CN101007631A - Mono-layer carbon nanotube and its preparation method, and electronic element preparation method - Google Patents
Mono-layer carbon nanotube and its preparation method, and electronic element preparation method Download PDFInfo
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- CN101007631A CN101007631A CN 200610002907 CN200610002907A CN101007631A CN 101007631 A CN101007631 A CN 101007631A CN 200610002907 CN200610002907 CN 200610002907 CN 200610002907 A CN200610002907 A CN 200610002907A CN 101007631 A CN101007631 A CN 101007631A
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Abstract
The invention discloses a making method of one-layer carbon nanometer pipe and electronic element through the single-layer carbon nanometer pipe, which is characterized by the following: adopting alcohol or alcohol solution of gasifying alcohol as reacting gas; making single-layer carbon nanometer pipe under normal pressure through chemical gas-phase sediment method; guiding gas from evaporated gasifying alcohol or alcohol solution into reacting part to react; setting the alcohol density at 50-95% in the alcohol solution.
Description
Technical field
The present invention relates to the preparation method of preparation method, single-layer carbon nano-tube and the electronic component of single-layer carbon nano-tube, for example, preferably be applied to use in the various electronic components of single-layer carbon nano-tube.
Background technology
Single-layer carbon nano-tube (SWNT) has distinctive electricity, machinery, electrooptics and electromechanical characteristic, therefore, all be considered the attracting structural unit (for example, with reference to non-patent literature 1～5) of following nanoelectronic elements such as field emission element, field-effect transistor, single-electronic transistor, molecule sensor all the time.In order to realize such attracting application, must expect to prepare high-quality single-layer carbon nano-tube with controlled structure.In order to prepare single-layer carbon nano-tube, people had paid a large amount of effort in the period of past 10, for high yield and prepare high-quality single-layer carbon nano-tube at low cost, various technology have been developed, comprise: arc-over (for example, with reference to non-patent literature 6), laser ablation (for example, with reference to non-patent literature 7) and chemical vapor deposition (CVD) (for example, with reference to non-patent literature 8～10).Application of single-layer carbon nano-tube (for example) and basic science (for example) with reference to non-patent literature 12～16 with reference to non-patent literature 11, approach and the adaptability that in preparation, will look for novelty.
Above-mentioned CVD method is considered to prepare with low cost a strong method of high-quality single-layer carbon nano-tube usually.Therefore, for by exploring composition, carrier/baseplate material, temperature of reaction and the carbon-source gas of catalyzer, make CVD method optimization, big quantity research (for example, with reference to non-patent literature 17～20) has been carried out in the people concentrated area.Reported that recently ethanol is in order to prepare the desirable carbon source (for example, with reference to non-patent literature 21～23) of high-quality single-layer carbon nano-tube by the CVD method under reduced pressure.In addition, also proposed by making by the carbon source of compound formation or have the compound of Sauerstoffatom and the mixture of the compound with carbon atom contacts with catalyzer under Heating temperature with Sauerstoffatom, under reduced pressure, utilize the CVD legal system to be equipped with the method for single-layer carbon nano-tube, as the example of above-mentioned carbon source, can enumerate the alcohols or the ethers of ethanol etc.; As the example of said mixture, can enumerate the mixture of hydrocarbon such as water and acetylene, perhaps NO
x, SO
x(for example, with reference to patent documentations 1) such as mixtures with hydrocarbon such as acetylene.
