in deionized water, ultrasonically cleaning t 1 min,t1 =4.0, and then placing the copper foil in alcohol, and ultrasonically cleaning t 2 min,t2 =9.0.
Step 3, comprising the following operation steps:
And 31, placing the copper foil obtained in the step 2 on one layer of graphite sheet, and covering the copper foil with the other layer of graphite sheet to obtain the copper foil graphite sheet composite structure. Further, the specification and the size of the graphite flake exceed 1.8cm of the copper foil in all directions.
And step 32, placing the copper foil graphite sheet composite structure in a crucible, and integrally placing the crucible in a CVD furnace.
Step 33, vacuuming the CVD furnace to 25.0Pa, introducing argon with n 1 sccm into the CVD furnace and keeping, wherein n 1 =240.0, then heating the CVD furnace to T 0 ℃ and keeping, T 0 = 1065.0, then introducing hydrogen with n 2 sccm into the CVD furnace and keeping, and n 2 =15.0, and annealing for 12.0min.
Step 34, cooling the CVD furnace to T 1 ℃ and keeping, T 1 = 1025.0, then introducing n 3 sccm of methane into the CVD furnace and keeping, n 3 =3.0, adjusting the flow rate of hydrogen to n 4 sccm and keeping, n 4 =25.0, adjusting the flow rate of argon to n 5 sccm and keeping, and n 5 =240.0, so that the single-layer graphene grows for 1.3h.
And 35, after the growth of the single-layer graphene is completed, stopping introducing hydrogen and methane into the CVD furnace, and cooling the CVD furnace to room temperature within the time t 3.
Example 5:
the process method for growing the single-layer graphene in the embodiment comprises the following operation steps:
And step 1, fixing the copper foil on a cathode, placing the copper foil in a sulfuric acid aqueous solution with the mass concentration of 4.5%, applying voltage V 0 to be 2.1V between a working electrode and a counter electrode, treating the copper foil, and keeping the time t 0 to be 13.0min.
And 2, placing the copper foil obtained in the step 1 in deionized water, ultrasonically cleaning t 1 min,t1 =6.0, and then placing the copper foil in alcohol, and ultrasonically cleaning t 2 min,t2 =10.0.
Step 3, comprising the following operation steps:
And 31, placing the copper foil obtained in the step 2 on one layer of graphite sheet, and covering the copper foil with the other layer of graphite sheet to obtain the copper foil graphite sheet composite structure. Further, the specification and the size of the graphite flake exceed 2.2cm of the copper foil in all directions.
And step 32, placing the copper foil graphite sheet composite structure in a crucible, and integrally placing the crucible in a CVD furnace.
Step 33, vacuuming the CVD furnace to 15.0Pa, introducing argon with n 1 sccm into the CVD furnace and keeping, wherein n 1 =240.0, then heating the CVD furnace to T 0 ℃ and keeping, T 0 = 1055.0, then introducing hydrogen with n 2 sccm into the CVD furnace and keeping, and n 2 =15.0, and annealing for 8.0min.
Step 34, cooling the CVD furnace to T 1 ℃ and keeping, T 1 = 975.0, then introducing n 3 sccm of methane into the CVD furnace and keeping, n 3 =2.5, adjusting the flow rate of hydrogen to n 4 sccm and keeping, n 4 =14.0, adjusting the flow rate of argon to n 5 sccm and keeping, and n 5 =160.0, so that the single-layer graphene grows for 1.1h.
And 35, after the growth of the single-layer graphene is completed, stopping introducing hydrogen and methane into the CVD furnace, and cooling the CVD furnace to room temperature within the time t 3.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (10)
1. The process method for growing the single-layer graphene is characterized by comprising the following steps of:
step 1, fixing a copper foil on a cathode, placing the copper foil in an acidic electrolyte, applying a voltage V 0 between a working electrode and a counter electrode, and treating the copper foil for a duration t 0;
step 2, the copper foil obtained in the step 1 is sequentially placed in deionized water and alcohol for cleaning, and the copper foil is dried by nitrogen;
and 3, placing the copper foil obtained in the step 2 between two layers of graphite sheets, stacking the graphite sheets and the copper foil together, wherein the specification and the size of the graphite sheets are larger than those of the copper foil, and growing single-layer graphene on two sides of the copper foil by adopting a chemical vapor deposition method.
2. The process for growing single-layer graphene according to claim 1, wherein:
In the step 1, the acid electrolyte is sulfuric acid aqueous solution with the mass concentration of 3.0% -5.0%, the voltage V 0 is less than or equal to 2.0V and less than or equal to 2.5V, and the time t 0 is less than or equal to 5.0 min.
3. The process for growing single-layer graphene according to claim 2, wherein:
In the step 1, the acid electrolyte is sulfuric acid aqueous solution with the mass concentration of 4.0%, the voltage V 0 is 2.0V, and the time t 0 is 10.0min;
Or in the step 1, the acid electrolyte is sulfuric acid aqueous solution with the mass concentration of 4.0%, the voltage V 0 is 2.3V, and the time t 0 is 20.0min.
