CN109023291B - Graphene film and preparation method and application thereof - Google Patents

Graphene film and preparation method and application thereof Download PDF

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CN109023291B
CN109023291B CN201810923236.0A CN201810923236A CN109023291B CN 109023291 B CN109023291 B CN 109023291B CN 201810923236 A CN201810923236 A CN 201810923236A CN 109023291 B CN109023291 B CN 109023291B
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CN109023291A (en
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冯贺
田陆
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Hebei radium Technology Co.,Ltd.
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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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
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/0254—Physical treatment to alter the texture of the surface, e.g. scratching or polishing
    • 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
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Abstract

The invention relates to a graphene film and a preparation method and application thereof, wherein the preparation method comprises the following specific steps: 1) respectively carrying out physical impurity removal and chemical impurity removal on a substrate; 2) placing the substrate after impurity removal in a CVD system for annealing treatment; 3) placing the substrate subjected to annealing treatment in an inert atmosphere, and introducing a gaseous carbon source and hydrogen to grow graphene; wherein the flow rate of the carbon source is 1-10 sccm; the flow ratio of the carbon source to the hydrogen is 1: 5-100. The preparation method can prepare the high-quality single-layer or few-layer graphene film, the growth speed of the graphene film is high, the production cost can be greatly reduced, and the wide application of the graphene in the fields of display screens, electronic devices, MEMS sensors and the like is promoted.

Description

Graphene film and preparation method and application thereof
Technical Field
The invention relates to a preparation technology of graphene, in particular to a single-layer or few-layer graphene film and a preparation method and application thereof.
Background
Graphene is a two-dimensional honeycomb lattice formed by arranging single-layer carbon atoms in an sp2 hybridization manner in a regular hexagon, and the two-dimensional planar crystal material with the thickness of only one atomic layer shows a series of excellent characteristics, such as submicron-order ballistic transport, extremely high carrier mobility, excellent mechanical properties and thermal conductivity, good optical properties and chemical stability and the like. With the further reduction of the device size, the graphene is expected to open a new carbon-based integrated circuit in the 'silicon after the' age, and has a wide application prospect in the fields of flexible electronic devices, high-frequency devices, memories, sensors, transparent conductive films, touch screens, energy storage devices and the like. The new physics and the new applied carrier are realized when the material with high quality is used, so the material preparation of the graphene also becomes an important problem in the research of the graphene.
The existing methods for preparing graphene two-dimensional materials can be divided into two main categories of top-down methods and bottom-up methods, wherein the top-down methods comprise a micro-mechanical stripping method, a chemical stripping method, a laser etching stripping method and the like, and the bottom-up methods comprise a Chemical Vapor Deposition (CVD), an epitaxial growth method, a molecular precursor synthesis method and the like. The stripping method is a simple, practical and effective method for stripping graphene from a high-quality graphene block material by utilizing mechanical, electrostatic and electromagnetic interaction forces. The method is the first choice for preparing high-quality graphene at present, but is only suitable for scientific research and cannot be used for batch production. Chemical Vapor Deposition (CVD) is the main method for producing single crystal graphene and large-area polycrystalline graphene at present, and the obtained graphene has high quality, is easy to transfer to various substrates for use, and is widely used for electronic or optoelectronic devices such as graphene transistors and transparent conductive films. At present, the CVD method is gradually becoming the main method for preparing high-quality graphene.
Disclosure of Invention
The invention aims to provide a preparation method of a single-layer or few-layer graphene film, which specifically comprises the following steps:
1) carrying out physical impurity removal and chemical impurity removal on the substrate in sequence;
2) placing the substrate after impurity removal in a CVD system for annealing treatment;
3) placing the substrate subjected to annealing treatment in an inert atmosphere, and introducing a gaseous carbon source and hydrogen to grow graphene; wherein the flow rate of the carbon source is 1-10 sccm; the flow ratio of the carbon source to the hydrogen is 1: 5-100.
At present, most methods for preparing graphene cannot quickly obtain a single-layer or few-layer graphene film; if a single-layer or few-layer graphene film is to be obtained, a carbon source with a lower concentration is generally adopted for slow growth; the method not only has long growth time, but also has very high cost. According to the method, the single-layer or few-layer graphene thin layer can be prepared quickly and efficiently by highly removing impurities from the substrate material and optimizing the growth conditions.
According to the method, a mode of combining physical impurity removal and chemical impurity removal is adopted, and a mode of degradation treatment is optimized, so that the substrate material can be leveled on a micro-nano level, and a guarantee is provided for growing a single layer or few layers of graphene single layers.
