CN101041427B - Manufacturing method of carbon material, carbon material and manufacturing method of electronic components - Google Patents
Manufacturing method of carbon material, carbon material and manufacturing method of electronic components Download PDFInfo
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- CN101041427B CN101041427B CN2006100655672A CN200610065567A CN101041427B CN 101041427 B CN101041427 B CN 101041427B CN 2006100655672 A CN2006100655672 A CN 2006100655672A CN 200610065567 A CN200610065567 A CN 200610065567A CN 101041427 B CN101041427 B CN 101041427B
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Abstract
The invention discloses a preparing method of carbon material to remove graphitic carbon and metal particle incorporating in carbon material as impurity selectively, which comprises the following steps: keeping in aqueous vapor and/or hydrochloride atmosphere through carbon material of carbon nanometer pipe; proceeding purify; heating to 250-650 deg.c; or exposing ultraviolet light; setting the pressure at 0.1-10 pa; keeping time at for example 10min-10h; making carbon material grow in the react room of CVD device also; proceeding purify of carbon in this react room.
Description
Technical field
The present invention relates to the method for manufacture of method of manufacture, carbon material and the electronic component of carbon material, for example, preferably be applied to use in the preparation of various elements of carbon nanotube.
Background technology
In order to use the useful element of made of carbon nanotubes, the method for manufacture of the carbon nanotube that process residues such as decolorizing carbon, metal particle are few is necessary.As the method for removing decolorizing carbon, metal particle etc., known existing the whole bag of tricks (for example, with reference to patent documentation 1,2 and non-patent literature 1～6).As the method for removing decolorizing carbon, the method that has mixture with carbon nanotube and decolorizing carbon to remain in the acid atmosphere such as heated nitric acid several hours.On the other hand, as the method for removing metal particle, the method for the acid bath that utilizes hydrochloric acid etc. is arranged.
[patent documentation 1]
U.S. Patent application discloses communique No. 20020092984
[patent documentation 2]
U.S. Patent application discloses communique No. 20050234263
[non-patent literature 1]
K.Hernadi?et?al.，“Reactivity?of?different?kinds?ofcarbon?during?oxidative?purification?of?catalyticallyprepared?carbon?nanotubes”Solid?State?Ionics，vol.141-142(2001)，pp.203-209
[non-patent literature 2]
M.Monthioux?et?al.，“Sensitivity?of?single-wall?carbonnanotubes?to?chemical?processing：an?electron?microscopyinvestigation”Carbon，vol.39(2001)，pp.1251-1272
[non-patent literature 3]
J.M.Moon?et?al.，“High-Yield?Purification?Process?ofsingle?walled?Carbon?Nanotubes”J.Phys.Chem.B，vol.105(2001)，pp.5677-5681
[non-patent literature 4]
J.L.Zimmerman?et?al.，“Gas-Phase?Purification?ofSingle-Wall?Carbon?Nanotubes”Chem.Mater.，vol.12(2000)，pp.1361-1366
[non-patent literature 5]
S.R.C.Vivekchand?et?al.，“New?Method?of?Purificationof?Carbon?Nanotubes?Based?on?Hydrogen?Treatment”J.Phys.Chem.B，vol.108(2004)，pp.6935-6937
[non-patent literature 6]
D.Nepal?et?al.，“A?facile?and?rapid?purification?methodfor?single-walled?carbon?nanotubes”Carbon，vol.43(2005)，pp.660-662
Summary of the invention
Yet, remain in the method in the heated acid atmosphere at mixture carbon nanotube and decolorizing carbon, not only be difficult to optionally remove decolorizing carbon, but also can make carbon nanotube produce damage.In addition, remove in the method for metal particle, not only be difficult to optionally remove metal particle, and owing to usually also and use ultrasonication, damage and carbon nanotube is produced in the acid bath of using hydrochloric acid etc.Therefore, behind carbon nano tube growth, can remove the material that decolorizing carbon, metal particle etc. are not expected, and the method that carbon nanotube is sustained damage is necessary, is not suggested but in fact up to the present still there is effective means.
Therefore; The problem that the present invention will solve provides and can not bring this carbon material damage ground and optionally remove decolorizing carbon in the carbon materials such as being comprised in carbon nanotube as impurity, metal particle etc.; And the method for manufacture of the carbon material of purifying is utilized the carbon material of this method preparation and the method for manufacture of using the electronic component of this method.
In order to solve above-mentioned problem, first aspect of the present invention is a kind of method of manufacture of carbon material, it is characterized in that, through carbon material is remained in the atmosphere that comprises water vapour and/or hydrogenchloride, and purifies.
