CN1962427B - Production method of nano-carbon tube - Google Patents
Production method of nano-carbon tube Download PDFInfo
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- CN1962427B CN1962427B CN2005101012276A CN200510101227A CN1962427B CN 1962427 B CN1962427 B CN 1962427B CN 2005101012276 A CN2005101012276 A CN 2005101012276A CN 200510101227 A CN200510101227 A CN 200510101227A CN 1962427 B CN1962427 B CN 1962427B
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Abstract
The invention discloses a growing method of nanometer carbon pipe, which comprises the following steps: providing base; preparing nanometer catalyst solution with certain viscosity; dripping nanometer catalyst solution on the base surface through injecting device of micrometer-grade injecting needle array; forming catalyst layer; growing nanometer carbon pipe on the base surface; making catalyst drip as micrometer grade.
Description
[technical field]
The present invention relates to a kind of growth method of CNT (carbon nano-tube), relate in particular to that a kind of processing procedure is simple, the reaction times is short, the growth method of the CNT (carbon nano-tube) of the fine structure of can growing.
[background technology]
CNT (carbon nano-tube) is a kind of tubular graphene, and it is found in 1991 by Japanology personnel Iijima, sees also " Helical Microtubules of Graphitic Carbon ", S Iijima, Nature, Vol.354, P.56 (1991).Because it has performances such as extremely excellent conduction, one-way heat conduction, be widely used in each field such as an emission, hydrogen storage and photoinduction element.
The method for preparing at present CNT (carbon nano-tube) have arc discharge method (Arc Discharge), laser disappear molten method (Laserablation), chemical Vapor deposition process (Chemical Vapor Deposition, CVD) and high-temperature decomposition (Pyrolysis) etc.Wherein the CVD method all obviously is better than other preparation method at the aspects such as selective control, vertical orientation, size control and output of CNT (carbon nano-tube) growth patterns.
The method of traditional employing chemical Vapor deposition process growing nano carbon pipe comprises the steps: at first to provide a silicon substrate; Then at this silicon substrate surface deposition one catalyst layer; Carry out thermal pretreatment, temperature is about 400～500 ℃, makes its annealing or reduction, becomes nano level granules of catalyst; And then hydrocarbon reaction gas is fed temperature be about in 1000～1200 ℃ the high-temperature reactor, hydrocarbon gas Yin Gaowen and catalytic pyrolysis becomes carbon is adsorbed on the substrate catalyst surface, thereby carries out deposition growing, obtains CNT (carbon nano-tube) at last.
But the size of catalyzer is being played the part of key role in the CNT (carbon nano-tube) process of growth, and it not only determines CNT (carbon nano-tube) whether to grow, and also can influence the growth diameter and the growth kenel of CNT (carbon nano-tube).And in this traditional method, at first, catalyzer is the continous way solution layer that deposition forms, the required particle type of CNT (carbon nano-tube) that can't obtain growing up distributes, therefore must be through thermal pretreatment, make it form particulate state, the catalyst layer particle that obtains like this is bigger, the CNT (carbon nano-tube) of the fine structure of can't growing; Secondly, this method must adopt heating processing twice: a preheating catalyst layer makes it form granules of catalyst, another time is the heating pyrolyze hydrocarbon polymer, processing procedure is loaded down with trivial details, and catalyst layer is become granules of catalyst also needs certain hour, causes the W-response time longer.
In view of this, provide that a kind of processing procedure is simple, the reaction times is short, the growth method of the CNT (carbon nano-tube) of the fine structure of can growing is real in essential.
[summary of the invention]
Below will illustrate that a kind of processing procedure is simple, the reaction times short, the growth method of the CNT (carbon nano-tube) of the fine structure of can growing with embodiment.
The growth method of this kind CNT (carbon nano-tube) comprises the steps: to provide a substrate; The nano-catalytic agent solution that preparation has certain viscosity; The nanocatalyst solution that forms is instiled in substrate surface, form the catalyst layer that constitutes by the catalyzer drop; And at the substrate surface growing nano carbon pipe that forms catalyst layer.