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Dresselhaus，M.S.；Dresslhaus，G.；Eklund，P.C.，Science ofFullerenes and Carbon Nanotubes；Academic Press：San Diego，1996
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Thess，A.；Lee，R.；Nikolaev，P.；Dai，H.；Petit，P.，Robert，J.；Xu，C.；Lee，Y.H.；Kim，S.G.；Rinzler，A.G.；Colbert，D.T.；Scuseria，G.E.；Tomanek，D.；Fischer，J.E.；Smalley，R.E.，Science 1996，273，483
[non-patent literature 8]
lsmach，A.；Segev，L.；Wachtel，E.；Joselevich，E.，Angew.Chem.Int.Ed.2004，43，6140
[non-patent literature 9]
Huang，Sh.M.；Cai，X.Y.；Liu，J.，J.Am.Chem.Soc.2003，125，5636
[non-patent literature 10]
Kong，J.；Soh，H.T.；Cassell，A.M.；Quate，C.F.；Dai，H.，Nature1998，395，878
[non-patent literature 11]
Tanaka，K.；Yamabe，T.；Fukui，K.，The Science and Technology ofCarbon Nanotubes；Elsevier：Oxford，1999
[non-patent literature 12]
Wong，S.；Joselevich，E.；Woolley，A.；Cheung，C.；Lieber，C.，Nature 1998，394，52
[non-patent literature 13]
Fan，S.；Chapline，M.；Franklin，N.；Tombler，T.；Cassell，A.；Dai，H.，Science 1999，283，512
[non-patent literature 14]
Wang，X.B.；Liu，Y.Q.；Zhu，D.B.，Chem.Commun.2001，751
[non-patent literature 15]
Wang，X.B.；Liu，Y.Q.；Zhu，D.B.，Adv.Mater.2002，14，165
[non-patent literature 16]
Wang，X.B.；Liu，Y.Q.；Hu，P.A.；Yu，G.；Xiao，K.；Zhu，D.B.，Adv.Mater.2002，14，1557
[non-patent literature 17]
Song，L.；Ci，L.J.；Zhou，Zh.P.；Xie，S.Sh.，Adv.Mater.2004，16，1529
[non-patent literature 18]
Huang，Sh.M.；Woodson，M.；Smalley，R.；Liu，J.，Nano Lett.2004，4，1025
[non-patent literature 19]
Shi，Z.J.；Okazaki，T.；Shimada，T.；Sugai，T.；Suenaga，K.；Shinohara，H.，J.Phys.Chem.B 2003，107，2485
[non-patent literature 20]
Mukhopadhyay，K.；Koshio，A.；Tanaka，N.；Shinohara，H.，Jpn.J.Appl.Phys.1998，37，1257
[non-patent literature 21]
Okamoto，A.；Shinohara，H.，Carbon 2000，43，1691
[non-patent literature 22]
Mukhopadhyay，K.；Koshio，A.；Sugai，T.；Tanaka，N.；Shinohara，H.；Konya，Z.，Chem.Phys.Lett.，1999，303，117
[non-patent literature 23]
Murakami，Y.；Einarsson，E.；Edamura，T.；Maruyama，S.，Carbon 2005，43，2664
[patent documentation 24]
The international brochure that discloses No. 03/068676
Summary of the invention
Yet when utilizing the CVD method, when preparing single-layer carbon nano-tube under reduced pressure, owing to be difficult to control the growth parameter(s) of single-layer carbon nano-tube, therefore, very difficult preparation has the high-quality single-layer carbon nano-tube of controlled structure.
Therefore, the problem that the present invention will solve provides a kind ofly can easily prepare the high-quality single-layer carbon nano-tube with controlled structure, and can easily prepare the method for the extremely narrow single-layer carbon nano-tube of the distribution range that comprises extremely little single-layer carbon nano-tube of diameter and diameter, provide a kind of by this method preparation single-layer carbon nano-tube and utilize this method to prepare the method for electronic component.
In order to solve above-mentioned problem, a first aspect of the present invention is a kind of preparation method of single-layer carbon nano-tube, it is characterized in that: use the gas that obtains by the gasify alcohol or the pure aqueous solution as reactant gases, utilize chemical Vapor deposition process, under normal pressure, make the single-layer carbon nano-tube growth.
A second aspect of the present invention is a kind of single-layer carbon nano-tube, it is characterized in that: the gas that this single-layer carbon nano-tube is pure by the use gasification or the pure aqueous solution obtains is as reactant gases, utilize chemical Vapor deposition process, under normal pressure, make single-layer carbon nano-tube growth and prepare.
A third aspect of the present invention is a kind of method of using single-layer carbon nano-tube to prepare electronic component, it is characterized in that: use the gas that obtains by the gasify alcohol or the pure aqueous solution as reactant gases, utilize chemical Vapor deposition process, under normal pressure, make above-mentioned single-layer carbon nano-tube growth.
In the present invention, typically, the gas that obtains by the aqueous solution that will utilize spontaneous evaporation to wait to gasify alcohol or alcohol in the outside of the reactive site of chemical vapor deposition unit imports this reactive site and reacts.Determining alcohol (volumetric concentration) scope is greater than 0% and less than 100% in the aqueous solution of alcohol, so long as in this scope, determining alcohol substantially without limits, if and determining alcohol is more than 75% or 75%, and more near 100%, just can prepare the more single-layer carbon nano-tube of minor diameter more, if determining alcohol is 50%～95%, be preferably 50%～80%, the narrow single-layer carbon nano-tube of distribution range that just can prepare diameter, especially when determining alcohol is 70%～80%, can prepare the extremely narrow single-layer carbon nano-tube of distribution range of diameter.
