CN116588919A - Graphene nanoribbon embedded between two-dimensional material layers and preparation method thereof - Google Patents
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- 239000002074 nanoribbon Substances 0.000 title claims abstract description 99
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 163
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- 238000000034 method Methods 0.000 claims description 83
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- 239000010439 graphite Substances 0.000 claims description 4
- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 claims description 4
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/06—Graphene nanoribbons
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- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The application provides a graphene nanoribbon embedded between two-dimensional material layers and a preparation method thereof, wherein the graphene nanoribbon structure comprises the following components: the substrate with atomic-level flatness is formed by sequentially stacking at least two atomic layers in parallel, and two adjacent atomic layers are combined through Van der Waals force; at least one longitudinal section formed from the substrate surface extending one or more atomic layer thicknesses from the substrate surface in the substrate thickness direction; at least one graphene nanoribbon breaks through van der Waals force of any two adjacent atomic layers exposed at the longitudinal section, is embedded between the two atomic layers, and is encapsulated by a substrate material. The formed graphene nanoribbon is embedded in a substrate with atomic-level flatness and isolated from the external environment, so that the graphene nanoribbon has physical properties close to those of the intrinsic nanoribbon and a regular edge structure; in addition, the preparation method is simple to operate, low in cost, capable of large-scale production and good in industrialization value.
Description
Technical Field
The application belongs to the technical field of chemical material synthesis, and particularly relates to a graphene nanoribbon embedded between two-dimensional material layers and a preparation method thereof.
Background
In recent years, graphene nanoribbons as one-dimensional materials have attracted attention. The special energy band structure of the graphene nanoribbon enables the graphene nanoribbon to have unique electrical, magnetic and optical properties. The graphene nanoribbon has a huge application prospect in the fields of field effect transistors, gas sensing, optical detectors, energy storage and the like.
The graphene nanoribbon is a graphene ribbon with the width of a few nanometers to tens of nanometers, not only inherits most of excellent characteristics of graphene, but also has physical properties such as adjustable band gap, spin polarization boundary state, boundary magnetic transport and the like, and is very suitable for constructing high-performance carbon-based electronic devices. At present, the commonly used preparation methods of graphene nanoribbons are mainly divided into two main types: the first is a top-down method, in which large-area graphene is cut into nanoribbons by micro-nano processing technology; the second type is a bottom-up method, which adopts chemical synthesis technology to catalyze and synthesize graphene nanoribbons with small carbon-containing molecules. The first class is limited by the processing precision, and the edge structure of the prepared graphene nanoribbon is disordered, so that the intrinsic property of the nanoribbon is lost; in addition, the nanoribbon energy gap is too small to be suitable for processing field effect transistors. Although the second method can obtain ultra-narrow graphene nanoribbons on the surface of a substrate, the graphene nanoribbons are exposed to high temperature and high energy particles in the growth process, so that some defects still exist in the graphene nanoribbons, and the structures of the graphene nanoribbons may be further damaged in the subsequent device processing process. In summary, the graphene nanoribbons prepared by the existing methods are difficult to meet the requirements of preparing high-performance carbon-based electronic devices.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present application is to provide a graphene nanoribbon embedded between two-dimensional material layers and a preparation method thereof, which are used for solving the problems of disordered boundary morphology, defects, and the like of the graphene nanoribbon obtained by the method for preparing the graphene nanoribbon in the prior art.
To achieve the above and other related objects, the present application provides a graphene nanoribbon embedded between two-dimensional material layers, the graphene nanoribbon comprising:
the substrate with atomic-level flatness is formed by sequentially stacking at least two atomic layers in parallel, and two adjacent atomic layers are combined through Van der Waals force;
at least one longitudinal section formed from the substrate surface extending one or more of the atomic layer thicknesses from the substrate surface in the substrate thickness direction;
at least one graphene nanoribbon breaks through van der Waals force of any two adjacent atomic layers with exposed longitudinal sections, is embedded between the two atomic layers, and is encapsulated by the substrate.