4. The process for growing single-layer graphene according to claim 1, wherein:
In the step 2, the copper foil obtained in the step 1 is placed in deionized water, ultrasonic cleaning t 1min,3.0≤t1 is less than or equal to 7.0, then the copper foil is placed in alcohol, and ultrasonic cleaning t 2min,8.0≤t2 is less than or equal to 12.0.
5. The process for growing single-layer graphene according to claim 4, wherein:
In step 2, the copper foil obtained in step 1 is placed in deionized water, and then the copper foil is ultrasonically cleaned t 1min,t1 =5.0, and then the copper foil is placed in alcohol, and then the copper foil is ultrasonically cleaned t 2min,t2 =10.0.
6. The process for growing single-layer graphene according to claim 1, wherein:
Step 3 comprises the following operation steps:
step 31, placing the copper foil obtained in the step 2 on one layer of graphite sheet, and covering the copper foil with another layer of graphite sheet to obtain a copper foil graphite sheet composite structure;
step 32, placing the copper foil graphite sheet composite structure in a crucible, and integrally placing the crucible in a CVD furnace;
Step 33, vacuumizing a CVD furnace to 10.0-30.0Pa, then introducing argon with n 1 sccm into the CVD furnace and keeping the argon at 120.0-n 1 -280, then heating the CVD furnace to T 0 ℃ and keeping the temperature of the CVD furnace, 1050.0-T 0 -1070.0, then introducing hydrogen with n 2 sccm into the CVD furnace and keeping the hydrogen at 10.0-n 2 -30.0, and annealing for 5.0-15.0min;
Step 34, cooling the CVD furnace to T 1 ℃ and keeping the temperature, wherein T 1 is less than or equal to 950.0 and less than or equal to 1050.0, then introducing n 3 sccm of methane into the CVD furnace and keeping the temperature, n 3 is less than or equal to 2.0 and less than or equal to 5.0, adjusting the flow of hydrogen to n 4 sccm and keeping the temperature, n 4 is less than or equal to 12 and less than or equal to 30, adjusting the flow of argon to n 5 sccm and keeping the temperature, and n 5 is less than or equal to 120 and less than or equal to 280, so that single-layer graphene grows for 1.0-1.5h;
and 35, after the growth of the single-layer graphene is completed, stopping introducing hydrogen and methane into the CVD furnace, and cooling the CVD furnace to room temperature.
7. The process for growing single-layer graphene according to claim 6, wherein:
In the step 33, the CVD furnace is vacuumized to 20.0Pa, then n 1 sccm argon is introduced into the CVD furnace and kept, n 1 =120.0, then the CVD furnace is heated to T 0 ℃ and kept, T 0 = 1070.0, then n 2 sccm hydrogen is introduced into the CVD furnace and kept, n 2 =20.0, and annealing is performed for 10.0min;
In step 34, the CVD furnace is cooled to T 1 ℃ and maintained, T 1 =1000.0, then n 3 sccm of methane is introduced into the CVD furnace and maintained, n 3 =2.0, the flow rate of hydrogen is adjusted to n 4 sccm and maintained, n 4 =12.0, and the flow rate of argon is adjusted to n 5 sccm,n5 =120.0, so that single-layer graphene is grown for 1.5h.
8. The process for growing single-layer graphene according to claim 6, wherein:
In the step 33, the CVD furnace is vacuumized to 20.0Pa, then n 1 sccm argon is introduced into the CVD furnace and kept, n 1 =280.0, then the CVD furnace is heated to T 0 ℃ and kept, T 0 = 1070.0, then n 2 sccm hydrogen is introduced into the CVD furnace and kept, and n 2 =20.0 is annealed for 10min;
In step 34, the CVD furnace is cooled to T 1 ℃ and kept, T 1 =1000.0, then n 3 sccm of methane is introduced into the CVD furnace and kept, n 3 =5.0, n 4 sccm of hydrogen is adjusted and kept, n 4 =30.0, the flow rate of argon is adjusted and kept, n 5 sccm and n 5 =120.0, and single-layer graphene is grown for 1.0h;
In the step 35, the temperature of the CVD furnace is reduced to the room temperature within the time t 3, and t 3 is more than 0 and less than or equal to 2.0 hours.
9. The process for growing single-layer graphene according to claim 6, wherein: the graphite sheets and the copper foil are stacked together by means of self gravity.
10. The process for growing single-layer graphene according to claim 9, wherein: the size of the graphite flake exceeds the copper foil by 1.5-2.5cm in all directions; the thickness of the graphite flake is d nm, and d is 150-300 nm.
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| CN104498902A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Preparation method of graphene film by virtue of normal-pressure chemical vapor deposition |
| CN112746263A (en) * | 2020-12-23 | 2021-05-04 | 正大能源材料(大连)有限公司 | Method for preparing few-layer graphene film through normal-pressure chemical vapor deposition |
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| CN104099577A (en) * | 2014-07-29 | 2014-10-15 | 苏州斯迪克新材料科技股份有限公司 | Preparation method for graphene |
| CN104498902A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Preparation method of graphene film by virtue of normal-pressure chemical vapor deposition |
| CN112746263A (en) * | 2020-12-23 | 2021-05-04 | 正大能源材料(大连)有限公司 | Method for preparing few-layer graphene film through normal-pressure chemical vapor deposition |
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