CN103011130A - Method for growing high-quality semiconductor single-walled carbon nanotube through in-situ weak hydrogen etching - Google Patents

Method for growing high-quality semiconductor single-walled carbon nanotube through in-situ weak hydrogen etching Download PDF

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CN103011130A
CN103011130A CN2012105660687A CN201210566068A CN103011130A CN 103011130 A CN103011130 A CN 103011130A CN 2012105660687 A CN2012105660687 A CN 2012105660687A CN 201210566068 A CN201210566068 A CN 201210566068A CN 103011130 A CN103011130 A CN 103011130A
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walled carbon
carbon nanotube
hydrogen
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carbon nanotubes
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CN103011130B (en
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侯鹏翔
李文山
刘畅
成会明
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Institute of Metal Research of CAS
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Abstract

The invention relates to the field of fabrication of a high-quality semiconductor single-walled carbon nanotube, in particular to a method for directly growing the high-quality semiconductor single-walled carbon nanotube through in-situ weak hydrogen etching. A metallic and small-diameter single-walled carbon nanotube can be etched in situ at a certain reaction temperature by regulating and optimizing a flow of carrier gas, namely hydrogen and under the conditions of taking dicyclopentadienyl iron as a catalyst precursor, sulfur powder as a growth promoter and organic low-carbon hydrocarbon as a carbon source; and the high-quality semiconductor-superior single-walled carbon nanotube is finally obtained. The content of the semiconductor single-walled carbon nanotube is greater than or equal to 91wt%, the diameter distribution is between 1.5nm and 2.5nm, and the highest concentrated oxidation temperature reaches 800 DEG. With the adoption of the method, the massive, fast and low-cost controlled growth of the semiconductor single-walled carbon nanotube with the narrower diameter distribution and the high quality is realized, and the problems such as serious damages to a sample due to a strong etching agent, complexity of a fabrication process, low output and high cost during a selective fabrication course of a conduction-superior single-walled carbon nanotube can be effectively solved.

Description

The method of the weak etching growing high-quality semi-conductive single-walled carbon nanotubes of hydrogen original position
Technical field
The present invention relates to direct, a large amount of, the controlled preparation field of high-quality semiconductor conductive single-walled carbon nanotubes, be specially the method for the weak etching direct growth high-quality semiconductor conductive single-walled carbon nanotubes of a kind of hydrogen original position, in floating catalytic agent chemical vapor deposition growth Single Walled Carbon Nanotube process, original position is regulated the flow of carrier gas and etching gas-hydrogen, has realized magnanimity, controllable growth than the semi-conductive single-walled carbon nanotubes of narrow diameter distribution.
Background technology
Single Walled Carbon Nanotube is to be formed around a certain vector is curling by single-layer graphene, and different according to chirality and diameter, and Single Walled Carbon Nanotube can be divided into metallicity or semi-conductive single-walled carbon nanotubes.Because Single Walled Carbon Nanotube has excellent electron transport property, thereby be considered to make up the ideal material of nanometer electronic device, yet the key issue that the restricting current Single Walled Carbon Nanotube is used in the nanometer electronic device field is how to realize the selective growth of Single Walled Carbon Nanotube.The ultimate aim of selective growth is exactly to realize a large amount of, the homogeneity preparation of single chiral or conductive properties Single Walled Carbon Nanotube, and then can build the consistent nanometer electronic device of performance and design and printing goes out large-scale integrated circuit.Therefore, the preparation research of the Single Walled Carbon Nanotube of single conductive properties, structure homogeneous receives much attention.
