CN102020262B - Method for growing single-walled carbon nanotubes in high efficiency without metal catalyst - Google Patents
Method for growing single-walled carbon nanotubes in high efficiency without metal catalyst Download PDFInfo
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- CN102020262B CN102020262B CN 200910187296 CN200910187296A CN102020262B CN 102020262 B CN102020262 B CN 102020262B CN 200910187296 CN200910187296 CN 200910187296 CN 200910187296 A CN200910187296 A CN 200910187296A CN 102020262 B CN102020262 B CN 102020262B
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Abstract
The invention relates to the preparation technology of single-walled carbon nanotubes, in particular to a method for growing single-walled carbon nanotubes in high efficiency without a metal catalyst, which is suitable for preparing the high-quality single-walled carbon nanotubes without metal impurity residues in high efficiency. In the method, the single-walled carbon nanotubes are prepared by using a silicon dioxide membrane which is prepared by an ionic sputtering process as a catalyst precursor and by cracking a carbon source at the temperature of between 600 and 1,100 DEG C, wherein the carbon source is hydrocarbon such as methane, ethane, ethane, ethyne, benzene, methylbenzene, cyclohexane and the like or ethanol, methanol, acetone, carbon monoxide and the like, and carrier gas is hydrogen or mixed gas of the hydrogen and inert gases such as argon, helium and the like. In the method, the high-quality single-walled carbon nanotubes without any metal impurities are grown in high efficiency by taking an SiO2 coating membrane obtained by the ionic sputtering method as the catalyst precursor, so the method has the characteristics of simplicity and convenience for operation and low cost, and the single-walled carbon nanotubes are easy to grow on a silicon substrate in modes of positioning and patterning; and the method establishes the foundation for the application of the single-walled carbon nanotubes without the metal impurities.
Description
Technical field:
The present invention relates to the technology of preparing of SWNT, be specially a kind of any metal catalyst that do not use, with the silicon-dioxide (SiO of ion sputtering method preparation
2) film is catalyst precursor; Method at the efficient growing high-quality SWNT in high temperature resistant block materials surface that the random shapes such as silicon substrate of thermal oxide layer (one dimension, two dimension, three-dimensional) are arranged is applicable to that efficient production does not contain the high quality SWNT sample that any metallic impurity pollute.
Background technology:
SWNT is typical case's representative of monodimension nanometer material; Its good electricity, optics, calorifics and mechanical property make it all have wide application prospect in fields such as nanometer electronic device, opto-electronic device, transmitter, support of the catalyst, matrix material and drug delivery and biomedicines.Since CNT was found, its theoretical investigation all was the forward position and the hot subject of domestic and international physical chemistry circle and material educational circles with using exploration all the time.Wherein, the preparation research of SWNT is to its rerum natura research and uses prerequisite and the basis of exploring.
Through various countries scientist effort for many years; At present obtaining multinomial achievement aspect the preparation of SWNT; As utilize transition-metal catalysts such as iron, cobalt, nickel; People have successfully realized the preparation of macroscopic bodies such as single wall, double-walled, multiple-wall carbon nanotube and array thereof, film, directed rope, and realize located growth, oriented growth and the patterned growth etc. of SWNT on the surface of silicon basically.These achievements have greatly promoted the progress of CNT, but still have many difficulties and challenge aspect the preparation of CNT at present.Such as; Present nearly all method for preparing SWNT all will be used metal catalyst, and the metallic impurity that remain in the SWNT can greatly influence the practical application (like nanometer electronic device, opto-electronic device, support of the catalyst, biological and medical field etc.) of SWNT at numerous areas.The method of purification that has grown up not only can not thoroughly be removed the metal catalyst impurity in the SWNT, and these last handling processes can be inevitably damage the structure of SWNT, reduces its quality.Therefore, metal remained impurity has hindered people to a certain extent to its intrinsic structure and Study on Properties in the SWNT, simultaneously its practical application in a lot of fields has been caused great obstacle.According to the process of growth of CNT,, will do not contained the SWNT sample of any metallic impurity so if in the preparation process, do not use metallics as catalyzer.This SWNT that does not contain any metallic impurity has huge potential advantages and magnetism to the application based on the nanometer electronic device of SWNT, opto-electronic device, support of the catalyst, biological and medical field.
