CN117383551A - Method for preparing polyethylene terephthalate substrate graphene film by hot-pressing method - Google Patents

Method for preparing polyethylene terephthalate substrate graphene film by hot-pressing method Download PDF

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CN117383551A
CN117383551A CN202311321187.0A CN202311321187A CN117383551A CN 117383551 A CN117383551 A CN 117383551A CN 202311321187 A CN202311321187 A CN 202311321187A CN 117383551 A CN117383551 A CN 117383551A
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graphene
graphene film
polyethylene terephthalate
copper foil
film
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智丽丽
王芸菲
王光耀
李英豪
李艳青
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CHANGJI UNIVERSITY
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CHANGJI UNIVERSITY
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
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    • C01B32/186—Preparation by chemical vapour deposition [CVD]
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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
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    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • 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
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/246—Vapour deposition

Abstract

The invention relates to a method for preparing a polyethylene terephthalate substrate graphene film by a hot pressing method, which comprises the steps of horizontally placing a copper foil on a quartz plate in a chemical vapor deposition tube furnace, introducing hydrogen and methane into the furnace to prepare Cu/graphene, covering a flexible polyethylene terephthalate substrate on the Cu/graphene, hot-pressing the Cu/graphene by a hot press, and placing the Cu/graphene/polyethylene terephthalate into FeCl 3 And (3) completely etching the copper foil in the solution to obtain the transparent polyethylene terephthalate/graphene film. And preparing the graphene film with high quality and large area by adjusting the growth temperature of the graphene, the concentration of carbon source methane, the growth time and the flow rate of the introduced gas. The thermal compression method can transfer the graphene onto other substrates with zero loss and has high repeatability. The preparation method provided by the invention can effectively improve the area of the prepared graphene film, and has the advantages of simple process, low preparation cost, economy, practicability and high production efficiency.

Description

Method for preparing polyethylene terephthalate substrate graphene film by hot-pressing method
Technical Field
The invention belongs to the field of material synthesis, and particularly relates to a method for preparing a polyethylene terephthalate (PET) substrate graphene film by using a hot-pressing method.
Background
Graphene (Graphene) is a two-dimensional carbon atom crystal with only one layer of atoms, and Graphene is obtained by a mechanical exfoliation method for the first time by a group of teaching topics of Geim, manchester university, 2004, and the Graphene obtained by the method has high quality, but has small area and low yield. The redox method generally adopts graphite as a raw material, and graphene is obtained by oxidation treatment, ultrasonic separation and reduction of separated graphene oxide, which is a main method for preparing the graphene in a large amount at low cost at present, but the graphene has small size due to the defect of some physical and chemical properties of the graphene in a severe redox process. In 2006, berger et al obtained ultrathin epitaxial graphene on a SiC single crystal wafer for the first time, and this method could obtain large-area graphene, but the quality of graphene is greatly affected by the SiC substrate, and the growth cost is also high.
In the Chemical Vapor Deposition (CVD) method, hydrocarbon gas is adsorbed on a non-metal or metal surface with catalytic activity, and is dehydrogenated on the surface of a substrate by heating to form a graphene structure, so that a plurality of non-metal substrates are currently studied, such as MgO, znS, BN, and graphene prepared by using the substrate cannot be doped with metal impurities, but the obtained graphene has a small size, is difficult to separate from the substrate, and a plurality of metal substrates are studied, such as Ni, ru, ir, and the like. Since these metal substrates can be evaporated on silicon wafers, this method has potential in the fabrication of large area graphene, but these metals have a large solid solubility for carbon, and it is difficult to control the number of layers and uniformity of graphene formation. In 2011 Su et al successfully realized CVD growth of single-layer graphene at low pressure using a Cu substrate with low solid solubility, unlike the growth mode of metal substrates such as Ni, ru, etc., graphene growth on Cu substrates is a self-limiting growth mode, and the low solid solubility of carbon in Cu limits the process of carbon precipitation at high temperature.