Current, be subjected to increasing concern for the Single Walled Carbon Nanotube that how to prepare electrical properties and mechanical property homogeneous.The method that at present obtains single conductive properties Single Walled Carbon Nanotube is mainly divided two kinds: i.e. aftertreatment separation method and direct growth method.Wherein, aftertreatment separation method (document 1, T Tanaka, H Jin, Y Miyata, S Fujii, H Suga, Y Naitoh, T Minari, T Miyadera, K Tsukagoshi, H Kataura.Nano Lett.9 (4): 1497-1500 (2009); Document 2, YY Zhang, Y Zhang, XJ Xian, J Zhang, ZF Liu.J.Phys.Chem.C112 (10): 3849-3856 (2008)) relates to inevitably chemistry and the physical processes such as some functionalisation of surfaces processing, high speed centrifugation, easily in carbon nanotube, introduce textural defect and impurity, thereby affect its intrinsic performance and practical application; Simultaneously, separating technology is usually comparatively complicated, and is also higher to equipment requirements.On the other hand, the research of the single conductive properties Single Walled Carbon Nanotube of direct growth has obtained greater advance in recent years.Especially the selectivity of semi-conductive single-walled carbon nanotubes prepares (document 3, L Ding, A Tselev, JY Wang, DNYuan, HB Chu, TP Mcnicholas, Y Li, J Liu.Nano Lett.9 (2): 800-8055 (2009); Document 4, Wei-Hung Chiang and R.Mohan Sankaran.Nature Materials8,882-886 (2009)), but the semi-conductive single-walled carbon nanotubes that these methods obtain or amount are seldom or diameter is very little or diameter Distribution is very wide, and the semi-conductive single-walled carbon nanotubes preparation in macroscopic quantity narrower for diameter Distribution rarely has report.Recently, this research group utilizes oxygen to assist floating catalytic agent chemical Vapor deposition process direct growth semi-conductive single-walled carbon nanotubes, has realized the breakthrough of amount.Yet because the strong oxidizing property of oxygen, meeting etched portions semi-conductive single-walled carbon nanotubes causes the structural homogeneity of carbon pipe and structural integrity relatively poor, and directly impact makes up performance and the stability of nanometer electronic device by it.
Present subject matter is: the growth in situ etching agent that How to choose is suitable, under the precursor that does not destroy semi-conductive single-walled carbon nanotubes intrinsic structure, original position selective removal metallicity and minor diameter Single Walled Carbon Nanotube are for use in constructing the electron devices such as unit molecule field-effect transistor with higher on-off ratio and mobility.
Summary of the invention
The object of the present invention is to provide the method for the weak etching direct growth high quality of a kind of hydrogen original position, semi-conductive single-walled carbon nanotubes, under the prerequisite of not destroying major diameter, semi-conductive single-walled carbon nanotubes intrinsic structure, selective removal metallicity, minor diameter Single Walled Carbon Nanotube, the method of original position preparation in macroscopic quantity high-quality semiconductor attribute Single Walled Carbon Nanotube has realized high quality, convenient, the efficient controlled preparation of hanging down pollution, low-loss semiconductor conductive single-walled carbon nanotubes first.
The technical problem that the present invention solves is to have overcome complex steps in current preparation and the sepn process, cost is higher and Single Walled Carbon Nanotube intrinsic structure is brought the problems such as havoc; Another technical problem that the present invention solves is to have overcome few, the problems such as loss large, introducing impurity of the output that has directly preparation semi-conductive single-walled carbon nanotubes method existence now.
Technical scheme of the present invention is:
The method of the weak etching growing high-quality semi-conductive single-walled carbon nanotubes of a kind of hydrogen original position, with ferrocene, nickelocene, dicyclopentadienylcobalt or cuprocene are catalyst precursor, the sulphur powder is growth stimulant, hydrogen is carrier gas and etching gas, under temperature 1000-1100 ℃, pass into simultaneously carbon-source gas, and the regulation and control hydrogen flowing quantity carries out growth and the original position etching of Single Walled Carbon Nanotube, remove minor diameter semi-conductive single-walled carbon nanotubes and metallic single-wall carbon nano-tube, the final sample that semi-conductive single-walled carbon nanotubes is dominant, the semi-conductive single-walled carbon nanotubes content 〉=91wt% of obtaining.