Wherein the physical impurity removal comprises one or more of ultrasonic cleaning, mechanical grinding and polishing;
preferably, the ultrasonic frequency adopted for ultrasonic cleaning is 40-80 KHz, the ultrasonic time is 1-3 hours, and the temperature is 20-30 ℃.
The mechanical grinding and polishing is carried out specifically by using the concentration of 0.3-0.5 kg/cm2The time of the alumina or silicon oxide suspension is 30-100 min.
Preferably, after the physical impurity removal, acetone, ethanol and water are respectively adopted for cleaning.
Wherein, the chemical impurity removal is respectively carried out by soaking one of sulfuric acid, hydrochloric acid, nitric acid, acetic acid and phosphoric acid;
preferably, the concentration of acid adopted for chemical impurity removal is 1-18 mol/L, and the soaking time is 1-5 min; wherein, the soaking time of strong acid is slightly short, and the soaking time of weak acid is slightly long.
Preferably, the acid soaking is followed by washing with water.
Wherein the annealing treatment temperature is 600-1500 ℃, and the time is 30-300 min;
preferably, the annealing treatment temperature is 900-1050 ℃, and the time is 30-120 min;
preferably, the annealing treatment is performed in an inert atmosphere, and the inert atmosphere contains 1-20% by volume of hydrogen.
More preferably, the inert atmosphere contains 15-20% by volume of hydrogen.
The invention further provides that the substrate is one or more alloys of metal foil Co, Ni, Fe, Cu, Pt, Au, Ag, Ir and Ru;
or the substrate is a ceramic or quartz substrate coated with one or more alloys of metal foil Co, Ni, Fe, Cu, Pt, Au, Ag, Ir and Ru on the surface layer;
or the substrate is one or more of metal carbides of Co, Ni, Fe, Cu, Pt, Au, Ag, Ir and Ru.
Wherein, the different substrate selection has great difference to annealing condition and growth condition; in practical application, the corresponding conditions of annealing, growth temperature and time and the like need to be selected according to the specific metal type.
The invention most preferably adopts the copper foil, and when the substrate is the copper foil, after physical impurity removal and chemical impurity removal, annealing treatment is combined, so that micro-nano level flatness can be easily obtained; and the copper foil is used, so that reasonable annealing and growth conditions are optimized, and a single-layer film is easier to obtain.
The invention further provides that the gaseous carbon source is selected from one or more of alkanes, alkenes, alkynes, benzenes or small molecular alcohols; preferably C1～C5For example methane.
The invention further provides that the growth temperature is 600-1200 ℃, and the time is not less than 15 min;
preferably, the growth temperature is 900-1000 ℃, and the growth time is 100-150 min.
Preferably, in the inert atmosphere for growth, the inert atmosphere contains 1-10% by volume of hydrogen.
Preferably, the flow rate of the carbon source is 1-5 sccm, and the volume ratio (flow rate ratio) of the hydrogen to the carbon source is 5-100: 1.
The invention provides a preferable scheme, and the preparation method comprises the following specific steps:
1) the copper foil is firstly cleaned by ultrasonic waves, then is soaked in acid solution after being mechanically ground or polished, and is taken out after being cleaned;
2) placing the cleaned copper foil in a CVD system, introducing inert gas containing 15-20% by volume of hydrogen, and annealing at 900-1050 ℃ for 30-120 min;
3) placing the annealed substrate in an inert atmosphere, introducing a gaseous carbon source and hydrogen, and growing graphene at 900-1000 ℃ for 100-150 min;
wherein the flow rate of the carbon source is 1-5 sccm; the flow ratio of the hydrogen to the carbon source is 5-100: 1.
According to the method, the physical method and the chemical method are respectively adopted to highly remove impurities from the substrate for growing the graphene, and the substrate is annealed, so that the substrate is leveled on a micro-nano level, the graphene has few nucleation sites in the growth process, the single-crystallization degree is high, the defects are few, and the growth of high-quality single-layer or few-layer graphene can be realized. Moreover, when a high-concentration carbon source enters the reaction system, fewer nucleation sites can still be ensured, the rapid growth of the graphene film is realized, the production cost is reduced, and the wide application of the graphene in the fields of display screens, electronic devices, MEMS sensors and the like is promoted.