The growth temperature of single-layer carbon nano-tube is generally 500 ℃～1500 ℃, is preferably 650 ℃～900 ℃, and more preferably 800 ℃～900 ℃, but be not limited thereto.The growth of single-layer carbon nano-tube typically, is under this growth temperature, contacts with metal catalyst by the gas that the gasification alcohol or the pure aqueous solution are obtained and carries out.As metal catalyst, can use the known various catalyzer in the growth that all the time is used to carbon nanotube.
As alcohol, can use any alcohol basically, can be monohydroxy-alcohol, also can be polyvalent alcohol, can be saturated alcohol, also can be unsaturated alcohol.Generally speaking, the monohydroxy-alcohol that carbonatoms is few is liquid at normal temperatures, at random mix with water, thereby can also easily prepare the high aqueous solution of determining alcohol, and be preferred therefore.As alcohol, can enumerate methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol (Virahol), 1-butanols, 2-butanols (sec-butyl alcohol), 2-methyl isophthalic acid-propyl alcohol (isopropylcarbinol), 2-methyl-2-propyl alcohol (trimethyl carbinol) etc. particularly, but be not limited thereto.
By the determining alcohol in the adjusting alcohol solution and/or the gasification rate of alcohol solution, can control the diameter and/or the diameter Distribution of single-layer carbon nano-tube.The gasification rate of alcohol solution for example can be regulated by the temperature that change is added with the container of alcohol solution.
Preferably after forming single-layer carbon nano-tube by chemical Vapor deposition process, the composition that carries out product is refining.Owing in product, except single-layer carbon nano-tube, also comprise decolorizing carbon or metallic impurity etc. usually, therefore carry out for removing them that this is refining.Described making with extra care preferably undertaken by the acid treatment that utilizes hydrochloric acid, the backflow that utilizes nitric acid and atmospheric oxidation.
This single-layer carbon nano-tube is so long as use the element of its exclusive electricity, machinery, electrooptics or electromechanical characteristic, just applicable to any element.For example, as the electronic component that utilizes this single-layer carbon nano-tube, can enumerate field emission element, field-effect transistor (FET) (also comprising thin film transistor (TFT)), single-electronic transistor, molecule sensor, solar cell, the components of photo-electric conversion, luminous element, storer etc. particularly.
In the present invention who as above constitutes, by utilizing chemical Vapor deposition process under normal pressure, to make the single-layer carbon nano-tube growth, it under reduced pressure makes the situation of single-layer carbon nano-tube growth compare with utilizing chemical Vapor deposition process, the control growing parameter makes the growth of the high-quality single-layer carbon nano-tube with controlled structure become easy easily.In addition, by using gas that the gasification alcohol or the pure aqueous solution obtains as reactant gases, make the possibility that is grown to serve as of the extremely narrow single-layer carbon nano-tube of the distribution range that comprises extremely little single-layer carbon nano-tube of diameter and diameter.
By the present invention, can easily prepare high-quality single-layer carbon nano-tube, and can easily prepare the extremely narrow single-layer carbon nano-tube of distribution range that comprises extremely little single-layer carbon nano-tube of diameter and diameter with controlled structure.And, by using single-layer carbon nano-tube obtained by this method, can access the high performance electronic element.
Description of drawings
Fig. 1 is the sectional view of the structure of the CVD device that uses in one embodiment of the present of invention of expression.
Fig. 2 is the sketch of the Raman spectrum of the sample after the alcohol concn of use 100% in expression one embodiment of the present of invention has just prepared.
To be expression carry out the sketch of the Raman spectrum after nitric acid refluxes to the sample after using 100% alcohol concn just to prepare in one embodiment of the present of invention to Fig. 3.
To be expression carry out the sketch of the Raman spectrum after the polishing to the sample after using 100% alcohol concn just to prepare in one embodiment of the present of invention to Fig. 4.
Fig. 5 a～Fig. 5 d is sample, the HNO after sample, the HCl after the alcohol concn of use 100% in expression one embodiment of the present of invention has just prepared handles
3The picture of the sample after the backflow and the SEM image of the sample after the polishing substitutes photo.
Fig. 6 picture that to be expression proceed to the TEM image of the sample till the polishing to the sample after using 100% alcohol concn just to prepare in one embodiment of the present of invention substitutes photo.
Fig. 7 is the sketch of the thermogravimetric analysis measurement result of the sample after the alcohol concn of use 100% in expression one embodiment of the present of invention has just prepared.
