CN102020262A - 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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- CN102020262A CN102020262A CN 200910187296 CN200910187296A CN102020262A CN 102020262 A CN102020262 A CN 102020262A CN 200910187296 CN200910187296 CN 200910187296 CN 200910187296 A CN200910187296 A CN 200910187296A CN 102020262 A CN102020262 A CN 102020262A
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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 Single Walled Carbon Nanotube, 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 in the efficient growing high-quality Single Walled Carbon Nanotube in high temperature resistant block materials surface that the arbitrary 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 Single Walled Carbon Nanotube sample that any metallic impurity pollute.
Background technology:
Single Walled Carbon Nanotube 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 (carbon nano-tube) was found, it all was the forward position and the hot subject of domestic and international physical chemistry circle and material educational circles that its theoretical investigation and application are explored all the time.Wherein, the preparation research of Single Walled Carbon Nanotube 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 Single Walled Carbon Nanotube, 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 Single Walled Carbon Nanotube on the surface of silicon substantially.These achievements have greatly promoted the progress of CNT (carbon nano-tube), but still have many difficulties and challenge aspect the preparation of CNT (carbon nano-tube) at present.Such as, present nearly all method for preparing Single Walled Carbon Nanotube all will be used metal catalyst, and the metallic impurity that remain in the Single Walled Carbon Nanotube can greatly influence the practical application (as nanometer electronic device, opto-electronic device, support of the catalyst, biological and medical field etc.) of Single Walled Carbon Nanotube at numerous areas.The method of purification that has grown up not only can not thoroughly be removed the metal catalyst impurity in the Single Walled Carbon Nanotube, and these last handling processes can be inevitably damage the structure of Single Walled Carbon Nanotube, reduces its quality.Therefore, metal remained impurity has hindered the research of people to its intrinsic structure and character to a certain extent in the Single Walled Carbon Nanotube, simultaneously its practical application in a lot of fields has been caused great obstacle.According to the process of growth of CNT (carbon nano-tube),, will do not contained the Single Walled Carbon Nanotube sample of any metallic impurity so if in preparation process, do not use metallics as catalyzer.This Single Walled Carbon Nanotube that does not contain any metallic impurity has huge potential advantages and magnetism to the application based on the nanometer electronic device of Single Walled Carbon Nanotube, 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 Single Walled Carbon Nanotube of any metallic impurity, it is the method for non-metal catalyst growing single-wall CNT (carbon nano-tube).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 (carbon nano-tube) 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 arbitrary 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, silicon carbide etc. is a substrate, and the cracking by carbon source at high temperature prepares Single Walled Carbon Nanotube.Concrete steps are as follows:
At first, handle at substrate surface formation SiO by 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 Single Walled Carbon Nanotube.
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 Single Walled Carbon Nanotube 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 Single Walled Carbon Nanotube, 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, the growth velocity of the Single Walled Carbon Nanotube that therefore can greatly slow down, and then can realize preparation by accurate controlling reaction time to the control of Single Walled Carbon Nanotube length and short Single Walled Carbon Nanotube, be suitable for the get everything ready Single Walled Carbon Nanotube of different lengths, the shortest reaching～20nm of may command.
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 Single Walled Carbon Nanotube 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 Single Walled Carbon Nanotube 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 Single Walled Carbon Nanotube.Wherein, (a) be electron scanning micrograph; (b) be the atomic force microscope 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 Single Walled Carbon Nanotube of catalyzer.
Fig. 5 is with silicon-dioxide (SiO
2) be the atomic force microscope photo of the short Single Walled Carbon Nanotube 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.The corresponding respectively figure in (a) and (b), (c) figure right side is the length statistical Butut of Single Walled Carbon Nanotube under the corresponding growth time.
Fig. 6 is that the located growth and the patterned growth of Single Walled Carbon Nanotube (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 Single Walled Carbon Nanotube 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 Single Walled Carbon Nanotube is not found in this zone in the zone of film.
Fig. 7 is that the located growth and the patterned growth of Single Walled Carbon Nanotube (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 Single Walled Carbon Nanotube (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 Single Walled Carbon Nanotube (dark space) in this zone.
Fig. 8 is with silicon-dioxide (SiO
2) be catalyzer, the patterned growth and the located growth of short Single Walled Carbon Nanotube.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 Single Walled Carbon Nanotube of patterned growth and located growth, (c) being the atomic force microscope photo in solid-line rectangle district among the b figure, (d) is the atomic force microscope photo in dashed rectangle district among the b figure.
Embodiment:
Be described in further detail the present invention below by embodiment and accompanying drawing.