However, the metal substrate is only used as a catalyst and a carrier for graphene growth, which is not beneficial to effectively characterizing physical and chemical properties of graphene, prevents application of transparent electric conduction, heat conduction and other properties of graphene, cannot be used for preparing an electronic device by utilizing a micro-processing technology, and large-area graphene cannot be separated from a support substrate to exist independently and stably, so that the graphene must be peeled off from an initial metal substrate and transferred to a new target substrate mainly comprising an insulating substrate, and development of subsequent application functions is realized. For the problems facing the industrialization of graphene films, which are more focused in the industry, a transfer technology is needed to be solved. The current common method is to spin-coat PMMA on copper foil with graphene, attach graphene film to PMMA by curing, and then etch the copper foil of substrate to transfer graphene to other new substrate. However, since the method adopts the spin coating method, the graphene is easily damaged and wrinkled during the transfer process. Moreover, the hydroxyl groups on the surface of the graphene react with the organic supporting layer, so that more polymer residues are caused, the large-area graphene film is not easy to transfer, and a new transfer method is required to be found.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a method for preparing a polyethylene terephthalate substrate graphene film by using a hot-pressing method. And using methane as a carbon source, using copper foil as a substrate, using copper atoms provided by the copper foil as a catalyst to assist the growth of graphene, and adjusting the carbon source concentration of the graphene. And preparing a large-area graphene film. And (3) adopting a hot pressing technology, directly hot-pressing the flexible polyethylene terephthalate substrate on the copper foil with the graphene film by a hot press, and then obtaining the polyethylene terephthalate/graphene film with a large area by a method of etching the copper foil.
The invention relates to a method for preparing a polyethylene terephthalate substrate graphene film by using a hot pressing method, which comprises the following steps:
a. selecting copper foil with the same size and a glass plate with the same size according to the size of the prepared graphene film, respectively carrying out ultrasonic cleaning on the copper foil and the glass plate for 30min by using acetone, ethanol and deionized water in sequence, and then drying the copper foil and the glass plate by using nitrogen;
b. c, horizontally placing the copper foil cleaned in the step a on a quartz plate in a chemical vapor deposition tube furnace, continuously introducing 2000sccm argon, and heating the temperature in the furnace from room temperature to 1000 ℃ at a speed of 6-10 ℃/min;
c. after the furnace temperature reaches the target temperature, introducing 15sccm of hydrogen and 2-5sccm of methane into a chemical vapor deposition tubular furnace, keeping the temperature at 1000 ℃ for 30-60min, closing the hydrogen and methane gas, keeping the continuous introduction of argon until the furnace temperature naturally drops to room temperature, obtaining copper foil with a graphene film growing on the surface, and closing the argon gas;
d. c, enabling one surface of the copper foil of the graphene film, which is obtained in the step c, to be attached with the graphene film, covering the graphene film with a flexible polyethylene terephthalate base film, and hot-pressing the graphene film for 25-35s at the temperature of 250-280 ℃ by using a hot press to obtain a Cu/graphene/polyethylene terephthalate composite film;
e. putting the Cu/graphene/polyethylene terephthalate composite film obtained in the step d into FeCl with the concentration of 5g/100mL 3 And (3) in the solution, after the metal Cu is completely dissolved, fishing out the graphene film by using a glass sheet after ultrasonic cleaning, and cleaning by using deionized water until the copper foil is completely etched, thus obtaining the transparent polyethylene terephthalate/graphene film.
According to the method for preparing the polyethylene terephthalate (PET) substrate graphene film by using the hot pressing method, the copper foil used in the method is 99.9% pure, the acetone and the ethanol are both analytically pure ARs, the nitrogen is 99.99% pure, and the argon, the hydrogen and the methane are all 99.999%.
Compared with the prior art, the method for preparing the polyethylene terephthalate (PET) substrate graphene film by using the hot pressing method has the following beneficial effects:
the method has the advantages that the graphene film is prepared by adopting a chemical vapor deposition method, accurate control can be realized in the area direction, namely, during the growth of graphene on a monocrystalline substrate, the graphene is spliced seamlessly by controlling variables such as gas flow, temperature, pressure and the like, and graphene with fewer defects is grown.
The flexible polyethylene terephthalate (PET) substrate is hot-pressed on the Cu/graphene by the hot press, so that the graphene can be transferred to other substrates in a zero-loss manner, and the high repeatability is realized. Avoiding the damage of the film caused by the introduction of impurities in the transfer process by the traditional solution etching method.
According to the preparation method, the area of the prepared graphene film can be effectively increased.
