CN100467369C - Preparation method of carbon nanometer pipe - Google Patents
Preparation method of carbon nanometer pipe Download PDFInfo
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- CN100467369C CN100467369C CNB200510034955XA CN200510034955A CN100467369C CN 100467369 C CN100467369 C CN 100467369C CN B200510034955X A CNB200510034955X A CN B200510034955XA CN 200510034955 A CN200510034955 A CN 200510034955A CN 100467369 C CN100467369 C CN 100467369C
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Abstract
A process for preparing carbon nano-tube includes such steps as providing a substrate, depositing multiple layers of catalyst onto said substrate, and filling carbon source gas to grow carbon nano-tube. Each catalyst layer contains Fe film, C film and V film between them.
Description
[technical field]
The present invention relates to a kind of preparation method of carbon nanotube.
[background technology]
Carbon nanotube is the hollow tubular thing that a kind of diameter of being made up of carbon atom is a nanometer scale, is six-ring at carbon nanotube graphite linings central part, endways or turnover five-ring or seven-membered ring are partly then arranged.Carbon nanotube is to find first in by the product of Lijima at arc-over in 1991, is published on Nature the 354th phase 56-58 page or leaf of publishing in 1991.
The special construction of carbon nanotube determines it to have good comprehensive mechanical property, as high elastic coefficient, high yang type modulus and low density, and excellent electric property, thermal property and absorption property.Along with the variation of length, diameter and the spiral way of carbon nanotube, carbon nanotube can present metallicity or semiconductor property.Because therefore the excellent specific property of carbon nanotube is expected it and plays a significant role in fields such as nanoelectronics, Materials science, biology, chemistry.
The method for preparing at present carbon nanotube has arc discharge method, the radium-shine method of evaporation of pulse and chemical Vapor deposition process etc.Shortcoming that the carbon nanotube that arc-over and pulsed laser method of evaporation form has that carbon nanotube yields poorly, carbon nanotube and other nano particle mix so that carbon nano pipe purity is low etc.At present mainly use chemical Vapor deposition process to prepare carbon nanotube, this method mainly be the transition metal of utilization nanoscale or its oxide compound as catalyzer, the carbonaceous gas of pyrolysis at a certain temperature prepares carbon nanotube.
But, the catalyzer of prior art is generally the unitary film design, after the thermal treatment under the reducing gas, form nano-scale particle, these nm-class catalyst particles are at the substrate skewness, the carbon laydown that carbon-source gas decompose to produce is grown to carbon nanotube in containing on this particulate zone, so also skewness of carbon nanotube.
[summary of the invention]
Below, a kind of preparation method of the carbon nanotube that is evenly distributed will be described with embodiment.
For realizing foregoing, a kind of preparation method of carbon nanotube is provided, it may further comprise the steps:
(1) provides a substrate;
(2) the deposit multilayer catalyst layer is in substrate, and described each catalyst layer comprises iron film, carbon film and the vanadium film between the two;
(3) feed the carbon-source gas carbon nano-tube.
Wherein, deposit Fe in this each catalyst layer deposition process earlier, deposit V, C then successively, catalyzer is approximately the 10-30 layer, the thickness of iron film is approximately the 10-30 nanometer, is preferably 6 nanometers, the thickness of vanadium film is approximately the 1-5 nanometer, is preferably 2 nanometers, and the thickness of carbon film is approximately the 3-18 nanometer, is preferably 5 nanometers.
Compared with prior art, the preparation method of the carbon nanotube that present embodiment provides adopts multilayer to contain the catalyzer of Fe, V, C, and Fe, V, C answer chemical reaction to generate Fe with evenly melting concurrent looks mutually under the condition of high temperature
3C, VC, when reducing to room temperature, oversaturated C will separate out and be evenly distributed on Fe
3Around C, the VC, carbon-source gas is that the basis is grown to carbon nanotube because of the C that thermolysis produces with supersaturation C, and because of oversaturated C is a uniform distribution, so carbon nanotubes grown also is a uniform distribution.
[description of drawings]
Fig. 1 is the schema of the embodiment of the invention.