To be expression proceed to the sketch of the thermogravimetric analysis measurement result of the sample till HCl handles to the sample after using 100% alcohol concn just to prepare in one embodiment of the present of invention to Fig. 8.
To be expression to the sample after using 100% alcohol concn just to prepare in one embodiment of the present of invention proceed to Fig. 9 utilizes HNO
3Backflow till the sketch of thermogravimetric analysis measurement result of sample.
To be expression proceed to the sketch of the thermogravimetric analysis measurement result of the sample till the polishing to the sample after using 100% alcohol concn just to prepare in one embodiment of the present of invention to Figure 10.
Figure 11 is the sketch of measurement result that changes the diameter Distribution of the single-layer carbon nano-tube that alcohol concn grows in expression one embodiment of the present of invention.
Embodiment
Below, with reference to accompanying drawing an embodiment of the invention are described.
In this embodiment, on substrate, form metal catalyst, use the gas that makes by the gasification alcohol (carbon source) or the pure aqueous solution, utilize the CVD method, synthetic single-layer carbon nano-tube under normal pressure as reactant gases.At this moment, obtain gas, this gas is imported this reactive site and react at the outside of the reactive site (stretching into the part of the reaction tubes in the stove) of CVD device gasification alcohol or the pure aqueous solution.Then, form refining to such synthetic single-layer carbon nano-tube.
The substrate of growth single-layer carbon nano-tube is the substrate that is formed by inorganic materials and/or organic materials, and its material can be selected as required.As the substrate that is formed by inorganic materials, for example can using, silicon substrate (comprises and forms SiO from the teeth outwards
2The substrate of film), glass substrate, quartz base plate etc.As the substrate that forms by organic materials, can use for example polymeric substrates.As the substrate that forms by inorganic materials and organic materials, the substrate that can use these materials of combination to form.
As the metal catalyst that is formed on the substrate, can use the metal of for example Fe, Co, Ni, Mo, Pt, Pd, Rh, Ir etc. or make up two or more material in these metals, for example Fe-Co, Ni-Co, Fe-Mo, Co-Mo etc. still are not limited to these materials.Typically, this metal catalyst loads on the carrier of regulation.As this carrier, can use for example MgO, silicon-dioxide, aluminum oxide, zeolite, zirconium white, titanium dioxide etc., but be not limited to these materials.
Growth temperature is 500 ℃～1500 ℃, is preferably 650 ℃～900 ℃, more preferably 800 ℃～900 ℃.
Determining alcohol in the aqueous solution of alcohol is greater than 0% and less than 100%, but is preferably 50%～95%, more preferably 50%～80%, more preferably 70%～80%.As alcohol, can use for example methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 2-methyl-2-propyl alcohol etc.
According to this embodiment, use the gas that obtains by the gasify alcohol or the pure aqueous solution as reactant gases, utilize the CVD method, under normal pressure, make the single-layer carbon nano-tube growth, therefore can easily prepare high-quality single-layer carbon nano-tube with controlled structure.And can easily prepare and comprise diameter for example is that the extremely little single-layer carbon nano-tube of the diameter of 0.6～1.8nm and the distribution range of diameter for example are the extremely narrow single-layer carbon nano-tube of amplitude of 0.6～0.7nm.
Embodiment
(1) Preparation of catalysts
As catalyzer, chemical impregnation (chemical impregnation) legal system by in the past is equipped with Fe-Co.Particularly, at first, by with iron nitrate (Fe (NO
3)
39H
2O) and Xiao Suangu (Co (NO
3)
39H
2O) be dissolved in the ethanol (typically being 40ml) preparation nitric acid metallic solution.Then, will be added in this solution as carrier by the magnesium oxide (MgO) that decomposition carbonic acid magnesium salts obtains.Then, become evenly, it is carried out 3 hours ultrasonication in order to make the mixture that makes like this.Use rotary evaporator, from this mixture, remove ethanol, under 115 ℃, make dry 12 hours of the material of gained then.Afterwards, this material is made powder.Catalyzer total amount in the MgO carrier is fixed as 10 weight %, and the mol ratio of transition metal is Fe/Co=1: 2.