The preparation method is simple in process, low in preparation cost, economical, practical and high in production efficiency.
The graphene prepared by the chemical vapor deposition method has the advantages of controllability, expandability and feasibility. The method has great potential in industrialization, and lays a good foundation for the practical application of the graphene.
The flexible polyethylene terephthalate (PET) substrate is hot-pressed on the Cu/graphene prepared by the chemical vapor deposition method by adopting a hot press, so that the crease generated when the graphene film is fished out by using the substrate can be avoided, the defects of difficult production and high cost of the traditional spin-coating PMMA can be avoided, and the preparation of the polyethylene terephthalate (PET) substrate graphene film by using a hot-pressing method can be realized.
Drawings
FIG. 1 is a schematic diagram of a flow of a graphene film transferred into a PET substrate by a hot pressing method;
FIG. 2 is a Raman spectrum of graphene with different hydrogen and methane input amounts;
FIG. 3 is a finished graphene film view of a polyethylene terephthalate (PET) substrate of the present invention;
wherein: (a) A finished graphene film graph of a polyethylene terephthalate (PET) substrate with an inlet amount of 15:2; (b) For a 15:3 throughput of polyethylene terephthalate (PET)
A graphene film finished product diagram of the substrate; (c) Is a finished graphene film graph of a polyethylene terephthalate (PET) substrate with a throughput of 15:5.
Detailed description of the preferred embodiments
In order to describe the technical contents, the achieved objects and effects of the present invention in detail, the following description will be made with reference to the embodiments in conjunction with the accompanying drawings.
Referring to fig. 1, the method for preparing the polyethylene terephthalate base graphene film by using the hot pressing method according to the invention comprises the following steps:
a. selecting copper foil with the same size and a glass plate with the same size according to the size of the prepared graphene film, respectively carrying out ultrasonic cleaning on the copper foil and the glass plate for 30min by using acetone, ethanol and deionized water in sequence, and then drying the copper foil and the glass plate by using nitrogen; the copper foil is easy to purchase and has uniform thickness, and is suitable for being used as a substrate; the ultrasonic cleaning can remove the protective layer on the surface of the copper foil, so that the copper foil can be used as a growth carbon source for preparing the graphene film. The glass sheet is used for salvaging the graphene film, so that the film is prevented from being damaged;
b. c, horizontally placing the copper foil cleaned in the step a on a quartz plate in a chemical vapor deposition tube furnace, continuously introducing 2000sccm argon, and heating the temperature in the furnace from room temperature to 1000 ℃ at a speed of 6-10 ℃/min; the argon is introduced to remove air in the quartz tube, so that impurities in the air are prevented from being generated on the copper foil, and meanwhile, oxides on the surface of the copper foil are fully reduced and the copper grain boundary is grown;
c. after the furnace temperature reaches the target temperature, introducing 15sccm of hydrogen and 2-5sccm of methane into a chemical vapor deposition tubular furnace, keeping the temperature at 1000 ℃ for 30-60min, closing the hydrogen and methane gas, keeping the continuous introduction of argon until the furnace temperature naturally drops to room temperature, obtaining copper foil with a graphene film growing on the surface, and closing the argon gas; methane is used as a gas carbon source of the graphene film, under the action of a metal matrix catalyst of copper, after hydrogen atoms are removed by high-temperature decomposition of the methane carbon source, the rest carbon atoms are attached to the surface of the copper foil, and continuous graphene grows on the surface of the copper foil in the cooling process;
d. c, enabling one surface of the copper foil of the graphene film, which is obtained in the step c, to be attached with the graphene film, covering the graphene film with a flexible polyethylene terephthalate base film, and hot-pressing the graphene film for 25-35s at the temperature of 250-280 ℃ by using a hot press to obtain a Cu/graphene/polyethylene terephthalate composite film; the composite film obtained by the hot pressing method is beneficial to transferring the graphene to other substrates with zero loss, and can avoid the wrinkles generated when the graphene film is fished out by the substrates;
e. putting the Cu/graphene/polyethylene terephthalate composite film obtained in the step d into FeCl with the concentration of 5g/100mL 3 In the solution, after the metal Cu is completely dissolved, the glass cleaned by ultrasonic is usedAnd fishing out the graphene film by the glass flakes, and cleaning the graphene film by deionized water until the copper foil is completely etched, thus obtaining the transparent polyethylene terephthalate/graphene film.