Summary of the invention:
The object of the present invention is to provide a kind of high quality, do not contain the high efficiency preparation method of the SWNT of any metallic impurity, it is the method for non-metal catalyst growing single-wall CNT.But advantages such as this method has, and cost is low, simple to operate, good reproducibility located growth and patternable growth.
Technical scheme of the present invention is:
The method of the efficient growing single-wall CNT of a kind of non-metal catalyst, this method is with the silicon-dioxide (SiO of ion sputtering method preparation
2) film is catalyst precursor; High temperature resistant block materials with plane body, spherical surface body or the random shape (one dimension, two dimension, three-dimensional) of silicon, silicon-dioxide, silica/silicon (" silica/silicon " refers to that there is the silicon base of silicon-dioxide thermal oxide layer on the surface), aluminum oxide, quartz, silit etc. is a substrate, and the cracking through carbon source at high temperature prepares SWNT.Concrete steps are following:
At first, handle at substrate surface formation SiO through reduction
2The catalyst nano particle; Then, at high temperature feed carbon source and carrier gas, carbon source is decomposed the carbon active specy that discharges and is adsorbed on SiO
2The catalyst nano particle surface, and at SiO
2The auxiliary nucleation down of catalyst nano particulate finally forms SWNT.
Among the present invention, SiO
2Catalyst film thickness is 5～100nm, and preferable range is 30～100nm;
Among the present invention; Carbon source is one or more of hydrocarbon polymers such as methane, ethane, ethene, acetylene, benzene, toluene, hexanaphthene and ethanol, methyl alcohol, acetone or carbon monoxide etc.; The carbon source flow velocity is 1～1000 ml/min, and preferable range is 5～500 ml/min.
Among the present invention, carrier gas is a hydrogen; Perhaps, carrier gas is the gas mixture (wherein hydrogen volume is than >=1/10) of hydrogen and rare gas elementes such as argon gas or helium, and flow rate of carrier gas is 1～2000 ml/min, and preferable range is 20～800 ml/min.
Temperature of reaction is 600～1100 ℃ among the present invention, and preferable range is 650～950 ℃.
Adopting the diameter of the SWNT of the present invention's acquisition is 0.8～2nm.
The invention has the beneficial effects as follows:
1, the present invention proposes to adopt silicon-dioxide (SiO
2) film is catalyst precursor, do not use any metal catalyst to prepare the high quality SWNT, no any metallic impurity pollutent in the product.
2, the silicon-dioxide (SiO of the present invention's employing
2) catalyzer do not have the ability of catalytic pyrolysis carbon source; So growth velocity of the SWNT that can greatly slow down; And then can realize preparation through accurate controlling reaction time to the control of SWNT length and short SWNT, be suitable for get everything ready different lengths, weak point of may command and can reach～SWNT of 20nm.
3, simple, efficient, the good reproducibility of the inventive method, cost are low.
4, the present invention can realize located growth, the patterned growth and integrated of SWNT in surface of silicon, for its application in the nanometer electronic device field is laid a good foundation.
Description of drawings:
Fig. 1 prepares the reaction unit synoptic diagram of SWNT for non-metal catalyst.Among the figure, 1 gas inlet; 2 surface sputterings have silicon-dioxide (SiO
2) the high temperature resistant block materials of film; 3 thermopairs; 4 pneumatic outlets.
Fig. 2 is the sign of product SWNT.Wherein, (a) be electron scanning micrograph; (b) be the AFM photo; (c) be the resonance laser Raman spectroscopy; (d) be the high-resolution-ration transmission electric-lens photo.
Fig. 3 is that the x-ray photoelectron spectroscopy on product surface characterizes.Wherein, (a) be full spectrum; (b) be the high resolution x-ray photoelectron spectroscopy of Fe element; (c) be the high resolution x-ray photoelectron spectroscopy of Co element; (d) be the high resolution x-ray photoelectron spectroscopy of Ni element.Dark spectral line is from sample surfaces, and light spectral line is the spectrogram of sample through gathering again after the ion sputtering.
Fig. 4 is with silicon-dioxide (SiO
2) be the speed of growth curve of the SWNT of catalyzer.
Fig. 5 is with silicon-dioxide (SiO
2) be the AFM photo of the short SWNT of Preparation of Catalyst.Wherein, (a) growth time is 20 seconds, and (b) growth time is 40 seconds, and (c) growth time is 60 seconds.(a) and (b), the corresponding respectively figure in (c) figure right side are the length statistical Butut of SWNT under the corresponding growth time.
