CN111573658A - Twisted angle double-layer graphene directly grown in large area and preparation method thereof - Google Patents

Twisted angle double-layer graphene directly grown in large area and preparation method thereof Download PDF

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Publication number
CN111573658A
CN111573658A CN202010456080.7A CN202010456080A CN111573658A CN 111573658 A CN111573658 A CN 111573658A CN 202010456080 A CN202010456080 A CN 202010456080A CN 111573658 A CN111573658 A CN 111573658A
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graphene
layer
metal film
single crystal
carbon
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潘孟春
李裴森
邱伟成
彭俊平
胡佳飞
胡悦国
张琦
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National University of Defense Technology
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/184Preparation
    • C01B32/186Preparation by chemical vapour deposition [CVD]
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
    • C01B2204/02Single layer graphene
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
    • C01B2204/04Specific amount of layers or specific thickness

Abstract

The invention discloses a preparation method of large-area directly-grown twisted angle double-layer graphene, which comprises the steps of taking a single crystal metal film with carbon dissolving capacity as a substrate, controlling the temperature by adopting a CVD (chemical vapor deposition) method to firstly grow a first layer of graphene on the upper surface of the single crystal metal film, then controlling the cooling rate, utilizing a mechanism of dissolving carbon and then separating out the single crystal metal film, and separating out a second layer of graphene between the substrate and the first layer of graphene, thereby directly preparing the twisted angle double-layer graphene. The method has the characteristics of simple and convenient operation, low cost and the like, and the prepared twisted angle double-layer graphene can be directly applied to the research of electronic devices and the research of high-temperature superconducting mechanism.