The specific implementation method is as follows:
example 1
See fig. 1:
a. selecting copper foil (purity 99.9%) with the same size and glass plates with the same size according to the size of the prepared graphene film, respectively carrying out ultrasonic cleaning on the copper foil and the glass plates by using acetone (analytically pure AR), ethanol (analytically pure AR) and deionized water for 30min, and then drying the copper foil and the glass plates by using nitrogen (99.99%);
b. c, horizontally placing the copper foil cleaned in the step a on a quartz plate in a chemical vapor deposition tube furnace, continuously introducing 2000sccm argon (99.99%), and heating the temperature in the furnace from room temperature to 1000 ℃ at a speed of 6 ℃/min;
c. after the furnace temperature reaches the target temperature, introducing 15sccm of hydrogen (99.999%) and 2sccm of methane (99.999%) into a chemical vapor deposition tubular furnace, maintaining the temperature at 1000 ℃ for 60min, closing the hydrogen and methane gas, maintaining continuous introduction of argon (99.999%) until the furnace temperature naturally drops to room temperature, obtaining copper foil with a graphene film growing on the surface, and closing the argon gas;
d. c, enabling the copper foil of the graphene film obtained in the step c to be attached to one side of the graphene film, covering a flexible polyethylene terephthalate base film on the graphene film, and hot-pressing for 25 seconds at the temperature of 280 ℃ by using a hot press to obtain a Cu/graphene/polyethylene terephthalate composite film;
e. putting the Cu/graphene/polyethylene terephthalate composite film obtained in the step d into FeCl with the concentration of 5g/100mL 3 And (3) in the solution, after the metal Cu is completely dissolved, fishing out the graphene film by using a glass sheet after ultrasonic cleaning, and cleaning by using deionized water until the copper foil is completely etched, thus obtaining the transparent polyethylene terephthalate/graphene film.
Through detection, the transparent polyethylene terephthalate/graphene film with the light transmittance reaching 91.1% is finally obtained, and the obtained film has a thickness of 3.6 inches(FIG. 3 a). The graphene film can be prepared in a zero-loss large-area manner. When graphene is prepared by introducing hydrogen and methane according to the ratio of 15:2, laser with wavelength of 633nm is selected to perform Raman spectrum test on Cu/graphene, and the result is shown in FIG. 2. The D, G and 2D peaks associated with graphene appear at 1330, 1590, 2650cm, respectively -1 Nearby. The D peak is formed by sp 2 The vibration modes outside the carbon atom plane cause the vibration to be activated only in the presence of defects. The G peak is defined by the in-plane optical phonon E 2g The first order scattering of the mode causes, whereas the 2D peak is caused by second order scattering, and the G and 2D peaks are considered characteristic peaks of graphene, in relation to the inelastic scattering of two phonons with opposite momentum. In example 1, the D peak intensity was smaller, showing less defects in the prepared graphene film; the number of layers of graphene can be judged through the intensity ratio of the 2D peak to the G peak, and the I of the sample 2D /I G Approximately 1.001 and a 2D peak half height (FWHM) of 40cm -1 And the characteristics of double-layer graphene are shown.
Experiment will be SiO 2 Hot-pressing on Cu/graphene film, and then placing FeCl 3 In the solution, finally obtain SiO 2 Graphene and electrical properties of the graphene were tested. And measuring the absolute value of the resistivity and the sheet resistance of the graphene by using a four-probe method, wherein the measured sheet resistance is 2007 omega/≡c, and the sheet resistivity is 143.6Ω & cm. These results indicate that: the polyethylene terephthalate substrate graphene film graphene obtained by the method has excellent transparency and conductivity.