Fig. 6 is that the located growth and the patterned growth of SWNT (uses the ribbon silicon chip as plating SiO
2Baffle plate during film).Wherein, (a) be the low power electron scanning micrograph; (b) be the high power electron scanning micrograph.Among the figure, the clear zone, left side is for being coated with SiO
2The SWNT of growth can be found to have in the zone of film in this zone; The dark space, right side is not for being coated with SiO
2Any SWNT is not found in this zone in the zone of film.
Fig. 7 is that the located growth and the patterned growth of SWNT (uses the little grid of used in transmission electron microscope Cu as plating SiO
2Baffle plate during film).Wherein, (a) be the low power electron scanning micrograph; (b) be the high power electron scanning micrograph.Among the figure, each hollow out place of little grid is for being coated with SiO
2The SWNT (clear zone) of growth can be found to have in the zone of film in this zone; Covering place of little grid skeleton does not have SiO
2Film is not found any SWNT (dark space) in this zone.
Fig. 8 is with silicon-dioxide (SiO
2) be catalyzer, the patterned growth and the located growth of short SWNT.Wherein, (a) for plating SiO
2The synoptic diagram of the little grid of employed tungsten (W) during film; (b) be the electron scanning micrograph of the short SWNT of patterned growth and located growth; (c) be the AFM photo in solid-line rectangle district among the b figure, (d) for b scheme in the AFM photo in dashed rectangle district.
Embodiment:
Through embodiment and accompanying drawing the present invention is detailed further below.
As shown in Figure 1, apparatus of the present invention adopt the horizontal Reaktionsofen, and horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, and surface sputtering has silicon-dioxide (SiO
2) the high temperature resistant block materials 2 of film places horizontal Reaktionsofen high-temperature zone, thermopair 3 stretches into the high-temperature zone of horizontal Reaktionsofen, with real-time monitoring temperature of reaction.
At first, will adopt the ion sputtering method to be coated with SiO
2Silicon substrate (the SiO of film
2The thickness of film is 30nm) be positioned over horizontal Reaktionsofen middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); Then, with SiO
2Film is heated to 900 ℃ (hydrogen and argon gas flow velocity are respectively 200 ml/min and 500 ml/min in the heat-processed, and the Reaktionsofen heat-up rate is 40 ℃/minute) in hydrogen and argon gas gas mixture atmosphere; After treating that furnace temperature rises to 900 ℃, feed the mixed gas (gas flow rate is respectively methane 500 ml/min and hydrogen 500 ml/min) of methane and hydrogen, beginning growing single-wall CNT, growth time is 20 minutes.In the present embodiment, the diameter of SWNT is 0.8～2nm, and mean length is about 10 μ m.
Sem, AFM, resonance laser Raman spectroscopy and high resolution transmission electron microscopy are observed and are shown, sample is fine and close SWNT network, surface clean, and quality is high, and wherein the density of SWNT is greater than 100/μ m
2
Embodiment 2
Device is like accompanying drawing 1.
At first, will adopt the ion sputtering method to be coated with SiO
2Silicon substrate (the SiO of film
2The thickness of film is 100nm) be positioned over horizontal Reaktionsofen middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); Then, with SiO
2Film is heated to 900 ℃ (hydrogen and argon gas flow velocity are respectively 200 ml/min and 500 ml/min in the heat-processed, and the Reaktionsofen heat-up rate is 40 ℃/minute) in hydrogen and argon gas gas mixture atmosphere; After treating that furnace temperature rises to 900 ℃, feed the mixed gas (gas flow rate is respectively methane 500 ml/min and hydrogen 500 ml/min) of methane and hydrogen, beginning growing single-wall CNT, growth time is 20 minutes.In the present embodiment, the diameter of SWNT is 0.8～2nm, and mean length is about 10 μ m.
Sem, AFM and resonance laser Raman spectroscopy are observed and are shown, sample is fine and close SWNT network, and wherein the density of SWNT is about 100/μ m
2
Device is like accompanying drawing 1.
