CN115676805A - Single-walled carbon nanotube horizontal array and preparation method thereof - Google Patents
Single-walled carbon nanotube horizontal array and preparation method thereof Download PDFInfo
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Images
Abstract
The invention discloses a method for preparing a single-walled carbon nanotube horizontal array, which comprises the following steps: s1, loading a catalyst precursor on a single crystal substrate, carrying out pre-oxidation treatment to obtain the single crystal substrate suitable for growing the carbon nano tube, and placing the single crystal substrate in vapor deposition equipment; s2, introducing inert gas and hydrogen into the chemical vapor deposition equipment to form a protective atmosphere; and S3, uniformly spraying the reaction materials in a spraying mode, wherein the spraying direction is vertical to the growth surface of the single crystal substrate. The preparation method of the invention introduces the reaction materials into the vapor deposition equipment by vertically spraying in a spraying mode, thereby forming relatively uniform and stable airflow which is uniformly acted on the surface of the reaction substrate, and being beneficial to improving the uniformity of the carbon nanotube array, so that the prepared single-walled carbon nanotube horizontal array has excellent crystallinity, and the horizontal array area can reach 3.24cm 2 The average density can reach 20-40 roots/micron, and the preparation method has the advantages of stability, controllability, easy amplification and the likeIs characterized in that.
Description
Technical Field
The invention relates to the technical field of carbon nanotube preparation, in particular to a large-area high-density single-walled carbon nanotube horizontal array and a preparation method thereof.
Background
Since the discovery of single-walled carbon nanotubes in 1993, single-walled carbon nanotubes have received a great deal of attention in various application fields due to their unique structures and excellent properties. As a one-dimensional Dirac material, the carbon nano tube has outstanding electrical performance, the effective mass of electrons and holes is zero, so that the carbon nano tube has extremely high carrier mobility, and the electron transportation shows ballistic transport characteristics, so that the carbon nano tube is considered as one of the most potential star materials in micro-nano electronic devices in ' post Mohs ', is expected to break the limitation that the operation speed and the performance optimization of silicon transistors in the traditional chip industry are close to physical limits, and replaces semiconductor silicon so as to continue the Mohs ' law.
The carbon nano tube horizontal array is a carbon nano tube integrated type which is orderly arranged on the surface of a flat substrate, the preparation method comprises a direct growth method and a post-treatment method, and the directly grown horizontal array carbon nano tube has lower structural defect concentration and better electric, force and thermal properties; the post-treatment process tends to degrade the quality of the carbon nanotubes, resulting in a reduction in the length of the carbon nanotubes, resulting in surface contamination and possible damage to the horizontal array integrity, etc. Compared with other existing forms and treatment modes of the carbon nano tubes, the directly grown carbon nano tube horizontal array has higher research and application values.
The application of the carbon nanotube horizontal array in the field of field effect transistors and the like puts very strict requirements on indexes such as semiconductor purity, density and the like. During the research of carbon nanotubes, there have been many excellent works to date to realize the direct preparation of high density horizontal arrays of carbon nanotubes, the local density can reach as high as 130 pieces/μm, the goal of 125 pieces/μm proposed by IBM research center in 2012 has been met, and the attempt of using carbon nanotubes to replace semiconductor silicon to construct field effect transistors and even computer prototypes has been a breakthrough in recent years. However, although the density of the carbon nanotube horizontal array obtained by the direct growth method reported at present has satisfied the basic requirements of electronics application, it is only a local level of achievement, and the overall density non-uniformity and the relatively small size of the carbon nanotube horizontal array are in the process of carbon nanotube-based field effect transistor and are going to be truly industrialized. Therefore, how to directly grow a large-area, even wafer-level, high-quality, high-density, and uniform horizontal array of carbon nanotubes is the key to determine the practical application value of carbon nanotubes in the field of nanoelectronics.
Disclosure of Invention
In order to overcome the defects, the invention provides a preparation method of a single-walled carbon nanotube horizontal array and the single-walled carbon nanotube horizontal array prepared by the method.