Description

Twisted angle double-layer graphene directly grown in large area and preparation method thereof
Technical Field
The invention belongs to the fields of material growth, sensor technology and the like, and particularly relates to large-area twisted angle double-layer graphene on a single-crystal metal material by adopting a CVD (chemical vapor deposition) technology and a direct preparation method thereof.
Background
The graphene serving as a two-dimensional material has excellent physicochemical characteristics and a very wide application prospect. Meanwhile, the development of the intrinsic graphene in the fields of transistor electronic devices, photoelectric devices and the like is limited by the zero-band-gap energy band structure of the intrinsic graphene. And because a certain rotation angle exists between the two layers of the twisted angle double-layer graphene, the interlayer symmetry is broken, and the interlayer coupling effect is greatly enhanced, so that the characteristics of an energy band structure, phonon dispersion and the like can be adjusted, and the twisted angle double-layer graphene shows a plurality of novel physical phenomena. For example: when the rotation angle is 1.1 degrees, the twisted-angle double-layer graphene has an insulator-superconductor phase transition regulated by an electric field. The emergence of twisted-angle graphene provides a new opportunity for novel transistors and photoelectric devices. In the current stage, the method for preparing the twisted angle double-layer graphene by adopting the transfer stacking of the single-layer graphene has complex and fussy process and extremely low efficiency; although the twisted-angle double-layer graphene obtained by the existing Cu-substrate CVD growth method simplifies the preparation process, the twisted-angle double-layer graphene is small in size and difficult to control, and the twisted-angle double-layer graphene is difficult to meet the requirements.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the twisted-angle double-layer graphene which is simple to operate, has few wrinkles and directly grows in a large area and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of large-area directly-grown twisted-angle double-layer graphene comprises the following steps:
s1, growing a carbon-dissolved ferromagnetic metal film on the insulating substrate;
s2, annealing and surface reducing the carbon-dissolved ferromagnetic metal film to obtain a single crystal metal film;
s3, taking the single crystal metal film as a metal catalytic substrate, placing the single crystal metal film in a chemical vapor deposition system, introducing inert gas and precursor gas containing a carbon source, catalytically growing a first layer of graphene on the single crystal metal film at 800-900 ℃, stopping introducing the precursor gas containing the carbon source, cooling at a cooling rate of 20-200 ℃/min, and separating out a second layer of graphene with a torsion angle different from that of the first layer of graphene between the single crystal metal film and the first layer of graphene by utilizing a single crystal metal film carbon dissolving and re-separating mechanism to obtain the torsion angle double-layer graphene.
As a further improvement to the above technical solution:
the precursor gas containing the carbon source is a mixed gas of hydrogen and methane, and the flow ratio of the hydrogen to the methane is 20-50: 1.
In the step S1, the carbon-dissolved ferromagnetic metal thin film is a nickel metal thin film or a cobalt metal thin film.
In the step S2, the temperature of the annealing treatment is 800-1000 ℃.
The gas for surface reduction treatment is hydrogen or a mixed gas of hydrogen and inert gas, and the temperature for surface reduction treatment is 800-900 ℃.
The insulating substrate is Al2O3(0001) Or YSZ (111).
Growing a carbon-dissolved ferromagnetic metal film on an insulating substrate by adopting an electron beam evaporation method or a magnetron sputtering method.
As a general inventive concept, the present invention further provides a twisted angle double-layer graphene directly grown in a large area, which is prepared according to the preparation method, wherein the twisted angle double-layer graphene comprises a first layer of graphene and a second layer of graphene, and the twisted angles of the first layer of graphene and the second layer of graphene are different.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, the dissolved carbon ferromagnetic metal film is subjected to single crystallization and surface pretreatment, on one hand, the dissolved carbon ferromagnetic metal film has certain carbon dissolving capacity and can catalyze to generate highly oriented graphene, on the other hand, the dissolved carbon ferromagnetic metal film has the characteristics of a ferromagnetic material and can form an epitaxial interface with the graphene to promote the generation of the graphene, on the other hand, the dissolved carbon ferromagnetic metal film is subjected to single crystallization to improve the uniformity of surface catalysis, and a foundation is laid for better generation of the graphene by a subsequent CVD method.
2. The invention adopts CVD technology to realize large-area direct growth of twisted angle double-layer graphene on a single crystal metal film, the growth temperature is 800-900 ℃ when growing a first layer of graphene, the carbon dissolution amount of catalytic metal is controlled, the cooling rate is 20-200 ℃/min when precipitating a second layer of graphene, the carbon precipitation amount of the catalytic metal is controlled by regulating and controlling the non-thermal equilibrium dynamic process of metal carbon dissolution and precipitation, compared with the traditional single-layer graphene transfer stacking method, the method has the characteristics of simple operation, low cost, high efficiency, convenience and the like, can quickly prepare large-area twisted angle double-layer graphene with different rotation angles, has less wrinkles of the prepared twisted angle double-layer graphene, has lattice constants of ferromagnetic metal films (nickel and cobalt) which are matched with the graphene, has stable interface structure, and adopts the CVD method to directly grow the graphene on the single crystal metal film to form an interface acting force as a covalent bond, the coupling effect is strong, the application requirements of the twisted angle double-layer graphene are met, the twisted angle double-layer graphene can be directly applied to the development of electronic devices and the research of high-temperature superconducting mechanisms, and a technical basis is provided for the development of high-performance electronic devices and the research of high-temperature superconducting mechanisms.
