CN116462186A - Single chiral and closely arranged carbon tube array film and preparation method thereof - Google Patents
Single chiral and closely arranged carbon tube array film and preparation method thereof Download PDFInfo
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- CN116462186A CN116462186A CN202310517901.7A CN202310517901A CN116462186A CN 116462186 A CN116462186 A CN 116462186A CN 202310517901 A CN202310517901 A CN 202310517901A CN 116462186 A CN116462186 A CN 116462186A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 171
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000010408 film Substances 0.000 claims description 93
- 239000000758 substrate Substances 0.000 claims description 89
- 239000007789 gas Substances 0.000 claims description 79
- 239000011943 nanocatalyst Substances 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 61
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 60
- 239000002184 metal Substances 0.000 claims description 50
- 229910052751 metal Inorganic materials 0.000 claims description 50
- 239000002245 particle Substances 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 35
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 229910052786 argon Inorganic materials 0.000 claims description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- 229910052582 BN Inorganic materials 0.000 claims description 18
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 18
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 16
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000010453 quartz Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000004973 liquid crystal related substance Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 4
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- 238000001704 evaporation Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002109 single walled nanotube Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 238000005461 lubrication Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
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Classifications
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/164—Preparation involving continuous processes
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
Abstract
The invention provides a single chiral and closely-spaced carbon tube array film and a preparation method thereof, wherein the film comprises the following components: a plurality of single-wall carbon tubes arranged in parallel; wherein the diameter of the single-wall carbon tube is 1 nm-2 nm; the interval between two adjacent single-wall carbon tubes is 0.3 nm-0.4 nm. The area of the carbon tube array film can be arbitrarily selected; excellent performance, carrier mobility of more than 4000cm 2 V ‑1 S ‑1 The on-state current density is larger than 1 mA/mu m, and the current carrying capacity is larger than 8 mA/mu m; the preparation method is simple to operate, low in cost and capable of mass production.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a single-chiral close-packed carbon tube array film and a preparation method thereof.
Background
Single-wall carbon nanotubes (SWCNTs) have unique one-dimensional hollow tubular structures and excellent performances, the broad spectral response and the high light absorption coefficient of the single-wall carbon nanotubes make the single-wall carbon nanotubes become one of the material bases of future carbon-based high-performance devices, and the unique one-dimensional hollow tubular structures make the single-wall carbon nanotubes have excellent electrical, thermal and mechanical properties, so that the single-wall carbon nanotubes have potential application range related to electronic devices, energy storage, photoelectric sensing, flexible display, biological medicine, composite materials and the like. However, the premise of the carbon nanotubes being widely applied in electronic devices is to realize the macro-controllable preparation of the carbon nanotubes.
In the beginning of this century, SWCNTs were mainly single carbon tubes grown based on CVD, and were used for demonstrating field effect transistors, and the main problem to be solved at that time was how to improve the device quality of single carbon tubes, such as using metals with different work functions for contact. When the contact problem is solved, the research of preparing large-scale devices based on carbon tube films is gradually increased, but the device can obtain optimal performance only when the carbon tubes in the device channels are completely parallel because the orientation of the carbon tubes in the carbon tube films greatly influences the performance of the carbon tube devices. Efforts have been made to obtain films based on parallel alignment of carbon tubes. At present, the method is mainly realized through the following two paths: firstly, directly growing a carbon tube film on a substrate; and secondly, assembling independent carbon tubes into a collimated film through a series of post-treatment methods. In technical applications, where several parallel single-wall carbon tube channels are required per transistor, patil et al predict that the single-wall carbon tube density must be greater than 250 tubes per square micron in order to exceed the performance of silicon-based complementary metal oxide semiconductor (Si-CMOS). In addition, high density large scale parallel single wall carbon tube arrays are also needed in the fields of radio frequency applications, plastic electronics, display technology, sensors and electrodes, etc. The ideal carbon tube film should be a chiral single, fully collimated, closely spaced single wall carbon tube array film, which may even be referred to as a carbon tube crystal, but such perfect carbon tube films are not currently controllably produced.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is directed to providing a single chiral and closely-spaced carbon tube array film and a preparation method thereof, which are used for solving the problems that the prior art does not have a larger chiral single, fully-collimated closely-spaced single-walled carbon tube array film and a preparation method thereof.