Drawings
Fig. 1 is a picture of a graphene thin film prepared in example 1;
FIG. 2 is a photo-graphic image of the graphene film prepared in example 1 transferred to a silicon substrate;
FIG. 3 is a Raman spectrum of the graphene film prepared in example 1, with a laser wavelength of 532 nm;
fig. 4 is a picture of the graphene thin film prepared in comparative example 1.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The embodiment provides a preparation method of a graphene film, which specifically comprises the following steps:
1) removing impurities: using 0.5kg/cm2Mechanically polishing the copper foil for 30min by using the alumina suspension, then respectively placing the copper foil in de-acetone, ethanol and ionized water for ultrasonic cleaning for 30min, then placing the copper foil in concentrated sulfuric acid for soaking for 1min, and cleaning the copper foil by using deionized water;
2) annealing: placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 12sccm, and then heating to 800 ℃ within 30 min; then introducing hydrogen with the flow of 2sccm, heating to 1000 ℃ within 30min, and preserving the temperature for 30 min.
3) Growing: after heat preservation treatment, stopping introducing argon, adjusting the hydrogen flow to be 12sccm, introducing methane at the flow of 2sccm, starting to grow graphene, and after 120min of growth, stopping introducing methane, adjusting the hydrogen flow to be 2sccm, and adjusting the argon flow to be 12 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
As shown in fig. 1, a bright copper foil can be seen from the picture of the graphene film prepared by using the copper foil as a substrate, which indicates that the prepared graphene film has good light transmittance. As shown in fig. 2 and fig. 3, in the optical display picture and raman spectrum analysis after the graphene film transfer, a 2D/G peak value greater than 2 indicates that the graphene is a single layer and no defect peak exists, indicating that a single-layer stone high-quality graphene film is obtained.
Example 2
The embodiment provides a preparation method of a graphene film, which specifically comprises the following steps:
1) removing impurities: using 0.5kg/cm2Mechanically polishing the copper foil by using the alumina suspension for 30min, then respectively placing the copper foil in acetone, ethanol and ionized water for ultrasonic cleaning for 30min, then placing the copper foil in concentrated nitric acid for soaking for 1min, and cleaning the copper foil by using deionized water;
2) annealing: placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 12sccm, and then heating to 800 ℃ within 30 min; then introducing hydrogen with the flow of 2sccm, heating to 1000 ℃ within 30min, and preserving the temperature for 30 min.
3) Growing: after heat preservation treatment, stopping introducing argon, adjusting the hydrogen flow to be 12sccm, introducing methane at the flow of 2sccm, starting to grow graphene, and after 120min of growth, stopping introducing methane, adjusting the hydrogen flow to be 2sccm, and adjusting the argon flow to be 12 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
The same single-layer stone high-quality graphene film as in example 1 was obtained.
Example 3
The embodiment provides a preparation method of a graphene film, which specifically comprises the following steps:
1) removing impurities: using 0.5kg/cm2Alumina suspension into copper foilMechanically polishing for 30min, ultrasonic cleaning copper foil in acetone, ethanol and ionized water for 30min, soaking in acetic acid for 5min, and cleaning with deionized water;
2) annealing: placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 12sccm, and then heating to 800 ℃ within 30 min; then introducing hydrogen with the flow of 2sccm, heating to 1000 ℃ within 30min, and preserving the temperature for 30 min.
3) Growing: after heat preservation treatment, stopping introducing argon, adjusting the hydrogen flow to be 12sccm, introducing methane at the flow of 2sccm, starting to grow graphene, and after 120min of growth, stopping introducing methane, adjusting the hydrogen flow to be 2sccm, and adjusting the argon flow to be 12 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
The same single-layer stone high-quality graphene film as in example 1 can be obtained
Example 4
The embodiment provides a preparation method of a graphene film, which specifically comprises the following steps:
1) removing impurities: using 0.5kg/cm2Mechanically polishing the copper foil by using the alumina suspension for 30min, then respectively placing the copper foil in acetone, ethanol and ionized water for ultrasonic cleaning for 30min, then placing the copper foil in 5mol/L HCl for soaking for 2min, and cleaning by using deionized water;
2) annealing: placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 12sccm, and then heating to 800 ℃ within 30 min; then introducing hydrogen with the flow of 2sccm, heating to 1000 ℃ within 30min, and preserving the temperature for 30 min.
3) Growing: after heat preservation treatment, stopping introducing argon, adjusting the hydrogen flow to be 12sccm, introducing methane at the flow of 2sccm, starting to grow graphene, and after 120min of growth, stopping introducing methane, adjusting the hydrogen flow to be 2sccm, and adjusting the argon flow to be 12 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
The same single-layer stone high-quality graphene film as in example 1 was obtained.