Second aspect of the present invention is a kind of carbon material, it is characterized in that, this carbon material is through remaining in the atmosphere that comprises water vapour and/or hydrogenchloride, carries out the purification of carbon material and prepares.
The 3rd aspect of the present invention is a kind of method of manufacture of electronic component, it is characterized in that, in the method for manufacture of the electronic component that uses carbon material, purifies through above-mentioned carbon material is remained in the atmosphere that comprises water vapour and/or hydrogenchloride.
In first～third aspect of the present invention; Carbon material comprises that all have the carbon atom carbon material of structure arranged regularly basically; In other words, comprise all carbon materials beyond the decolorizing carbon, particularly; For example, carbon nanotube (single-layer carbon nano-tube and multilayer carbon nanotube), carbon nanofiber, soccerballene, graphite etc.This carbon material is through grow (synthesizing) such as arc discharge method, laser ablation method, plasma body synthesis method, chemical vapor deposition (CVD) method, hydrocarbon oxidation catalyst decomposition methods, but is not limited thereto.This carbon material comprises that typically when growth is as process residues and residual decolorizing carbon and/or the metal particle that becomes impurity.Metal particle typically is to be used for the formed metal particle of catalytic metal when being grown by carbon material, but is not limited thereto.
The temperature and pressure and the time of the atmosphere when remaining on carbon material in the atmosphere that comprises water vapour and/or hydrogenchloride are corresponding to the employed method of growth of the kind of carbon material, carbon material, be included in the amount of decolorizing carbon and/or metal particle in the carbon material and have form etc. and suitable selection.Particularly; From giving energy and seek to improve the viewpoint of the speed of removing of decolorizing carbon and/or metal particle to water vapour and/or hydrogenchloride; The atmosphere that comprises water vapour and/or hydrogenchloride for example is heated to 250 ℃～650 ℃ temperature, but is not limited thereto.Because the specific inductivity of water vapour reduces with the rising of temperature, therefore can utilize water vapour to remove decolorizing carbon more selectively here, as apolar substance.This pressure that comprises the atmosphere of water vapour and/or hydrogenchloride for example is 0.1 normal atmosphere～10 normal atmosphere, but is not limited thereto.In addition, the time that remains in this atmosphere that comprises water vapour and/or hydrogenchloride for example is 10 minutes～10 hours, but is not limited thereto.The atmosphere that also can replace heat packs containing water vapor and/or hydrogenchloride, perhaps with heating simultaneously, through the irradiation hertzian wave, for example high frequency waves, microwave, infrared rays, visible light, ultraviolet ray wait and make it to excite particularly.
In carbon material, comprise under the situation of decolorizing carbon, when this carbon material contacted with water vapour, the oxidation of this decolorizing carbon just was removed by promotion.In addition, in carbon material, comprise under the situation of metal particle, when this carbon material contacted with hydrogenchloride, this metal particle was removed with regard to being decomposed.In addition, generate in decomposition under the situation of degradation production of hydrogen etc. through water vapour and/or hydrogenchloride, the also reaction through this degradation production and carbon material, and decolorizing carbon and/or metal particle are decomposed and are removed.Can contain air or oxygen through making in the atmosphere that comprises water vapour and/or hydrogenchloride, obtain the oxidized and effect that is removed of decolorizing carbon by the effect of oxygen simultaneously.Perhaps, can contain hydrogen (neutrality or state of charge) in the atmosphere that comprise water vapour and/or hydrogenchloride, obtain decolorizing carbon simultaneously by the effect of hydrogen, metal particle is hydrogenated and the effect that is removed through making.
Preferably, through being remained in the atmosphere that comprises water vapour and hydrogenchloride, carbon material purifies.In this case, can the decolorizing carbon and the metal particle that be included in the carbon material be removed through primary treatment, be extremely efficient.When carbon material is grown, use under the situation of metal catalyst; Because metal particle exists with the state that is covered by decolorizing carbon mostly; Therefore when carbon material being remained in the atmosphere that comprises water vapour and hydrogenchloride; Can think under the effect of water vapour it at first is that decolorizing carbon is removed, the metal particle that then exposes is removed under the effect of hydrogenchloride.Earlier carbon material is remained in the atmosphere that only comprises water vapour, then remain in the atmosphere that only comprises hydrogenchloride, decolorizing carbon and the metal particle that also can remove in the carbon material to be comprised.
