CN114686861A - Method for controlling network morphology of single-walled carbon nanotube grown by using crystal face step orientation and height - Google Patents
Method for controlling network morphology of single-walled carbon nanotube grown by using crystal face step orientation and height Download PDFInfo
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/46—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for heating the substrate
Abstract
The invention relates to the field of controllable preparation of single-walled carbon nanotube network morphology, in particular to a method for controlling the growth of the single-walled carbon nanotube network morphology by the step orientation and the height of a crystal face. Selecting magnesium aluminate spinel MgAl2O4The (100), (110) and (111) surfaces of the substrate are subjected to heat treatment conditions to regulate and control the crystallinity, the orientation and the height of atomic steps of crystal surfaces of the substrate, and a normal-pressure chemical vapor deposition method is utilized to directly grow orthogonal, parallel and disorderly oriented single-walled carbon nanotube networks on the three crystal surfaces respectively. The invention respectively realizes orthogonality and flatness based on strong interaction of single-walled carbon nanotubes and crystal face atoms by selecting a substrate crystal face and regulating the orientation and height of a stepThe control of the network morphology of the single-walled carbon nano-tube with rows and disordered orientations lays a material foundation for exploring a novel carbon nano-tube nano electronic device.
Description
Technical Field
The invention relates to the field of controllable preparation of single-walled carbon nanotube network morphology, in particular to a method for controlling growth of single-walled carbon nanotube network morphology by crystal face step orientation and height.
Background
The single-walled carbon nanotubes arranged in an oriented mode can be used as electrode materials of future nano electronic devices and chips, interconnection wires, semiconductor channel materials of regulating and controlling electronic switches and the like. For example, the mutually orthogonal single-walled carbon nanotubes are beneficial to building a novel micro-nano device, the parallel array of the single-walled carbon nanotubes is beneficial to regulating and controlling one-way conduction through grid voltage so as to realize logic and storage, and the disordered single-walled carbon nanotube network can be used for building a display and photovoltaic device. Currently, the network morphology of the single-walled carbon nanotubes is mainly of parallel arrays and disordered networks, the network morphology of the single-walled carbon nanotubes can be regulated by using different growth substrates, and the commonly used single-crystal substrates are limited to quartz (document 1, Qian L.; Shao Q.; Zhang J.et. al.; Advanced Functional Materials,2021,2106643) and sapphire (document 2, Hu, Y., Zhang, H., J., Zhang J.et. al.; Small,2021,2103433), and the commonly used non-single-crystal substrates are silicon wafers plated with amorphous silicon oxide on the surface (document 3, Zhang, L.L.; Sun, D.M.; Liu, C.et., Advanced Materials,2017,29, 32; document 4, Zhang F.; Hou P.X.; Liu C.et., Nature Communication,2016, 1117, 11160). The main problems faced at present are: the single orientation of the single-walled carbon nanotube is regulated and controlled by the single crystal substrate, so that multiple orientation regulation and control of the same single crystal substrate cannot be realized; further, Al2O3And SiO2The requirement on the bevel cutting crystal face is strict, and the errors of more than +/-0.5 degrees can cause the growth of waved and zigzag single-walled carbon nanotubes; the heat treatment requirement of the substrate is also strict, the substrate needs to be subjected to heat treatment at the high temperature of over 1100 ℃ for more than 8 hours, otherwise, the substrate is not heatedThe step cannot meet the requirement of orientation control of the single-walled carbon nanotube.
The main problem at present is how to obtain a novel substrate with atomic steps on the same single crystal substrate (which is convenient for deep mechanism analysis of the growth mechanism and device performance of a carbon tube) by a simple heat treatment process, and further regulate and control the orientation of a single carbon nanotube network.