The method of the weak etching growing high-quality semi-conductive single-walled carbon nanotubes of described hydrogen original position is directly transferred to the Single Walled Carbon Nanotube sample for preparing on the quartz plate with transmittance 80%-90% first, carries out infrared-visible-ultra-violet absorption spectrum test; Then measured curve is carried out background subtraction, and by the absorption spectrum quantitative Analysis of going after the back end, obtain in the Single Walled Carbon Nanotube sample of this method preparation semi-conductive single-walled carbon nanotubes content 〉=91wt%.
The method of the weak etching growing high-quality semi-conductive single-walled carbon nanotubes of described hydrogen original position, the carbon nanotube diameter Distribution adopts transmission, Raman Characterization, and the carbon nanotube diameter is between 1.5-2.5nm; Transmission, Raman spectrum also are used for characterizing the quality of micro-example, and high quality refers to that the carbon-coating structural integrity is good, I G/ I DRatio is higher than 78, I g/ I DRatio for G peak intensity and D peak intensity.
The method of the weak etching growing high-quality semi-conductive single-walled carbon nanotubes of described hydrogen original position, concrete steps are as follows:
Under hydrogen shield, first the chemical gas phase furnace temperature is risen to 1000-1100 ℃; The re-adjustment hydrogen flowing quantity is to analog value, and passes into carbon-source gas; Then with ferrocene; nickelocene; dicyclopentadienylcobalt or cuprocene and sulphur powder place simultaneously furnace temperature to be 80-90 ℃ and locate; ferrocene; nickelocene; dicyclopentadienylcobalt or cuprocene decomposite catalyst nano iron particle under described temperature; nano nickle granules; nano cobalt granule or nano copper particle; in the growth of catalysis Single Walled Carbon Nanotube; also hydrogen catalyzed decomposition hydroperoxyl radical; then metallicity and minor diameter Single Walled Carbon Nanotube are carried out the original position etching; hydrogen flowing quantity is the 500-4000 ml/min; ferrocene; nickelocene; the weight ratio of dicyclopentadienylcobalt or cuprocene and sulphur powder is 200-50; the flow of carbon-source gas is the 1-30 ml/min, and the time is 5-60 minute.
The method of the weak etching growing high-quality semi-conductive single-walled carbon nanotubes of described hydrogen original position, preferably, hydrogen flowing quantity is the 1700-3000 ml/min, the weight ratio of ferrocene, nickelocene, dicyclopentadienylcobalt or cuprocene and sulphur powder is 200-100, the flow of carbon-source gas is the 10-30 ml/min, and the time is 20-40 minute.
The method of the weak etching growing high-quality semi-conductive single-walled carbon nanotubes of described hydrogen original position, take organic low-carbon (LC) hydrocarbon gas: methane, acetylene, ethene or propylene are as carbon-source gas, and the Microamounts of Hydrogen free radical of organic low-carbon (LC) hydrocarbon gas Pintsch process and alkyl diradical also can etching metallicity and minor diameter Single Walled Carbon Nanotube.
The method of the weak etching growing high-quality semi-conductive single-walled carbon nanotubes of described hydrogen original position; hydrogen is not only as carrier gas but also as etching gas; the etching of hydrogen comes under the high temperature more than 1000 ℃ and catalyst nano iron particle, nano nickle granules, nano cobalt granule or nano copper particle effect; the hydrogen catalyzed hydroperoxyl radical that is dissociated into, and react with carbon nanotube.
The method of the weak etching growing high-quality semi-conductive single-walled carbon nanotubes of described hydrogen original position, the high-quality characteristics of magnanimity sample characterizes by thermal analysis experiment, and the concentrated oxidizing temperature of high-quality semiconductor conductive single-walled carbon nanotubes is higher than 720 ℃; Before thermal analysis experiment, semi-conductive single-walled carbon nanotubes adopts low-temperature oxidation to purify, step is: low temperature, long-time oxidation are to remove amorphous carbon impurity under air atmosphere with the Single Walled Carbon Nanotube sample for preparing, and temperature is 350-380 ℃, and oxidization time is 3-10 hour; Be that the hydrochloric acid soln of 15-35wt% soaks above-mentioned sample removing metal catalyst particles with concentration again, and clean up and vacuum-drying with deionized water.