Optionally, all the graphene nanoribbons are located between the same two atomic layers or at least two graphene nanoribbons are located between different two atomic layers.
Optionally, all the graphene nanoribbons have a parallel or 60 ° or 120 ° regularly arranged morphology.
Optionally, the substrate comprises a hexagonal boron nitride substrate or a graphite substrate or a mica substrate or a molybdenum disulfide substrate or an indium selenide substrate or a chromium oxychloride substrate.
The application also provides a preparation method of the graphene nanoribbon embedded between two-dimensional material layers, which is used for preparing the graphene nanoribbon embedded between two-dimensional material layers according to any one of the above, and comprises the following steps:
providing a substrate with atomic-level flatness, wherein the substrate is formed by sequentially stacking at least two atomic layers in parallel, two adjacent atomic layers are combined through Van der Waals force, and at least one longitudinal section is formed on the substrate and extends from the surface of the substrate along the thickness direction of the substrate;
forming nano-catalyst particles on the substrate surface and the longitudinal section surface, and combining the nano-catalyst particles with the substrate surface and the longitudinal section surface;
the growth process comprises the following steps: carrying out a chemical vapor deposition process on the substrate with the nano catalyst particles to form a carbon product layer on the surface of the substrate and form a graphene nano belt in the substrate, wherein the graphene nano belt breaks through van der Waals force of any two adjacent atomic layers exposed on the longitudinal section, is embedded between the two atomic layers, and is covered and packaged by the substrate, the introduced reaction gas is carbon source gas, and the growth temperature is 600-1000 ℃;
and (3) a cooling process: after the growth is finished, closing the carbon source gas, and cooling to room temperature under the action of the protective gas and taking out;
etching: and removing the carbon product layer formed on the surface of the substrate in the growth process, so that the graphene nanoribbons are formed only inside the substrate.
Optionally, the method for forming the longitudinal section comprises: providing a base wafer, and preparing the substrate on the base wafer by a mechanical peeling method, wherein an outer Zhou Jie surface of the substrate in the thickness direction is formed into the longitudinal section; or providing a base wafer, preparing a substrate film on the base wafer by a mechanical stripping method, and preparing the longitudinal section with a preset shape on the substrate film by a photoetching process and a reactive ion etching process; or providing a base wafer, preparing a substrate film on the base wafer by a mechanical stripping method, forming an etchant film on the substrate film, and finally etching the substrate film based on the etchant film at 800-1200 ℃ by introducing a reaction gas to form the substrate, wherein a section formed after etching the substrate film and an outer Zhou Jie surface of the substrate film in the thickness direction are formed into the longitudinal section.
Optionally, the method of forming the nanocatalyst particles comprises: firstly, forming a nano catalyst film on the surface of the substrate and the longitudinal section surface; and then, heating the substrate with the nano catalyst film formed thereon to enable the nano catalyst film to agglomerate to form nano catalyst particles, and simultaneously moving and combining with the surface of the substrate and the surface of the longitudinal section.
Optionally, the nano-catalyst particles are one of metal nano-catalyst particles, alloy nano-catalyst particles and metal oxide nano-catalyst particles which are eutectic with carbon.
Optionally, the carbon source gas includes at least one of methane, acetylene, and ethanol.
Optionally, the chemical vapor deposition process is a furnace tube process, and hydrogen is simultaneously introduced into the furnace tube in the growth process.
As described above, the graphene nanoribbon embedded between two-dimensional material layers and the preparation method thereof form the graphene nanoribbon embedded in the substrate with atomic-level flatness and isolated from the external environment, so that the graphene nanoribbon has physical properties close to those of the intrinsic nanoribbon, has better quality, and has regular edge structure; in addition, the preparation method is simple, has lower cost, can realize large-scale production, and has better industrialization value.
