CN110607517B - Method for cleaning graphene - Google Patents

Method for cleaning graphene Download PDF

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Publication number
CN110607517B
CN110607517B CN201810615694.8A CN201810615694A CN110607517B CN 110607517 B CN110607517 B CN 110607517B CN 201810615694 A CN201810615694 A CN 201810615694A CN 110607517 B CN110607517 B CN 110607517B
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graphene
curved surface
adsorbent
cleaning
rolling
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CN110607517A (en
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刘忠范
彭海琳
孙禄钊
李杨立志
刘晓婷
林立
张金灿
贾开诚
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Peking University
Beijing Graphene Institute BGI
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Peking University
Beijing Graphene Institute BGI
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • 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
    • C01B32/196—Purification
    • 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
    • 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
    • C23C16/56—After-treatment

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention provides a method for cleaning graphene, which comprises the step of rolling the surface of the graphene through a curved surface body with an adsorbent on the curved surface to obtain the clean graphene. The method for cleaning the surface of the graphene can quickly clean the graphene on a metal foil grown by CVD, the graphene transferred to a functional substrate and the like, and the obtained graphene has good Raman property and light transmittance and is very helpful for the fields of electronic and optoelectronic devices and selective transmission films.

Description

Method for cleaning graphene
Technical Field
The invention relates to graphene, in particular to a method for cleaning graphene.
Background
Surface contamination is a problem that is widely concerned in the scientific research and industrial fields, and particularly in the scientific and technological industries such as adhesion, adsorption, friction, lubrication, device processing, printed circuit boards and the like, surface contamination can have a great influence. Generally, surface contamination is mostly from air adsorbates, mainly hydrocarbons, and also from intrinsic contamination during material synthesis. For general materials, the surface cleaning by a wet method is mainly ultrasonic cleaning, ultrasonic vibration is utilized to form micro bubbles, and the adsorption of pollutants on the surface is damaged, so that the cleaning effect is realized; the dry cleaning method mainly comprises plasma cleaning or ultraviolet ozone oxidation and the like, and mainly achieves the purpose of removing the surface pollution of an object by means of the physical and chemical reaction between the activation of active particles in plasma and pollutants.
In recent years, graphene, a two-dimensional atomic crystal composed of carbon atoms, has attracted attention because of its excellent electrical, mechanical, thermal, and optical properties, and has a wide application prospect in the fields of electronics, optoelectronics, thermal management, and the like. However, graphene also has the problem of surface pollution, and because graphene is a two-dimensional material, the influence of the surface pollution on the properties of graphene is amplified due to the characteristic of large specific surface area of graphene.
Different from the traditional material, because graphene is a carbon material, most of surface pollutants are hydrocarbon compounds, and the removal of the surface pollutants is very difficult. Traditional surface cleaning methods cannot be simply replicated because both wet ultrasonic and dry plasma cleaning introduce relatively high energy and the process is severe. For example, a plasma cleaning method is adopted, so that the graphene lattice is easily damaged, and point defects (Robinson, j.a.et al.contacting graphene.appl.phys.lett.98,053103, doi:10.1063/1.3549183 (2011)) are introduced; although no literature is dedicated to the damage of the graphene by ultrasonic cleaning, our experiments show that the damage of the graphene is very serious.
Disclosure of Invention
The invention mainly aims to provide a method for cleaning graphene, which comprises the step of performing rolling treatment on the surface of the graphene through a curved surface body provided with an adsorbent on the curved surface to obtain the clean graphene.
According to an embodiment of the invention, the adsorbent is activated carbon.
According to an embodiment of the present invention, the adsorbent is provided on the curved surface of the curved body by an adhesive.
According to an embodiment of the invention, the binder comprises polyvinylidene fluoride and N-methyl pyrrolidone.
According to an embodiment of the present invention, a plurality of holes are formed on the curved surface of the curved surface body.
According to an embodiment of the present invention, the curved body is a cylinder.
According to an embodiment of the present invention, the curved body is made of copper foam, nickel foam or iron foam.
According to an embodiment of the present invention, the voids of the copper foam are 10 μm to 1 mm.
According to an embodiment of the present invention, the pressure applied to the curved body during the cleaning process is 102～106Pa。
According to one embodiment of the present invention, the rolling process of graphene is performed at a temperature of 100 to 200 ℃.
According to the method for cleaning graphene, disclosed by the embodiment of the invention, the surface of the graphene can be treated to be atomic-level clean.
Drawings
Fig. 1 is a schematic structural diagram of rolling processing on a graphene surface according to an embodiment of the present invention;
fig. 2a is an AFM image of graphene before the rolling process of example 1 of the present invention;
fig. 2b is an AFM image of graphene after the rolling process according to example 1 of the present invention;
FIG. 2c is a statistical distribution of the heights of the surface features of FIGS. 2a and 2 b;
fig. 3 is a raman spectrum of ultra-clean graphene according to example 2 of the present invention;
fig. 4 is a characterization diagram of the ultraviolet-visible transmittance of the ultra-clean graphene according to example 3 of the present invention.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below in the specification. It is to be understood that the invention is capable of other embodiments and that various changes in form and details may be made therein without departing from the scope of the invention and the description and drawings are to be regarded as illustrative in nature and not as restrictive.
An embodiment of the invention provides a method for cleaning graphene, which comprises the step of rolling a curved surface body with an adsorbent on a curved surface on the surface of graphene to be cleaned, wherein the adsorbent can adsorb pollutants on the surface of the graphene in the process, so that the cleaned graphene is obtained.