Example 5
The embodiment provides a preparation method of a graphene film, which specifically comprises the following steps:
1) removing impurities: using 0.5kg/cm2Mechanically polishing the copper foil for 30min by using the alumina suspension, then respectively placing the copper foil in de-acetone, ethanol and ionized water for ultrasonic cleaning for 30min, then placing the copper foil in phosphoric acid for soaking for 3min, and cleaning the copper foil by using deionized water;
2) annealing: placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 12sccm, and then heating to 800 ℃ within 30 min; then introducing hydrogen with the flow of 2sccm, heating to 1000 ℃ within 30min, and preserving the temperature for 30 min.
3) Growing: after heat preservation treatment, stopping introducing argon, adjusting the hydrogen flow to be 12sccm, introducing methane at the flow of 2sccm, starting to grow graphene, and after 120min of growth, stopping introducing methane, adjusting the hydrogen flow to be 2sccm, and adjusting the argon flow to be 12 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
The same single-layer stone high-quality graphene film as in example 1 was obtained.
Example 6
The embodiment provides a preparation method of a graphene film, which specifically comprises the following steps:
1) removing impurities: using 0.5kg/cm2Mechanically polishing the nickel foil for 30min by using the alumina suspension, then respectively placing the nickel foil in acetone, ethanol and ionized water for ultrasonic cleaning for 30min, then placing the nickel foil in concentrated sulfuric acid for soaking for 1min, and cleaning the nickel foil by using deionized water;
2) annealing: placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 12sccm, and then heating to 800 ℃ within 30 min; then introducing hydrogen with the flow of 2sccm, heating to 1400 ℃ within 30min, and preserving the temperature for 60 min.
3) Growing: after heat preservation treatment, reducing the temperature to 1000 ℃, stopping introducing argon, adjusting the hydrogen flow to 12sccm, introducing methane at the flow of 2sccm, starting to grow graphene, stopping introducing methane after 120min of growth, adjusting the hydrogen flow to 2sccm, and adjusting the argon flow to 12 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
A single-layer stone high-quality graphene film can be obtained, and the quality is inferior to that of the graphene film obtained in example 1.
Example 7
The embodiment provides a preparation method of a graphene film, which specifically comprises the following steps:
1) removing impurities: using 0.5kg/cm2Mechanically polishing the platinum sheet for 30min by using the alumina suspension, then respectively placing the platinum sheet in acetone, ethanol and ionized water for ultrasonic cleaning for 30min, then placing the platinum sheet in concentrated sulfuric acid for soaking for 1min, and cleaning the platinum sheet by using deionized water;
2) annealing: placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 12sccm, and then heating to 800 ℃ within 30 min; then introducing hydrogen with the flow of 2sccm, heating to 1100 ℃ within 30min, and preserving the temperature for 200 min.
3) Growing: after heat preservation treatment, reducing the temperature to 1000 ℃, stopping introducing argon, adjusting the hydrogen flow to 12sccm, introducing methane at the flow of 2sccm, starting to grow graphene, stopping introducing methane after 120min of growth, adjusting the hydrogen flow to 2sccm, and adjusting the argon flow to 12 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
A single-layer stone high-quality graphene film can be obtained, and the quality is inferior to that of the graphene film obtained in example 1.
Example 8
The embodiment provides a preparation method of a graphene film, which specifically comprises the following steps:
1) removing impurities: using 0.5kg/cm2Mechanically polishing gold foil with alumina suspension for 30min, ultrasonic cleaning the gold foil in acetone, ethanol and ionized water for 30min, soaking in concentrated sulfuric acid for 1min, and washing with deionized water;
2) annealing: placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 12sccm, and then heating to 800 ℃ within 30 min; then introducing hydrogen with the flow of 2sccm, heating to 900 ℃ within 30min, and preserving the temperature for 120 min.
3) Growing: after heat preservation treatment, heating to 1000 ℃ within 30min, stopping introducing argon, adjusting the hydrogen flow to 12sccm, introducing methane at the flow of 2sccm, starting to grow graphene, stopping introducing methane after 120min of growth, adjusting the hydrogen flow to 2sccm, and adjusting the argon flow to 12 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
A single-layer stone high-quality graphene film can be obtained, and the quality is inferior to that of the graphene film obtained in example 1.