Disclosure of Invention
The invention aims to provide a method for controlling the network morphology of the grown single-walled carbon nanotube by the step orientation and height of the crystal surface, which can simply and conveniently control the network morphology of the grown single-walled carbon nanotube on the same single crystal substrate and select MgAl of a crystal surface with low index2O4Is used as a substrate, and MgAl is treated by simple heat treatment at a lower temperature (500-900 ℃), so that the MgAl is prepared2O4The step orientation and height of different crystal faces of the substrate are controlled, and then the MgAl is directly coated on the MgAl through chemical vapor deposition2O4The network of the single-walled carbon nanotubes which are arranged orthogonally, parallelly and disorderly grows on different crystal faces, and lays a material foundation for promoting the application of the single-walled carbon nanotubes in micro-nano devices and carbon-based chips.
The technical scheme of the invention is as follows:
a method for controlling the appearance of a single-walled carbon nanotube network grown by crystal face step orientation and height utilizes the strong interaction between crystal face atoms of a single crystal substrate and the single-walled carbon nanotube and the limiting effect of steps on the crystal face to control the appearance of the single-walled carbon nanotube network on the single crystal substrate; selecting magnesium aluminate spinel MgAl2O4The (100), (110) and (111) planes of the substrate are subjected to heat treatment conditions to regulate and control the crystallinity of the crystal plane of the substrate and the height and orientation of atomic steps; then through the normal pressure chemical vapor deposition method, magnesium aluminate spinel MgAl is formed2O4The (100) surface of the substrate grows a mutually orthogonal single-walled carbon nanotube network shape on magnesium aluminate spinel MgAl2O4Growing single-walled carbon nanotube parallel arrays on the (110) surface of the substrate, and growing MgAl on magnesium aluminate spinel2O4A disordered single-walled carbon nanotube network is grown on the (111) surface of the substrate.
Said crystal faceMethod for controlling network morphology of grown single-walled carbon nanotubes by step orientation and height, magnesium aluminate spinel MgAl2O4And (100), (110) and (111) surfaces of the substrate are subjected to heat treatment for 2 to 4 hours at 500 to 900 ℃, so that the crystallinity of the substrate is improved, and the orientation and the height of atomic steps suitable for the growth of the carbon nano tube are obtained.
The crystal face step orientation and height control method for growing the network morphology of the single-walled carbon nanotube, and the heat treatment atmosphere is air, argon or hydrogen.
The method for controlling the crystal face step orientation and height to grow the single-walled carbon nanotube network morphology obtains orthogonal steps on a (100) plane, parallel steps on a (110) plane and a disordered rough surface on a (111) plane through heat treatment.
The method for controlling the crystal face step orientation and height to grow the single-walled carbon nanotube network morphology, wherein the height distribution range of the orthogonal steps obtained on the (100) face is as follows: the height range of the parallel steps obtained on the (110) surface is 0.75 nm-1.5 nm as follows: the distribution range of the roughness of the disordered rough surface of the (111) surface is 0.5 nm-1 nm as follows: 1nm to 3.5 nm.
The method for controlling the appearance of the single-walled carbon nanotube network grown on the crystal face steps by orientation and height adopts a chemical vapor deposition method to directly regulate the appearance of the single-walled carbon nanotube network grown on different crystal faces, and the chemical vapor deposition temperature is 780-900 ℃.
The method for controlling the network appearance of the single-walled carbon nanotube by crystal face step orientation and height controls the crystallinity of the crystal face of the substrate and the height and orientation of the atomic steps, and then the single-walled carbon nanotube is grown on magnesium aluminate spinel MgAl2O4Catalyst nanoparticles are deposited on the substrate surface.
The crystal face step orientation and height control method for growing the network morphology of the single-walled carbon nanotube, and the preparation method of the catalyst is a block copolymer self-assembly method, a spin coating method, a magnetron sputtering method or a pulling method.
The crystal face step orientation and height control method for growing the single-walled carbon nanotube network morphology, and the catalyst is transition metal Fe, Co or Ni nanoparticles.