3. Compared with a twisted angle double-layer CVD growth method of a low-carbon-solubility catalytic substrate, the preparation method of the invention adopts the single-crystal metal film with carbon-solubility as the catalytic substrate, and adjusts and controls the non-thermal equilibrium dynamic process of metal carbon dissolution and precipitation, so that the prepared twisted angle double-layer graphene has large area (the highest coverage rate can reach 90 percent), and can better meet the preparation requirement of devices.
Drawings
FIG. 1 is a schematic diagram of a CVD growth experimental system in example 1 of the present invention.
FIG. 2 shows the AFM results (different magnifications) of the single crystal Ni thin film after high temperature annealing in example 1 of the present invention.
FIG. 3 shows XRD results of Ni films before and after high temperature annealing in example 1 of the present invention.
Fig. 4 shows the results of the twisted-angle bilayer graphene AFM grown in example 1 of the present invention.
Fig. 5 shows the results of the twisted-angle double-layer graphene optical microscope transferred to the silicon wafer and the raman characterization in example 1 of the present invention.
Fig. 6 shows the characterization results of twisted-angle bilayer graphene SAED transferred onto TEM mesh in example 1 of the present invention.
Fig. 7 is an optical microscope image of twisted-angle bilayer graphene grown in examples 1 and 2 at different cooling rates.
Fig. 8 is an optical microscope image of twisted angle bilayer graphene grown at different growth temperatures in examples 1 and 3.
Illustration of the drawings: 1. an intake valve; 2. a slidable heating furnace; 3. a sample stage; 4. and an air outlet valve.
Detailed Description
The invention will be described in further detail below with reference to the drawings and specific examples. Unless otherwise specified, the instruments or materials employed in the present invention are commercially available.
Example 1:
the embodiment provides a preparation method of a large-area directly-grown twist angle double-layer graphene, which comprises the steps of taking a single crystal metal film as a metal catalytic substrate, carrying out high-temperature cracking on a precursor at 800-900 ℃ by adopting a CVD (chemical vapor deposition) method, growing a first layer of graphene on the single crystal metal film, then utilizing a single crystal metal film carbon dissolving and re-precipitation mechanism, cooling at a cooling rate of 20-200 ℃/min, and precipitating a second layer of graphene with a twist angle different from that of the first layer of graphene between the single crystal metal film and the first layer of graphene, thereby preparing the twist angle double-layer graphene. The size of the twisted angle double-layer graphene can be changed by adjusting the growth temperature, the cooling rate and the like of the system, so that the large-area twisted angle double-layer graphene is obtained.
The CVD growth experiment system of this embodiment is as shown in fig. 1, and both ends of the quartz tube are respectively communicated with an air inlet valve 1 and an air outlet valve 4, and a sample stage 3 is placed in the quartz tube, and a slidable heating furnace 2 is sleeved outside the quartz tube.
The preparation method of the twisted-angle double-layer graphene with large area direct growth in this embodiment adopts the CVD growth system shown in fig. 1, and includes the following specific steps:
1) cleaning of the insulating substrate 2 inch α -Al was chosen2O3(0001) The substrate is an insulating base, and acetone, isopropanol and water are respectively carried out on the insulating base,Ultrasonic cleaning with deionized water for 5-10 min (5 min in this embodiment), and then placing the tube-type annealing furnace for high-temperature annealing at 1000-1300 ℃ (1200 ℃ in this embodiment) in an oxygen-argon mixed gas atmosphere for 4 hours.
The insulating substrate and the carbon-dissolved metal film adopted by the embodiment have good lattice property matching, and can induce the hexagonal symmetry lattice orientation of the ferromagnetic film.
In other embodiments, the same or similar technical effects can be achieved by using a YSZ (111) substrate as the insulating base.
2) Preparation of single crystal metal film by electron beam evaporation at 2 inch α -Al2O3(0001) A300 nm thick nickel metal film (i.e., a carbon-soluble metal film) is deposited on the substrate at a deposition rate of 0.05-0.5 nm/s (0.2 nm/s in this embodiment) at 300-480 deg.C (480 deg.C in this embodiment). Then using an ultrahigh vacuum chamber at 10-6The nickel metal thin film is annealed at a high temperature for 1 hour at a rate of 20 ℃/min to 850 ℃ under a very low Torr pressure to form a single crystal Ni (111) thin film (i.e., a single crystal nickel thin film) having a uniform orientation.
In other embodiments, the Ni (111) single crystal thin film (i.e., single crystal nickel thin film) can also be obtained by performing high temperature annealing at 800 to 1000 ℃ on a nickel metal thin film in a mixed atmosphere of hydrogen and argon using a quartz tube furnace in a CVD system.
In other embodiments, the cobalt metal film may also achieve the same or similar technical effects as the carbon-dissolved metal film. The carbon-soluble metal film has good lattice matching with graphene, has certain carbon-soluble capacity, and can catalyze and generate highly-oriented graphene.
In other embodiments, the annealing temperature is 800-1000 ℃ and the annealing time is 0.5-2 hours, which can achieve the same or similar technical effects.
The results of AFM (different magnification) and XRD characterization of the single-crystal Ni (111) thin films prepared in this example are shown in FIGS. 2 and 3. As can be seen from FIG. 2, the single crystal Ni (111) film after high temperature annealing has a smooth and clean surface, presents atomic steps, and has no domain boundary. As can be seen from the figure 3 of the drawings,θ-2θthe scanning curve has a unique diffraction peak at Ni (111), which indicates that the Ni thin film before and after annealing has (111) out-of-plane orientationφThe Ni thin films before and after annealing in the scanning curve respectively show diffraction peaks with six-fold and three-fold symmetry, which shows that the Ni (111) texture is converted into the Ni (111) single crystal thin film under the high-temperature annealing effect.