Example 9
The embodiment provides a preparation method of a graphene film, which specifically comprises the following steps:
1) removing impurities: using 0.5kg/cm2Mechanically polishing the copper foil for 30min by using the alumina suspension, then respectively placing the copper foil in de-acetone, ethanol and ionized water for ultrasonic cleaning for 30min, then placing the copper foil in concentrated sulfuric acid for soaking for 1min, and cleaning the copper foil by using deionized water;
2) annealing: placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 100sccm, and then heating to 800 ℃ within 30 min; then introducing hydrogen with the flow of 20sccm, heating to 1000 ℃ within 30min, and preserving the temperature for 30 min.
3) Growing: after heat preservation treatment, stopping introducing argon, adjusting the hydrogen flow to be 120sccm, introducing methane at the flow of 5sccm, starting to grow graphene, and after 60min of growth, stopping introducing methane, adjusting the hydrogen flow to be 10sccm and adjusting the argon flow to be 100 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
The same single-layer stone high-quality graphene film as in example 1 was obtained.
Example 10
The embodiment provides a preparation method of a graphene film, which specifically comprises the following steps:
1) removing impurities: using 0.5kg/cm2Mechanically polishing copper foil with alumina suspension for 30min, ultrasonic cleaning the copper foil in acetone, ethanol and ionized water for 30min, and concentratingSoaking in sulfuric acid for 1min, and cleaning with deionized water;
2) annealing: placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 85sccm, and then heating to 800 ℃ within 30 min; then introducing hydrogen with the flow of 15sccm, heating to 1000 ℃ within 30min, and preserving the temperature for 30 min.
3) Growing: after heat preservation treatment, stopping introducing argon, adjusting the hydrogen flow to be 300sccm, introducing methane at the flow of 5sccm, starting to grow graphene, and after 60min of growth, stopping introducing methane, adjusting the hydrogen flow to be 2sccm, and adjusting the argon flow to be 12 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
The same single-layer stone high-quality graphene film as in example 1 was obtained.
Comparative example 1
The comparative example provides a preparation method of a graphene film, which specifically comprises the following steps:
1) removing impurities: respectively placing copper foil in acetone, ethanol and ionized water, ultrasonic cleaning for 30min, soaking in concentrated sulfuric acid for 1min, and cleaning with deionized water;
2) annealing: placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 12sccm, and then heating to 800 ℃ within 30 min; then introducing hydrogen with the flow of 2sccm, heating to 1000 ℃ within 30min, and preserving the temperature for 30 min.
3) Growing: after heat preservation treatment, stopping introducing argon, adjusting the hydrogen flow to be 12sccm, introducing methane at the flow of 2sccm, starting to grow graphene, and after 120min of growth, stopping introducing methane, adjusting the hydrogen flow to be 2sccm, and adjusting the argon flow to be 12 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
As shown in fig. 4, the graphene film prepared on the surface of the copper foil has a phenomenon of carbon deposition, and the graphene has poor transmittance, and a single-layer or few-layer stone high-quality graphene film cannot be obtained by the method.
As shown in fig. 4, a picture of a graphene film prepared by using a copper foil as a substrate can clearly observe a black substance on the surface of the copper foil, which is carbon deposition formed during the preparation of graphene, and indicates that the number of layers of graphene is large and the quality of graphene is poor.
Comparative example 2
The comparative example provides a preparation method of a graphene film, which specifically comprises the following steps:
1) removing impurities: using 0.5kg/cm2Mechanically polishing the copper foil for 30min by using the alumina suspension, and then respectively placing the copper foil in de-acetone, ethanol and ionized water for ultrasonic cleaning for 30 min;
2) annealing: placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 12sccm, and then heating to 800 ℃ within 30 min; then introducing hydrogen with the flow of 2sccm, heating to 1000 ℃ within 30min, and preserving the temperature for 30 min.
3) Growing: after heat preservation treatment, stopping introducing argon, adjusting the hydrogen flow to be 12sccm, introducing methane at the flow of 2sccm, starting to grow graphene, and after 120min of growth, stopping introducing methane, adjusting the hydrogen flow to be 2sccm, and adjusting the argon flow to be 12 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
The same multilayer low-quality graphene thin film as in comparative example 1 can be obtained.
Comparative example 3
The comparative example provides a preparation method of a graphene film, which specifically comprises the following steps:
1) removing impurities: using 0.5kg/cm2Mechanically polishing the copper foil by using the alumina suspension for 30min, then respectively placing the copper foil in de-acetone, ethanol and ionized water for ultrasonic cleaning for 30min, then respectively placing the copper foil in concentrated sulfuric acid for soaking for 1min, and cleaning the copper foil by using deionized water;
2) annealing: and (3) placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 12sccm, and heating to 1000 ℃ within 60 min.