To achieve the above and other related objects, the present invention provides a single chiral and closely spaced carbon tube array film comprising: a plurality of single-wall carbon tubes arranged in parallel; wherein, the liquid crystal display device comprises a liquid crystal display device,
the diameter of the single-wall carbon tube is 1 nm-2 nm;
the interval between two adjacent single-wall carbon tubes is 0.3 nm-0.4 nm.
Optionally, the carbon tube array film grows on a substrate with atomic-level flatness, and the distance between the carbon tube array film and the substrate with atomic-level flatness is 0.3 nm-0.5 nm.
Further, the substrate with atomic-level flatness is a hexagonal boron nitride substrate or a graphite substrate.
The invention also provides a preparation method of the single-chiral and closely-arranged carbon tube array film, which is used for preparing the single-chiral and closely-arranged carbon tube array film, and comprises the following steps:
providing a substrate with atomic-level flatness;
evaporating metal nano catalyst particles on the surface of the substrate;
placing the substrate evaporated with the metal nano catalyst particles in a furnace tube for heating, and introducing carbon source gas of methane or acetylene or ethanol to grow a single chiral and closely arranged carbon tube array film on the substrate; wherein the growth temperature is 600-1200 ℃, the growth time for keeping the growth temperature unchanged is longer than 30min, and hydrogen is introduced in the growth process as the gas for keeping the activity of the metal nano catalyst particles; when the carbon source gas is methane, the flow ratio of the carbon source gas to the hydrogen in the growth process is greater than 10:1; when the carbon source gas is acetylene, the flow ratio of the carbon source gas to the hydrogen in the growth process is greater than 1:2;
and closing the carbon source gas, and cooling to room temperature under the action of the protective gas.
Optionally, the substrate with atomic level flatness is a hexagonal boron nitride substrate or a graphite substrate.
Optionally, the metal nano-catalyst particles are iron nano-catalyst particles or cobalt nano-catalyst particles or nickel nano-catalyst particles, and the diameter of the metal nano-catalyst particles is 1 nm-10 nm.
Further, the step of growing a single chiral and closely spaced carbon tube array film on the substrate comprises:
providing a quartz tube furnace, and placing the substrate evaporated with the metal nano catalyst film in the quartz tube furnace, wherein the thickness of the metal nano catalyst film is as follows
And (3) heating: introducing hydrogen and argon shielding gas into the quartz tube furnace, and heating for 10-20 min to the growth temperature so as to form the metal nano catalyst thin film into the metal nano catalyst particles;
the growth process comprises the following steps: stopping introducing the argon in the heating process, keeping the flow of the hydrogen and the growth temperature unchanged in the heating process, and introducing the carbon source gas into the quartz tube furnace, wherein the flow of the carbon source gas is the same as the flow of the argon in the heating process;
and (3) a cooling process: and after the growth is finished, closing the carbon source gas, continuously introducing the hydrogen and the argon shielding gas, wherein the flow rates of the hydrogen and the argon are the same as those in the heating process, and naturally cooling to room temperature.
Further, the substrate with the atomic-level flatness is a hexagonal boron nitride substrate; the metal nano catalyst particles are cobalt nano catalyst particles, and the thickness of the metal nano catalyst film is as followsThe method comprises the steps of carrying out a first treatment on the surface of the The flow of the hydrogen is 200SCCM in the heating process, the flow of the argon is 100SCCM, and the air pressure is kept to be 10pa in the heating process; the carbon source gas is acetylene, the air pressure is kept at 10pa in the growth process, the growth time is 60min, and the carbon source gas is rawThe long temperature was 700 ℃.
Optionally, the substrate with atomic level flatness is a hexagonal boron nitride substrate; the metal nano catalyst particles are iron nano catalyst particles, and the thickness of the metal nano catalyst film is as followsThe method comprises the steps of carrying out a first treatment on the surface of the The flow of the hydrogen is 40SCCM in the heating process, the flow of the argon is 400SCCM, and the air pressure is kept to be 1 standard atmosphere in the heating process; the carbon source gas is methane, the air pressure is kept at 1 standard atmosphere in the growth process, the growth time is 60min, and the growth temperature is 850 ℃.