In one embodiment, in the reaction chamber of chemical vapor deposition unit, make carbon material pass through chemical Vapor deposition process growth after, purify through in this reaction chamber, this carbon material being remained in the atmosphere that comprises water vapour and/or hydrogenchloride.Through doing like this, can in the reaction chamber of chemical vapor deposition unit, carry out the growth and the purification of carbon material continuously, therefore be not only efficiently, and, therefore can prevent to pollute because carbon material on the way is not exposed in the atmosphere just finishes.
At carbon material is under the situation of single-layer carbon nano-tube; One preferred embodiment in; Gas through the gasification of alcohol or alcohol solution will be obtained is used for reaction gas; After utilizing chemical Vapor deposition process under normal pressure, to make single-layer carbon nano-tube growth, this single-layer carbon nano-tube remained in the atmosphere that comprises water vapour and/or hydrogenchloride purify.Most preferably; In the reaction chamber of chemical vapor deposition unit; Gas through the gasification of alcohol or alcohol solution will be obtained is used for reaction gas; After utilizing chemical Vapor deposition process under normal pressure, to make the single-layer carbon nano-tube growth, in this reaction chamber,, this single-layer carbon nano-tube purifies through being remained in the atmosphere that comprises water vapour and/or hydrogenchloride.Utilizing chemical Vapor deposition process to make under the normal pressure under the situation that single-layer carbon nano-tube grows up, be typically and the gas that utilizes spontaneous evaporation gasification alcohol or alcohol solution to obtain through the outside at the reactive site of the reaction chamber of chemical vapor deposition unit is imported this reactive site react.Through utilizing chemical Vapor deposition process under normal pressure, to make the single-layer carbon nano-tube growth in this wise; It under reduced pressure makes the situation of single-layer carbon nano-tube growth compare with utilizing chemical Vapor deposition process; Easy control growing parameter, the high-quality single-layer carbon nano-tube of growing and having controlled structure easily.In addition, be used for reaction gas, the extremely narrow single-layer carbon nano-tube of distribution range that can grow and comprise extremely little single-layer carbon nano-tube of diameter and diameter through the gas that utilizes gasification alcohol or alcohol solution to obtain.
Determining alcohol in the alcohol solution (volumetric concentration) is greater than 0% less than 100%, so long as in this scope, determining alcohol does not have restriction basically; And if determining alcohol is more than 75% or 75%; And, just can prepare the more single-layer carbon nano-tube of small dia more, if determining alcohol is 50%～95% more near 100%; 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 through the gas that gasification alcohol or alcohol 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.
Through the determining alcohol in the adjusting alcohol solution and/or the gasification rate of alcohol solution, can control the distribution of the diameter and/or the diameter of single-layer carbon nano-tube.The gasification rate of alcohol solution for example can be regulated through the temperature that changes the container that adds alcohol solution.
This single-layer carbon nano-tube can be used in the various elements.This element can be any element basically, for example, and the element of electricity, machinery, electrooptics or the electromechanical characteristic of application carbon material etc.As utilizing carbon nanotube in the carbon material, the electronic component of single-layer carbon nano-tube separately, 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.
As among the present invention of above-mentioned formation, even carbon material is exposed in the atmosphere that comprises water vapour and/or hydrogenchloride, almost or fully can not have influence on carbon material yet, therefore in fact can produce damage to the regularly arranged atomic structure of carbon of this carbon material.In addition, utilize the effect of water vapour and/or hydrogenchloride or its degradation production, can be optionally and remove decolorizing carbon and/or the metal particle that is included in the carbon material efficiently.
Utilize the present invention can easily prepare highly purified carbon material.And,, can obtain the high performance electronic element through using highly purified carbon material by this method preparation.
Description of drawings
Fig. 1 is the sectional view of the structure of the purifying plant of use in the expression embodiment of the invention 1.
Fig. 2 is the sketch that has situation that the picture of the TEM image of sample before the purification of expression in the embodiment of the invention 1 substitutes decolorizing carbon and metal particle in photo and the expression sample.
Fig. 3 is that the picture of the TEM image of the sample after the purification in the expression embodiment of the invention 1 substitutes photo.
Fig. 4 is the sketch of the Raman spectrum of the sample after the purification in the expression embodiment of the invention 1.
Fig. 5 is that the picture of the TEM image of the sample after sample, the sample after the purification and the utilization method of purification in the past before the purification in the expression embodiment of the invention 1 purified substitutes photo.