Embodiment 1
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 (carbon nano-tube), growth time is 20 minutes.In the present embodiment, the diameter of Single Walled Carbon Nanotube is 0.8～2nm, and mean length is about 10 μ m.
Scanning electronic microscope, atomic force microscope, resonance laser Raman spectroscopy and high resolution transmission electron microscopy are observed and are shown, sample is fine and close Single Walled Carbon Nanotube network, surface clean, and the quality height, wherein the density of Single Walled Carbon Nanotube is greater than 100/μ m
2
Embodiment 2
Device is as 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 (carbon nano-tube), growth time is 20 minutes.In the present embodiment, the diameter of Single Walled Carbon Nanotube is 0.8～2nm, and mean length is about 10 μ m.
Scanning electronic microscope, atomic force microscope and resonance laser Raman spectroscopy are observed and are shown, sample is fine and close Single Walled Carbon Nanotube network, and wherein the density of Single Walled Carbon Nanotube is about 100/μ m
2
Embodiment 3
Device is as 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 by 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 (carbon nano-tube), growth time is 20 minutes.In the present embodiment, the diameter of Single Walled Carbon Nanotube is 0.8～2nm, and mean length is about 8 μ m.
Scanning electronic microscope, atomic force microscope, resonance laser Raman spectroscopy and high resolution transmission electron microscopy are observed and are shown, sample is fine and close Single Walled Carbon Nanotube network, sample surfaces is very clean, is of high quality, and wherein the density of Single Walled Carbon Nanotube is greater than 100/μ m
2
Embodiment 4
Device is as 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 ℃, the mixed carbon source of bringing ethanol and methyl alcohol into by the mode of argon gas bubbling (wherein, the argon gas flow velocity is 50 ml/min, ethanol and methyl alcohol are positioned in 0 ℃ the Meng Shi wash bottle, volume ratio is 10: 1), feed hydrogen (gas flow rate is 500 ml/min) simultaneously, beginning growing single-wall CNT (carbon nano-tube), growth time is 20 minutes.In the present embodiment, the diameter of Single Walled Carbon Nanotube is 0.8～2nm, and mean length is about 9 μ m.
Scanning electronic microscope, atomic force microscope, resonance laser Raman spectroscopy and high resolution transmission electron microscopy are observed and are shown, sample is fine and close Single Walled Carbon Nanotube network, and sample surfaces is very clean, and wherein the density of Single Walled Carbon Nanotube is about 80/μ m
2
Device is as 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 (carbon nano-tube), growth time is 20 minutes.In the present embodiment, the diameter of Single Walled Carbon Nanotube is 0.8～2nm, and mean length is about 10 μ m.
Scanning electronic microscope, atomic force microscope, resonance laser Raman spectroscopy and high resolution transmission electron microscopy are observed and are shown, sample is fine and close Single Walled Carbon Nanotube network, surface clean, and the quality height, wherein the density of Single Walled Carbon Nanotube is greater than 100/μ m
2
Embodiment 6
Device is as 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 (carbon nano-tube), growth time is 20 seconds.In the present embodiment, the diameter of Single Walled Carbon Nanotube is 0.8～2nm, and mean length is about 149nm, the shortest reaching～20nm.
Scanning electronic microscope, atomic force microscope, resonance laser Raman spectroscopy and high resolution transmission electron microscopy are observed and are shown, surface clean, and the quality height, wherein the density of Single Walled Carbon Nanotube is greater than 50/μ m
2
Embodiment 7
Device is as 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 (carbon nano-tube), growth time is 40 seconds.In the present embodiment, the diameter of Single Walled Carbon Nanotube is 0.8～2nm, and mean length is about 342nm.
Scanning electronic microscope, atomic force microscope, resonance laser Raman spectroscopy and high resolution transmission electron microscopy are observed and are shown, surface clean, and the quality height, wherein the density of Single Walled Carbon Nanotube is greater than 60/μ m
2
Embodiment 8
Device is as accompanying drawing 1.
Use the little grid of used in transmission electron microscope Cu as template, at the subregion of surface of silicon selectivity evaporation SiO
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 (carbon nano-tube), growth time is 2 minutes.In the present embodiment, the diameter of Single Walled Carbon Nanotube is 0.8～2nm, and mean length is about 1 μ m.
Scanning electronic microscope, atomic force microscope 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 Single Walled Carbon Nanotube 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 (as ethanol, methyl alcohol, benzene, toluene, hexanaphthene etc.) places 0 ℃ Meng Shi wash bottle, brings into by the gas mixture bubbling of argon gas or argon gas and helium.