At first, will adopt the ion sputtering method to be coated with SiO
2Silicon substrate (the SiO of film
2The thickness of film is 30nm) be positioned over horizontal Reaktionsofen middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); Then, with SiO
2Film is heated to 650 ℃ (hydrogen and argon gas flow velocity are respectively 200 ml/min and 200 ml/min in the heat-processed, and the Reaktionsofen heat-up rate is 30 ℃/minute) in hydrogen and argon gas gas mixture atmosphere; After treating that furnace temperature rises to 650 ℃, (wherein, the flow velocity of argon gas is 50 ml/min to bring ethanol into through the mode of argon gas bubbling; Ethanol is positioned in 0 ℃ the Meng Shi wash bottle); Feed hydrogen (gas flow rate is 500 ml/min) simultaneously, beginning growing single-wall CNT, growth time is 20 minutes.In the present embodiment, the diameter of SWNT is 0.8～2nm, and mean length is about 8 μ m.
Sem, AFM, resonance laser Raman spectroscopy and high resolution transmission electron microscopy are observed and are shown; Sample is fine and close SWNT network; Sample surfaces is very clean, is of high quality, and wherein the density of SWNT is greater than 100/μ m
2
Embodiment 4
Device is like accompanying drawing 1.
At first, will adopt the ion sputtering method to be coated with SiO
2Silicon substrate (the SiO of film
2The thickness of film is 30nm) be positioned over horizontal Reaktionsofen middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); Then, with SiO
2Film is heated to 700 ℃ (hydrogen and argon gas flow velocity are respectively 200 ml/min and 200 ml/min in the heat-processed, and the Reaktionsofen heat-up rate is 30 ℃/minute) in hydrogen and argon gas gas mixture atmosphere; After treating that furnace temperature rises to 700 ℃; (wherein, the argon gas flow velocity is 50 ml/min, and ethanol and methyl alcohol are positioned in 0 ℃ the Meng Shi wash bottle to bring the mixed carbon source of ethanol and methyl alcohol into through the mode of argon gas bubbling; Volume ratio is 10: 1); Feed hydrogen (gas flow rate is 500 ml/min) simultaneously, beginning growing single-wall CNT, growth time is 20 minutes.In the present embodiment, the diameter of SWNT is 0.8～2nm, and mean length is about 9 μ m.
Sem, AFM, resonance laser Raman spectroscopy and high resolution transmission electron microscopy are observed and are shown, sample is fine and close SWNT network, and sample surfaces is very clean, and wherein the density of SWNT is about 80/μ m
2
Embodiment 5
Device is like accompanying drawing 1.
At first, will adopt the ion sputtering method to be coated with SiO
2Quartz ball (the SiO of film
2The thickness of film is 30nm) be positioned over horizontal Reaktionsofen middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); Then, with SiO
2Film is heated to 900 ℃ (hydrogen and argon gas flow velocity are respectively 200 ml/min and 500 ml/min in the heat-processed, and the Reaktionsofen heat-up rate is 40 ℃/minute) in hydrogen and argon gas gas mixture atmosphere; After treating that furnace temperature rises to 900 ℃, feed the mixed gas (gas flow rate is respectively methane 500 ml/min and hydrogen 500 ml/min) of methane and hydrogen, beginning growing single-wall CNT, growth time is 20 minutes.In the present embodiment, the diameter of SWNT is 0.8～2nm, and mean length is about 10 μ m.
Sem, AFM, resonance laser Raman spectroscopy and high resolution transmission electron microscopy are observed and are shown, sample is fine and close SWNT network, surface clean, and quality is high, and wherein the density of SWNT is greater than 100/μ m
2
Embodiment 6
Device is like accompanying drawing 1.
At first, will adopt the ion sputtering method to be coated with SiO
2Silicon substrate (the SiO of film
2The thickness of film is 30nm) be positioned over horizontal Reaktionsofen middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); Then, with SiO
2Film is heated to 900 ℃ (hydrogen and argon gas flow velocity are respectively 200 ml/min and 500 ml/min in the heat-processed, and the Reaktionsofen heat-up rate is 40 ℃/minute) in hydrogen and argon gas gas mixture atmosphere; After treating that furnace temperature rises to 900 ℃, feed the mixed gas (gas flow rate is respectively methane 500 ml/min and hydrogen 500 ml/min) of methane and hydrogen, beginning growing single-wall CNT, growth time is 20 seconds.In the present embodiment, the diameter of SWNT is 0.8～2nm, and mean length is about 149nm, and weak point can reach～20nm.
Sem, AFM, resonance laser Raman spectroscopy and high resolution transmission electron microscopy are observed and are shown, surface clean, and quality is high, and wherein the density of SWNT is greater than 50/μ m
2
Embodiment 7
Device is like accompanying drawing 1.