Optionally, the substrate with atomic level flatness is a graphite substrate; the metal nano catalyst particles are cobalt nano catalyst particles, and the thickness of the metal nano catalyst film is as followsThe method comprises the steps of carrying out a first treatment on the surface of the The flow of the hydrogen is 200SCCM in the heating process, the flow of the argon is 100SCCM, and the air pressure is kept to be 10pa in the heating process; the carbon source gas is acetylene, the air pressure is kept at 10pa in the growth process, the growth time is 60min, and the growth temperature is 700 ℃.
As described above, the invention provides a single chiral and closely arranged carbon tube array film and a preparation method thereof, wherein the area of the carbon tube array film can be arbitrarily selected; excellent performance, carrier mobility of more than 4000cm 2 V -1 S -1 The on-state current density is larger than 1 mA/mu m, and the current carrying capacity is larger than 8 mA/mu m; the preparation method is simple to operate, low in cost and capable of mass production.
Drawings
FIG. 1 shows a schematic and simplified schematic diagram of a growth apparatus used to prepare a single chiral and closely spaced carbon tube array film of the present invention.
FIG. 2 is a schematic three-dimensional structure of a single chiral and closely spaced carbon tube array film according to an embodiment of the present invention.
FIG. 3 is an enlarged schematic view of a single chiral and closely spaced carbon tube array film according to another embodiment of the present invention.
Fig. 4 shows an atomic force microscope picture of a carbon tube array film prepared by the preparation method of the single chiral and closely arranged carbon tube array film of the present invention.
Description of element reference numerals
10. Single-wall carbon tube
11. Carbon tube array film
12. Substrate and method for manufacturing the same
13. Metal nano catalyst particles
14. Tube furnace
15. Furnace tube
16. Carbon source gas
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention 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 invention.
As described in detail in the embodiments of the present invention, 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 invention. 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 this 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.
Example 1
Please refer to fig. 1 to 4. It should be noted that, the illustrations provided in the present embodiment merely illustrate the basic concept of the present invention by way of illustration, and only the components related to the present invention 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.
As shown in fig. 2 and 3, the present embodiment provides a single chiral and closely-spaced carbon tube array film, and the carbon tube array film 11 includes: a plurality of single-walled carbon tubes 10 (as shown in FIG. 2) arranged in parallel; wherein, the liquid crystal display device comprises a liquid crystal display device,
the diameter D of the single-walled carbon tube 10 is 1nm to 2nm, for example, may be 1nm, 1.5nm, 2nm, or the like;
the spacing L1 between two adjacent single-walled carbon tubes 10 is 0.3nm to 0.4nm, for example, may be 0.3nm, 0.33nm, 0.4nm, or the like, where L1 refers to the minimum distance between two adjacent single-walled carbon tubes 10.
It should be noted that the single-wall carbon tubes 10 in the carbon tube array film 11 may be straight tubes or bent tubes, for example, the single-wall carbon tubes 10 in fig. 4 are bent tubes, so long as the parallel arrangement among a plurality of single-wall carbon tubes 10 is satisfied.
The single chiral and close-packed carbon tube array film of the embodiment can be any size, and is specifically selected according to practical needs, and the semiconductor device carrier prepared by adopting the single chiral and close-packed carbon tube array film of the embodimentMobility of the flow is more than 4000cm 2 V -1 S -1 The on-state current density is larger than 1 mA/mu m, the current carrying capacity is larger than 8 mA/mu m, and the performance is excellent.
As shown in fig. 2 and 3, as a preferred example, the carbon tube array film 11 is grown on the substrate 12 with atomic level flatness, and the distance L2 between the carbon tube array film 11 and the substrate 12 with atomic level flatness is 0.3nm to 0.5nm, for example, may be 0.3nm, 0.4nm, or 0.5nm, etc., where L2 refers to the minimum distance between the two, which is determined by the equilibrium position of van der waals force between the carbon tube array film 11 and the substrate 12 with atomic level flatness, the mechanism of using the substrate 12 with atomic level flatness as the growth base of the carbon tube array film 11 is as follows: the super lubrication effect exists between the carbon nano tube and the substrate with atomic level flatness, and the carbon nano tube growing on the super lubrication effect can slide on the substrate at will, so that the state with the lowest energy is found, and finally the carbon nano tube is stacked into a regular close-packed carbon tube array. As a more preferable example, the substrate 12 with the atomic level flatness is a hexagonal boron nitride substrate or a graphite substrate, which is easy to form better super lubrication effect with the single-walled carbon tube 10, that is, the friction resistance between the single-walled carbon tube 10 and the substrate 12 is very low, and because van der waals attractive force exists between the single-walled carbon tube 10 and the single-walled carbon tube 10, the single-walled carbon tube 10 and the single-walled carbon tube 10 can spontaneously adsorb together on the surface of the substrate 12 with the atomic level flatness without resistance, so as to form a single-chiral carbon tube and close-packed carbon tube film.