It is to adopt one to have pinhole size be that the injection device of micron-sized injection needles array is finished that the nanocatalyst solution that forms is instiled in substrate surface.
The catalyzer drop that injection device forms is a micron order.
With respect to prior art, the growth method of the described CNT (carbon nano-tube) of present embodiment has following advantage: at first, the catalyst solution of preparation is a nano level, and has certain viscosity, makes it to instil and form mobile little drop on substrate.Secondly, adopting pinhole size is the micron-sized injection device size and the uniform distribution of control catalyst drop as required, the nanometer carbon pipe array of the fine structure that helps growing; And can be by the density of control drop on substrate, the quantity of control CNT (carbon nano-tube) growth; By the uniformity coefficient of control droplet distribution, the homogeneity of control CNT (carbon nano-tube) spatial distribution.Once more, this growth method need not thermal pretreatment, catalyzer can form equally distributed drop, when the carbon that the high-temperature catalytic cracking produces diffuses into the catalyzer drop, because of it is thermopositive reaction, promoted the volatilization of binder constituents in the drop, and increased solubleness to carbon, therefore, for twice heating of prior art, processing procedure obtains simplifying, and total reaction time shortens.
[description of drawings]
Fig. 1 is the substrate synoptic diagram that present embodiment provides.
Fig. 2 is a present embodiment instillation catalyzer drop synoptic diagram.
Fig. 3 is the device synoptic diagram of present embodiment growing nano carbon pipe.
[embodiment]
The growth method of described CNT (carbon nano-tube) comprises the steps:
The first step provides a substrate 10, and as shown in Figure 1, it can be glass, silicon chip or quartz plate etc.;
Second step, the nano-catalytic agent solution that preparation has certain viscosity.
The catalyzer of present embodiment can be nano level metal iron, cobalt, nickel, or the oxide compound of the alloy of metallic iron, cobalt or nickel or metallic iron, cobalt or nickel, and this nanocatalyst is to be formulated in the solution, is convenient to follow-up formation catalyst layer.
Lift the described preparation method of an example explanation below with nano-catalytic agent solution of certain viscosity:
With 8.6 gram FeCl
2Tetrahydrate and 23.5 the gram FeCl
3Hexahydrate be dissolved in the distilled water.The ammoniacal liquor that adds 20～50 milliliters then, heating this aqueous solution to 80 ℃ under vigorous stirring, by co-precipitation, obtaining particle diameter is the magnetite (Fe of 1～100 nanometer
3O
4) the nanoparticle precipitation.
The solution that 1 gram capric acid is dissolved in 25 milliliters of acetone formation adds in the above-mentioned solution, forms the tensio-active agent that is coated on nanoparticle surface.The vigorous stirring of solution makes new sedimentary nanoparticle fully contact with tensio-active agent, and thus, nanoparticle surface all is coated with above-mentioned tensio-active agent.When nanoparticle is near each other, because the repulsion effect of interparticle space, make to form steady suspension in the solution.
Then, the solution that again 2 gram capric acid is dissolved in 50 milliliters of acetone formation adds in the above-mentioned suspension, adds once in per five minutes, divides to add for five times, makes tensio-active agent at the abundant overlay film of the nanoparticle surface that is settled out.
Then solution is cooled to room temperature, the Fe of tensio-active agent overlay film
3O
4Nanoparticle, magnetic fluid forms the colloidal dark solution in other words.
With Fe
3O
4The magnetic fluid of nanoparticle is dissolved in tackiness agent, as polyvinyl alcohol (Polyvinyl Alcohol, PVA) in to obtain certain viscosity, help solution and instil.
In this step, the catalyst particle size preferably is controlled to be nano level; The viscosity of catalyst solution preferably is controlled to be moderate, guarantees simultaneously to be sprayed at not influence spraying that drop on the substrate keep to drip a shape, not joining together is as the criterion, and this viscosity controller can be regulated by the method for volatilization tackiness agent.
Except that above-mentioned preparation method, the preparation of other nano-catalytic agent solution also can be adopted similar methods, as for metal catalyst, nano metal particles can be added vigorous stirring in the surfactant soln, make its surface coating form colloidal solution, and then colloidal solution is dissolved in obtains certain viscosity in the tackiness agent.
