CN102757033B - Method for preparing carbon nanotube with specific quantities of walls and specific diameters - Google Patents
Method for preparing carbon nanotube with specific quantities of walls and specific diameters Download PDFInfo
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- CN102757033B CN102757033B CN201210229402.XA CN201210229402A CN102757033B CN 102757033 B CN102757033 B CN 102757033B CN 201210229402 A CN201210229402 A CN 201210229402A CN 102757033 B CN102757033 B CN 102757033B
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Abstract
The invention discloses a method for preparing a carbon nanotube with specific quantities of walls and specific diameters. The method comprises the following steps of: (1) loading markers on a carbon nanotube which is placed in a multi-wall carbon nanotube horizontal array( on a substrate on which a groove is formed), strides over the groove and grows in a suspended mode; (2) fixing two ends of the carbon nanotube which grows in a suspended mode on a probe; moving the probe, pulling cut the outer wall of the carbon nanotube which grows in a suspended mode when a distance between two markers is monitored to be enlarged; continuously moving the probe to prepare the carbon nanometer which has removed outer wall; and monitoring the pull-cut process by a microscope; and (3) repeatedly performing the step (2) and the step (3) to prepare the carbon nanotube with specific quantities of walls and specific diameters. Compared with the conventional preparation method, the method can be carried out under an optical microscope, is easy to operate and is high in controllability; and the inner layer of the multi-wall carbon nanotube with the length of more than centimeter grades can be continuously drawn out so as to have the significance in preparing the carbon nanotube with specific quantities of walls and specific diameters.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nanotube, be specifically related to the preparation method of the carbon nanotube of a kind of particular wall number and diameter, belong to nano material and preparing technical field thereof.
Background technology
Carbon nanotube is a kind of nano material of finding the nineties in 20th century, and since it is found, the character due to aspects such as its excellent electricity having, mechanics, calorifics, has caused numerous investigators' research interest.More than 20 years, it is the focus of Material Field research always.An important prerequisite that realizes carbon nanotube application is to realize the selectivity preparation of ad hoc structure carbon nanotube.Carbon nanotube can be divided into Single Walled Carbon Nanotube and multi-walled carbon nano-tubes (tube wall number can from double-walled to hundreds of walls) according to the difference of its wall number, its caliber can from below a nanometer to nanometers up to a hundred.Difference along with carbon nanotube wall number and diameter, its structure and character are also very different, such as Single Walled Carbon Nanotube often has lower defect concentration, there is dividing of semiconductive and metallicity in its electroconductibility, and multi-walled carbon nano-tubes often trends towards presenting metallicity.The difference of structure and character can have a huge impact for the application of carbon nanotube.
The preparation method of carbon nanotube comprises arc process, laser ablation method and chemical Vapor deposition process, than first two method, chemical Vapor deposition process has that parameter is easily controlled, temperature of reaction is lower, use system extensively, be easy to the advantages such as amplification, in the preparation work of carbon nanotube, be widely applied.Even so, the accurate controlled preparation that wants to realize ad hoc structure carbon nanotube is still a very difficult thing.
Between tube wall due to multi-walled carbon nano-tubes, be weak Van der Waals force, between its tube wall, easily occur relative slippage.If can realize by certain method the separation between the difference pipe layer of multi-walled carbon nano-tubes, just can extract the carbon nanotube with less wall number and diameter out from a multi-walled carbon nano-tubes.This method of preparing carbon nanotube will have application prospect very widely for building micro-nano electron device.Although in theory predicted between carbon nanotube tube wall, can realize at an easy rate slippage or peel off, up to the present still there is no a kind of simple controlled mode to realize this target.Therefore, develop a kind of simple, that effectively means are extracted the carbon nanotube that the internal layer carbon nanotube of multi-walled carbon nano-tubes has particular wall number and diameter for preparation out is significant.
Summary of the invention
The object of the invention is to overcome the restriction of existing carbon nanotube preparation means, by a kind of simple mode, realize the controlled extraction of multi-walled carbon nano-tubes inner layer pipe, and can realize the preparation of particular wall number and diameter carbon nanotube.
The preparation method of the carbon nanotube of a kind of particular wall number provided by the present invention and diameter, comprises the steps:
(1) be placed in load marker on the carbon nanotube of establishing the unsettled growth of the described groove of striding across of reeded suprabasil multi-walled carbon nano-tubes horizontal array;
(2) two ends of the carbon nanotube of described unsettled growth are all fixed on probe, then move described probe, when monitoring two spacing between described marker and become large, the carbon nanotube outer wall of described unsettled growth is pulled off, and continues the carbon nanotube that mobile described probe obtains removing outer wall; Described in monitoring by microscope, break process;
(3) repeating step (2) and step (3) can obtain the carbon nanotube of particular wall number and diameter.