(2) atmospheric pressure cvd
Fig. 1 represents the CVD device that present inventors design for preparation single-layer carbon nano-tube under normal pressure.As shown in Figure 1, will put into stove 12 as the silica tube 11 of reaction tubes.Make the two ends of silica tube 11 reach the outside of stove 12.The temperature of stove 12 is measured by thermopair 13, and controls by temperature-control device 14.In the inside of an end of the silica tube 11 of the outside that is positioned at stove 12, place the container 16 that is added with ethanol or aqueous ethanolic solution 15.The concentration of ethanol or aqueous ethanolic solution 15 is 100%～50%.Load the catalyzer 18 of about 1g on quartz boat 17 as the catalyst metal particulate, this catalyzer is made of the MgO of load Fe/Co particulate, and in the silica tube 11 with the centre of quartz boat 17 insertion stoves 12.Then, lateral dominance Ar/H
2Mixed airflow (Ar:250ml/min, H
2: 20ml/min) carry the alcohol gas that forms by ethanol in the container 16 or aqueous ethanolic solution 15 gasifications or the gas of ethanol and water, the limit under normal pressure, with 850 ℃, typically with 30 minutes reaction times, utilize the CVD legal system to be equipped with single-layer carbon nano-tube.The gasification rate of ethanol or aqueous ethanolic solution 15 is controlled by the following method: in advance at the bottom surface of container 16 fixed iron piece 19, move along silica tube 11 by the magnetite 20 that makes the outside that is arranged on silica tube 11 container 16 is moved, thereby change and stove 12 between distance, utilize the radiant heat of heated silica tube 11 to control the temperature variation of ethanol or aqueous ethanolic solution 15.
(3) refining
To the sample after just being equipped with, use and form refining step with the atmospheric pressure cvd legal system.At first, remove catalyzer (MgO carrier and metal particle both) by the acid treatment that utilizes concentrated hydrochloric acid (HCl).Typically, 30 minutes ultrasonication is carried out on the sample limit after just preparing, the limit is positioned over it in 6N concentrated hydrochloric acid of 50ml.Then, in order to remove decolorizing carbon, kish particulate and MgO carrier, will carry out the sample of HCl processing at 4N nitric acid (HNO
3) refluxed 12 hours down in 120 ℃ in the solution.The gained sample is filtered and utilizes distilled water to wash, up to the color bleach of filtrate.In the final stage of refining step, with sample in air in 470 ℃ down after the heating 30 minutes, handle with the 6N concentrated hydrochloric acid again, remove residual impurity.The rinsing sample after making it drying under 120 ℃, finally obtains canescent thin pad in the black.
(5) characterize
Use scanning electron microscope (SEM, Hitachi prepares prepared S-4300,15kV), high resolution transmission electron microscope (CM200, the 200kV of the preparation of HRTEM, Phillips company) and raman spectroscopy instrument (632.8nm, Renishaw1000), carry out the sign of sample.The content of metal catalyst particulate and MgO carrier (metallic impurity) is to use thermogravimetric analysis device (TGA, the 951TGA of Dupont Instrument company preparation) to measure.In dry air, after removing the moisture of sample under 105 ℃, the limit is with the logical dry air of the speed of 100ml/min, and the limit is heated to 1000 ℃ with the speed of 5 ℃/min.So-called residual weight is meant the content of the metallic impurity in the sample.
(6) result and discussion
The Raman spectrum of the sample after Fig. 2 represents to use 100% alcohol concn just to prepare, Fig. 3 represents to utilize the Raman spectrum after nitric acid refluxes to this sample, and Fig. 4 represents the Raman spectrum of the sample after the polishing.From Fig. 2, at 130～350cm
-1Low frequency region can observe clearly one of the feature Raman scattering pattern of single-layer carbon nano-tube radially breathing pattern (radial-breathing mode, RBM).The frequency of RBM pattern and the diameter of single-layer carbon nano-tube are inversely proportional to, its relation can be expressed as ω=223.75/d+6.5 (for example, with reference to Lyu, S.C.; Liu, B.C.; Lee, T.J.; Liu, Z.Y.; Yang, C.W.; Park, C.Y.; Lee, C.J., Chem.Commun.2003,734).Wherein, ω is that unit is cm
-1The RBM frequency, d is that unit is the diameter of the single-layer carbon nano-tube of nm, and the boundling effect is taken in.130～350cm
-1The RBM frequency corresponding to the diameter of 0.6～1.8nm.At 1586cm
-1The 1552cm that occurs of the left side of main peak (G band)
-1Acromion be derived from the E of graphite
2gThe division of pattern.And this acromion also is one of feature Raman scattering pattern of single-layer carbon nano-tube (for example, with reference to A.Kasuya, Y.Sasaki, Y.Saito, K.Tohji, Y.Nishina, Phys.Rev.Lett.1997,78,4434).Except these characteristic peaks, at 1320cm
-1Appearance is by the pattern of defect inducing, so-called D band, and this shows and contains the such carbon that has defective of decolorizing carbon in the sample.The G band is 2.8 to the strength ratio (G/D ratio) of D band.G/D is than being the yardstick of weighing the purity formedness of single-layer carbon nano-tube, this ratio with the increase of single-layer carbon nano-tube purity increase (for example, with reference to H.Kataura, Y.Kumazawa, Y.Maniwa, Y.Ohtsuka, R.Sen, S.Suzuki, Y.Achiba, Carbon 2000,38, and 1691).