Example 2
Referring to fig. 1:
a. selecting copper foil (purity 99.9%) with the same size and glass plates with the same size according to the size of 5.5 inches for preparing the graphene film, respectively carrying out ultrasonic cleaning on the copper foil and the glass plates with acetone (analytically pure AR), ethanol (analytically pure AR) and deionized water for 30min respectively, and then drying the copper foil and the glass plates with nitrogen (99.99 percent);
b. c, horizontally placing the copper foil cleaned in the step a on a quartz plate in a chemical vapor deposition tube furnace, continuously introducing 2000sccm argon (99.99%), and heating the temperature in the furnace from room temperature to 1000 ℃ at a speed of 8 ℃/min;
c. after the furnace temperature reaches the target temperature, introducing 15sccm of hydrogen (99.999%) and 3sccm of methane (99.999%) into a chemical vapor deposition tubular furnace, keeping the temperature at 1000 ℃ for 45min, closing the hydrogen and methane gas, keeping continuous introduction of argon (99.999%) until the furnace temperature naturally drops to room temperature, obtaining copper foil with a graphene film growing on the surface, and closing the argon gas;
d. c, enabling the copper foil of the graphene film obtained in the step c to be attached to one side of the graphene film, covering a flexible polyethylene terephthalate base film on the graphene film, and hot-pressing for 30s at the temperature of 250 ℃ by using a hot press to obtain a Cu/graphene/polyethylene terephthalate composite film;
e. putting the Cu/graphene/polyethylene terephthalate composite film obtained in the step d into FeCl with the concentration of 5g/100mL 3 And (3) in the solution, after the metal Cu is completely dissolved, fishing out the graphene film by using a glass sheet after ultrasonic cleaning, and cleaning by using deionized water until the copper foil is completely etched, thus obtaining the transparent polyethylene terephthalate/graphene film.
After detection, the transmittance of the transparent polyethylene terephthalate/graphene film can reach 95.5%, and the obtained film has 5.5 inches (figure 3 b). The graphene film can be prepared in a zero-loss large-area manner. When graphene is prepared by introducing hydrogen and methane according to the ratio of 15:3, laser with wavelength of 633nm is selected to perform Raman spectrum test on Cu/graphene, and the result is shown in FIG. 2. In example 2, the D peak intensity was smaller, showing less defects in the prepared graphene film; the number of layers of graphene can be judged through the intensity ratio of the 2D peak to the G peak, and the I of the sample 2D /I G 2.359 and the full width at half maximum (FWHM) of the 2D peak is 42cm -1 And on the left and right, the characteristics of single-layer graphene are shown.
Experiment will be SiO 2 Hot-pressing on Cu/graphene film, and then placing FeCl 3 In the solution, finally obtain SiO 2 Graphene and electrical properties of the graphene were tested. The absolute value of the resistivity and the sheet resistance of the graphene is measured by using a four-probe method, and the measured sheet resistance is 3980 Ω/≡, sheet resistivity 182.3 Ω·cm. These results indicate that: the polyethylene terephthalate substrate graphene film graphene obtained by the method has excellent transparency and conductivity.
Example 3
Referring to fig. 1:
a. selecting copper foil (purity 99.9%) with the same size and glass plates with the same size according to the size of 7.87 inches for preparing the graphene film, respectively carrying out ultrasonic cleaning on the copper foil and the glass plates with acetone (analytically pure AR), ethanol (analytically pure AR) and deionized water for 30min respectively, and then drying the copper foil and the glass plates with nitrogen (99.99 percent);
b. c, horizontally placing the copper foil cleaned in the step a on a quartz plate in a chemical vapor deposition tube furnace, continuously introducing 2000sccm argon (99.99%), and heating the temperature in the furnace from room temperature to 1000 ℃ at a speed of 10 ℃/min;
c. after the furnace temperature reaches the target temperature, introducing 15sccm of hydrogen (99.999%) and 5sccm of methane (99.999%) into a chemical vapor deposition tubular furnace, maintaining the temperature at 1000 ℃ for 60min, closing the hydrogen and methane gas, maintaining continuous introduction of argon (99.999%) until the furnace temperature naturally drops to room temperature, obtaining copper foil with a graphene film growing on the surface, and closing the argon gas;
d. c, enabling the copper foil of the graphene film obtained in the step c to be attached to one side of the graphene film, covering a flexible polyethylene terephthalate base film on the graphene film, and hot-pressing for 35s at the temperature of 260 ℃ by using a hot press to obtain a Cu/graphene/polyethylene terephthalate composite film;
e. putting the Cu/graphene/polyethylene terephthalate composite film obtained in the step d into FeCl with the concentration of 5g/100mL 3 And (3) in the solution, after the metal Cu is completely dissolved, fishing out the graphene film by using a glass sheet after ultrasonic cleaning, and cleaning by using deionized water until the copper foil is completely etched, thus obtaining the transparent polyethylene terephthalate/graphene film.