Drawings
Fig. 1 shows a schematic and simplified diagram of a growth device used in the preparation process of graphene nanoribbons embedded between two-dimensional material layers according to the present application.
Fig. 2 is a schematic structural view showing an example of a graphene nanoribbon embedded between two-dimensional material layers according to the present application.
Fig. 3 shows a schematic structural diagram of another example of a graphene nanoribbon embedded between two-dimensional material layers according to the present application.
Fig. 4 shows a top view of a graphene nanoribbon scanning electron microscope embedded between two-dimensional material layers according to the present application, with a scale of 10 μm.
Fig. 5 shows a cross-sectional view of a graphene nanoribbon Scanning Transmission Electron Microscope (STEM) embedded between two-dimensional material layers according to the present application, with a scale of 2nm.
Description of element reference numerals
10. Heating furnace
11. Furnace tube
12. Substrate and method for manufacturing the same
13. Longitudinal section
14. Graphene nanoribbons
15. Catalyst particles
16. Gas and its preparation method
Detailed Description
Other advantages and effects of the present application will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present application with reference to specific examples. The application may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present application.
As described in detail in the embodiments of the present application, the cross-sectional view of the device structure is not partially enlarged to a general scale for convenience of explanation, and the schematic drawings are only examples, which should not limit the scope of the present application. In addition, the three-dimensional dimensions of length, width and depth should be included in actual fabrication.
For ease of description, spatially relative terms such as "under", "below", "beneath", "above", "upper" and the like may be used herein to describe one element or feature's relationship to another element or feature as illustrated in the figures. It will be understood that these spatially relative terms are intended to encompass other orientations of the device in use or operation in addition to the orientation depicted in the figures. Furthermore, when a layer is referred to as being "between" two layers, it can be the only layer between the two layers or one or more intervening layers may also be present. As used herein, "between … …" is meant to include both endpoints.
In the context of the present application, a structure described as a first feature being "on" a second feature may include embodiments where the first and second features are formed in direct contact, as well as embodiments where additional features are formed between the first and second features, such that the first and second features may not be in direct contact.
Please refer to fig. 1 to 5. It should be noted that, the illustrations provided in the present embodiment merely illustrate the basic concept of the present application by way of illustration, and only the components related to the present application are shown in the drawings rather than the number, shape and size of the components in actual implementation, and the form, number and proportion of each component in actual implementation may be arbitrarily changed, and the layout of the components may be more complex.
Example 1
As shown in fig. 1 to 5, the present embodiment provides a graphene nanoribbon embedded between two-dimensional material layers, the graphene nanoribbon including:
a substrate 12 having atomic level flatness, wherein the substrate 12 is formed by stacking at least two atomic layers in parallel in sequence, and two adjacent atomic layers are bonded by van der waals force, and here, it should be noted that specific atomic layers are not illustrated in the figure;
at least one longitudinal section 13 formed from the substrate 12 surface extending one or more of the atomic layer thicknesses of the substrate 12 in the thickness direction of the substrate 12;
at least one graphene nanoribbon 14 breaks through van der Waals forces of any two adjacent atomic layers exposed by the longitudinal section 13, is embedded between the two atomic layers, and is covered and packaged by the substrate 12.
In order to easily understand the structure of the graphene nanoribbons embedded between two-dimensional material layers in this embodiment, fig. 2 and 3 only illustrate several graphene nanoribbons, and actually there are several graphene nanoribbons in the substrate.
The graphene nanoribbon embedded between two-dimensional material layers is embedded in a substrate with atomic-level flatness and isolated from the external environment, so that the graphene nanoribbon has physical properties close to those of an intrinsic nanoribbon and is good in quality.
As an example, as shown in fig. 2 and 3, all of the graphene nanoribbons 14 are located between the same two layers of the atomic layers or at least two of the graphene nanoribbons 14 are located between different two layers of the atomic layers. That is, whether the horizontal heights of all the graphene nanoribbons 14 in the substrate 12 are uniform is not limited, and they may be between the same two atomic layers, between different two atomic layers, or between the same two atomic layers partially. That is, the graphene nanoribbons 14 may not be separated by an atomic layer, but may be separated by one or more atomic layers.