The invention provides a method for preparing a single-walled carbon nanotube horizontal array on one hand, which comprises the following steps: s1, loading a catalyst precursor on a single crystal substrate, carrying out pre-oxidation treatment to obtain a single crystal substrate suitable for growing a carbon nano tube, and placing the single crystal substrate in vapor deposition equipment; s2, introducing inert gas and hydrogen into the chemical vapor deposition equipment to form a protective atmosphere; and S3, uniformly spraying the reaction materials in a spraying mode, wherein the spraying direction is vertical to the growth surface of the single crystal substrate.
According to an embodiment of the present invention, the single crystal substrate is a single crystal alumina substrate or a single crystal quartz substrate, and the area of the growth surface of the single crystal substrate is 0.24 to 3.24cm 2 。
According to another embodiment of the present invention, the catalyst precursor is one or more of salt solutions containing Fe, co, ni, cu, au, mo and W ions, and is loaded on the growth surface of the single crystal substrate by spin coating.
According to another embodiment of the invention, the pre-oxidation treatment is to heat the single crystal substrate loaded with the catalytic precursor at a constant temperature of 500-1100 ℃ for 0.5-8 hours, and then controllably cool the single crystal substrate to room temperature according to a certain cooling rate.
According to another embodiment of the present invention, the inert carrier gas is selected from one or more of nitrogen, argon, krypton and xenon, and has a flow rate of 50sccm to 1000sccm, and a flow rate of hydrogen of 50sccm to 400sccm.
According to another embodiment of the present invention, the carbon source is selected from one or more of hydrocarbons, alcohols, ethers, ketones, phenols and carbon monoxide.
According to another embodiment of the invention, the carbon source is cracked in a high temperature zone of 750 ℃ to 950 ℃.
According to another embodiment of the present invention, the spray pattern is such that the high-temperature cracked carbon source gas is sprayed through a spray head, and the distance from the outlet of the spray head to the growth surface of the single crystal substrate is 2mm to 27mm.
The invention also provides a horizontal array of the single-walled carbon nanotubes prepared by the method.
The preparation method of the invention introduces the reaction materials into the vapor deposition equipment in a spraying mode. In the traditional horizontal chemical vapor deposition system, carbon source molecules enter a substrate airflow viscous layer in a diffusion mode, and the carbon source concentration and the gas phase near the catalyst have deviation, so the utilization efficiency of the catalyst is low, while the spraying system changes the introduction mode of the gas phase carbon source, so the gas phase carbon source is vertically sprayed in a spraying mode to form relatively uniform and stable airflow which is uniformly applied to the surface of the reaction substrate, thereby ensuring that the carbon source concentration and the gas phase carbon source concentration on the surface of the substrate are basically consistent, improving the gas mixing uniformity of a growth area and being beneficial to improving the uniformity of a carbon nanotube array, and further ensuring that the prepared single-walled carbon nanotube horizontal array has excellent crystallinity, and the area of the horizontal array can reach 3.24cm 2 The average density can reach 20-40 roots/micron, and the preparation method has the characteristics of stability, controllability, easy amplification and the like. By utilizing the preparation method, the large-scale preparation of the high-density semiconductor carbon nano tube horizontal array is expected to be realized by screening proper catalysts and substrates, so that the preparation method has a wide application prospect.
Drawings
Fig. 1 is a schematic view of a spray chemical vapor deposition apparatus of example 1.
FIG. 2 is a view showing a-Al in example 1 2 O 3 AFM photograph of initial surface appearance of the substrate and AFM photograph of the surface after annealing.
FIG. 3 shows α -Al of 10mm × 12mm in example 1 2 O 3 Optical photographs of a single crystal substrate and SEM photographs of horizontal arrays of single-walled carbon nanotubes grown on different areas of the single crystal substrate.
FIG. 4 shows α -Al of 10mm × 12mm in example 1 2 O 3 SEM photograph of horizontal array of single-walled carbon nanotubes on single crystal substrate.
FIG. 5 shows α -Al of 10mm × 12mm in example 1 2 O 3 AFM photographs of horizontal arrays of single-walled carbon nanotubes on a substrate.
FIG. 6 Raman spectroscopy characterization of α -Al in example 1 2 O 3 The distribution schematic diagram of the actually measured area of the horizontal array of the single-walled carbon nanotubes on the substrate and the Raman spectrogram of the horizontal array of the single-walled carbon nanotubes grown in different areas of the substrate.