At first, will adopt the ion sputtering method to be coated with SiO
2Silicon substrate (the SiO of film
2The thickness of film is 30nm) be positioned over horizontal Reaktionsofen middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); Then, with SiO
2Film is heated to 900 ℃ (hydrogen and argon gas flow velocity are respectively 200 ml/min and 500 ml/min in the heat-processed, and the Reaktionsofen heat-up rate is 40 ℃/minute) in hydrogen and argon gas gas mixture atmosphere; After treating that furnace temperature rises to 900 ℃, feed the mixed gas (gas flow rate is respectively methane 500 ml/min and hydrogen 500 ml/min) of methane and hydrogen, beginning growing single-wall CNT, growth time is 40 seconds.In the present embodiment, the diameter of SWNT is 0.8～2nm, and mean length is about 342nm.
Sem, AFM, resonance laser Raman spectroscopy and high resolution transmission electron microscopy are observed and are shown, surface clean, and quality is high, and wherein the density of SWNT is greater than 60/μ m
2
Embodiment 8
Device is like accompanying drawing 1.
Use the little grid of used in transmission electron microscope Cu as template, selectivity vapor deposition SiO in the subregion of surface of silicon
2Film; At first, selectivity is coated with SiO
2Silicon substrate (the SiO of film
2The thickness of film is 30nm) be positioned over horizontal Reaktionsofen middle section (reaction zone has thermopair to monitor furnace temperature in real time in this position); Then, with SiO
2Film is heated to 900 ℃ (hydrogen and argon gas flow velocity are respectively 200 ml/min and 500 ml/min in the heat-processed, and the Reaktionsofen heat-up rate is 40 ℃/minute) in hydrogen and argon gas gas mixture atmosphere; After treating that furnace temperature rises to 900 ℃, feed the mixed gas (gas flow rate is respectively methane 500 ml/min and hydrogen 500 ml/min) of methane and hydrogen, beginning growing single-wall CNT, growth time is 2 minutes.In the present embodiment, the diameter of SWNT is 0.8～2nm, and mean length is about 1 μ m.
Sem, AFM and resonance laser Raman spectroscopy are observed and are shown, only are coated with SiO at patterning
2The region growing of film goes out the SWNT network.
As shown in Figure 1, inlet mouth one end has four mass flowmeters among the figure, and optionally control feeds gases such as argon gas, helium, hydrogen, methane, ethane, carbon monoxide.Liquid carbon source (like ethanol, methyl alcohol, benzene, toluene, hexanaphthene etc.) places 0 ℃ Meng Shi wash bottle, brings into through the gas mixture bubbling of argon gas or argon gas and helium.
As shown in Figure 2, can find out from (a) sem and (b) AFM photo, adopt SiO
2The sample that grows as catalyzer is fine and close film, and surface clean; Can find out that from (c) resonance laser Raman spectroscopy D mould and G mould strength ratio are about 0.04, show that the product SWNT has very high quality; Can output from (d) high-resolution-ration transmission electric-lens photo, product is the SWNT of perfect structure, and exists with the form of single or little tube bank mostly.
As shown in Figure 3, can find out from the x-ray photoelectron spectroscopy on product surface, only contain Si, O and C element in the sample, do not contain any other metallic impurity, wherein Si and O come from SiO
2Plated film.
As shown in Figure 4, with 20 seconds, the length computation of the SWNT of 40 seconds and 60 seconds growth come out with SiO
2The growth velocity of SWNT has only 8.3nm/s during for catalyzer, and this speed is much smaller than the speed (as under the same conditions, the speed of metal Co catalyzer growing single-wall CNT is 2.5 μ m/s) of base metal catalyst growing single-wall CNT.Explain and use SiO
2During for catalyzer, the speed of growth of SWNT that can significantly slow down, and then reach its length of accurate control, the purpose of the short SWNT of selective growth.
As shown in Figure 5; The atomic power photo and the length statistical graph of the SWNT that obtains from the different reaction times can be found out; Through experiment parameter such as control growing time simply, can selectivity obtain the short SWNT sample of a series of adjustable in length.Like growth time is that 20 seconds sample average length has only 149nm, and shortest length has only～20nm.