As a preferred example, as shown in fig. 4 and 5, all the graphene nanoribbons 14 have parallel or 60 ° or 120 ° regular arrangement morphology. The graphene nanoribbon has a neat graphene nanoribbon edge structure, and the graphene nanoribbon can reach tens of micrometers to hundreds of micrometers in length, is narrow in width and wide in range, and is approximately 1nm to 10nm.
As another preferred example, the substrate 12 is selected from substrates of atomic-level flatness, for example, hexagonal boron nitride substrates or graphite substrates or mica substrates or molybdenum disulfide substrates or indium selenide substrates or chromium oxychloride substrates, or the like.
As an example, the longitudinal section 13 may be a naturally formed longitudinal section of the outer circumferential section in the thickness direction of the substrate 12; or a longitudinal section formed by etching the substrate 12 in the thickness direction thereof. The method is specifically set according to actual needs.
Example two
The present embodiment provides a preparation method of a graphene nanoribbon embedded between two-dimensional material layers, which can be used to prepare the graphene nanoribbon embedded between two-dimensional material layers in the above embodiment, and the effect of the prepared graphene nanoribbon can be found in the above embodiment one, and will not be described in detail. The preparation method comprises the following steps:
providing a substrate with atomic-level flatness, wherein the substrate is formed by sequentially stacking at least two atomic layers in parallel, two adjacent atomic layers are combined through Van der Waals force, and at least one longitudinal section is formed on the substrate and extends from the surface of the substrate along the thickness direction of the substrate;
forming nano-catalyst particles on the substrate surface and the longitudinal section surface, and combining the nano-catalyst particles with the substrate surface and the longitudinal section surface;
the growth process comprises the following steps: carrying out a chemical vapor deposition process on the substrate with the nano catalyst particles to form a carbon product layer on the surface of the substrate and form a graphene nano belt in the substrate, wherein the graphene nano belt breaks through van der Waals force of any two adjacent atomic layers exposed on the longitudinal section, is embedded between the two atomic layers, and is covered and packaged by the substrate, the introduced reaction gas is carbon source gas, and the growth temperature is 600-1000 ℃;
and (3) a cooling process: after the growth is finished, closing the carbon source gas, and cooling to room temperature under the action of the protective gas and taking out;
etching: and removing the carbon product layer formed on the surface of the substrate in the growth process, so that the graphene nanoribbons are formed only inside the substrate.
The formation mechanism of the graphene nanoribbon in the preparation method of the graphene nanoribbon embedded between two-dimensional material layers in the embodiment is as follows: firstly, combining nano catalyst particles with the surface of a longitudinal section, in the growth process, at the growth temperature of 600-1000 ℃, cracking carbon source gas with the assistance of the nano catalyst particles and releasing carbon atoms and carbon-containing free radicals, after the carbon content in the nano catalyst particles at the surface of the longitudinal section reaches a certain supersaturation degree, separating out and nucleation from the nano catalyst particles, breaking Van der Waals force between two adjacent atomic layers and intercalating into a substrate with atomic-level flatness, thereby growing carbon product layers inlaid between the atomic layers of the substrate, namely between two-dimensional substrate material layers, and finally removing the carbon product layers formed on the surface of the substrate. The graphene nanoribbon prepared by the method is inlaid in the substrate and is not exposed on the surface of the substrate, so that the graphene nanoribbon has physical properties close to those of the intrinsic nanoribbon, and meanwhile, the edge structure of the graphene nanoribbon is regular; in addition, the preparation method is simple, has lower cost, can realize large-scale production, and has better industrialization value.
The preparation method of the present embodiment is described in detail below with reference to the accompanying drawings, as shown in fig. 1 to 3.