In the present invention, the adsorbent may be activated carbon, activated alumina, molecular sieve, etc., such as coconut shell activated carbon, but not limited thereto.
In one embodiment, the adsorbent may be adhered to the curved surface of the curved body by a binder.
In one embodiment, the mass ratio of binder to adsorbent may be 3: 1.
In one embodiment, the binder may be a solution of polyvinylidene fluoride (PVDF) in N-methylpyrrolidone (NMP), and the mass ratio of the two solutions may be NMP to PVDF 4:1 to 9:1, for example, 5:1, 6:1, 8:1, and the like.
The invention has no limitation on the specific structure of the curved surface body, and can realize rolling on the surface of graphene. For example, the cylindrical body may be a solid cylinder, a solid cylinder with holes, a hollow cylinder, a hollow tubular body with openings at both ends, or the like.
In one embodiment, the adsorbent is disposed on the curved surface (side surface) of the cylinder.
In one embodiment, the curved surface of the cylinder is provided with a plurality of holes, so that the adsorbent is more firmly arranged on the curved surface.
In the present invention, the material of the curved body is preferably a flexible material, and may be, for example, copper foam, nickel foam, or iron foam, and more preferably copper foam, and the voids of the copper foam may be 10 micrometers to 1mm, for example, 100 micrometers, 500 micrometers, or 800 micrometers.
In one embodiment, the curved surface body is a copper foam tube, and the specific dimensions thereof may be: 6mm in inner diameter, 8mm in outer diameter and 40mm in length.
In one embodiment, the rolling process is performed on the surface of the graphene by a roller composed of the adsorbent and the curved surface body, and the rolling process can be repeated for multiple times to improve the cleanliness of the graphene.
In an embodiment, the surface of the graphene may be subjected to rolling under a certain pressure, and the pressure applied to the roller may be 102～106Pa, e.g. 103Pa、104Pa, and the like.
In one embodiment, the rolling of the roller on the surface of the graphene may be performed at a temperature of 20 to 200 ℃, for example, 50 ℃, 100 ℃, 150 ℃, 180 ℃, etc.
In one embodiment, the rolling process for graphene may be performed in an inert gas atmosphere, and the inert gas may be, for example, argon, nitrogen, or the like.
In one embodiment, the rolling processing speed of the roller is >0.01 mm/s.
In one embodiment, as shown in fig. 1, the process of cleaning the surface of the graphene includes:
uniformly mixing activated carbon powder and a binder to form slurry, uniformly coating the slurry on the curved surface of a porous cylinder, and airing to form a roller 30 with an adsorbent 31;
the roller 30 is placed on the surface of the graphene 10 with the contaminant 11 stained on the surface to roll, and the contaminant 11 is adsorbed by the adsorbent 31, so as to obtain the clean graphene 20.
In one embodiment, the binder may be formed by dispersing PVDF in NMP, wherein the mass fraction of PVDF is 3% to 20%.
The method for rolling and cleaning the surface of the graphene can realize rapid cleaning of the graphene on a CVD-grown metal foil, the graphene transferred to a functional substrate and the like, and the obtained graphene has good Raman property and light transmittance and is very helpful for the fields of electronic and optoelectronic devices and selective transmission films.
In an embodiment, the obtained ultra-clean graphene can be used in a transparent conductive film, a transparent electrode, a high-frequency electronic device, a light emitting device, a photovoltaic device, a photoelectric detection device, an electro-optical modulation device, a heat dissipation device, or a hydrophobic device package.
The following describes a method for cleaning graphene according to an embodiment of the present invention in detail with reference to specific examples:
example 1
1) Preparing a PVDF/NMP solution with the mass fraction of 15%;
2) uniformly mixing the PVDF/NMP solution with activated carbon powder according to the mass ratio of 3:1 to form activated carbon-PVDF-NMP slurry;
3) uniformly coating the slurry on a foam copper pipe to form a porous activated carbon roller; the inner diameter of the foam copper pipe is 6mm, the outer diameter of the foam copper pipe is 8mm, the length of the foam copper pipe is 40mm, and the gap of the foam copper pipe is 0.1 mm;
4) placing graphene grown by a chemical vapor deposition method on a copper foil on a quartz plate in a tubular furnace with the diameter of 2 inches, and placing the porous active carbon roller on the graphene;
5) evacuating the gas in the cavity of the tubular furnace (the vacuum degree is about 1Pa), introducing 500sccm argon gas, and keeping the pressure in the cavity at about 5000 Pa;
6) heating the tubular furnace to make the temperature in the furnace reach 150 ℃;
7) and rolling the porous active carbon roller at the temperature and in the atmosphere, and performing rolling operation on the graphene at a rolling speed of 50 mm/min. Fig. 1 is a schematic structural diagram of ultra-clean graphene prepared by rolling with an activated carbon roller.
And 7) repeating the step 7) for five times, cooling the cavity, discharging gas, and taking out the sample.
8) The graphene before treatment and after cleaning was characterized by atomic force microscopy, and the results are shown in fig. 2a to 2 c. Fig. 2a shows the appearance of ordinary graphene on a copper foil before treatment, and it can be seen that the surface of the graphene has large surface relief and many particles; fig. 2b is the surface topography after the above rolling cleaning, and it can be seen that almost no contamination remains except for the copper steps. Fig. 2c is a statistical distribution of the heights of the surface features of fig. 2a and 2b, and it can also be seen that the difference is significant, i.e., the height of the sample after rolling cleaning has less fluctuation, indicating that the surface is cleaner.
Example 2
The specific steps are the same as steps 1) to 7) of example 1.
And transferring the obtained ultra-clean graphene to a silicon dioxide/silicon substrate, and performing Raman spectrum characterization. Fig. 3 is a raman spectrum of the obtained ultra-clean graphene, and it can be seen that the defect peak (D peak) is very small, and the 2D peak/G peak is very high (> 2.5), indicating that the graphene after rolling treatment has high quality and no additional defect is introduced into the crystal lattice.
Example 3
The specific steps are the same as steps 1) to 7) of example 1.
And transferring the obtained ultra-clean graphene onto a quartz glass substrate, and characterizing the ultraviolet visible light transmittance. It can be seen from FIG. 4 that the light transmittance approaches very close to 97.7% at a wavelength of 800nm and is about 97.4% at a wavelength of 550nm, and such high light transmittance indicates extremely high surface cleanliness.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.