Example two
The present embodiment provides a method for preparing a single chiral and close-packed carbon tube array film, which can be used to prepare the single chiral and close-packed carbon tube array film in the above embodiment, and the effect of the prepared carbon tube array film can be seen in the above embodiment, and the details are omitted. The preparation method comprises the following steps:
providing a substrate with atomic-level flatness;
evaporating metal nano catalyst particles on the surface of the substrate;
placing the substrate evaporated with the metal nano catalyst particles in a furnace tube for heating, and introducing carbon source gas of methane or acetylene or ethanol to grow a single chiral and closely arranged carbon tube array film on the substrate; wherein the growth temperature is 600-1200 ℃, the growth time for keeping the growth temperature unchanged is not less than 30min, and hydrogen is introduced in the growth process as the gas for keeping the activity of the metal nano catalyst particles; when the carbon source gas is methane, the flow ratio of the carbon source gas to the hydrogen in the growth process is greater than 10:1; when the carbon source gas is acetylene, the flow ratio of the carbon source gas to the hydrogen in the growth process is greater than 1:2;
and closing the carbon source gas, and cooling to room temperature under the action of the protective gas.
The film formation mechanism in the preparation method of the carbon tube array film of the embodiment is as follows: when single-wall carbon tubes grow on the surface of an atomically flat substrate, super-lubrication effect is formed between the carbon tubes and the substrate, namely, the friction resistance between the carbon tubes and the substrate is extremely low, so that the carbon tubes can slide on the substrate at will to find the state with the lowest energy, and further, because van der Waals attractive force exists between the carbon tubes, the carbon tubes and the carbon tubes can be spontaneously adsorbed together on the atomically flat substrate surface without resistance, thereby forming a single chiral carbon tube and close-packed carbon tube film, the film area can reach 10 mu m multiplied by 1 mu m, and the carrier mobility is larger than 4000cm 2 V -1 S -1 The on-state current density is larger than 1 mA/mu m, the current carrying capacity is larger than 8 mA/mu m, and the performance is excellent. In the growth process of the carbon tube array film, hydrogen is introduced to ensure that the metal nano catalyst particles keep the activity of the metal nano catalyst particles, and carbon source gases of methane or acetylene or ethanol with higher carbon source proportion are adopted, for example, the flow ratio of methane to hydrogen is more than 10:1, or the flow ratio of acetylene to hydrogen is more than 2:1, the metal nano catalyst particles can dissolve the carbon source and separate out single-wall carbon nano tubes; in addition, the preparation method is simple to operate, low in cost and capable of mass production; finally, the preparation method of the embodiment can be used for forming the carbon tube array film with any size.
The preparation method of the present embodiment is described in detail below with reference to the accompanying drawings, as shown in fig. 1 to 4.
As shown in fig. 1, step S1 is first performed to provide a substrate 12 having atomic-level flatness.
As an example, the substrate 12 may be a hexagonal boron nitride substrate or a graphite substrate. Specifically, in the conventional preparation method based on hexagonal boron nitride and graphite, a mechanical stripping method is generally adopted, and when a hexagonal boron nitride substrate or a graphite substrate is adopted in this embodiment, the hexagonal boron nitride substrate or the graphite substrate can be bonded on a silicon wafer by the mechanical stripping method. In the present application, hexagonal boron nitride and graphite are used as the preferred substrate for growing the carbon tube array film, but the present invention is not limited thereto, and other substrate materials with atomic level flatness are also suitable for the substrate of the present embodiment. The atomic-level flatness substrate is used as a growth substrate of the carbon tube array film, an ultra-lubrication effect can be formed between the atomic-level flatness substrate and the carbon tube array film in the growth process of the carbon tubes, and the formed carbon tube array film is formed into a single-chiral and closely-arranged form by combining Van der Waals attractive force between the carbon tubes.