3) And cleaning the CVD equipment. Placing the single crystal nickel film in the center of a quartz tube heating furnace, starting a mechanical pump, opening a vacuum valve, and vacuumizing the quartz tube to 0.1 Pa; and then closing the vacuum valve, introducing argon until the quartz tube is filled with argon, closing the argon valve, and repeating the steps for three times.
4) And (3) reducing the surface of the single crystal nickel film. Vacuumizing a quartz tube to the limit pressure of 0.1Pa, introducing hydrogen and argon (the ratio is 50: 50) to normal pressure, operating a heating program of a slidable heating furnace, raising the growth temperature to 850 ℃, and carrying out reduction treatment on the oxidized surface of the single crystal nickel film for 35-45 minutes (35 minutes in the embodiment).
5) A first layer graphene growth process. The method comprises the steps of taking a single-crystal metal film as a metal catalytic substrate, introducing argon and precursor gas containing a carbon source under normal pressure, wherein the precursor gas containing the carbon source is mixed gas of methane and hydrogen, the flow ratio of the methane to the hydrogen to the argon is 2(sccm) to 50(sccm), timing at 850 ℃ for 20 minutes, and growing a first layer of graphene on the single-crystal nickel film.
In other embodiments, a high H is employed2/CH4Mixing ratio of H2/CH4And the ratio of the nucleation density to the nucleation density is 20-50: 1, so that the growth uniformity of the graphene is improved.
6) And (5) a second layer graphene precipitation process. And closing methane and hydrogen, reducing the temperature to room temperature at a cooling rate of 200 ℃/min under the argon atmosphere, and separating out a second graphene layer with a twist angle different from that of the first graphene layer between the single crystal nickel film and the first graphene layer by utilizing a single crystal nickel film carbon dissolving and re-separating mechanism to obtain the twist angle double-layer graphene.
In other embodiments, the temperature reduction rate is 20 ℃/min-200 ℃/min, the carbon precipitation amount of the catalytic metal is controlled, and the same or similar technical effects can be obtained.
Fig. 4 is a result of the twisted-angle double-layer graphene AFM in example 1 of the present invention, and it can be known that the twisted-angle double-layer graphene prepared by the present invention has a clean and flat surface without wrinkles, and the roughness is only 2 nm.
Fig. 5 is an optical microscope image (5 a) and a raman result (5 b) of graphene in example 1 of the present invention, respectively. Region a is lighter in color in fig. 5a, and a single-layer signal is shown in the raman result plot in fig. 5b, as single-layer graphene; region B is darker in color in fig. 5a, and the raman result in fig. 5B also shows a single-layer signal, which is a rotated double-layer graphene.
FIG. 6 shows SAED characterization results of graphene transferred to TEM mesh in example 1 of the present invention. FIG. 6a shows that there is a set of graphene diffraction spots in this region, which are single-layer graphene; fig. 6b shows that there are multiple sets of spots (two sets of lighter spots, one set of darker spots) for the graphene diffraction spot in this region, which is illustrated as non-AB-stacked rotating bilayer graphene with at least two different rotation angles. Therefore, the prepared graphene sample contains both twisted-angle double-layer graphene and single-layer graphene.
Example 2:
this embodiment is basically the same as embodiment 1, and differs therefrom only in that: the cooling rate of the second layer of graphene in the precipitation process is 20 ℃/min.
Example 3:
this embodiment is basically the same as embodiment 1, and differs therefrom only in that: the growth temperature of the first layer of graphene in the growth process is 900 ℃.
Fig. 7 and 8 are optical microscope images of graphene grown at different cooling rates and different growth temperatures according to the present invention transferred to a silicon wafer. Where 7a and 8a are examples 1 and 7b and 8b are examples 2 and 3, respectively. The results show that by adjusting the cooling rate or growth temperature, the diameter of the double-layer twisted-angle graphene increases from about 30 μm to 100 μm, and the coverage rate increases from 30% to more than 90% (the prior art generally fails to reach the coverage rate value of the application). This is simply that under the current magnification view, the actual twisted angle bilayer graphene size may be larger. The invention realizes the preparation of twisted angle double-layer graphene with different sizes and rotation angles by taking the single crystal metal film as a metal catalytic substrate. Because carbon precipitation in the single crystal metal film belongs to a non-thermal equilibrium process during cooling, a certain rotation angle is easily generated between the precipitated second layer graphene and the first layer graphene on the surface, and when the cooling rate is too fast (more than 200 ℃/min), carbon in the nickel metal cannot be precipitated in time; when the temperature reduction rate is too slow (< 20 ℃/min), carbon can diffuse into the metal body but not precipitate out of the surface layer due to the concentration gradient of the carbon content in the nickel metal body (the carbon content in the bottom layer is the lowest), so that the twisted double-layer graphene which directly grows in a large area can be obtained only in a proper temperature reduction rate range. Meanwhile, the growth temperature can affect the dissolved carbon amount in the nickel metal and the integrity of the first layer of graphene grown by surface catalysis, and further affect the preparation of the twisted double-layer graphene, when the growth temperature is too low (< 800 ℃), the dissolved carbon amount in the nickel metal is low, the catalytic activity is weak, and the first layer of graphene is difficult to grow on the metal surface; when the growth temperature is too high (> 900 ℃), carbon is completely dissolved in the nickel metal body and cannot catalyze and grow the first layer of graphene on the surface of the metal. Therefore, the proper growth temperature is also a key factor for preparing the large-area twisted angle double-layer graphene.
The foregoing is considered as illustrative of the preferred embodiments of the invention and is not to be construed as limiting the invention in any way. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.