FIG. 7 characterization of α -Al by SEM as in example 2 2 O 3 Schematic distribution diagram of actually measured areas of the horizontal array of the single-walled carbon nanotubes on the substrate and SEM pictures of the shapes of the horizontal arrays of the single-walled carbon nanotubes in different areas of the substrate.
FIG. 8 characterization of α -Al by SEM for example 3 2 O 3 Schematic distribution diagram of actually measured areas of the horizontal array of the single-walled carbon nanotubes on the substrate and SEM pictures of the shapes of the horizontal arrays of the single-walled carbon nanotubes in different areas of the substrate.
FIG. 9 is a 4mm X6 mm size α -Al of example 4 2 O 3 SEM photograph of horizontal array of single-walled carbon nanotubes on substrate.
FIG. 10 shows the 15mm size of α -Al in example 5 2 O 3 SEM representation of the actually measured area distribution schematic diagram of the morphology of the single-walled carbon nanotube on the substrate.
FIG. 11 is a 18 mm. Times.18 mm size α -Al of example 6 2 O 3 SEM representation of the actually measured area distribution schematic diagram of the morphology of the single-walled carbon nanotube on the substrate.
Detailed Description
The present invention will be further described with reference to the following examples, but the practice of the present invention is not limited thereto. It is intended that all modifications and equivalents of the technical aspects of the present invention be included within the scope of the present invention without departing from the spirit and scope of the technical aspects of the present invention.
The invention provides a method for preparing a single-walled carbon nanotube horizontal array on one hand, which comprises the following steps: s1, loading a catalyst precursor on a single crystal substrate, carrying out pre-oxidation treatment to obtain the single crystal substrate suitable for growing the carbon nano tube, and placing the single crystal substrate in vapor deposition equipment; s2, introducing inert gas and hydrogen into the chemical vapor deposition equipment to form a protective atmosphere; and S3, uniformly spraying the reaction materials in a spraying mode, wherein the spraying direction is vertical to the growth surface of the single crystal substrate. The 'reaction material' in the patent is a substance introduced into a vapor deposition system and comprises a carbon source, inert carrier gas, hydrogen and the like; "spray direction" means the direction in which the reaction mass is sprayed; "growth surface" refers to the surface used to grow horizontal arrays of single-walled carbon nanotubes. The preparation method introduces the carbon source and other reaction gases into the vapor deposition equipment in a spraying mode, wherein the spraying direction is vertical to the substrate. In a traditional horizontal chemical vapor deposition system, carbon source molecules enter a substrate airflow viscous layer in a diffusion mode, the utilization efficiency of a catalyst is low because the concentration of the carbon source near the catalyst is deviated from the gas phase, and a spraying system changes the introduction mode of the gas phase carbon source and enables the gas phase carbon source to be vertically sprayed out in a spraying mode to form relatively uniform and stable airflow which is uniformly applied to the surface of a reaction substrate, so that the carbon source concentration on the surface of the substrate is basically consistent with the gas phase carbon source concentration, the gas mixing uniformity of a growth area can be improved, the uniformity of a carbon nanotube array is improved, and the prepared single-walled carbon nanotube horizontal array is excellent in crystallinity. The reaction materials entering the vapor deposition system can be respectively sprayed into the deposition system, or can be premixed and then enter the deposition system in a spraying mode. The gas mixing uniformity of the growth area can be further improved by fully premixing in the early stage, which is helpful for improving the uniformity of the carbon nanotube arrayAnd (4) sex. For carbon sources, they may be introduced into the deposition system by pyrolysis followed by spraying. The single-walled carbon nanotube horizontal array prepared by the method has excellent crystallinity, and the area of the horizontal array can reach 3.24cm 2 The average density can reach 20-40 roots/micron, and the preparation method has the characteristics of stability, controllability, easy amplification and the like.