As shown in fig. 1, step S1 is first performed to provide a substrate 12 with atomic-level flatness, where the substrate 12 is formed by stacking at least two atomic layers in parallel, two adjacent atomic layers are bonded by van der waals force, and at least one longitudinal section 13 is formed on the substrate 12, and the longitudinal section 13 extends from the surface of the substrate 12 in the thickness direction of the substrate 12.
For ease of understanding, only one etched longitudinal section 13 is shown in fig. 1, and those skilled in the art will appreciate that in practice, several longitudinal sections 13 may be formed on the substrate 12 as desired. And the depths of the plurality of longitudinal sections 13 may be the same or different, without being excessively limited thereto.
By way of example, the substrate 12 may be selected from any suitable substrate having atomic-level flatness, such as hexagonal boron nitride substrates, graphite substrates, mica substrates, molybdenum disulfide substrates, indium selenide substrates, chromium oxychloride substrates, and the like.
As an example, the method of forming the longitudinal section 13 may be: providing a base wafer on which the substrate 12 is formed by a mechanical lift-off method, wherein an outer Zhou Jie surface in the thickness direction of the substrate 12 is formed into the longitudinal section 13 (as shown in fig. 2 and 3); or, providing a base wafer, preparing a substrate film on the base wafer by a mechanical stripping method, forming an etchant film on the substrate film, and finally etching the substrate film based on the etchant film at 800-1200 ℃ by introducing a reaction gas to form the substrate 12, wherein a section formed after etching the substrate film and an outer Zhou Jie surface of the substrate film in the thickness direction are formed into the longitudinal section 13; or providing a base wafer, preparing a substrate film on the base wafer by a mechanical stripping method, and preparing the longitudinal section 13 with a preset shape on the substrate film by a photoetching process and a reactive ion etching process, wherein the photoetching process can be selected from ultraviolet photoetching or EBL.
As shown in fig. 1, step S2 is performed to form nano-catalyst particles 15 on the surface of the substrate 12 and the surface of the longitudinal section 13, and bond the nano-catalyst particles 15 to the surface of the substrate 12 and the surface of the longitudinal section 13.
By way of example, the nanocatalyst particles may be selected from any material suitable for the catalytic growth of nanoparticles, typically selected from one of metal nanocatalyst particles, alloy nanocatalyst particles, and metal oxide nanocatalyst particles that are eutectic with carbon, such as iron, cobalt, nickel, copper, molybdenum, tungsten, titanium dioxide, silicon dioxide, and the like.
As a specific example, the method of forming the nano-catalyst particles 15 includes: firstly, forming a nano catalyst film on the surface of the substrate 12 and the surface of the longitudinal section 13, namely forming a nano catalyst film on the whole exposed surface of the substrate 12, which is required to be deposited subsequently, wherein the nano catalyst film can be deposited by adopting a vapor deposition, spin coating or dip coating method; then, a heating process is performed to heat the substrate 12 on which the nano catalyst thin film is formed, so that the nano catalyst thin film is agglomerated to form the nano catalyst particles 15, and simultaneously moves and is combined with the surface of the substrate 12 and the surface of the longitudinal section 13, during which the nano catalyst thin film is agglomerated at a high temperature to form the nano catalyst particles, and at the longitudinal section 13, the nano catalyst particles are combined with the substrate.
As a preferred example, the process of forming the nano-catalyst particles 15 may be formed in a tube furnace in the form of a furnace tube 11 with a heating furnace 10 outside, which may provide good sealability, insulation and temperature control stability. And in the heating process, the substrate 12 is placed in the furnace tube 11 for heating. Preferably, the furnace tube 11 is a quartz furnace tube. More preferably, in the heating process, the gas 16 of hydrogen and argon is introduced into the furnace tube 11 as a protective gas, and can also be used as a reducing gas, so as to reduce oxidized nano catalyst particles and some carbon-containing impurity substances generated by the carbon source gas in the subsequent high-temperature growth process, and the flow rate of the carbon source gas introduced in the subsequent growth process is the same as the flow rate of the argon in the heating process, so that the stability of the total flow rate of the gas in the growth process is ensured, and the growth quality of the graphene nanoribbon is ensured.