Fig. 2 is the substrate synoptic diagram that the present invention deposits catalyst layer.
Fig. 3 is the enlarged view of multi-layer catalyst layer of the present invention.
[embodiment]
See also Fig. 1, it is preparation method's schema of the carbon nanotube that provides of the embodiment of the invention, and this method may further comprise the steps:
Step 1 provides a substrate.The substrate that this step provided is as the support base of carbon nano-tube, and this substrate can be selected Si (silicon), Ta (tantalum), Ni (nickel), Ag (silver), stainless steel or other alloy for use.
Step 2 be the deposit multilayer catalyst layer in substrate, each catalyst layer comprises iron film, carbon film and the vanadium film between the two.Deposition n layer catalyzer in the substrate that step 1 provides, this each catalyst layer comprises Fe film, C film and the V film between the two.Wherein, n can be 10-30, and the thickness that the thickness that the thickness of Fe film is approximately 10-30 nanometer, V film is approximately 1-5 nanometer, C film is approximately the 3-18 nanometer.The method that forms catalyst layer has: methods such as thermal evaporation sedimentation, electron beam heating evaporation method, the catalyzer of present embodiment are to adopt the vacuum splashing and plating method to make.
Step 3 is to feed the carbon-source gas carbon nano-tube.Utilize hot CVD method carbon nano-tube in substrate, Fe, V, C film melt mutually and produce the supersaturated solution of C at a certain temperature, and supersaturation C separates out at Fe when being cooled to room temperature
3Around C, the VC, the C that the carbon-source gas thermolysis is produced is that the basis is grown to carbon nanotube with supersaturation C.
Implementation procedure below in conjunction with specific embodiment explanation the inventive method.
See also Fig. 2 and Fig. 3, the present invention selects for use Si as substrate 10, the size of this substrate 10 is decided by specific requirement, the catalyzer 14 of deposition n layer nanometer grade thickness in this substrate 10, wherein, n can be 10-30, and catalyzer 14 is to adopt sputtering process to form, and each layer catalyzer 14 comprises Fe film 142, C film 146 and the V film 144 between the two.
The forming process of catalyzer 14 is as follows: elder generation's sputter-deposited Fe film 142 in substrate 10, sputter-deposited V film 144 on Fe film 142, sputter C film 146 is on V film 144, then deposition Fe film 142 on the C film 146, deposition V film 144 on the Fe film 142, on V film 144 sputter-deposited C film, ..., sputter-deposited multilayer Fe film 142, V film 144 and C film 146 so repeatedly.
Wherein, the thickness of Fe film 142 is that the thickness of 10-30 nanometer, V film 144 is that the thickness of 1-5 nanometer, C film 146 is the 3-18 nanometer, and the thickness of the preferred Fe film 142 of present embodiment is that the thickness of 6 nanometers, V film 144 is that the thickness of 2 nanometers, C film 146 is 5 nanometers.
The substrate 10 that will have catalyzer 14 places Reaktionsofen (figure does not show); feed shielding gas or in vacuum state; the temperature of Reaktionsofen is increased to 500 ℃-1000 ℃; when the temperature of Reaktionsofen reaches preset temperature (carbon-source gas decomposition temperature; different and different according to carbon-source gas) time, the reaction of supply carbon-source gas can grow carbon nanotube in 10-30 minute in Reaktionsofen.
Wherein, this shielding gas can be argon gas, nitrogen, hydrogen or its mixed gas, and present embodiment is selected argon gas for use, and this carbon-source gas is a hydrocarbon polymer; can be methane, acetylene, ethene, propylene, propane or its mixture, present embodiment selects for use acetylene gas as carbon-source gas.
Under the condition of high temperature, the Fe in the catalyzer 14, V and C evenly melt mutually, the concurrent row reaction generation Fe that gives birth to
3C and VC:
Fe+C->Fe
3C
V+C->VC
In the catalyzer 14 not the carbon of complete reaction will produce the supersaturated solution of carbon, then with the Reaktionsofen short annealing to room temperature (generally being 25 ℃), at this moment, oversaturated carbon will be separated out at Fe
3Around C and the VC.Based on the carbon that supersaturation is separated out, the carbon that the acetylene thermolysis produces will be grown to carbon nanotube on the carbon of separating out because of supersaturation.