According to alternative embodiments, the single crystal substrate is a single crystal alumina substrate or a single crystal quartz substrate. The area of the growth surface of the single crystal substrate is 0.24-3.24 cm 2 。
According to an alternative embodiment, the catalyst precursor is one or more of a salt solution containing Fe, co, ni, cu, au, mo and W ions, and is loaded on the growth surface of the single crystal substrate by spin coating. The spin coating method can uniformly form a catalyst precursor on the surface of the single crystal substrate, and the catalyst precursor is oxidized into an oxide of the catalyst during subsequent pre-oxidation treatment, and the oxide is reduced into metal catalyst nanoparticles in the vapor deposition process to catalyze the growth of the single-walled carbon nanotubes. Preferably, the pre-oxidation treatment is to heat the single crystal substrate loaded with the catalytic precursor at a constant temperature of 500-1100 ℃ for 0.5-8 hours, and then controllably reduce the temperature to room temperature according to a certain cooling rate. Of course, the loading mode of the catalyst can be other modes as long as the catalyst can catalyze the growth of the single-walled carbon nanotubes.
According to an alternative embodiment, the inert carrier gas is selected from one or more of nitrogen, argon, krypton and xenon. The flow rates of the inert carrier gas and the hydrogen gas may be in a commonly used flow range, for example, but not limited to, the inert carrier gas may be in a flow range of 50sccm to 1000sccm, and the hydrogen gas may be in a flow range of 50sccm to 400sccm.
According to an alternative embodiment, the carbon source may be selected from commonly used vapor deposited carbon sources. For example one or more selected from the group consisting of hydrocarbons, alcohols, ethers, ketones, phenols and carbon monoxide. The time for introducing the carbon source may be appropriately selected according to the actual need, for example, but not limited to, 1min to 60min.
According to an alternative embodiment, the carbon source is cracked in a high temperature zone of 750 ℃ to 950 ℃.
According to an optional embodiment, the spraying manner is to spray the carbon source gas pre-cracked by the high temperature part through a spray head, and the distance from the outlet of the spray head to the growth surface of the single crystal substrate is 2mm to 27mm. The distance between the outlet of the spray head and the single crystal substrate has certain influence on the distribution of the carbon source gas, and the practice proves that the performance of the horizontal array of the carbon nano tubes formed by the distance between the outlet of the spray head and the substrate is not good enough (< 2 mm) or too far (> 27 mm). The skilled person can select suitable distances according to the actual need, such as, but not limited to, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm, 15mm, 16mm, 17mm, 18mm, 19mm, 20mm, 21mm, 22mm, 23mm, 24mm, 25mm, 26mm, 27mm, etc.
The invention also provides a single-walled carbon nanotube horizontal array prepared by the method. The single-walled carbon nanotube horizontal array prepared by the method has excellent crystallinity, and the area of the horizontal array can reach 3.24cm 2 The average density is 20-40 roots/micron.
The present invention is further described below by way of specific examples. However, these examples are merely illustrative and do not limit the scope of the present invention in any way.
In the following examples and comparative examples, reagents, materials and instruments used therefor were commercially available unless otherwise specified.
Example 1
FIG. 1 shows a spray CVD apparatus for preparing large-area high-density single-walled carbon nanotube horizontal arrays, the main body of the apparatus is a dual-temperature zone thermal resistance type vertical tube furnace, the maximum experimental temperature can reach 1100 ℃, and the actual temperature floats within +/-1 ℃ of the set temperature in a constant temperature state. The tube furnace is internally provided with a spray header 100 and a lifting platform 200. Various carriers or substrates required for growing the single-walled carbon nanotubes can be placed on the lifting platform 200, and the distance between the surface of the substrate and the spray header 100 can be controlled by regulating the height of the lifting platform, so that the growth uniformity of the large-area single-walled carbon nanotube horizontal array can be regulated.
Taking 10mm multiplied by 12mm single-side polished alpha-Al 2 O 3 As a growth substrate, respectively adding deionized water, high-purity acetone and anhydrous ethyl acetateUltrasonic cleaning in alcohol, deionized water for 10 minutes, as shown in a) of fig. 2.
And then putting the single crystal substrate into a muffle furnace, heating to 1100 ℃ for 3h, keeping the temperature for 8h, cooling to 300 ℃ for 10h, and then naturally cooling to room temperature. Surface reconstruction of the surface optimized exposed clean (11-20) face was obtained as shown in b) in fig. 2.