As shown in fig. 2 and 3, step S3 is performed, and the growth process is performed: and carrying out a chemical vapor deposition process on the substrate 12 with the nano catalyst particles 15 to form a graphene nano belt 14 inside the substrate 12, wherein the graphene nano belt 14 breaks through any two adjacent atomic layers exposed by the longitudinal section 13, van der Waals force of the two atomic layers is embedded between the two atomic layers, the two atomic layers are encapsulated by the substrate 12, the introduced reaction gas is carbon source gas, and the growth temperature is 600-1000 ℃.
As an example, the process of forming the nano catalyst particles 15 and the growth process may be both formed in the same tube furnace, that is, a furnace tube process is adopted, so that the preparation process achieves consistent consistency to improve the preparation quality and efficiency, at this time, in the growth process, continuous introduction of the hydrogen shielding gas is maintained, introduction of the argon shielding gas is stopped, and then the carbon source gas is replaced, and the flow rate of the carbon source gas is the same as the flow rate of the argon shielding gas, so as to raise the temperature and ensure the stability of the total flow rate of the gas in the growth process.
As an example, the carbon source gas may be a single gas or a mixture of several gases, such as methane, acetylene, and ethanol.
Then, step S4 is performed, and the temperature is reduced: and after the growth is finished, closing the carbon source gas, and cooling to room temperature under the action of the protective gas and taking out.
As a specific example, in the cooling process, the carbon source gas is turned off, and the hydrogen and the argon are continuously introduced as the protective gas, and the flow rates of the hydrogen and the argon are the same as those of the argon in the heating process, so that the temperature is naturally cooled to the room temperature, and the stability of the total flow rate of the gas in the whole cooling process is ensured.
Finally, step S5 is carried out, and the etching process is carried out: the carbon product layer formed on the surface of the substrate 12 during the growth process is removed, thereby forming the graphene nanoribbons only inside the substrate 12.
It should be noted here that the carbon product layer formed on the surface of the substrate 12 generally includes graphene nanoribbons, graphene, carbon nanotubes, amorphous carbon, and the like.
The preparation method of the graphene nanoribbon embedded between two-dimensional material layers in this embodiment is further described below through specific experimental examples.
Experimental example 1
1) A silicon wafer having an oxide layer with a thickness of 300nm on the surface thereof was cut into 1cm X1 cm pieces.
2) Hexagonal boron nitride (hBN) flakes having various shapes of longitudinal sections, which are naturally formed from the outer circumferential sections of hexagonal boron nitride in the thickness direction, were prepared on the above silicon wafer by a mechanical lift-off method.
3) Vapor plating on the hexagonal boron nitride sheet by adopting a thermal evaporation coating methodAn iron nanoparticle catalyst film of thickness, as a growing catalyst.
4) And placing the silicon wafer plated with the catalyst in a tube furnace, wherein the atmosphere of the furnace gas is hydrogen, the flow rate is 50SCCM and argon, the flow rate is 100SCCM, the temperature is raised for about 15 minutes, the room temperature is gradually raised to the growth temperature of 850 ℃, and the air pressure is kept at 1 standard atmosphere in the temperature raising process.
5) After the temperature reaches the target growth temperature of 850 ℃, stopping introducing argon, and on the basis that the original hydrogen and the flow rate of 50SCCM are kept unchanged, introducing methane gas of 100SCCM as growth gas, and growing for 10 minutes at 850 ℃, wherein the air pressure is kept to be 1 standard atmosphere in the growth process.
6) And after the growth is finished, closing methane gas, naturally cooling to room temperature, and taking out the sample.