In the 3rd step, the nanocatalyst solution that second step was formed instils in substrate surface, forms the catalyst layer that is made of the catalyzer drop.
See also Fig. 2, present embodiment adopts an injection device 20, and this injection device 20 comprises a container 22 and is arranged at the injection needles array 24 of these container 22 bottoms.This injection needles array 24 comprises a plurality of injection needless 242.Arranging of this injection needles array 24 can be adopted various arranging according to droplet distribution to be instiled, and is evenly distributed as droplet distribution to be instiled, and then injection needles array 24 arranges also for evenly distributed.These container 22 tops have a piston 26, in order to sealing this container 22, during the drop of desire instillation simultaneously, piston 26 are applied the thrust of a specific size, make drop just instil one, and do not form continuous drop post for well.This piston 26 is to adopt computer control, and the thrust size is to set through computer.The aperture size of this injection needles 242 is 0.01～0.5 millimeter (promptly 10～500 microns).
The size of above-mentioned catalyzer drop and uniform distribution help follow-up CNT (carbon nano-tube) growth.In the present embodiment, control the stand density of follow-up CNT (carbon nano-tube) by the distribution density of control injection needles array.By the uniformity coefficient of control injection needles array distribution, the homogeneity of control CNT (carbon nano-tube) spatial distribution.
The 4th step is at the substrate surface growing nano carbon pipe of above-mentioned formation catalyst layer.
See also Fig. 3, typical C VD method growth CNT (carbon nano-tube) equipment comprises that a heating unit 110, a Quartz stove tube 120, are arranged at being used to place and waiting to grow up the carrier 130 of CNT (carbon nano-tube) substrate 10 in the Quartz stove tube 120.General carrier 130 is flat, and substrate 10 lies against on the carrier 130.
Temperature in the boiler tube 120 rises to 1000～1200 ℃, feeds carbon source gas, and the composition of this carbon source gas is hydrocarbon polymers such as methane, ethane, ethene or benzene.Understand the Yin Gaowen catalytic decomposition because of the gas of hydrocarbon polymer and become carbon, be adsorbed in the catalyst layer of substrate surface, thus the growth CNT (carbon nano-tube).
Its principle is: hydrocarbon gas such as acetylene, ethene equimolecular are heated, with be the chain rupture cracking after catalyzer contacts, carbon is just then overflowed by the surface to catalyzer internal divergence hydrogen this moment, this process is extremely strong thermopositive reaction, thereby the temperature of absorption position raises fast in the catalyzer, impel the binder constituents volatilization of catalyzer drop, increased the solubleness of catalyzer simultaneously carbon.
When entering carbon molecule in the catalyzer and surpass saturation concentration via surface diffusion, the carbon molecule is promptly separated out by stablizing in the mode that forms tubulose and obtain force balance each other in the catalyzer, and this is thermo-negative reaction.Carbon enters the balance of setting up heat release-heat absorption in catalyzer or the precipitation process, and follow-up carbon then can diffuse to whole catalyst particle by this hot motivating force, thereby constantly will separate out above the carbon of saturation concentration.
If the excessive carbon distribution of catalyst pellets sub-surface, when making carbon molecular diffusion rate deficiency or surpassing CNT (carbon nano-tube) nucleation and growth velocity, catalyst surface is promptly sealed by carbon and stops growing.
Because of the technology of the long-pending growth CNT (carbon nano-tube) in chemical gas phase Shen is ripe, except that the equipment of above-mentioned growth CNT (carbon nano-tube), also can adopt the device growth of other chemical vapour deposition.