The design idea of the invention is as follows:
MgAl2O4the crystal face is of a face-centered cubic structure, has low-index crystal faces (100), (110) and (111) which are special for the face-centered cubic structure, and can obtain orthogonal, parallel and disordered step orientations on the crystal faces (100), (110) and (111) and control the step height by utilizing the characteristics that the surface atom density of the low-index crystal faces is high and is beneficial to heat treatment to form steps; the single-walled carbon nanotubes grow along the orientation of atomic steps by utilizing the strong interaction between atoms on the crystal face and the single-walled carbon nanotubes and the limiting effect of the steps on the single-walled carbon nanotubes, and finally the single-walled carbon nanotubes with different network appearances are prepared.
The invention has the advantages and beneficial effects that:
(1) the invention selects magnesium aluminate spinel MgAl2O4The (100), (110) and (111) surfaces of the substrate are subjected to heat treatment conditions to regulate the crystallinity of the crystal surface of the substrate and the orientation and height of atomic steps, and a normal-pressure chemical vapor deposition method is utilized to directly grow mutually orthogonal, parallel and disorderly oriented single-walled carbon nanotube networks on the three crystal surfaces respectively.
(2) The invention realizes the controllable preparation of the single-walled carbon nanotubes with three different network morphologies on the same single crystal substrate, and is expected to lay a material foundation for the interconnection of the leads of the carbon nanotube integrated circuit chip, the regulation of the current and the switching direction.
(3) The method is simple and controllable, and is beneficial to industrial production.
(4) The invention clarifies the influence mechanism of the height and orientation of atomic steps on the network morphology of the single-walled carbon nanotube, realizes the control of the network morphology of the orthogonal, parallel and disorderly oriented single-walled carbon nanotube based on the strong interaction of the single-walled carbon nanotube and crystal face atoms by selecting the crystal face of the substrate and regulating the orientation and height of the steps, provides a new idea for regulating the network morphology of the single-walled carbon nanotube, and lays a material foundation for exploring a novel carbon nanotube-based nanoelectronic device.
Drawings
FIG. 1 is a surface atomic force microscope photograph of each crystal orientation of a spinel substrate after heat treatment: (a) (100) face; (b) a (110) surface; (c) (111) plane.
FIG. 2 is a scanning electron microscope photograph of single-walled carbon nanotubes of an orthogonal morphology grown on the surface of a spinel substrate (100);
FIG. 3 is a scanning electron micrograph of a parallel array of single-walled carbon nanotubes grown on the surface of a spinel substrate (110);
FIG. 4 is a scanning electron micrograph of randomly oriented single-walled carbon nanotubes grown on the (111) plane of a spinel substrate;
FIG. 5 is a scanning electron microscope photograph of the network morphology of the grown single-walled carbon nanotube after heat treatment of the spinel substrate (110) surface at 1100 ℃ for 2 h;
FIG. 6 is a scanning photograph of single-walled carbon nanotubes grown by chemical vapor deposition at 925 ℃ on the surface of a spinel substrate (110);
FIG. 7. sapphire substrate
Carrying out heat treatment at 1100 ℃ for 10h on the surface, and then carrying out a scanning electron microscope photo of the network morphology of the grown carbon nanotube;
FIG. 8A sapphire substrate
And (3) carrying out heat treatment at 600 ℃ for 4h to obtain a scanning electron microscope photo of the network morphology of the grown wall carbon nanotube.
Detailed Description
In the specific implementation process, the single crystal spinel is used as a substrate, crystal faces (100), (110) and (111) with different symmetries are selected, and the atomic steps with different orientations are obtained by heat treatment for 2-4 hours at 500-900 ℃ in a certain atmosphere; depositing catalyst nanoparticles on the surface thereof; and growing single-walled carbon nanotubes with different network appearances on the crystal face by adopting a chemical vapor deposition method.