Fig. 6 is the sketch of the X-ray diffraction pattern of the sample after sample, the sample after the purification and the utilization method of purification in the past before the purification in the expression embodiment of the invention 1 purified.
Fig. 7 is the sketch of the XPS spectrum of the sample after sample, the sample after the purification and the utilization method of purification in the past before the purification in the expression embodiment of the invention 1 purified.
Fig. 8 is near the enlarged view the peak of carbon 1s track of the XPS spectrum that in Fig. 7, shows.
Fig. 9 is near the enlarged view the peak of oxygen 1s track of the XPS spectrum that in Fig. 7, shows.
Figure 10 is the sketch of leakage current-drain voltage curve of the expression single-layer carbon nano-tube FET that uses the specimen preparation after the purification in the embodiment of the invention 1.
Figure 11 is the sectional view of the structure of the purifying plant of use in the expression embodiment of the invention 2.
Figure 12 is the sectional view of the structure of the CVD device of use in the expression embodiment of the invention 3.
Figure 13 is the sketch of the Raman spectrum of the sample after the alcohol concn of use 100% in the expression embodiment of the invention 3 has just prepared.
Figure 14 is mensuration result's the sketch that changes the diameter Distribution of the single-layer carbon nano-tube that alcohol concn grows in the expression embodiment of the invention 3.
Embodiment
Below, with reference to accompanying drawing an embodiment of the invention are described.
The 1st embodiment of the present invention at first is described.
In the 1st embodiment, the carbon material that the known method in the past of utilizing arc discharge method, laser ablation method, plasma body synthesis method, decompression CVD method etc. is grown is purified.When this carbon material is included in the growth of this carbon material as the process residue and residual decolorizing carbon and/or the metal particle that becomes impurity.
At first, the carbon material that utilizes known method growth is in the past put into from the isolated container of space outerpace.Then, in this container, this carbon material is remained in the atmosphere that comprises water vapour and/or hydrogenchloride.Usually produce water vapour and/or hydrogenchloride through outside and it is imported in container, thereby make the atmosphere that comprises water vapour and/or hydrogenchloride at container.This atmosphere that comprises water vapour and/or hydrogenchloride for example is heated to 250 ℃～650 ℃, preferred 350 ℃～400 ℃ temperature, and pressure is for example 0.1 normal atmosphere～10 normal atmosphere.In addition, comprise at this that to keep the time of carbon material in atmosphere of water vapour and/or hydrogenchloride be 10 minutes～10 hours, be typically 1～5 hour.
In this wise; According to the 1st embodiment; Through carbon material being remained in the atmosphere that comprises water vapour and/or hydrogenchloride; In carbon material, comprise under the situation of decolorizing carbon, through the effect that water vapour or water vapour decompose the degradation productions such as hydrogen that generate, the oxidation of this decolorizing carbon is decomposed by promotion and removes; In carbon material, comprise under the situation of metal particle, through the effect that hydrogenchloride or hydrogenchloride decompose the degradation productions such as hydrogen that generate, this metal particle is decomposed and removes.Like this, be included in impurity such as decolorizing carbon in the carbon material, metal particle and be removed, and purify.In this case, can be in water vapour and/or the hydrogenchloride even carbon material is exposed to carbon atom structure arranged generation regularly damage yet.In addition, owing to when purifying, do not need ultrasonication, the therefore also damage problem of the carbon material that causes of this ultrasonication not.
< embodiment 1 >
Purify through the sample of arc discharge method carbon nanotubes grown to using the Ni catalyzer.
Fig. 1 representes the employed purifying plant of the purification of sample.As shown in Figure 1, the horizontal type container 1 of quartz system is put into stove 2.Make the two ends of container 1 reach the outside of stove.The temperature of stove 2 is measured through thermopair (not shown), and controls through temperature-control device 3.The temperature of stove 2 can be carried out time variable control through temperature-control device 3.On an end of the container 1 of the outside that is positioned at stove 2, connect bubblers 5 through pipe arrangement 6, in the bubbler 5 as the raw material adding hydrochloric acid 4 of water vapour and hydrogenchloride.Carrier gas through the hydrochloric acid 4 of pipe arrangement 7 in bubbler 5 is supplied air, oxygen etc. can produce water vapour and hydrogenchloride through bubbling.The other end from the gas that water vapour, hydrogenchloride, air or oxygen and these gas and specimen reactions generated of an end supply of stove 2 from container 1 is discharged into the outside.