With respect to prior art, the growth method of the described nano-sized carbon pipe of present embodiment has following advantage: at first, the catalyst solution of preparation is the nanometer level, and has certain viscosity, so that it can adopt the little injection device of needle sizes to instil, and form mobile little drop at substrate, thus the size of drop can be controlled, and then by the grow up nano-sized carbon pipe of meticulous structure of this drop. Secondly, adopting pinhole size is that micron-sized injection needle array can be controlled arranging of injection needle array as required, and then the size of control catalyst drop and evenly distribution, the nanometer carbon pipe array of meticulous structure is conducive to grow, and can be by the density of control drop on substrate, the quantity of control nano-sized carbon pipe growth; By the uniformity of control droplet distribution, the uniformity that control nano-sized carbon tube space distributes. Again, this growth method need not The pre-heat treatment, catalyst can form equally distributed drop, when the carbon that the high-temperature catalytic cracking produces diffuses into the catalyst drop, because it is exothermic reaction, promoted the volatilization of adhesive composition in the drop, and increased solubility to carbon, therefore, for twice heating of prior art, processing procedure is simplified, and total reaction time shortens.
Claims (5)
1. the growth method of a CNT (carbon nano-tube), it comprises the steps:
One substrate is provided;
One catalyst solution is dissolved in a tackiness agent, and with the nano-catalytic agent solution that preparation has certain viscosity, this nanocatalyst is metallic iron, cobalt, nickel, or the alloy of metallic iron, cobalt, nickel, or the oxide compound of iron, cobalt, nickel;
Adopt an injection device that the nanocatalyst solution that forms is instiled in substrate surface, the catalyst layer that formation is made of the catalyzer drop, described injection device has the injection needles array that a container, a piston and are arranged at this container, described container is in order to hold described nano-catalytic agent solution, described piston is in order to seal described container, and to producing pressure in the container, described injection needles array comprises a plurality of micron order pin holes; And
At the substrate surface growing nano carbon pipe that forms catalyst layer.
2. the growth method of CNT (carbon nano-tube) as claimed in claim 1 is characterized in that described tackiness agent is a polyvinyl alcohol.
3. the growth method of CNT (carbon nano-tube) as claimed in claim 1, the aperture size that it is characterized in that described injection device is 10～500 microns.
4. the growth method of CNT (carbon nano-tube) as claimed in claim 1 is characterized in that arranging of described injection needles array is consistent with the distribution of catalyzer drop to be instiled.
5. the growth method of CNT (carbon nano-tube) as claimed in claim 1 is characterized in that the catalyzer drop that described injection device forms is a micron order.
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| CN2005101012276A CN1962427B (en) | 2005-11-09 | 2005-11-09 | Production method of nano-carbon tube |
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| CN2005101012276A CN1962427B (en) | 2005-11-09 | 2005-11-09 | Production method of nano-carbon tube |
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| CN1962427B true CN1962427B (en) | 2010-11-10 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6232706B1 (en) * | 1998-11-12 | 2001-05-15 | The Board Of Trustees Of The Leland Stanford Junior University | Self-oriented bundles of carbon nanotubes and method of making same |
| US6361861B2 (en) * | 1999-06-14 | 2002-03-26 | Battelle Memorial Institute | Carbon nanotubes on a substrate |
| CN1388059A (en) * | 2002-04-17 | 2003-01-01 | 中山大学 | Controllable growth process of carbon nanotube in certain diameter and distribution density |
| US6630772B1 (en) * | 1998-09-21 | 2003-10-07 | Agere Systems Inc. | Device comprising carbon nanotube field emitter structure and process for forming device |
| CN1509982A (en) * | 2002-12-21 | 2004-07-07 | �廪��ѧ | Carbon nanometer tube array structure and growing method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6630772B1 (en) * | 1998-09-21 | 2003-10-07 | Agere Systems Inc. | Device comprising carbon nanotube field emitter structure and process for forming device |
| US6232706B1 (en) * | 1998-11-12 | 2001-05-15 | The Board Of Trustees Of The Leland Stanford Junior University | Self-oriented bundles of carbon nanotubes and method of making same |
| US6361861B2 (en) * | 1999-06-14 | 2002-03-26 | Battelle Memorial Institute | Carbon nanotubes on a substrate |
| CN1388059A (en) * | 2002-04-17 | 2003-01-01 | 中山大学 | Controllable growth process of carbon nanotube in certain diameter and distribution density |
| CN1509982A (en) * | 2002-12-21 | 2004-07-07 | �廪��ѧ | Carbon nanometer tube array structure and growing method thereof |
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