The method comprises the following specific preparation steps:
(1) pretreatment of the spinel substrate:
single crystal MgAl2O4Ultrasonically cleaning a spinel substrate in ethanol for 5-10 min, drying by a nitrogen gun, and placing in a quartz boat; is arranged in the tubeAnd (3) carrying out heat treatment in a furnace at 500-900 ℃ for 2-4 h to obtain atomic steps with higher crystallinity and suitable for the growth of the carbon nano tubes, wherein the height range of the atomic steps is 0.5-3.5 nm. As shown in FIG. 1, MgAl2O4Atomic force photographs of spinel after heat treatment of (100), (110) and (111) planes, the (100) crystal planes are atomic steps perpendicular to each other, the (110) planes are atomic steps parallel to each other, and the (111) planes form a disordered surface having a large roughness.
(2)MgAl2O4Growing a single-wall carbon nanotube on a spinel substrate surface: loading transition metal nanoparticles on the crystal face of the selected substrate as a catalyst, loading 10-20 sccm argon into ethanol (in an ice-water bath at 0 ℃) as a carbon source at the temperature of 780-850 ℃, and simultaneously introducing 1-5 sccm H2And 100-200 sccm argon gas, wherein the total gas flow is maintained at 111-225 sccm, and the growth of the single-walled carbon nanotube is carried out for 5-15 min.
In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is described in detail below by examples and accompanying drawings, but the present invention is not limited by the scope of the present application.
Example 1
(1) Selecting MgAl with (100) surface2O4The spinel is used as a substrate, the spinel is pretreated by adopting the specific preparation step (1), the heat treatment temperature is 900 ℃, the heat treatment time is 4 hours, the heat treatment atmosphere is air, the crystallinity of a crystal face of the substrate and the height and orientation of atomic steps are regulated and controlled through heat treatment conditions, and the height distribution range of the (100) plane obtained orthogonal steps is as follows: 0.75 nm-1.5 nm.
(2) MgAl on the (100) surface treated in the step (1) by adopting a block copolymer self-assembly method2O4Depositing cobalt catalyst with granularity of 1-3.5 nm on spinel, loading 15sccm argon gas into ethanol (in 0 ℃ ice water bath) as carbon source at 800 ℃, and simultaneously introducing 2sccm H2And argon gas of 200sccm is added for growing the single-walled carbon nanotube for 10 min. As shown in fig. 2, the scanning electron micrograph of the grown single-walled carbon nanotubes shows that the network morphology of the single-walled carbon nanotubes which are orthogonal to each other grows on the (100) surface.
Example 2
(1) MgAl of (110) surface is selected2O4The spinel is used as a substrate, the spinel is pretreated by adopting the specific preparation step (1), the heat treatment temperature is 600 ℃, the heat treatment time is 4 hours, the heat treatment atmosphere is argon, the crystallinity of a crystal face of the substrate and the height and orientation of an atomic step are regulated and controlled through heat treatment conditions, and the height range of the parallel step obtained on a (110) plane is as follows: 0.5nm to 1 nm.
(2) MgAl on the (110) surface treated in the step (1) by adopting a spin coating method2O4Depositing iron catalyst with the particle size of 1-3.5 nm on the spinel, loading 10sccm argon into ethanol (in ice-water bath at 0 ℃) as a carbon source at 780 ℃, and simultaneously introducing 1sccm H2And 150sccm argon gas, and growing the single-walled carbon nanotube for 5 min. As shown in fig. 3, the scanning electron micrograph of the grown single-walled carbon nanotubes shows that a parallel array of single-walled carbon nanotubes is grown on the (110) plane.
Example 3
(1) MgAl of (111) plane is selected2O4The spinel is used as a substrate, the spinel is pretreated by adopting the specific preparation step (1), the heat treatment temperature is 500 ℃, the heat treatment time is 3 hours, the heat treatment atmosphere is hydrogen, the crystallinity of a crystal face of the substrate and the height and orientation of an atomic step are regulated and controlled through heat treatment conditions, and the roughness distribution range of a disordered rough surface obtained on a (111) face is as follows: 1nm to 3.5 nm.