On the boat 8 of pottery system, place the sample 9 utilize the arc discharge method carbon nanotubes grown, place it among the container 1 in centre of stove 2.Then, at room temperature, will pass through the flow inflow container 1 of pipe arrangement 6 through water vapour, hydrogenchloride and the Air mixing gas that bubbling produces with 1 liter/min through the hydrochloric acid 4 supply air of pipe arrangement 7 in bubbler 5.Container 1 carries out time variable control by temperature-control device 3, is heated to 350 ℃ with the heat-up rate of 10 ℃/min from room temperature, and under this temperature, keeps 3 hours.After 350 ℃ keep 3 hours down, stop the heating of stove 2, utilize natural convection cooling vessel 1.Carry out the purification of sample 9 like this.
Afterwards, the sample 9 that will purify, under the different condition of change time and temperature, the limit applies UW, and hydrochloric acid soln (23wt%) is put on the limit disperses carbon nanotube, cleans.Suspension-s (suspension) spinning that will be obtained by The above results (with 14000rpm, 10 minutes) is removed to the outside with the acid of supernatant (top clarification part).Throw out (carbon nanotube) is suspended with deionized water once more, carry out three spinnings, vacuum-drying.
Transmission electron microscope (transmission electron microscopy, the TEM) image of the sample before the A of Fig. 2 representes to purify.Can know from the A of Fig. 2, before the purification, promptly in utilizing the sample of arc discharge method after just having grown, except that carbon nanotube, comprise decolorizing carbon and metal particle as impurity.The B of Fig. 2 representes that schematically carbon nanotube 11 mixes situation about existing with decolorizing carbon that comprises as impurity 12 and metal particle 13 in this sample.The situation that covers the formation of metal particle 13 ground with decolorizing carbon 12 is more.Usually these decolorizing carbon 12 separate from the opposing party with the side in the metal particle 13 is very difficult.
The A of Fig. 3 and B are the TEM images of the sample after purifying, and the A of Fig. 3 is a low range, and the B of Fig. 3 is powerful.A and B by Fig. 3 can know, almost do not observe decolorizing carbon and metal particle in the sample after the purification, and decolorizing carbon and metal particle almost completely are removed.Fig. 4 is the Raman spectrum of this sample.Can know by Fig. 4; Radially breathing pattern (the radial-breathing mode that the characteristic of single-layer carbon nano-tube only occurs; RBM), and show that the intensity of the D band that contains the such carbon that has defective of decolorizing carbon in the sample is extremely little, can know to comprise decolorizing carbon in this sample hardly.Thus can be clear and definite, the sample after this purification in fact only is made up of single-layer carbon nano-tube.The mean diameter of this single-layer carbon nano-tube is 1.55nm, this mean diameter of numeric representation of " 1.55nm " among Fig. 3 B.
The A of Fig. 5 is the TEM image of the sample (below be called " sample 1 ") before purifying; The B of Fig. 5 is the TEM image of the sample (below be called " sample 2 ") after purifying, and the C of Fig. 5 is the TEM image of the sample (below be called " sample 3 ") after purifying through the method for purification in the past of using acid atmosphere.Process sample 3 except that method of purification is identical with sample 2.Can know that from A and the B of Fig. 5 the sample 2 after the purification is compared with the preceding sample 1 of purifying, and does not almost observe decolorizing carbon and metal particle.With respect to this, shown in the C of Fig. 5, can know in the sample 3 after utilizing in the past method of purification to purify a large amount of remaining decolorizing carbon and metal particles.
The A of Fig. 6, B and C are X-ray diffraction (XRD) patterns of each sample 1,2,3.Can know that from A and the B of Fig. 6 the sample 2 after the purification is compared with the preceding sample 1 of purifying, near the carbon nanotube inherent diffraction peak the 20=26 degree occurs with high-intensity spike, can know through purification and remove most decolorizing carbon.In addition, the sample 2 after the purification is compared with the preceding sample 1 of purifying, and near the intensity of the metal particle diffraction peak that for example 2 θ=45 degree, occurs significantly reduces, and can know through purification processes and remove most metal particle.With respect to this, shown in the C of Fig. 6, in the sample 3 after the method for purification purification that utilizes in the past, the diffraction peak of metal particle occurs with HS, can know that removing of metal particle is also insufficient.