In above-mentioned preparation method, described substrate specifically can be at least one in silicon, silicon-dioxide, quartz, sapphire and corundum;
The length of described groove, width and the degree of depth all can be 50nm ~ 10cm, specifically can be 8mm, 1mm and 0.5mm or 5mm, 0.5mm and 0.3mm.
In above-mentioned preparation method, the length of described carbon nanotube horizontal array can be 1mm ~ 1000mm, specifically can be 50mm ~ 100mm, 50mm or 100mm, and the number of carbon nanotube can be from 1 to 100,000,000.
In above-mentioned preparation method, marker used specifically can be at least one in titanium oxide, silicon oxide, stannic oxide, vanadium oxide, zirconium white, bismuth oxide, niobium oxides, zinc oxide and silver suboxide.
In above-mentioned preparation method, described marker can be particulate state, and its particle diameter can be 10nm ~ 10 μ m, specifically can be 50nm ~ 500nm.
In above-mentioned preparation method, by the presoma of described marker by chemical Vapor deposition process or the physical deposition method described marker of growing on the carbon nanotube of described unsettled growth;
The presoma of described marker can be halogenide, oxyhydroxide or the nitride of metallic element in described marker.
In above-mentioned preparation method, described microscope specifically can be opticmicroscope, scanning electronic microscope, scanning transmission electron microscope or atomic force microscope; By one end of described probe by electrostatic force, deposition decolorizing carbon, use tackiness agent, utilize one or more in numerous modes such as holding force of two objects to be fixed on unsettled carbon nanotube.
A kind of internal layer of extracting out from multi-walled carbon nano-tubes provided by the invention has the method for specific tube wall number and diameter carbon nanotube with preparation, the internal layer that refers to above-mentioned carbon nanotube can be drawn out of wholly or in part, the internal layer carbon nanotube of extracting out can be fixed between two probes, by two probe generation relative displacements, internal layer carbon nanotube different tube walls are from outside to inside broken successively, thereby can be drawn out of thering is the still less internal layer carbon nanotube of wall number.Compare with existing preparation method, the method can be carried out under opticmicroscope, and simple to operate, controllability is strong, and can realize the continuous extraction of the multi-wall carbon nano-tube inner tube layer of the above length of centimetre-sized, significant for the carbon nanotube of preparation particular wall number and diameter.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 and embodiment 2 substrate used and suprabasil carbon nanotube horizontal array.
Fig. 2 is the photo of with probe, carbon nanotube being stirred under scanning electron microscope in the embodiment of the present invention 1.
Fig. 3 extracts internal layer out with schematic diagram and the transmission electron microscope photo of preparation Single Walled Carbon Nanotube from a double-walled carbon nano-tube in the embodiment of the present invention 1.
Fig. 4 is the photo of with probe, the inner layer pipe of carbon nanotube being extracted out in the embodiment of the present invention 1.
Fig. 5 is the photo of with probe, carbon nanotube being stirred under opticmicroscope in the embodiment of the present invention 2.
Fig. 6 is the transmission electron microscope photo of the carbon nanotube of the prepared several different wall numbers of the embodiment of the present invention 1 and embodiment 2 and diameter.
Embodiment
The experimental technique using in following embodiment if no special instructions, is ordinary method.
In following embodiment, material used, reagent etc., if no special instructions, all can obtain from commercial channels.
First on silicon chip as shown in Figure 1, utilize chemical Vapor deposition process to prepare the carbon nanotube horizontal array that length is 10cm; This carbon nanotube horizontal array can stride across the unsettled growth of groove on silicon chip, and wherein, the length of this groove is 8mm, and width is 1mm, and the degree of depth is 0.5mm; Utilize chemical Vapor deposition process many titanium dioxide granules in load on unsettled carbon nanotube, its particle diameter is 50nm ~ 500nm, the detailed process of chemical Vapor deposition process is: titanium tetrachloride vapors is contacted with above-mentioned carbon nano pipe array, titanium tetrachloride vapors can be decomposed, original position generates titanium dioxide granule, loads on unsettled carbon nanotube.
The above-mentioned carbon nanotube preparing is placed in scanning electronic microscope, utilize the mark effect of titanium dioxide, probe is contacted with unsettled carbon nanotube, as shown in Figure 2, then utilize the mode of beam bombardment that the two ends of unsettled carbon nanotube and probe are fixed.Be moved to the left probe, carbon nanotube is stretched.When the spacing between two particles on seeing the carbon nanotube being stretched becomes suddenly large, illustrate that the skin of carbon nanotube is pulled off.Continue traveling probe, now the inner layer pipe of carbon nanotube will be drawn out of.The carbon nanotube of extracting out, because diameter diminishes, is added and there is no the effect of the mark of titanium dioxide granule, the Relative Fuzzy that can become under Electronic Speculum, as shown in Figure 4.Continue to pull the inner layer pipe of carbon nanotube, until it is extracted out completely or ruptures from some places.Then the carbon nanotube inner layer pipe of extraction is transferred in target substrate.