As shown in Figure 2, from (a) scanning electronic microscope and (b) the atomic force microscope photo adopt SiO as can be seen
2The sample that grows as catalyzer is fine and close film, and surface clean; From (c) resonance laser Raman spectroscopy as can be seen, D mould and G mould strength ratio are about 0.04, show that the product Single Walled Carbon Nanotube has very high quality; Can output from (d) high-resolution-ration transmission electric-lens photo, product is the Single Walled Carbon Nanotube of perfect structure, and exists with the form of single or little tube bank mostly.
As shown in Figure 3, from the x-ray photoelectron spectroscopy on product surface as can be seen, 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 Single Walled Carbon Nanotube of 40 seconds and 60 seconds growth come out with SiO
2The growth velocity of Single Walled Carbon Nanotube 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 (carbon nano-tube) is 2.5 μ m/s) of base metal catalyst growing single-wall CNT (carbon nano-tube).Illustrate and use SiO
2During for catalyzer, the speed of growth of Single Walled Carbon Nanotube that can significantly slow down, and then reach its length of accurate control, the purpose of the short Single Walled Carbon Nanotube of selective growth.
As shown in Figure 5, the atomic power photo of the Single Walled Carbon Nanotube that obtains from the different reaction times and length statistical graph are as can be seen, by experiment parameter such as control growing time simply, can selectivity obtain the short Single Walled Carbon Nanotube sample of a series of adjustable in length.As 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 Single Walled Carbon Nanotube as plating SiO
2Baffle plate during film) as can be seen, only be coated with SiO
2Just there is Single Walled Carbon Nanotube in the zone of film, and explanation can be by using the located growth of specific template realization Single Walled Carbon Nanotube, 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 Single Walled Carbon Nanotube as plating SiO
2Baffle plate during film) as can be seen, only be coated with SiO
2Just there is Single Walled Carbon Nanotube in the zone of film, and explanation can realize the located growth of Single Walled Carbon Nanotube by 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 Single Walled Carbon Nanotube as plating SiO
2Baffle plate during film) as can be seen, only be coated with SiO
2Just there is Single Walled Carbon Nanotube in the zone of film, and explanation can realize the located growth of Single Walled Carbon Nanotube by using specific template.In addition, Single Walled Carbon Nanotube 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 Single Walled Carbon Nanotube 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 Single Walled Carbon Nanotube of any metallic impurity, have easy and simple to handle, cost low with the characteristics that are easy to located growth and patterned growth Single Walled Carbon Nanotube on silicon substrate, the application of the Single Walled Carbon Nanotube that requires not have metallic impurity is laid a good foundation.In addition, with SiO
2For the growth velocity of the Single Walled Carbon Nanotube of catalyzer significantly reduces than metal catalyst, therefore can accurately control its length, for the rerum natura and the application of research different lengths Single Walled Carbon Nanotube and ultrashort CNT (carbon nano-tube) provides prerequisite by controlling reaction time.
Claims (6)
1. the method for the efficient growing single-wall CNT (carbon nano-tube) 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 plane body, spherical surface body or the arbitrary shape of silicon, silicon oxide, silicon oxide/silicon, aluminum oxide, quartz or silicon carbide is a substrate, and the cracking by carbon source under 600～1100 ℃ prepares Single Walled Carbon Nanotube.
2. according to the method for the efficient growing single-wall CNT (carbon nano-tube) of the described non-metal catalyst of claim 1, it is characterized in that: at first, handle at substrate surface formation SiO by 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 granules of catalyst surface, and at SiO
2The auxiliary nucleation down of granules of catalyst finally forms Single Walled Carbon Nanotube.
3. according to the method for the efficient growing single-wall CNT (carbon nano-tube) of the described non-metal catalyst of claim 2, it is characterized in that: in the reaction process, carbon source is one or more of hydrocarbon polymer methane, ethane, ethene, acetylene, benzene, toluene, hexanaphthene and ethanol, methyl alcohol, acetone, carbon monoxide, and the carbon source flow velocity is 1～1000 ml/min.
4. according to the method for the efficient growing single-wall CNT (carbon nano-tube) of the described non-metal catalyst of claim 2, it is characterized in that: 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.
5. according to the method for the efficient growing single-wall CNT (carbon nano-tube) of the described non-metal catalyst of claim 2, it is characterized in that: temperature of reaction is 650～950 ℃.
6. according to the method for the efficient growing single-wall CNT (carbon nano-tube) of the described non-metal catalyst of claim 1, it is characterized in that: SiO
2Catalyst film thickness is 5～100nm.
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| 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 |
| CN107915217A (en) * | 2016-10-10 | 2018-04-17 | 中国科学院金属研究所 | A kind of method that non-metallic catalyst SiC prepares semi-conductive single-walled carbon nanotubes |
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