The A of Fig. 7, B and C are x-ray photoelectron power spectrum (the X-ray photoelectron spectroscopy of each sample 1,2,3; XPS); The A of Fig. 8, B and C are near the enlarged views in peak that is derived from the 1s track of carbon (C), and the A of Fig. 9, B and C are near the enlarged views in peak that is derived from the 1s track of oxygen (O).Can know that from this xps energy spectrum the intensity at the peak of the 1s track that is derived from carbon (C) of the sample 2 after the purification is compared with the preceding sample 1 of purifying does not have big variation.This means that the wall of single-layer carbon nano-tube does not sustain damage in the purification processes.In addition, the intensity at the peak of the 1s track that is derived from oxygen (O) of the sample after the purification 2 is compared with the preceding sample 1 of purifying does not have big variation yet.This means on the surface of single-layer carbon nano-tube, to have oxygen-containing functional group hardly, can think that oxygen is adsorbed on the surface of single-layer carbon nano-tube.
Represent to utilize XPS to measure the content of the composition element of the sample 1,2,3 of trying to achieve with wt% in the table 1.Can know that through table 1 sample 2 after the purification is compared with the preceding sample 1 of purifying, the content of carbon reduces about 1.4 percentage points, and the content of nickel reduces about 0.23 percentage point, and decolorizing carbon and metal particle all have minimizing.In the sample 3 after purifying through method of purification in the past, the content of carbon is more less slightly than sample 2, and the content of Ni and O is than sample more than 2.
Table 1
| ? | C(wt％) | O(wt％) | Ni(wt％) |
| Sample 1 | 94.244 | 5.252 | 0.503 |
| |
92.821 | 6.901 | 0.277 |
| |
92.163 | 7.529 | 0.308 |
Figure 10 is in order to estimate leakage current-drain voltage curve of the single-layer carbon nano-tube FET that the degree from sample, remove decolorizing carbon and metal particle through purifying makes.This single-layer carbon nano-tube FET makes according to following method.At first, the SiO that on electroconductibility Si substrate, forms
2Mutual subtend ground makes the Au/Ti microelectrode as source electrode and drain electrode use on the surface of film; Then; Between this Au/Ti microelectrode, drip single-layer carbon nano-tube is distributed to the solution that forms in the ethanol, the single-layer carbon nano-tube that afterwards this Au/Ti microelectrode is obtained with dripping is connected with Pt.Through reverse grid (electroconductibility Si substrate) by the single-layer carbon nano-tube FET that processes like this, gate voltage is changed into-1V, 0V, 1V, 2V and add, measure leakage current-drain voltage characteristic.Mensuration is depressed at atmosphere at room temperature and is carried out.Can know from Figure 10, can regulate leakage current through gate voltage, the purity of this expression carbon nanotube sample is high.
< embodiment 2 >
In embodiment 2, the purifying plant that the purification of sample uses Figure 11 to represent.Shown in figure 11, in this purifying plant, use the longitudinal type container 1 of quartzy system, put it in the stove 2 of longitudinal type.Other structure of this purifying plant is identical with the purifying plant of use among the embodiment 1.In this case,, place the boat 8 of pottery system, be loaded with sample 9 on this boat 8 in the lower end of the container 1 of the outside that is positioned at stove 2.
Use this purifying plant, with embodiment 1 likewise, the sample that uses the Ni catalyzer to grow up through arc discharge method is purified, obtain the result identical with embodiment 1.
Then, the 2nd embodiment of the present invention is described.
In the 2nd embodiment; On substrate, form metal catalyst; Gas through obtaining as the alcohol or the alcohol solution gasification of carbon source is used for reaction gas and utilizes the CVD method after making the single-layer carbon nano-tube growth under the normal pressure, remains in the atmosphere that comprises water vapour and/or hydrogenchloride through the sample with this single-layer carbon nano-tube and purifies.Make single-layer carbon nano-tube when growth, reacting through importing this reactive site at the outside gasification alcohol of the reactive site (putting into the reaction tubes part of stove) of the reaction chamber of CVD device or gas that alcohol solution obtains.
Making the substrate of single-layer carbon nano-tube growth is the substrate that is formed by inorganic materials and/or organic materials, can select its material as required.As the substrate that is formed by inorganic materials, for example can using, the Si substrate (comprises the surface and forms SiO
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; For example can use the metal of Fe, Co, Ni, Mo, Pt, Pd, Rh, Ir etc. or the material that combines more than 2 kinds or 2 kinds in these metals; For example, Fe-Co, Ni-Co, Fe-Mo, Co-Mo etc., but be not limited thereto.These metal catalysts typically load on the carrier.As this carrier, can use for example MgO, silicon-dioxide, aluminum oxide, zeolite, zirconium white, titanium oxide etc., but be not limited to this.