As shown in fig. 1, step S2 is then performed to deposit metal nano-catalyst particles 13 on the surface of the substrate 12.
As an example, the metal nano-catalyst particles 13 are selected to be iron nano-catalyst particles or cobalt nano-catalyst particles or nickel nano-catalyst particles. Preferably, the diameter of the metal nano-catalyst particles 13 is 1nm to 10nm, for example, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, etc. The metal nano catalyst particles 13 are used as a dissolver for carbon source gas 16 in the growth process of the carbon tube, so as to separate out the single-wall carbon tube 10.
As a specific example, a metal nano-catalyst film is first deposited on the surface of the substrate 12, and the metal nano-catalyst film has a thickness ofFor example +.>Or (b)Etc.; then, the substrate 12 on which the metal nano catalyst film is evaporated is placed in a furnace tube 15 of a tube furnace 14 for heating, hydrogen and argon shielding gas are introduced into the furnace tube 15 during heating, the temperature is raised for 10-20 min to the growth temperature required by the subsequent carbon tube array film, and the metal nano catalyst film can be agglomerated during heating, so that the metal nano catalyst particles 13 are formed.
By way of example, the tube furnace 14 is in the form of a furnace tube 15 with a heating furnace outside, which provides good sealing, insulation and temperature control stability. The substrate 12 is placed in the furnace tube 15 in the heating process to perform the heating process. Preferably, the furnace tube 15 is a quartz furnace tube.
In the heating process, hydrogen and argon are introduced into the furnace tube 15 as protective gases, and the protective gases can be used as reducing gases, so that oxidized metal nano catalyst particles and some carbon-containing impurity substances generated by the carbon source gas 16 in the subsequent high-temperature growth process can be reduced, the flow of the carbon source gas 16 introduced in the subsequent growth process is the same as the flow of the argon in the heating process, the stability of the overall flow of the gases in the growth process is ensured, and the growth quality of the carbon tube array film is ensured.
As shown in fig. 1 and 4, step S3 is performed, in which the substrate 12 on which the metal nano-catalyst particles 13 are evaporated is placed in a furnace tube 15 to be heated, and a carbon source gas 16 of methane, acetylene or ethanol is introduced to grow a single chiral and closely arranged carbon tube array film 11 on the substrate 12; wherein the growth temperature is 600-1200 ℃, the growth time for keeping the growth temperature unchanged is not less than 30min, and hydrogen gas is introduced in the growth process as the gas for keeping the activity of the metal nano catalyst particles 13; when the carbon source gas 16 is methane, the flow ratio of the carbon source gas 16 to the hydrogen gas in the growth process is greater than 10:1; when the carbon source gas 16 is acetylene, the flow ratio of the carbon source gas 16 to the hydrogen gas in the growth process is greater than 1:2.
As a specific example, after the above heating process is finished, the growth process is performed, that is, the heating process and the growth process are performed in the same tube furnace 14, and the continuous process is performed, in which the argon gas is stopped being introduced during the heating process, the flow rate of the hydrogen gas and the growth temperature are kept unchanged during the heating process, and the carbon source gas 16 is introduced into the tube furnace 14, that is, the furnace tube 15, and the flow rate of the carbon source gas 16 is the same as the flow rate of the argon gas during the heating process, so as to ensure the stability of the total flow rate of the gas during the growth process and ensure the growth quality of the carbon tube array film.
Finally, step S4 is performed, the carbon source gas 16 is turned off, and the temperature is reduced to room temperature under the action of the protective gas.
As a specific example, in the cooling process, after the carbon source gas 16 is turned off, the hydrogen and the argon shielding gas are continuously introduced, 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 room temperature, and the stability of the total flow rate of the gas in the whole cooling process is ensured.
The preparation method of the single chiral and close packed carbon tube array film of this embodiment is further described below by specific experimental examples.
Experimental example 1
1) A silicon wafer was taken and cut into small pieces of about 1cm by 1cm in size.
2) A hexagonal boron nitride crystal is taken, and a hexagonal boron nitride sheet is prepared on the silicon wafer by a mechanical stripping method to serve as the substrate 12 with atomic-level flatness.
3) Vapor plating on the surface of the substrate 12 by adopting a thermal vapor plating methodA cobalt thin film of thickness, as a grown catalyst thin film.