(2) MgAl on the (111) surface treated in the step (1) by adopting a magnetron sputtering method2O4Depositing a nickel catalyst with the granularity of 1-3.5 nm on the spinel, loading 10sccm of argon into ethanol (in an ice-water bath at 0 ℃) as a carbon source at 760 ℃, and simultaneously introducing 1.5sccm of H2And argon gas of 200sccm is added for the growth of the single-walled carbon nanotube, and the growth time is 5 min. As shown in fig. 4, the scanning electron micrograph of the grown single-walled carbon nanotubes shows that a disordered single-walled carbon nanotube network is grown on the (111) plane.
Comparative example 1: regulation of carbon nanotube orientation by substrate heat treatment
(1) MgAl of (110) surface is selected2O4Spinel as substrate, using example 2The step (1) of (1), carrying out pretreatment on the mixture, wherein the pretreatment temperature is 1100 ℃, and the pretreatment time is 2 hours.
(2) Using step (2) of example 2, MgAl was formed on the (110) surface treated in step (1)2O4Depositing iron catalyst on spinel and growing single-wall carbon nanotube. As shown in fig. 5, the scanning electron micrograph of the grown single-walled carbon nanotubes shows that a disordered single-walled carbon nanotube network is grown on the (110) plane. The phenomenon that the atomic step grows up and the surface roughness is increased due to the overhigh temperature, and the effect of directionally inducing the appearance of the single-walled carbon nanotube is lost.
Comparative example 2: regulation of orientation of single-walled carbon nanotubes by growth temperature
(1) MgAl of (110) surface is selected2O4Spinel is a substrate, which is pretreated using step (1) in example 2.
(2) Using step (2) of example 2, MgAl was formed on the (110) surface treated in step (1)2O4Depositing iron catalyst and growing single-walled carbon nanotubes on the spinel, wherein the temperature for growing the single-walled carbon nanotubes is 925 ℃. As shown in fig. 6, the scanning electron micrograph of the grown single-walled carbon nanotubes shows that a disordered single-walled carbon nanotube network is grown on the (110) plane. Indicating that the single-walled carbon nanotube has been detached from the constraint of the substrate and grown in a floating manner.
Comparative example 3:
(1) choose to use
Surface Al2O3As a substrate, the substrate was pretreated by the procedure (1) of example 2 at 1100 ℃ for 10 hours.
(2) Using step (2) in example 2, treated in step (1)
Surface Al2O3Depositing iron catalyst on sapphire and growing single-wall carbon nano-tube. As shown in FIG. 7, the SEM image of the grown single-walled carbon nanotube can be seen in
The single-walled carbon nanotube array grows on the surface, and the density and the length of the single-walled carbon nanotube array are obviously lower than those of spinel MgAl2O4(110) And (5) kneading.
Comparative example 4:
(1) choose to use
Surface Al2O3For the substrate, it was pretreated by exactly the same procedure as in step (1) in example 2.
(2) Using step (2) in example 2, treated in step (1)
Surface Al2O3Sapphire supported catalyst and growing single-walled carbon nanotubes. As shown in FIG. 8, the grown single-walled carbon nanotubes have a disordered network morphology, and Al is observed2O3 
After the surface is subjected to low-temperature heat treatment at 600 ℃ for 4 hours, the surface has no orientation effect, and is compared with MgAl2O4The heat treatment conditions are more strict.
Examples and comparative examples illustrate the selection of MgAl in the present invention2O4Spinel is used as substrate, and MgAl is controlled by adjusting2O4The heat treatment condition of the spinel realizes the regulation and control of the height and orientation arrangement of atomic steps on different crystal faces of the spinel, and further realizes the regulation and control of the network morphology of the single-walled carbon nanotube. The invention realizes the controllable preparation of the single-walled carbon nanotube with the orthogonal morphology for the first time, and realizes the controlled growth of the single-walled carbon nanotubes with three different network morphologies on the same substrate; the mechanism of regulating the network morphology of the single-walled carbon nanotube by steps is clarified. Compared with the current common substrate regulation single-walled carbon nanotube parallel array method, the heat treatment process is greatly simplified. The invention is expected to lay a material for the wire interconnection, current regulation and control, switch and other applications of the carbon nano tube integrated circuit chipAnd (5) material foundation.