Growth temperature is 500 ℃～1500 ℃, preferred 650 ℃～900 ℃, and more preferably 800 ℃～900 ℃.
Determining alcohol in the alcohol solution is greater than 0% and less than 100%, but is preferably 50%～95%, more preferably 50%～80%, further be 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 the 2nd embodiment, the gas that gasifies alcohol or alcohol solution and obtain is used for reaction gas, 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.And; Remain in the atmosphere that comprises water vapour and/or hydrogenchloride through sample and to purify this single-layer carbon nano-tube; Can not bring single-layer carbon nano-tube damage ground and optionally remove decolorizing carbon and metal particle, can obtain highly purified single-layer carbon nano-tube.
< embodiment 3 >
(1) Preparation of catalysts
As catalyzer, chemical impregnation (chemical impregnation) legal system through in the past is equipped with Fe-Co.Particularly, at first, through 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 through the Natural manganese dioxide (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 the drying of materials 12 hours of gained then.Afterwards, this material is processed powder.Catalyzer total amount in the MgO carrier is fixed as 10wt%, and the mol ratio of transition metal is Fe/Co=1:2.
(2) atmospheric pressure cvd
Figure 12 representes to be used for the CVD device of preparation single-layer carbon nano-tube under normal pressure.Shown in figure 12, 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 through thermopair 13, and controls through 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%.On quartz boat 17, load the catalyzer 18 of about 1g as the catalyst metal particulate, this catalyzer 18 is made up 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 is used 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 through following method: the prior fixed iron piece 19 in the bottom surface of container 16; Move along silica tube 11 through 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 radiogenic heat of heated silica tube 11 to control the temperature variation of ethanol or aqueous ethanolic solution 15.
The Raman spectrum of the sample after Figure 13 representes to use 100% alcohol concn just to prepare is from Figure 13, at 130～350cm
-1Low frequency region can observe the radially breathing pattern (RBM) of one of the characteristic Raman scattering pattern of single-layer carbon nano-tube clearly.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 mm, 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 characteristic 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, and so-called D is with, and this shows the carbon that has defective that contains the decolorizing carbon that kind 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, Carbon2000,38,1691).
In embodiment 3, the formation reaction decision under the diameter of single-layer carbon nano-tube and chirality are existed by catalyzer.Therefore, can think that the structure of single-layer carbon nano-tube can control through the ethanol feed speed.For it is verified, prepare single-layer carbon nano-tube with different alcohol concn.Table 2 has been summed up alcohol concn and the gained result who makes an experiment.The distribution of diameter is inferred through the RBM frequency in the Raman spectrum.In addition, in Figure 14, the present in diagrammatic form result of table 2.
Table 2
Shown in figure 14, alcohol concn influences the diameter Distribution of single-layer carbon nano-tube significantly.In general, if alcohol concn is high, then the 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 14.
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 shown in figure 12; Be added with the container 16 of ethanol or aqueous ethanolic solution 15 in the set inside of an end of the silica tube 11 of the outside that is positioned at stove 12; Therefore; Through regulating alcohol concn and gasification rate, can under normal pressure, prepare high-quality single-layer carbon nano-tube with controlled diameter Distribution.
(3) purify
Sample to after just being equipped with the atmospheric pressure cvd legal system uses and purifies with embodiment 1 identical method.Particularly; In CVD device shown in Figure 12; Utilize the mechanism of elliptical regulation among the figure; Between the inside and container 16 of blocking silica tube 11, and utilization and embodiment 1 same structure supply to silica tube inside with water vapour and hydrogenchloride, the sample after just preparing remained in this atmosphere that comprises water vapour and hydrogenchloride purify.Its result can remove most of decolorizing carbon and the metal particle in this sample with embodiment 1 identical ground.
Below specifically clear embodiment of the present invention and embodiment, but 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 structure of the purifying plant of in the above-described embodiment and examples, enumerating, CVD device, numerical value, material, raw material, operation etc. eventually just for example can also be used and the structure of the structure of these different purifying plants, CVD device, numerical value, material, raw material, operation etc. as required.
The simple declaration of symbol is following in the accompanying drawing:
1: container
2: stove
3: temperature-control device
4: hydrochloric acid
5: bubbler
8: boat
9: sample
11: silica tube
12: stove
13: thermopair
14: temperature-control device
15: ethanol or aqueous ethanolic solution
16: container
17: quartz boat
18: catalyzer
19: iron plate
20: magnetite
Claims (12)
1. the method for manufacture of a carbon material is characterized in that, said carbon material is a single-layer carbon nano-tube; In the reaction chamber of chemical vapor deposition unit, the gas that the gasification of alcohol or alcohol solution is obtained is used for reaction gas, utilizes chemical Vapor deposition process; After under normal pressure, making said single-layer carbon nano-tube growth; In this reaction chamber, through said single-layer carbon nano-tube is remained in the atmosphere that comprises water vapour and/or hydrogenchloride, and purify.