Through detection, the transparent polyethylene terephthalate/graphene film with the light transmittance reaching 91.0% is finally obtained, and the obtained film has 7.87 inchesCun (FIG. 3 c). And can realize zero-loss large-area preparation of the graphene film. When graphene is prepared by introducing hydrogen and methane according to the ratio of 15:3, laser with wavelength of 633nm is selected to perform Raman spectrum test on Cu/graphene, and the result is shown in FIG. 2. In example 3, the D peak intensity was smaller, showing less defects in the prepared graphene film; the number of layers of graphene can be judged through the intensity ratio of the 2D peak to the G peak, and the I of the sample 2D /I G Approximately 0.921 and a 2D peak half height (FWHM) of 28cm -1 And the characteristics of double-layer graphene are shown.
Experiment will be SiO 2 Hot-pressing on Cu/graphene film, and then placing FeCl 3 In the solution, finally obtain SiO 2 Graphene and electrical properties of the graphene were tested. The absolute values of the resistivity and the sheet resistance of the graphene are measured by using a four-probe method, and the measured sheet resistance is 813 omega/≡c, and the sheet resistivity is 41.35 omega cm. These results indicate that: the polyethylene terephthalate substrate graphene film graphene obtained by the method has excellent transparency and conductivity.
In the embodiment of the invention, a chemical vapor deposition tube furnace of GCVD2-15-12 type CNT high vacuum CVD equipment manufactured by electric furnace Co Ltd, with the model number of West (Beijing) is utilized to prepare the graphene film, and the quartz tube of the furnace body has the size of phi 150 multiplied by 1200mm. The preparation experiment shows that the size of the prepared graphene film is in direct proportion to the area of a quartz plate in a quartz tube in a furnace body, and if a chemical vapor deposition tube furnace with a larger volume is used, the graphene film with a larger area can be prepared.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent changes made by the specification and drawings of the present invention, or direct or indirect application in the relevant art, are included in the scope of the present invention.

Claims (1)

1. A method for preparing a polyethylene terephthalate substrate graphene film by using a hot pressing method is characterized by comprising the following steps of: the method comprises the following steps:
a. selecting copper foil with the same size and a glass plate with the same size according to the size of the prepared graphene film, respectively carrying out ultrasonic cleaning on the copper foil and the glass plate for 30min by using acetone, ethanol and deionized water in sequence, and then drying the copper foil and the glass plate by using nitrogen;
b. c, horizontally placing the copper foil cleaned in the step a on a quartz plate in a chemical vapor deposition tube furnace, continuously introducing 2000sccm argon, and heating the temperature in the furnace from room temperature to 1000 ℃ at a speed of 6-10 ℃/min;
c. after the furnace temperature reaches the target temperature, introducing 15sccm of hydrogen and 2-5sccm of methane into a chemical vapor deposition tubular furnace, keeping the temperature at 1000 ℃ for 30-60min, closing the hydrogen and methane gas, keeping the continuous introduction of argon until the furnace temperature naturally drops to room temperature, obtaining copper foil with a graphene film growing on the surface, and closing the argon gas;
d. c, enabling one surface of the copper foil of the graphene film, which is obtained in the step c, to be attached with the graphene film, covering the graphene film with a flexible polyethylene terephthalate base film, and hot-pressing the graphene film at the temperature of 250-280 ℃ by using a hot press for 25-35s to obtain a Cu/graphene/polyethylene terephthalate composite film;
e. putting the Cu/graphene/polyethylene terephthalate composite film obtained in the step d into FeCl of 5g/100mL 3 And (3) in the solution, after the metal Cu is completely dissolved, fishing out the graphene film by using a glass sheet after ultrasonic cleaning, and cleaning by using deionized water until the copper foil is completely etched, thus obtaining the transparent polyethylene terephthalate/graphene film.
CN202311321187.0A 2023-10-12 2023-10-12 Method for preparing polyethylene terephthalate substrate graphene film by hot-pressing method Pending CN117383551A (en)

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