(observe fibrous product in Fig. 5 scanning electron microscope (SEM) image a), this is considered to contain the bundle of the single-layer carbon nano-tube of the such impurity of decolorizing carbon and metal particle to sample after preparation just.The thermogravimetric analysis measurement demonstrates that metals content impurity is 54 weight % in the sample after the firm preparation.
Fig. 5 b, Fig. 5 c, Fig. 5 d represent the SEM image of sample, and Fig. 5 b represents that sample, Fig. 5 c after HCl handles represents HNO
3Sample after the backflow, Fig. 5 d represent final refining sample.As being used for the purified sample, present inventors use the sample with the preparation of 100% alcohol concn.HCl observes the many bundles (Fig. 5 b) that contain a large amount of decolorizing carbon after handling.Handle by HCl, the content of metallic impurity reduces to 18% by 54%.In order to remove decolorizing carbon and kish impurity, the sample after HCl handles is at HNO
3Refluxed 12 hours down at 120 ℃ in the solution.Sample after refluxing mainly constitutes (Fig. 5 c) by the big bundle of diameter, and the content of metallic impurity is reduced to 8%.Sample after refluxing, the result of its raman spectroscopy demonstrates the D band (Fig. 3) with remarkable intensity.Present inventors be sure of that this D band is derived from HNO
3Be produced and be coated on the small pieces of the decolorizing carbon on the single-layer carbon nano-tube bundle during middle the backflow.In order to remove residual impurity fully, to the sample after refluxing, the thermal treatment and the HCl that carry out 470 ℃ in air handle.The SEM pictorial display of polishing sample goes out to exist hardly impurity (Fig. 5 d).
Fig. 6 represents transmission electron microscope (TEM) image of polishing sample, (a) is low enlargement ratio, (b) is high enlargement ratio.This sample is made of the bundle of the single-layer carbon nano-tube that has impurity hardly basically.The Raman spectrum of polishing sample demonstrates the D band (Fig. 4) of insignificant intensity, and the major part that demonstrates decolorizing carbon is removed in final refining step.Composition by present inventors is refining, and G/D is than being increased to more than 100 by 2.8.
For the purity of the single-layer carbon nano-tube of confirming sample, carry out thermogravimetric analysis and measure.It the results are shown among Fig. 7～Figure 10.Fig. 7 represents the measurement result of the sample after the preparation just, and Fig. 8 represents that HCl handles the measurement result of sample afterwards, and Fig. 9 represents HNO
3The measurement result of the sample after refluxing, Figure 10 represents the measurement result of polishing sample.As shown in figure 10, the residual weight of polishing sample is below the 2 weight %.(dw/dT) in the analysis, only obtain one and have peaked peak near 585 ℃, this shows that sample contains a kind of combustible ingredient in changes in weight speed.This peaked temperature is consistent with the temperature of combustion of the single-layer carbon nano-tube that is in the news, and this enlightenment polishing sample is made of the single-layer carbon nano-tube of purity 98%.This enlightenment is by tem observation be confirmed (Fig. 6).
In this embodiment, the formation reaction decision under the diameter of single-layer carbon nano-tube and chirality are existed by catalyzer.Therefore, present inventors have set up such hypothesis: the structure of single-layer carbon nano-tube can be controlled by the ethanol feed speed.In order to verify this hypothesis, prepare single-layer carbon nano-tube with different alcohol concn.Table 1 has been summed up alcohol concn and the gained result who tests.The distribution of diameter is judged by the RBM frequency in the Raman spectrum.In addition, in Figure 11, the present in diagrammatic form result of table 1.