4) The above substrate 12 coated with the catalyst film was placed in a quartz tube furnace, the atmosphere of the furnace gas was hydrogen gas at a flow rate of 200SCCM and argon gas at a flow rate of 100SCCM during the temperature rising, the temperature rising was gradually raised from room temperature to a growth temperature of 700 c for about 15 minutes, and the air pressure was maintained at 10pa during the temperature rising.
5) And stopping introducing argon when the temperature reaches the target growth temperature of 700 ℃, and introducing acetylene gas of 100SCCM as growth gas on the basis that the flow of the original hydrogen is 200SCCM and the flow is kept unchanged, wherein the growth time is 60 minutes, and the air pressure is kept to be 10pa in the growth process.
6) After the growth is finished, closing acetylene gas, introducing hydrogen gas with the flow rate of 200SCCM and argon gas with the flow rate of 100SCCM, naturally cooling to room temperature, and taking out the sample.
7) The size of the carbon tube array film 11 can reach 10 μm×1 μm by characterization by a scanning electron microscope and an atomic force microscope.
Experimental example 2
1) A silicon wafer was taken and cut into small pieces of about 1cm by 1cm in size.
2) A hexagonal boron nitride crystal is taken, and a hexagonal boron nitride sheet is prepared on the silicon wafer by a mechanical stripping method to serve as the substrate 12 with atomic-level flatness.
3) Vapor plating on the surface of the substrate 12 by adopting a thermal vapor plating methodAn iron film of a thickness, as a grown catalyst film.
4) The above substrate 12 coated with the catalyst film was placed in a quartz tube furnace, the atmosphere of the furnace gas was hydrogen gas at a flow rate of 40SCCM and argon gas at a flow rate of 400SCCM during the temperature rising, the temperature rising was gradually raised from room temperature to a growth temperature of 850 ℃ for about 15 minutes, and the air pressure was maintained at 1 standard atmospheric pressure during the temperature rising.
5) And stopping introducing argon when the temperature reaches the target growth temperature of 850 ℃, and introducing methane gas of 400SCCM as growth gas on the basis that the flow of the original hydrogen is 40SCCM and the flow is unchanged, wherein the growth time is 60 minutes, and the air pressure is kept at 1 standard atmosphere in the growth process.
6) After the growth is finished, closing methane gas, introducing hydrogen gas with the flow rate of 40SCCM and argon gas with the flow rate of 400SCCM, naturally cooling to room temperature, and taking out the sample.
7) The size of the carbon tube array film 11 can reach 10 μm×1 μm by characterization by a scanning electron microscope and an atomic force microscope.
Experimental example 3
The experimental example is basically the same as experimental example 1, except that: the substrate 12 of the atomic level flatness in this experimental example was graphite, and the rest of the steps were the same as in experimental example 1. The dimensions of the carbon tube array film 11 obtained in this experimental example were 2 μm×50nm by characterization with a scanning electron microscope and an atomic force microscope.
In summary, the present invention provides a single chiral and closely arranged carbon tube array film and a preparation method thereof, wherein the area of the carbon tube array film can be arbitrarily selected; excellent performance, carrier mobility of more than 4000cm 2 V -1 S -1 The on-state current density is larger than 1 mA/mu m, and the current carrying capacity is larger than 8 mA/mu m; the preparation method is simple to operate, low in cost and capable of mass production. Therefore, the invention 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 invention and its effectiveness, and are not intended to limit the invention. 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 invention. Accordingly, it is intended that all equivalent modifications and variations of the invention 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. A single chiral and closely spaced carbon tube array film, the carbon tube array film comprising: a plurality of single-wall carbon tubes arranged in parallel; wherein, the liquid crystal display device comprises a liquid crystal display device,
the diameter of the single-wall carbon tube is 1 nm-2 nm;
the interval between two adjacent single-wall carbon tubes is 0.3 nm-0.4 nm.
2. The single chiral and close packed carbon tube array film of claim 1, wherein the carbon tube array film is grown on an atomically flat substrate and the spacing between the carbon tube array film and the atomically flat substrate is 0.3nm to 0.5nm.
3. The single chiral and closely spaced carbon tube array film of claim 2, wherein: the substrate with atomic-level flatness is a hexagonal boron nitride substrate or a graphite substrate.