Fig. 3 extracts internal layer out with schematic diagram and the transmission electron microscope photo of preparation Single Walled Carbon Nanotube from a double-walled carbon nano-tube in the present embodiment.
Fig. 6 is the transmission electron microscope photo of the carbon nanotube of several different tube wall numbers that obtain of the present embodiment and caliber.
With embodiment 1, first on the silicon chip shown in similar and Fig. 1, prepare the carbon nanotube horizontal array that length is 5cm; This carbon nanotube horizontal array can stride across the unsettled growth of groove on silicon chip, and wherein, the length of this groove is 5mm, and width is 0.5mm, and the degree of depth is 0.3mm; Utilize chemical Vapor deposition process many titanium dioxide granules in load on unsettled carbon nanotube, its particle diameter is 50nm ~ 500nm, and the detailed process of chemical Vapor deposition process is: by mode loaded with titanium dioxide particles on unsettled carbon nanotube of titanium tetrachloride decomposition in situ.
The above-mentioned carbon nanotube preparing is placed under opticmicroscope, utilize the mark effect of titanium dioxide, probe is contacted with unsettled carbon nanotube, as shown in Figure 5, the used mode that probe and unsettled carbon nanotube are fixed is on probe, to smear certain tackiness agent (conventional silver conductive adhesive) here.Then the probe that moves up, is stretched carbon nanotube.When the spacing between two particles on seeing the carbon nanotube being stretched becomes suddenly large, illustrate that the skin of carbon nanotube is pulled off.Continue traveling probe, now the inner layer pipe of carbon nanotube will be drawn out of.Although can't see the inner layer pipe of the carbon nanotube being drawn out of under opticmicroscope, but due to the carbon nanotube inner layer pipe the being drawn out of state in tightening always, in its outer tube, the titanium dioxide granule of load is by the state in tightening always, when carbon nanotube inner layer pipe is extracted or is pulled out out end completely, its outer tube will come off with it, and titanium dioxide granule above also will fall in groove and can't see.According to whether seeing that titanium dioxide granule just can judge whether the internal layer of carbon nanotube is drawn out of completely.Finally the carbon nanotube inner layer pipe of extraction is diverted the aim in substrate.
Fig. 6 is the transmission electron microscope photo of the carbon nanotube of several different tube wall numbers that obtain of the present embodiment and caliber.
Claims (7)
1. a preparation method for the carbon nanotube of particular wall number and diameter, comprises the steps:
(1) be placed in load marker on the carbon nanotube of establishing the unsettled growth of the described groove of striding across of reeded suprabasil multi-walled carbon nano-tubes horizontal array;
(2) two ends of the carbon nanotube of described unsettled growth are all fixed on probe, then move described probe, when monitoring two spacing between described marker and become large, the carbon nanotube outer wall of described unsettled growth is pulled off, and continues the carbon nanotube that mobile described probe obtains removing outer wall; Described in monitoring by microscope, break process;
(3) repeating step (1) and step (2) can obtain the carbon nanotube of particular wall number and diameter.
2. preparation method according to claim 1, is characterized in that: described substrate is at least one in silicon, silicon-dioxide, quartz, sapphire and corundum;
The length of described groove, width and the degree of depth are 50nm～10cm.
3. preparation method according to claim 1 and 2, is characterized in that: the length of described carbon nanotube horizontal array is 1mm～1000mm.
4. preparation method according to claim 1, is characterized in that: marker used is at least one in titanium oxide, silicon oxide, stannic oxide, vanadium oxide, zirconium white, bismuth oxide, niobium oxides, zinc oxide and silver suboxide.
5. preparation method according to claim 1, is characterized in that: described marker is particulate state, and its particle diameter is 10nm～10 μ m.
6. preparation method according to claim 1, is characterized in that: by the presoma of described marker by chemical Vapor deposition process or the physical deposition method described marker of growing on the carbon nanotube of described unsettled growth;
The presoma of described marker is halogenide, oxyhydroxide or the nitride of metallic element in described marker.
7. preparation method according to claim 1, is characterized in that: described microscope is opticmicroscope, scanning electronic microscope, scanning transmission electron microscope or atomic force microscope.
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| CN107101760B (en) * | 2017-04-26 | 2019-10-11 | 清华大学 | A kind of preparation method of precise torsion balance, precise torsion balance and application method |
| CN109399612B (en) * | 2018-10-30 | 2020-08-21 | 国家纳米科学中心 | Suspended carbon nanotube array and preparation method thereof |
| CN113023711B (en) * | 2019-12-24 | 2022-10-18 | 清华大学 | Preparation method of carbon nanotube bundle |
| CN115709984B (en) * | 2021-08-23 | 2024-04-05 | 北京大学 | Preparation method of surface-cleaning carbon nano tube |
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| CN1212189C (en) * | 2003-07-08 | 2005-07-27 | 浙江大学 | Bimetal oxide catalyst and method using it to prepare single-wall nano carbon tube whose diameter can be controlled |
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