Table 1
| Alcohol concn | The distribution of diameter (nm) |
| Ethanol (100%) ethanol: H 2O=4: 1 (80%) ethanol: H 2O=3: 1 (75%) ethanol: H 2O=2: 1 (67%) ethanol: H 2O＝1∶1(50％) | 0.6-1.8(Δ1.2) 0.7-1.6(Δ0.9) 0.8-1.4(Δ0.6) 0.8-1.5(Δ0.7) 0.7-1.5(Δ0.8) |
As shown in figure 11, alcohol concn influences the diameter Distribution of single-layer carbon nano-tube significantly.In general, if the alcohol concn height, then ethanol vapor concentration is corresponding also raises, and causes the carbon based on the many types of gas-liquid-solid (VLS) process of growth of carbon nanotube to adhere to.With it relatively, if alcohol concn is low, the then also corresponding reduction of ethanol vapor concentration, the kind of carbon type of attachment reduces.This trend can be seen in Figure 11.
The preparation of high-quality single-layer carbon nano-tube depends on the setting of the experiment as the shape of the reactive site of CVD device so greatly.In ethanol CVD in the past, the ethanol liquefaction of evaporating in order to prevent under reduced pressure prepares single-layer carbon nano-tube.Under reduced pressure, and under normal pressure, compare, be difficult to control the such growth parameter(s) of alcohol concn.In CVD device as shown in Figure 1, inside at an end of the silica tube 11 of the outside that is positioned at stove 12 is provided with the container 16 that is added with ethanol or aqueous ethanolic solution 15, therefore, by regulating alcohol concn and gasification rate, can under normal pressure, prepare high-quality single-layer carbon nano-tube with controlled diameter Distribution.
As mentioned above, the CVD device that uses present inventors to design voluntarily can prepare high-quality single-layer carbon nano-tube by ethanol or aqueous ethanolic solution under normal pressure.The quality of single-layer carbon nano-tube and diameter Distribution can be controlled by regulating alcohol concn and gasification rate.By the composition process for purification of combination HCl processing, nitric acid backflow and atmospheric oxidation, can make the single-layer carbon nano-tube of purity 98%.
Below specifically understand an embodiment of the invention and an embodiment, still, the present invention is not limited to the above-described embodiment and examples, can carry out various changes according to technical scheme of the present invention.
For example, the structure of the CVD device of enumerating in the above-described embodiment and examples, numerical value, material, raw material, operation etc. eventually just for example can also be used the structure, numerical value, material, raw material, operation of the CVD device different with these etc. as required.
Being simply described as follows of symbol in the accompanying drawing:
11: quartz ampoule
12: stove
13: thermocouple
14: temperature control equipment
15: ethanol or ethanol water
16: container
17: quartz boat
18: catalyst
19: iron plate
20: magnetite
Claims (12)
1. the preparation method of a single-layer carbon nano-tube is characterized in that, uses the gas that obtains by the gasify alcohol or the pure aqueous solution as reactant gases, utilizes chemical Vapor deposition process, makes the single-layer carbon nano-tube growth under normal pressure.
2. the preparation method of single-layer carbon nano-tube according to claim 1 is characterized in that, the aqueous solution in the outside of the reactive site of chemical vapor deposition unit by gasify above-mentioned alcohol or alcohol obtains gas, and this gas is imported above-mentioned reactive site.
3. the preparation method of single-layer carbon nano-tube according to claim 1 is characterized in that, range of alcohol concentration is greater than 0% and less than 100% in the aqueous solution of above-mentioned alcohol.
4. the preparation method of single-layer carbon nano-tube according to claim 1 is characterized in that, range of alcohol concentration is 50%～95% in the aqueous solution of above-mentioned alcohol.
5. the preparation method of single-layer carbon nano-tube according to claim 1 is characterized in that, range of alcohol concentration is 50%～80% in the aqueous solution of above-mentioned alcohol.
6. the preparation method of single-layer carbon nano-tube according to claim 1 is characterized in that, makes above-mentioned single-layer carbon nano-tube growth under 500 ℃～1500 ℃ growth temperature.
7. the preparation method of single-layer carbon nano-tube according to claim 1 is characterized in that, makes above-mentioned single-layer carbon nano-tube growth under 650 ℃～900 ℃ growth temperature.
8. the preparation method of single-layer carbon nano-tube according to claim 1 is characterized in that, above-mentioned alcohol is monohydroxy-alcohol.
9. the preparation method of single-layer carbon nano-tube according to claim 1, it is characterized in that, the gasification rate of the aqueous solution by determining alcohol in the aqueous solution of regulating above-mentioned alcohol and/or above-mentioned alcohol is controlled the distribution of the diameter and/or the diameter of above-mentioned single-layer carbon nano-tube.