4. A method for preparing the single chiral and close packed carbon tube array film according to any one of claims 1 to 3, wherein the method comprises the steps of:
providing a substrate with atomic-level flatness;
evaporating metal nano catalyst particles on the surface of the substrate;
placing the substrate evaporated with the metal nano catalyst particles in a furnace tube for heating, and introducing carbon source gas of methane or acetylene or ethanol to grow a single chiral and closely arranged carbon tube array film on the substrate; wherein the growth temperature is 600-1200 ℃, the growth time for keeping the growth temperature unchanged is longer than 30min, and hydrogen is introduced in the growth process as the gas for keeping the activity of the metal nano catalyst particles; when the carbon source gas is methane, the flow ratio of the carbon source gas to the hydrogen in the growth process is greater than 10:1; when the carbon source gas is acetylene, the flow ratio of the carbon source gas to the hydrogen in the growth process is greater than 1:2;
and closing the carbon source gas, and cooling to room temperature under the action of the protective gas.
5. The method for preparing the single chiral and closely spaced carbon tube array film according to claim 4, wherein the method comprises the following steps: the substrate with atomic-level flatness is a hexagonal boron nitride substrate or a graphite substrate.
6. The method for preparing the single chiral and closely spaced carbon tube array film according to claim 4, wherein the method comprises the following steps: the metal nano catalyst particles are iron nano catalyst particles or cobalt nano catalyst particles or nickel nano catalyst particles, and the diameter of the metal nano catalyst particles is 1 nm-10 nm.
7. The method of claim 6, wherein the step of growing a single chiral and close packed carbon tube array film on the substrate comprises:
providing a quartz tube furnace, and placing the substrate evaporated with the metal nano catalyst film in the quartz tube furnace, wherein the thickness of the metal nano catalyst film is as follows
And (3) heating: introducing hydrogen and argon shielding gas into the quartz tube furnace, and heating for 10-20 min to the growth temperature so as to form the metal nano catalyst thin film into the metal nano catalyst particles;
the growth process comprises the following steps: stopping introducing the argon in the heating process, keeping the flow of the hydrogen and the growth temperature unchanged in the heating process, and introducing the carbon source gas into the quartz tube furnace, wherein the flow of the carbon source gas is the same as the flow of the argon in the heating process;
and (3) a cooling process: and after the growth is finished, closing the carbon source gas, continuously introducing the hydrogen and the argon shielding gas, wherein the flow rates of the hydrogen and the argon are the same as those in the heating process, and naturally cooling to room temperature.
8. The method for preparing the single chiral and closely spaced carbon tube array film according to claim 7, wherein the method comprises the steps of: the substrate with the atomic-level flatness is a hexagonal boron nitride substrate; the saidThe metal nano catalyst particles are cobalt nano catalyst particles, and the thickness of the metal nano catalyst film is as followsThe flow of the hydrogen is 200SCCM in the heating process, the flow of the argon is 100SCCM, and the air pressure is kept to be 10pa in the heating process; the carbon source gas is acetylene, the air pressure is kept at 10pa in the growth process, the growth time is 60min, and the growth temperature is 700 ℃.
9. The method for preparing the single chiral and closely spaced carbon tube array film according to claim 7, wherein the method comprises the steps of: the substrate with the atomic-level flatness is a hexagonal boron nitride substrate; the metal nano catalyst particles are iron nano catalyst particles, and the thickness of the metal nano catalyst film is as followsThe flow of the hydrogen is 40SCCM in the heating process, the flow of the argon is 400SCCM, and the air pressure is kept to be 1 standard atmosphere in the heating process; the carbon source gas is methane, the air pressure is kept at 1 standard atmosphere in the growth process, the growth time is 60min, and the growth temperature is 850 ℃.
10. The method for preparing the single chiral and closely spaced carbon tube array film according to claim 7, wherein the method comprises the steps of: the substrate with atomic-level flatness is a graphite substrate; the metal nano catalyst particles are cobalt nano catalyst particles, and the thickness of the metal nano catalyst film is as followsThe flow of the hydrogen is 200SCCM in the heating process, the flow of the argon is 100SCCM, and the air pressure is kept to be 10pa in the heating process; the carbon source gas is acetylene, the air pressure is kept at 10pa in the growth process, the growth time is 60min, and the growth temperature is 700 ℃.
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