2. the method for manufacture of carbon material according to claim 1 is characterized in that, said carbon material is remained on comprise through in the atmosphere that makes water vapour that the hydrochloric acid bubbling generates and hydrogenchloride with air.
3. carbon material method of manufacture according to claim 1 is characterized in that, in the said atmosphere that comprises water vapour and/or hydrogenchloride that said carbon material is remained on the temperature that is heated to 250 ℃～650 ℃.
4. the method for manufacture of carbon material according to claim 1 is characterized in that, said carbon material is remained on by electromagnetic wave irradiation said comprise in the atmosphere of water vapour and/or hydrogenchloride.
5. the method for manufacture of carbon material according to claim 1 is characterized in that, the said pressure that comprises the atmosphere of water vapour and/or hydrogenchloride is 0.1 normal atmosphere～10 normal atmosphere.
6. the method for manufacture of carbon material according to claim 1; It is characterized in that; To utilize spontaneous evaporation to gasify through the outside at the reactive site of the reaction chamber of chemical vapor deposition unit gas that said alcohol or alcohol solution obtain imports said reactive site.
7. the method for manufacture of carbon material according to claim 1 is characterized in that, the volumetric concentration of the alcohol in the said alcohol solution is less than 100% greater than 0%.
8. the method for manufacture of carbon material according to claim 1 is characterized in that, the volumetric concentration of the alcohol in the said alcohol solution is 50%～95%.
9. the method for manufacture of carbon material according to claim 1 is characterized in that, the volumetric concentration of the alcohol in the said alcohol solution is 50%～80%.
10. the method for manufacture of carbon material according to claim 1 is characterized in that, said alcohol is monohydroxy-alcohol.
11. the method for manufacture of carbon material according to claim 1 is characterized in that, through regulating determining alcohol and/or the gasification rate of said alcohol solution in the said alcohol solution, controls the distribution of the diameter and/or the diameter of said single-layer carbon nano-tube.
12. the method for manufacture of an electronic component is characterized in that, in utilizing the manufacturing method of electronic elements of carbon material, comprises method according to claim 1, said carbon material is a single-layer carbon nano-tube.
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| JP5179979B2 (en) | 2008-04-16 | 2013-04-10 | 日信工業株式会社 | Carbon nanofiber and method for producing the same, method for producing carbon fiber composite material using carbon nanofiber, and carbon fiber composite material |
| JP2010222210A (en) * | 2009-03-25 | 2010-10-07 | Ube Kagaku Bunseki Center:Kk | Purification method of nanocarbon and analytical method of the same |
| CN102893351A (en) * | 2009-12-21 | 2013-01-23 | 优特拉有限公司 | High performance carbon nanotube energy storage device |
| EP2708506A4 (en) * | 2011-05-10 | 2014-11-26 | Univ Shizuoka Nat Univ Corp | Method and apparatus for producing carbon nanotubes |
| JP2014231444A (en) * | 2013-05-28 | 2014-12-11 | Jsr株式会社 | Carbon material |
| CN104192823A (en) * | 2014-08-08 | 2014-12-10 | 无锡东恒新能源科技有限公司 | Vapor purification method of carbon nanotubes |
| WO2017146218A1 (en) * | 2016-02-26 | 2017-08-31 | 学校法人早稲田大学 | Removal method and removal device for removing metal particles from carbon nanotube mixture containing metal particles, and composite of hollow carbon particles and carbon nanotubes obtained thereby |
| CN109126433B (en) * | 2018-06-30 | 2021-02-02 | 浙江工业大学 | Method and device for removing volatile organic compounds by using ultraviolet activated gas-phase persulfate |
| CN110642243B (en) * | 2019-10-28 | 2021-03-16 | 成都科汇机电技术有限公司 | Carbon nano tube purified by rotary binary secondary gas phase method and purification method |
| CN115536005B (en) * | 2022-10-31 | 2024-04-19 | 山东大展纳米材料有限公司 | Carbon nano tube purification method |
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| US20040253374A1 (en) * | 2003-04-23 | 2004-12-16 | Kyeong Taek Jung | Treatment of carbon nano-structure using fluidization |
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