The method of the weak etching growing high-quality semi-conductive single-walled carbon nanotubes of described hydrogen original position, hydrogen flowing quantity during by the control carbon nano tube growth is realized high quality, semi-conductive single-walled carbon nanotubes control growth, reactivity ratio's major diameter semi-conductive single-walled carbon nanotubes of metallic single-wall carbon nano-tube and minor diameter Single Walled Carbon Nanotube is high, by the corrasion of hydrogen original position, preferential original position selective etch falls metallicity and minor diameter Single Walled Carbon Nanotube, thereby obtains high quality, large diameter semi-conductive single-walled carbon nanotubes.
The content of the weak every batch of high-quality semiconductor attribute Single Walled Carbon Nanotube that obtains of etching growing high-quality of described hydrogen original position is determined by the diameter of reaction boiler tube, is the reaction boiler tube of 50mm for diameter, and every batch of sample size that obtains is 10-30mg.
Design philosophy of the present invention is:
Regulating the carrier gas airshed in the inventive method is the key that realizes semi-conductive single-walled carbon nanotubes control growth.In the presence of high temperature, iron nano-particle (the perhaps particles such as nickel, cobalt, copper), the hydrogen of minute quantity dissociates into hydroperoxyl radical, the hydroperoxyl radical of these free states can with the carbon nanotube Formed hydrogen compound that reacts.Because metallic single-wall carbon nano-tube is higher than the reactive behavior of semi-conductive single-walled carbon nanotubes, minor diameter carbon pipe is higher than the reactive behavior of major diameter carbon pipe; Therefore, regulate hydrogen flowing quantity to respective value, the free state hydroperoxyl radical of disassociation just original position etches away minor diameter and metallic single-wall carbon nano-tube, and does not react with the major diameter semi-conductive single-walled carbon nanotubes, thereby realizes the enrichment of high-quality semiconductor conductive single-walled carbon nanotubes.
Adopt in the resulting product of the inventive method, semiconductive or the metallic characterization technique of estimating Single Walled Carbon Nanotube have: wavelength Raman spectrum, absorption spectrum and field-effect transistor performance test, assess sample be original position collect, without the Single Walled Carbon Nanotube sample of any aftertreatment.The high-quality characterization technique of estimating Single Walled Carbon Nanotube has: high-resolution-ration transmission electric-lens, wavelength Raman spectrum, thermogravimetric analysis, be that sample that other characterization techniques adopt is the Single Walled Carbon Nanotube sample of original position collection the sample after low-temperature oxidation is purified except thermogravimetric analysis characterizes specimen in use wherein.The characterization technique of estimating the diameter of single-wall carbon nano tube distribution has: high-resolution-ration transmission electric-lens, wavelength Raman spectrum.
Among the present invention, the diameter of minor-diameter carbon nanotube is<1.5nm that the diameter of major diameter carbon nanotube is 1.5-2.5nm.The diameter Distribution of semi-conductive single-walled carbon nanotubes of the present invention is at the preferred 1.8-2.5nm of 1.5-2.5nm() between, the carbon pipe stability of this diameter Distribution is higher, contact resistance the is little (transmittance of 80%-90%, contact resistance reaches 60 Ω/-300 Ω/, and (this is the phraseology of sheet resistance, represent square resistance), be suitable for making up nanometer electronic device.
Among the present invention, the high quality Single Walled Carbon Nanotube refers to tube wall straight (high-resolution-ration transmission electric-lens observation), Raman spectrum I G/ I DHigh (the I of ratio G/ I DBe the ratio of G peak intensity and D peak intensity, I G/ I D>78), the differential thermogravimetric curve of magnanimity sample is the peak of sharp-pointed a, narrowly distributing, and its peak position is higher than 700 ℃.Wherein, the magnanimity sample after the thermal analysis experiment specimen in use is purified for process is simple, harmless.