7) Placing the grown sample into a PECVD system, vacuumizing, introducing hydrogen with the flow of 30SCCM, heating to 300 ℃, treating the sample for 1 hour by using plasma with the power of 30W, etching away impurity carbon products such as graphene nanobelts, carbon nanotubes, amorphous carbon and the like growing on the surface of the sample, and only retaining the graphene nanobelts among hexagonal boron nitride layers.
Experimental example 2
1) A silicon wafer having an oxide layer with a thickness of 300nm on the surface thereof was cut into 1cm X1 cm pieces.
2) Hexagonal boron nitride (hBN) flakes were prepared on the above silicon wafer by a mechanical lift-off method, in which no longitudinal section was formed in the hexagonal boron nitride flakes.
3) Vapor plating on the hexagonal boron nitride sheet material by adopting electron beam vapor plating methodA nickel film of a thickness, as an etchant.
4) The flow ratio of hydrogen to argon is 1:1, etching the surface of the hexagonal boron nitride film in an environment with the temperature of 1000 ℃ to form various longitudinal sections in the hexagonal boron nitride film.
5) Vapor plating the hexagonal boron nitride film with longitudinal section by adopting a thermal vapor plating methodA cobalt nanoparticle catalyst thin film of thickness, as a grown catalyst.
6) Placing the silicon wafer with the catalyst in a heating furnace, pumping out air in the furnace, and then introducing hydrogen and acetylene gas, wherein the flow ratio is 1:1, gradually raising the temperature of the heating furnace from room temperature to 750 ℃, wherein the temperature raising process is carried out for about 10 minutes, and the air pressure is kept to be 1 standard atmospheric pressure in the temperature raising process.
7) And after the temperature reaches the target growth temperature of 750 ℃, keeping the temperature and the air pressure stable, and growing for 30min.
8) And after the growth is finished, pumping out the residual gas in the furnace, introducing argon and hydrogen as protective gases, naturally cooling to room temperature, and taking out the sample.
9) Placing the grown sample into a PECVD system, vacuumizing, introducing hydrogen with the flow of 30SCCM, heating to 300 ℃, treating the sample with plasma with the power of 30W for 1 hour, etching away impurity carbon products such as graphene nanobelts, carbon nanotubes, amorphous carbon and the like grown on the surface of the substrate, and only retaining the graphene nanobelts among hexagonal boron nitride layers.
In summary, the application provides a graphene nanoribbon embedded between two-dimensional material layers and a preparation method thereof, wherein the graphene nanoribbon is embedded in a substrate with atomic-level flatness and isolated from the external environment, so that the graphene nanoribbon has physical properties close to those of an intrinsic nanoribbon, the quality is good, and meanwhile, the edge structure of the graphene nanoribbon is regular; in addition, the preparation method is simple, has lower cost, can realize large-scale production, and has better industrialization value. Therefore, the application effectively overcomes various defects in the prior art and has high industrial utilization value.
The above embodiments are merely illustrative of the principles of the present application and its effectiveness, and are not intended to limit the application. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the application. Accordingly, it is intended that all equivalent modifications and variations of the application be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. The graphene nanoribbon embedded between two-dimensional material layers is characterized in that the graphene nanoribbon embedded between two-dimensional material layers comprises:
the substrate with atomic-level flatness is formed by sequentially stacking at least two atomic layers in parallel, and two adjacent atomic layers are combined through Van der Waals force;
at least one longitudinal section formed from the substrate surface extending one or more of the atomic layer thicknesses from the substrate surface in the substrate thickness direction;
at least one graphene nanoribbon breaks through van der Waals force of any two adjacent atomic layers with exposed longitudinal sections, is embedded between the two atomic layers, and is encapsulated by the substrate.
2. The graphene nanoribbon embedded between two-dimensional material layers according to claim 1, wherein: all the graphene nanoribbons are located between the same two atomic layers or at least two graphene nanoribbons are located between different two atomic layers.