Configuration of 0.05mmol/L Fe (OH) 3 Taking an ethanol solution as a catalyst precursor, spin-coating 10 mu L of the catalyst precursor on the surface of the substrate on a spin coater at the rotating speed of 2500rpm, then putting the substrate into a muffle furnace, heating to 1100 ℃ for 3h, keeping the temperature for 8h, cooling to 300 ℃ for 10h, and naturally cooling to room temperature to obtain the catalyst-loaded alpha-Al 2 O 3 A substrate.
Configuration 0.05mmol/L (NH) 4 ) 6 Mo 7 O 24 Aqueous solution, 10. Mu.L of molybdenum catalyst precursor was spin coated onto the above-described alpha-Al on a spin coater using 2500rpm 2 O 3 Obtaining large-size alpha-Al simultaneously loading iron and molybdenum catalyst precursor on the surface of the substrate 2 O 3 A substrate.
The alpha-Al loaded with the Fe and Mo catalyst 2 O 3 The substrate is placed on a lifting platform 200 in the spraying chemical vapor deposition equipment, and the distance between the lifting platform 200 and the spray header 100 is adjusted to be 17mm. Heating the system to a growth temperature of 830 ℃ in air at a heating rate of 40 ℃/min, starting a mechanical pump, pumping the system to 20Pa to discharge air, and then introducing 1000sccm argon to clean for 5 minutes. Then adjusting the flow rate of argon to 300sccm, introducing 320sccm high-purity hydrogen for 5 minutes to reduce and separate out alpha-Al 2 O 3 Catalyst nanoparticles on a substrate. Then other reaction gases (hydrogen and argon) and liquid carbon source ethanol are uniformly sprayed to the large-area alpha-Al through the spray header 100 2 O 3 Starting to directionally grow the single-walled carbon nanotubes on the surface of the substrate, wherein a liquid carbon source ethanol is introduced in a bubbling mode by introducing 80sccm of argon into an ethanol tank. And after the growth time of 30 minutes is finished, keeping argon and hydrogen, closing the carbon source, naturally cooling to room temperature, and taking out the substrate.
The growth result of the large-area high-density horizontal array of carbon nanotubes obtained in this example is shown in the Scanning Electron Microscope (SEM) of fig. 3. In FIG. 3 a) is alpha-Al of horizontal array of single-walled carbon nanotubes that have not grown 2 O 3 An optical photograph of the substrate; b) And c) and d) are SEM pictures of the horizontal arrays of the single-walled carbon nanotubes grown in the areas b, c and d in the picture of a) respectively. It can be seen from FIG. 3 that the area is 1.2cm 2 alpha-Al of (2) 2 O 3 Different areas on the surface of the substrate can grow the carbon nano tube horizontal array with uniform distribution. Fig. 4 is a SEM photograph with a higher magnification of different regions of the substrate obtained in this example, and it can be seen from the photograph that the uniformity of the carbon nanotubes can be ensured, and the horizontal array density of the single-walled carbon nanotubes in different regions can reach 20 to 30 carbon nanotubes/micrometer. Fig. 5 is an Atomic Force Microscope (AFM) photograph of the horizontal array of single-walled carbon nanotubes obtained in this example, from which it can be seen that the density of the horizontal array of single-walled carbon nanotubes reaches 27 atoms/micrometer.
The quality of the horizontal array of single-walled carbon nanotubes grown by the method can be characterized by raman spectroscopy, as shown in fig. 6. FIG. 6 a) characterization of α -Al for Raman spectroscopy 2 O 3 Schematic distribution diagram of actually measured area of single-walled carbon nanotube horizontal array on the substrate; in FIG. 6, b) to f) correspond to the regions indicated by b to f in a), respectively, and Raman characterization was performed using excitation light with a wavelength of 532nm, respectively, to obtain spectrograms. From fig. 5, it is clear that the radial respiration vibration peak (RBM) and the tangential vibration peak (G) of the single-walled carbon nanotube are observed, while the defect-induced peak (D) representing the structural defect of the carbon nanotube or the carbon impurities other than the carbon nanotube is very weak, and the G/D peak intensity ratio of most regions is greater than 100, which indicates that the large-area horizontal array of single-walled carbon nanotubes prepared by the spraying method has very high quality.
Example 2
The conditions were the same as in example 1 except that the distance between the elevating table and the shower head was adjusted to 7mm.