Claims (6)

1. A method for cleaning graphene comprises the steps of carrying out rolling treatment on the surface of graphene through a curved surface body with an adsorbent on a curved surface to obtain the clean graphene;
the curved surface body is a cylinder, and the curved surface body is made of foamed copper, foamed nickel or foamed iron; the adsorbent and the curved surface body form a roller, and the pressure applied to the curved surface body is 10 at the temperature of 100-200 ℃ in an inert gas atmosphere2～106Pa rolling graphene, and the rolling processing speed of the roller>0.01mm/s。
2. The method of claim 1, wherein the adsorbent is one or more of activated carbon, activated alumina, molecular sieves.
3. The method of claim 1, wherein the adsorbent is disposed on the curved surface of the curved body by a binder.
4. The method of claim 3, wherein the binder comprises polyvinylidene fluoride and N-methyl pyrrolidone.
5. The method of claim 1, wherein a plurality of holes are formed on the curved surface of the curved body.
6. The method of claim 1, wherein the voids of the copper foam are between 10 microns and 1 millimeter.
CN201810615694.8A 2018-06-14 2018-06-14 Method for cleaning graphene Active CN110607517B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104192832A (en) * 2014-08-14 2014-12-10 常州二维碳素科技有限公司 Method for transferring graphene and graphene film obtained by method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104192832A (en) * 2014-08-14 2014-12-10 常州二维碳素科技有限公司 Method for transferring graphene and graphene film obtained by method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"A Simple Method for Cleaning Graphene Surfaces with an Electrostatic Force";Won Jin Choi等;《Advanecd Materials》;20140131;第26卷(第4期);第637-644页 *
"Mechanical cleaning of graphene";A. M. Goossens等;《APPLIED PHYSICS LETTERS》;20120216;第100卷(第7期);第073110-1至073110-3页 *
"Toward clean suspended CVD graphene";Alexander Yulaev等;《RSC Advances》;20160826;第87卷(第6期);第83954-83962页 *

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