10. the preparation method of single-layer carbon nano-tube according to claim 1 is characterized in that, make the growth of above-mentioned single-layer carbon nano-tube after, make with extra care by the acid treatment that utilizes hydrochloric acid, the backflow that utilizes nitric acid and atmospheric oxidation.
11. a single-layer carbon nano-tube is characterized in that, this single-layer carbon nano-tube is by being prepared as follows: use the gas that obtains by the gasify alcohol or the pure aqueous solution as reactant gases, utilize chemical Vapor deposition process, make the single-layer carbon nano-tube growth under normal pressure.
12. the preparation method of an electronic component, be to use single-layer carbon nano-tube to prepare the method for electronic component, it is characterized in that, use the gas that obtains by the gasify alcohol or the pure aqueous solution as reactant gases, utilize chemical Vapor deposition process, under normal pressure, make above-mentioned single-layer carbon nano-tube growth.
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| CN 200610002907 CN101007631A (en) | 2006-01-27 | 2006-01-27 | Mono-layer carbon nanotube and its preparation method, and electronic element preparation method |
| JP2006320340A JP5277535B2 (en) | 2006-01-27 | 2006-11-28 | Method for producing single-walled carbon nanotube, method for producing single-walled carbon nanotube and electronic device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009135344A1 (en) * | 2008-05-07 | 2009-11-12 | 中南大学 | Method of self-assembly growing carbon nanotubess by chemical-vapor-deposition without the use of metal catalyst |
| CN100581988C (en) * | 2007-09-03 | 2010-01-20 | 中国科学院理化技术研究所 | Device and method for stably preparing one-dimensional nano structure material by heat evaporation |
| CN101817522A (en) * | 2010-06-04 | 2010-09-01 | 温州大学 | Method for preparing carbon nanometer tubes by using soluble metallic salt as catalyst |
| CN102452646A (en) * | 2010-10-26 | 2012-05-16 | 清华大学 | Method for preparing hydrophilic carbon nanotube film |
| CN102020262B (en) * | 2009-09-09 | 2012-12-05 | 中国科学院金属研究所 | Method for growing single-walled carbon nanotubes in high efficiency without metal catalyst |
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| JP5680389B2 (en) * | 2010-12-03 | 2015-03-04 | 花王株式会社 | Method for producing fibrous carbon |
| JP6485866B2 (en) * | 2015-07-21 | 2019-03-20 | 昭和電工株式会社 | Method for manufacturing perpendicular magnetic recording medium and magnetic recording / reproducing apparatus |
| WO2019124026A1 (en) * | 2017-12-19 | 2019-06-27 | 日本ゼオン株式会社 | Fibrous carbon nanostructure, method for assessing fibrous carbon nanostructure, and method for producing surface-modified fibrous carbon nanostructure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4642658B2 (en) * | 2003-02-07 | 2011-03-02 | 茂夫 丸山 | Method for producing single-walled carbon nanotubes with uniform diameter |
| JP2007523822A (en) * | 2004-01-15 | 2007-08-23 | ナノコンプ テクノロジーズ インコーポレイテッド | Systems and methods for the synthesis of elongated length nanostructures |
| FI121334B (en) * | 2004-03-09 | 2010-10-15 | Canatu Oy | Method and apparatus for making carbon nanotubes |
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2006
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100581988C (en) * | 2007-09-03 | 2010-01-20 | 中国科学院理化技术研究所 | Device and method for stably preparing one-dimensional nano structure material by heat evaporation |
| WO2009135344A1 (en) * | 2008-05-07 | 2009-11-12 | 中南大学 | Method of self-assembly growing carbon nanotubess by chemical-vapor-deposition without the use of metal catalyst |
| CN102020262B (en) * | 2009-09-09 | 2012-12-05 | 中国科学院金属研究所 | Method for growing single-walled carbon nanotubes in high efficiency without metal catalyst |
| CN101817522A (en) * | 2010-06-04 | 2010-09-01 | 温州大学 | Method for preparing carbon nanometer tubes by using soluble metallic salt as catalyst |
| CN102452646A (en) * | 2010-10-26 | 2012-05-16 | 清华大学 | Method for preparing hydrophilic carbon nanotube film |
| US9073753B2 (en) | 2010-10-26 | 2015-07-07 | Tsinghua University | Method for making hydrophilic carbon nanotube film |
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| JP5277535B2 (en) | 2013-08-28 |
| JP2007197306A (en) | 2007-08-09 |
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