3) Growing: after heat preservation treatment, stopping introducing argon, introducing hydrogen at the flow rate of 12sccm, introducing methane at the flow rate of 2sccm, starting to grow graphene, and stopping introducing methane after 120min of growth, wherein the hydrogen flow rate is adjusted to 2sccm, and the argon flow rate is adjusted to 12 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
The same multilayer low-quality graphene thin film as in comparative example 1 can be obtained.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (3)

1. The preparation method of the graphene film is characterized by comprising the following specific steps:
the method comprises the following steps:
1) removing impurities: using 0.5kg/cm2Mechanically polishing the copper foil for 30min by using the alumina suspension, then respectively placing the copper foil in acetone, ethanol and deionized water for ultrasonic cleaning for 30min, then placing the copper foil in concentrated sulfuric acid for soaking for 1min, and cleaning the copper foil by using deionized water;
2) annealing: placing the soaked substrate in a CVD system, vacuumizing until the pressure is less than 1Pa, introducing argon with the flow of 12sccm, and then heating to 800 ℃ within 30 min; then introducing hydrogen with the flow of 2sccm, heating to 1000 ℃ within 30min, and preserving heat for 30 min;
3) growing: after heat preservation treatment, stopping introducing argon, adjusting the hydrogen flow to be 12sccm, introducing methane at the flow of 2sccm, starting to grow graphene, and after 120min of growth, stopping introducing methane, adjusting the hydrogen flow to be 2sccm, and adjusting the argon flow to be 12 sccm; stopping heating, and cooling to room temperature to obtain the graphene film.
2. The graphene thin film prepared by the preparation method of claim 1.
3. Use of the graphene thin film according to claim 2 in a display screen, an electronic device, and a MEMS sensor.
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CN111077455A (en) * 2019-10-18 2020-04-28 浙江遨优动力系统有限公司 Soft package lithium ion battery lithium separation detection method
EP4093897A1 (en) * 2020-01-20 2022-11-30 Ultra Conductive Copper Company, Inc. A method and system for coating a metal workpiece with graphene
CN113667960A (en) * 2020-05-13 2021-11-19 北京石墨烯研究院 Clean double-layer and few-layer graphene film and preparation method thereof
CN112830479B (en) * 2021-02-25 2022-09-30 山东大学 Method for preparing easy-to-strip near-free graphene by using sulfur beam decoupling technology
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103184425A (en) * 2013-03-13 2013-07-03 无锡格菲电子薄膜科技有限公司 Method for growing graphene film by using low-temperature chemical vapor deposition
CN103981507A (en) * 2014-05-21 2014-08-13 电子科技大学 Graphene preparation method
CN104773726A (en) * 2015-04-10 2015-07-15 武汉大学 Method for growing single-layer graphene thin film by virtue of low-temperature chemical vapor deposition
CN106884153A (en) * 2015-12-15 2017-06-23 中国科学院上海微系统与信息技术研究所 A kind of method that copper substrate is prepared based on dry method cleaning

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102134067B (en) * 2011-04-18 2013-02-06 北京大学 Method for preparing single-layer graphene
US9627485B2 (en) * 2013-03-15 2017-04-18 University Of Southern California Vapor-trapping growth of single-crystalline graphene flowers
CN103643288B (en) * 2013-11-29 2016-08-17 中国科学院金属研究所 A kind of preparation method of high-quality large-size monocrystal graphene
CN106283179A (en) * 2016-07-25 2017-01-04 福建师范大学 A kind of preparation method of grade monolayer single crystal graphene
CN106521450B (en) * 2016-12-02 2019-05-28 北京大学 A method of preparing super smooth graphene
CN106587030B (en) * 2017-01-11 2018-07-10 重庆大学 A kind of method that atmospheric cryochemistry vapor deposition prepares graphene film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103184425A (en) * 2013-03-13 2013-07-03 无锡格菲电子薄膜科技有限公司 Method for growing graphene film by using low-temperature chemical vapor deposition
CN103981507A (en) * 2014-05-21 2014-08-13 电子科技大学 Graphene preparation method
CN104773726A (en) * 2015-04-10 2015-07-15 武汉大学 Method for growing single-layer graphene thin film by virtue of low-temperature chemical vapor deposition
CN106884153A (en) * 2015-12-15 2017-06-23 中国科学院上海微系统与信息技术研究所 A kind of method that copper substrate is prepared based on dry method cleaning

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