Cause, the Fe in the substrate 10, V, C at high temperature evenly melt mutually, and concurrent looks answers chemical reaction to generate Fe
3C and VC, oversaturated carbon is separated out and is evenly distributed on Fe when reducing to room temperature
3Around C and the VC, the carbon that the thermolysis of carbon-source gas acetylene produces is that the basis is grown to carbon nanotube with oversaturated carbon, and therefore, even carbon nanotube distributes.
Claims (11)
1. the preparation method of a carbon nanotube, it may further comprise the steps:
(1) provides a substrate;
(2) the deposit multilayer catalyst layer is in substrate, and described each catalyst layer comprises iron film, carbon film and the vanadium film between the two;
(3) feed the carbon-source gas carbon nano-tube.
2. the preparation method of carbon nanotube as claimed in claim 1, it is characterized in that: the substrate in the step (1) is Si, Ta, Ni, Ag or stainless steel.
3. the preparation method of carbon nanotube as claimed in claim 1, it is characterized in that: described catalyst layer is 10 to 30 layers.
4. the preparation method of carbon nanotube as claimed in claim 1, it is characterized in that: the thickness of described iron film is the 3-30 nanometer.
5. the preparation method of carbon nanotube as claimed in claim 1, it is characterized in that: the thickness of described vanadium film is the 1-5 nanometer.
6. the preparation method of carbon nanotube as claimed in claim 1, it is characterized in that: the thickness of described carbon film is the 3-18 nanometer.
7. as the preparation method of the arbitrary described carbon nanotube of claim 1 to 6, it is characterized in that: described catalyst layer adopts thermal evaporation, electron beam heating evaporation method or sputter to form.
8. the preparation method of carbon nanotube as claimed in claim 7 is characterized in that: step (3) further comprise substrate sent into Reaktionsofen after, under shielding gas, be heated to 500 ℃-1000 ℃.
9. the preparation method of carbon nanotube as claimed in claim 8, it is characterized in that: described shielding gas is argon gas, nitrogen, hydrogen or its mixed gas.
10. the preparation method of carbon nanotube as claimed in claim 1, it is characterized in that: described carbon-source gas is methane, acetylene, ethene, propylene, propane or its mixture.
11. the preparation method of carbon nanotube as claimed in claim 1 is characterized in that: fed carbon-source gas 10-30 minute.
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| CNB200510034955XA CN100467369C (en) | 2005-05-28 | 2005-05-28 | Preparation method of carbon nanometer pipe |
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| CNB200510034955XA CN100467369C (en) | 2005-05-28 | 2005-05-28 | Preparation method of carbon nanometer pipe |
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| CN1868867A CN1868867A (en) | 2006-11-29 |
| CN100467369C true CN100467369C (en) | 2009-03-11 |
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| CNB200510034955XA Expired - Fee Related CN100467369C (en) | 2005-05-28 | 2005-05-28 | Preparation method of carbon nanometer pipe |
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| CN104718170A (en) | 2012-09-04 | 2015-06-17 | Ocv智识资本有限责任公司 | Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media |
| CN108085655B (en) * | 2016-11-22 | 2019-07-26 | 北京大学 | One kind (2m, m) carbon nanotube horizontal array and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004078348A1 (en) * | 2003-02-28 | 2004-09-16 | Commissariat A L'energie Atomique | Catalyst structure particularly for the production of field emission flat screens |
| CN1532143A (en) * | 2003-03-25 | 2004-09-29 | 清华大学 | Carbon nano tube array structure and its preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004078348A1 (en) * | 2003-02-28 | 2004-09-16 | Commissariat A L'energie Atomique | Catalyst structure particularly for the production of field emission flat screens |
| CN1532143A (en) * | 2003-03-25 | 2004-09-29 | 清华大学 | Carbon nano tube array structure and its preparing method |
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