As shown in Figure 6, (use the ribbon silicon chip from the located growth and the patterned growth of SWNT as plating SiO
2Baffle plate during film) can find out, only be coated with SiO
2Just there is SWNT in the zone of film, and explanation can be through using the located growth of specific template realization SWNT, for its application in the nanometer electronic device field is laid a good foundation.
As shown in Figure 7, (use the little grid of used in transmission electron microscope Cu from the located growth and the patterned growth of SWNT as plating SiO
2Baffle plate during film) can find out, only be coated with SiO
2Just there is SWNT in the zone of film, and explanation can realize the located growth of SWNT through using specific template.
As shown in Figure 8, (use the little grid of used in transmission electron microscope W from the located growth and the patterned growth of SWNT as plating SiO
2Baffle plate during film) can find out, only be coated with SiO
2Just there is SWNT in the zone of film, and explanation can realize the located growth of SWNT through using specific template.In addition, SWNT can located growth has only at width～the catalyzer band of 5 μ m on, do not take place and significantly intert phenomenon, show with SiO
2The precision of the located growth of SWNT and patterned growth is far above common metal catalyst during for catalyzer, and this lays a good foundation for its application in the nanometer electronic device field.
The above results shows, the SiO that the present invention's proposition obtains with the ion sputtering method
2Plated film is a catalyst precursor; Efficient growth does not contain the high quality SWNT of any metallic impurity; Have easy and simple to handle, cost low with the characteristics that are easy to located growth and patterned growth SWNT on silicon substrate, the application of the SWNT that requires not have metallic impurity is laid a good foundation.In addition, with SiO
2For the growth velocity of the SWNT of catalyzer significantly reduces than metal catalyst, therefore can accurately control its length, for the rerum natura and the application of research different lengths SWNT and ultrashort CNT provides prerequisite through controlling reaction time.
Claims (2)
1. the method for the efficient growing single-wall CNT of non-metal catalyst; It is characterized in that: this method is a catalyst precursor with the silica membrane of ion sputtering method preparation; High temperature resistant block materials with the random shape of silicon, silicon oxide, silicon oxide/silicon, aluminum oxide, quartz or silit is a substrate, and the cracking through carbon source under 600～1100 ℃ prepares SWNT;
At first, handle at substrate surface formation SiO through reduction
2The catalyst nano particle; Then, at high temperature feed carbon source and carrier gas, carbon source is decomposed the carbon active specy that discharges and is adsorbed on SiO
2The catalyst nano particle surface, and at SiO
2The auxiliary nucleation down of catalyst nano particulate finally forms SWNT;
In the reaction process, carrier gas is a hydrogen; Perhaps, carrier gas is the gas mixture of hydrogen and rare gas element, and wherein hydrogen volume is than >=1/10, and the carrier gas overall flow rate is 1～2000 ml/min;
Silicon oxide/silicon is meant that there is the silicon base of silicon-dioxide thermal oxide layer on the surface;
The carbon source flow velocity is 1～1000 ml/min;
SiO
2Catalyst film thickness is 5～100nm;
In the reaction process, carbon source is one or more of methane, ethane, ethene, acetylene, benzene, toluene, hexanaphthene, ethanol, methyl alcohol, acetone, carbon monoxide.
2. according to the method for the efficient growing single-wall CNT of the described non-metal catalyst of claim 1, it is characterized in that: temperature of reaction is 650～950 ℃.
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| CN102557006A (en) * | 2011-12-31 | 2012-07-11 | 温州大学 | Continuous preparation method of carbon nanotubes without metallic residues |
| WO2014071693A1 (en) * | 2012-11-08 | 2014-05-15 | 北京大学 | Single-walled carbon nanotube positioning and growing method |
| CN103303904B (en) * | 2013-06-13 | 2014-12-03 | 中国科学院金属研究所 | Method for preferentially growing metallic single-walled carbon nanotube by using non-metallic silicon oxide as catalyst |
| CN103922310B (en) * | 2014-04-09 | 2016-01-13 | 中国科学院金属研究所 | The method of low-temperature gaseous phase magnanimity growing high-quality, straight carbon nanotubes and device |
| CN104609392A (en) * | 2015-01-23 | 2015-05-13 | 贵州大学 | Method for directly growing carbon nano spirals or carbon nanospheres on surface of alumina substrate |
| CN107915217B (en) * | 2016-10-10 | 2020-10-16 | 中国科学院金属研究所 | Method for preparing semiconductor single-walled carbon nanotube by using non-metallic catalyst SiC |
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