In the presence of alpha-Al 2 O 3 A horizontal array of single-walled carbon nanotubes grown on the substrate is shown in fig. 7. In FIG. 7 a) is alpha-Al 2 O 3 Single-walled carbon nanotube horizontal array on a substrateSchematic distribution of the regions of the inter-measurement; SEM photographs of b) to d) in FIG. 7 correspond to the areas indicated by b to d in a), respectively. It can be seen from fig. 7 that the distribution uniformity is still good over the entire substrate, but the density of the carbon nanotubes is reduced.
Example 3
The conditions were the same as in example 1 except that the distance between the elevating table and the shower head was adjusted to 27mm.
In the presence of alpha-Al 2 O 3 A horizontal array of single-walled carbon nanotubes grown on the substrate is shown in fig. 8. In FIG. 8 a) is alpha-Al 2 O 3 Schematic distribution diagram of actually measured area of single-walled carbon nanotube horizontal array on the substrate; SEM photographs of b) to d) in FIG. 8 correspond to the areas indicated by b to d in a), respectively. FIG. 8 shows, α -Al 2 O 3 The growth of single-walled carbon nanotubes on the substrate is almost not performed, which indicates that the spraying chemical vapor deposition equipment can adjust the growth result of the large-area single-walled carbon nanotube horizontal array by adjusting the distance between the spray head 100 and the lifting platform 200.
Example 4
Except that 4mm 6mm of alpha-Al is used 2 O 3 The substrate was grown under the same conditions as in example 1 except that the flow rate of hydrogen gas introduced during the growth was 300 sccm.
Fig. 9 shows three photographs, which are SEM photographs at different magnifications. Fig. 9 shows that the single-walled carbon nanotubes are uniformly distributed on the substrate with a density of up to 20 per micron.
Example 5
Except using a larger area of 15mm by 15mm of alpha-Al 2 O 3 The conditions other than the substrate were the same as in example 1.
In the presence of alpha-Al 2 O 3 A horizontal array of single-walled carbon nanotubes grown on the substrate is shown in fig. 10. In FIG. 10 a) is α -Al 2 O 3 Schematic distribution diagram of actually measured area of single-walled carbon nanotube horizontal array on the substrate; SEM photographs of the regions b) to d) in a) in FIG. 10 correspond to the regions b to d, respectively. Fig. 10 shows that the single-walled carbon nanotubes remain uniformly distributed on the substrate and maintain a higher density.
Example 6
Except using a larger area of 18mm by 18mm of alpha-Al 2 O 3 The conditions other than the substrate were the same as in example 1.
In the presence of alpha-Al 2 O 3 A horizontal array of single-walled carbon nanotubes grown on the substrate is shown in fig. 11. In FIG. 11 a) is α -Al 2 O 3 Schematic distribution diagram of actually measured area of single-walled carbon nanotube horizontal array on the substrate; SEM photographs of b) to d) in FIG. 11 correspond to the areas indicated by b to d in a), respectively. Fig. 11 shows that the single-walled carbon nanotubes remain uniformly distributed on the substrate and maintain a higher density.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (9)
1. A method for preparing a horizontal array of single-walled carbon nanotubes comprises the following steps:
s1, loading a catalyst precursor on a single crystal substrate, carrying out pre-oxidation treatment to obtain the single crystal substrate suitable for growing the carbon nano tube, and placing the single crystal substrate in vapor deposition equipment;
s2, introducing inert gas and hydrogen into the chemical vapor deposition equipment to form a protective atmosphere; and
and S3, uniformly spraying the reaction materials in a spraying mode, wherein the spraying direction is vertical to the growth surface of the single crystal substrate.
2. The production method according to claim 1, wherein the single-crystal substrate is a single-crystal alumina substrate or a single-crystal quartz substrate, and the area of the growth surface of the single-crystal substrate is 0.24 to 3.24cm 2 。
3. The production method according to claim 1, wherein the catalyst precursor is one or more of salt solutions containing Fe, co, ni, cu, au, mo, and W ions, and is applied to the growth surface of the single crystal substrate by spin coating.
4. The preparation method according to claim 1, wherein the pre-oxidation treatment is to heat the single crystal substrate loaded with the catalytic precursor at a constant temperature of 500-1100 ℃ for 0.5-8 hours, and then controllably cool the single crystal substrate to room temperature at a certain cooling rate.