Claims (8)

1. A preparation method of large-area directly-grown twisted angle double-layer graphene is characterized by comprising the following steps: the method comprises the following steps:
s1, growing a carbon-dissolved ferromagnetic metal film on the insulating substrate;
s2, annealing and surface reducing the carbon-dissolved ferromagnetic metal film to obtain a single crystal metal film;
s3, taking the single crystal metal film as a metal catalytic substrate, placing the single crystal metal film in a chemical vapor deposition system, introducing inert gas and precursor gas containing a carbon source, catalytically growing a first layer of graphene on the single crystal metal film at 800-900 ℃, stopping introducing the precursor gas containing the carbon source, cooling at a cooling rate of 20-200 ℃/min, and separating out a second layer of graphene with a torsion angle different from that of the first layer of graphene between the single crystal metal film and the first layer of graphene by utilizing a single crystal metal film carbon dissolving and re-separating mechanism to obtain the torsion angle double-layer graphene.
2. The method of claim 1, wherein: the precursor gas containing the carbon source is a mixed gas of hydrogen and methane, and the flow ratio of the hydrogen to the methane is 20-50: 1.
3. The method of claim 2, wherein: in the step S1, the carbon-dissolved ferromagnetic metal thin film is a nickel metal thin film or a cobalt metal thin film.
4. The production method according to any one of claims 1 to 3, characterized in that: in the step S2, the temperature of the annealing treatment is 800-1000 ℃.
5. The method of claim 4, wherein: in the step S2, the gas for the surface reduction treatment is hydrogen or a mixed gas of hydrogen and an inert gas, and the temperature for the surface reduction treatment is 800 to 900 ℃.
6. The production method according to any one of claims 1 to 3, characterized in that: the insulating substrate is Al2O3(0001) Or YSZ (111).
7. The method according to claim 6, wherein the carbon-dissolved ferromagnetic metal thin film is grown on the insulating substrate by an electron beam evaporation method or a magnetron sputtering method.
8. A twisted angle double-layer graphene directly grown in a large area is characterized in that: the twisted-angle double-layer graphene prepared by the preparation method according to any one of claims 1 to 7 comprises a first layer of graphene and a second layer of graphene, and the twisted angles of the first layer of graphene and the second layer of graphene are different.
CN202010456080.7A 2020-05-26 2020-05-26 Twisted angle double-layer graphene directly grown in large area and preparation method thereof Pending CN111573658A (en)

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