Claims (9)
1. A method for controlling the appearance of a single-walled carbon nanotube network grown by crystal face step orientation and height is characterized in that the appearance of the single-walled carbon nanotube network on a single crystal substrate is controlled by utilizing the strong interaction between crystal face atoms of the single crystal substrate and the single-walled carbon nanotube and the limiting effect of steps on the crystal face; selecting magnesium aluminate spinel MgAl2O4The (100), (110) and (111) planes of the substrate are subjected to heat treatment conditions to regulate and control the crystallinity of the crystal plane of the substrate and the height and orientation of atomic steps; then through the normal pressure chemical vapor deposition method, magnesium aluminate spinel MgAl is formed2O4The (100) surface of the substrate grows a mutually orthogonal single-walled carbon nanotube network shape on magnesium aluminate spinel MgAl2O4Growing single-wall carbon nanotube parallel array on the (110) surface of the substrate, and forming MgAl spinel on magnesium aluminate2O4A disordered single-walled carbon nanotube network is grown on the (111) surface of the substrate.
2. The method for controlling the network morphology of the grown single-walled carbon nanotubes according to the orientation and height of crystal plane steps as claimed in claim 1, wherein magnesium aluminate spinel MgAl is used as the crystal plane step2O4And (100), (110) and (111) surfaces of the substrate are subjected to heat treatment for 2 to 4 hours at 500 to 900 ℃, so that the crystallinity of the substrate is improved, and the orientation and the height of atomic steps suitable for the growth of the carbon nano tube are obtained.
3. The method for controlling the growth of the network morphology of the single-walled carbon nanotube according to the orientation and the height of the crystal plane steps as claimed in claim 2, wherein the atmosphere of the heat treatment is air, argon or hydrogen.
4. The method for crystal plane step orientation and height control growth of single-walled carbon nanotube network morphology according to claim 1 or 2, characterized in that through heat treatment, orthogonal steps are obtained at the (100) plane, parallel steps are obtained at the (110) plane, and disordered rough surface is obtained at the (111) plane.
5. The method for controlling the growth of the network morphology of the single-walled carbon nanotube according to the orientation and the height of the crystal plane steps as claimed in claim 4, wherein the height distribution range of the (100) plane obtained orthogonal steps is as follows: the height range of the parallel steps obtained on the (110) surface is 0.75 nm-1.5 nm as follows: the distribution range of the roughness of the disordered rough surface of the (111) surface is 0.5 nm-1 nm as follows: 1nm to 3.5 nm.
6. The method for controlling the network morphology of the grown single-walled carbon nanotubes according to the crystal plane step orientation and height of claim 1, characterized in that a chemical vapor deposition method is adopted to directly regulate the morphology of the network of the grown single-walled carbon nanotubes on different crystal planes, and the chemical vapor deposition temperature is 780-900 ℃.
7. The method for controlling the network morphology of the grown single-walled carbon nanotube according to the crystal plane step orientation and height as claimed in claim 1, characterized in that after the crystallinity of the substrate crystal plane and the height and orientation of the atomic step are regulated and controlled, magnesium aluminate spinel MgAl is formed2O4Catalyst nanoparticles are deposited on the substrate surface.
8. The method for growing the network morphology of the single-walled carbon nanotube by controlling the orientation and height of the crystal plane steps as claimed in claim 7, wherein the preparation method of the catalyst is a block copolymer self-assembly method, a spin coating method, a magnetron sputtering method or a Czochralski method.
9. The method for controlling the network morphology of the grown single-walled carbon nanotube according to the orientation and height of the crystal plane steps as claimed in claim 7, wherein the catalyst is nanoparticles of transition metals Fe, Co or Ni.
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| XU LI ETAL: "Magnesia and Magnesium Aluminate Catalyst Substrates for Carbon Nanotube Carpet Growth", 《ACS APPL. NANO MATER. 》, vol. 3, pages 1830 * |
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