5. The method according to claim 1, wherein the inert carrier gas is selected from one or more of nitrogen, argon, krypton and xenon, and has a flow rate of 50sccm to 1000sccm, and a flow rate of hydrogen of 50sccm to 400sccm.
6. The method according to claim 1, wherein the carbon source is one or more selected from the group consisting of hydrocarbons, alcohols, ethers, ketones, phenols, and carbon monoxide.
7. The method of claim 1, wherein the carbon source is cracked in a high temperature zone of 750 ℃ to 950 ℃.
8. The method according to claim 1, wherein the high-temperature-cracked carbon source gas is sprayed through a shower head, and an outlet of the shower head is spaced from a growth surface of the single crystal substrate by a distance of 2mm to 27mm.
9. A horizontal array of single-walled carbon nanotubes produced by the method of any one of claims 1 to 8.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004065657A1 (en) * | 2003-01-13 | 2004-08-05 | Nantero, Inc. | Methods of making carbon nanotube films, layers, fabrics, ribbons, elements and articles |
| US20050053542A1 (en) * | 2003-09-08 | 2005-03-10 | Avetik Harutyunyan | Methods for preparation of one-dimensional carbon nanostructures |
| CN101027756A (en) * | 2004-08-04 | 2007-08-29 | 株式会社Eugene科技 | Thermal oxide formation apparatus and the method by chemical vapor deposition in wafer |
| CN103253650A (en) * | 2013-05-22 | 2013-08-21 | 恒正科技（苏州）有限公司 | Preparation method of nano-carbon material |
| CN105441904A (en) * | 2014-06-18 | 2016-03-30 | 中微半导体设备(上海)有限公司 | Gas spray device, chemical vapor deposition device and method |
| CN105565292A (en) * | 2014-10-29 | 2016-05-11 | 北京大学 | Ultra-high-density single-walled carbon nanotube horizontal array and controllable preparation method thereof |
| CN111560604A (en) * | 2020-06-15 | 2020-08-21 | 无锡盈芯半导体科技有限公司 | Vertical spraying device for spraying type gas inlet CVD |
| CN111778552A (en) * | 2020-08-03 | 2020-10-16 | 中国科学院长春光学精密机械与物理研究所 | MOCVD (Metal organic chemical vapor deposition) combined spray header and MOCVD equipment |
| CN111943171A (en) * | 2020-08-21 | 2020-11-17 | 温州大学 | Controllable preparation method of high-density single-walled carbon nanotube horizontal array |
-
2021
- 2021-07-26 CN CN202110842354.0A patent/CN115676805A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004065657A1 (en) * | 2003-01-13 | 2004-08-05 | Nantero, Inc. | Methods of making carbon nanotube films, layers, fabrics, ribbons, elements and articles |
| US20050053542A1 (en) * | 2003-09-08 | 2005-03-10 | Avetik Harutyunyan | Methods for preparation of one-dimensional carbon nanostructures |
| CN101027756A (en) * | 2004-08-04 | 2007-08-29 | 株式会社Eugene科技 | Thermal oxide formation apparatus and the method by chemical vapor deposition in wafer |
| CN103253650A (en) * | 2013-05-22 | 2013-08-21 | 恒正科技（苏州）有限公司 | Preparation method of nano-carbon material |
| CN105441904A (en) * | 2014-06-18 | 2016-03-30 | 中微半导体设备(上海)有限公司 | Gas spray device, chemical vapor deposition device and method |
| CN105565292A (en) * | 2014-10-29 | 2016-05-11 | 北京大学 | Ultra-high-density single-walled carbon nanotube horizontal array and controllable preparation method thereof |
| CN111560604A (en) * | 2020-06-15 | 2020-08-21 | 无锡盈芯半导体科技有限公司 | Vertical spraying device for spraying type gas inlet CVD |
| CN111778552A (en) * | 2020-08-03 | 2020-10-16 | 中国科学院长春光学精密机械与物理研究所 | MOCVD (Metal organic chemical vapor deposition) combined spray header and MOCVD equipment |
| CN111943171A (en) * | 2020-08-21 | 2020-11-17 | 温州大学 | Controllable preparation method of high-density single-walled carbon nanotube horizontal array |
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