3. The graphene nanoribbon embedded between two-dimensional material layers according to claim 1, wherein: all the graphene nanoribbons have a parallel or 60-120-degree regular arrangement morphology.
4. The graphene nanoribbon embedded between two-dimensional material layers according to claim 1, wherein: the substrate comprises a hexagonal boron nitride substrate or a graphite substrate or a mica substrate or a molybdenum disulfide substrate or an indium selenide substrate or a chromium oxygen chlorine substrate.
5. A method for preparing a graphene nanoribbon embedded between two-dimensional material layers, wherein the preparation method is used for preparing the graphene nanoribbon embedded between two-dimensional material layers according to any one of claims 1 to 4, and comprises the following steps:
providing a substrate with atomic-level flatness, wherein the substrate is formed by sequentially stacking at least two atomic layers in parallel, two adjacent atomic layers are combined through Van der Waals force, and at least one longitudinal section is formed on the substrate and extends from the surface of the substrate along the thickness direction of the substrate;
forming nano-catalyst particles on the substrate surface and the longitudinal section surface, and combining the nano-catalyst particles with the substrate surface and the longitudinal section surface;
the growth process comprises the following steps: carrying out a chemical vapor deposition process on the substrate with the nano catalyst particles to form a carbon product layer on the surface of the substrate, and forming a graphene nano belt in the substrate, wherein the graphene nano belt breaks through van der Waals force of any two adjacent atomic layers exposed on the longitudinal section, is embedded between the two atomic layers, and is packaged by the substrate, the introduced reaction gas is carbon source gas, and the growth temperature is 600-1000 ℃;
and (3) a cooling process: after the growth is finished, closing the carbon source gas, and cooling to room temperature under the action of the protective gas and taking out;
etching: and removing the carbon product layer formed on the surface of the substrate in the growth process, so that the graphene nanoribbons are formed only inside the substrate.
6. The method of claim 5, wherein the method of forming the longitudinal section comprises: providing a base wafer, and preparing the substrate on the base wafer by a mechanical peeling method, wherein an outer Zhou Jie surface of the substrate in the thickness direction is formed into the longitudinal section; or providing a base wafer, preparing a substrate film on the base wafer by a mechanical stripping method, forming an etchant film on the substrate film, and finally etching the substrate film based on the etchant film at 800-1200 ℃ by introducing a reaction gas to form the substrate, wherein a section formed after etching the substrate film and an outer Zhou Jie surface of the substrate film in the thickness direction are formed into the longitudinal section; or providing a base wafer, preparing a substrate film on the base wafer by a mechanical stripping method, and preparing the longitudinal section with a preset shape on the substrate film by a photoetching process and a reactive ion etching process.
7. The method of preparing graphene nanoribbons embedded between two-dimensional material layers according to claim 5, wherein the method of forming the nano-catalyst particles comprises: firstly, forming a nano catalyst film on the surface of the substrate and the longitudinal section surface; and then, heating the substrate with the nano catalyst film formed thereon to enable the nano catalyst film to agglomerate to form nano catalyst particles, and simultaneously moving and combining with the surface of the substrate and the surface of the longitudinal section.
8. The method for preparing the graphene nanoribbon embedded between two-dimensional material layers according to claim 5, wherein the method comprises the following steps: the nano catalyst particles are one of metal nano catalyst particles, alloy nano catalyst particles and metal oxide nano catalyst particles which are in eutectic connection with carbon.
9. The method for preparing the graphene nanoribbon embedded between two-dimensional material layers according to claim 5, wherein the method comprises the following steps: the carbon source gas includes at least one of methane, acetylene, and ethanol.
10. The method for preparing the graphene nanoribbon embedded between two-dimensional material layers according to claim 5, wherein the method comprises the following steps: the chemical vapor deposition process is a furnace tube process, and hydrogen is simultaneously introduced into the furnace tube in the growth process.
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