Advantage of the present invention is:
1, the present invention utilizes the standby Single Walled Carbon Nanotube of floating catalytic agent legal system, employing hydrogen is that iron (perhaps nickel, cobalt, the copper) nano particle of carrier gas, ferrocene (perhaps nickelocene, dicyclopentadienylcobalt, cuprocene) pyrolytic decomposition is these characteristics of catalyzer, has this characteristic of etching carbon nanotube in conjunction with the high growth temperature condition of preparation carbon nanotube and the hydroperoxyl radical of iron nano-particle situ catalytic hydrogen decomposition generation, by the regulation and control hydrogen flowing quantity, be the content of hydroperoxyl radical, realized the magnanimity controlled preparation of high quality, semi-conductive single-walled carbon nanotubes.
2, the inventive method is the level of response that the content of hydroperoxyl radical is regulated and control Single Walled Carbon Nanotube by the regulation and control hydrogen flowing quantity, both realized the selective etch of metallicity and minor diameter Single Walled Carbon Nanotube, the complete structure that has kept again major diameter, semi-conductive single-walled carbon nanotubes has overcome the problems such as the strong etching of existing preparation semi-conductive single-walled carbon nanotubes, many defectives and strong doping.
3, the present invention realized the high-quality semiconductor conductive single-walled carbon nanotubes a large amount of (size according to used chemical vapor deposition stove pipe is different, output be milligram-Ke/batch), convenient, efficient selective prepares.The method has simply, cost is low, output is large, be easy to the characteristics such as mass-producing, has good prospects for commercial application.
In a word, the weak etching of hydrogen original position of the present invention directly prepares the floating catalytic chemical gaseous phase depositing process of high quality, semi-conductive single-walled carbon nanotubes, in the process of floating catalytic agent chemical Vapor deposition process growing single-wall carbon nano tube, the original position regulation and control have the flow of the hydrogen of weak corrasion, realize the preparation in macroscopic quantity of high quality, narrow diameter distribution semi-conductive single-walled carbon nanotubes.Take ferrocene, nickelocene, dicyclopentadienylcobalt or cuprocene as catalyst precursor, an amount of sulphur powder as growth stimulant, organic lower carbon number hydrocarbons under the condition of carbon source, by regulating the flow of optimizing carrier gas hydrogen, but original position etches away metallicity and minor diameter Single Walled Carbon Nanotube under certain temperature of reaction, the Single Walled Carbon Nanotube that final acquisition high quality, semiconductive are dominant, content 〉=the 91wt% of semi-conductive single-walled carbon nanotubes wherein, diameter Distribution is between 1.5-2.5nm, and concentrated oxidation resistance temperature is up to 800 ℃.The present invention has realized a large amount of, quick, the low-cost control growths than narrow diameter distribution, high quality, semi-conductive single-walled carbon nanotubes, effectively avoided selectivity to prepare in the Single Walled Carbon Nanotube process that conductive properties is dominant, strong etching agent to sample well damage and complicated process of preparation, yield poorly, the problem such as cost is higher.
Description of drawings
Fig. 1. the principle schematic of the weak etching direct growth high-quality semiconductor conductive single-walled carbon nanotubes of hydrogen original position.
Fig. 2 (a). the transmission electron microscope photo of high quality, semi-conductive single-walled carbon nanotubes.Fig. 2 (b). the diameter Distribution figure of the semiconductor properties Single Walled Carbon Nanotube that statistics obtains from transmission electron microscope photo.
Fig. 3. under different hydrogen flow and the helium Raman spectrum RBM peak of prepared Single Walled Carbon Nanotube sample (excitation wavelength is 633nm).
Fig. 4. the differential thermogravimetric curve of high quality, semi-conductive single-walled carbon nanotubes.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1.
(1) Fig. 1 is the preparation high quality, the principle schematic of semi-conductive single-walled carbon nanotubes, concrete experimental procedure is: the ferrocene (weight ratio of sulphur powder and ferrocene is 1:200) of a slice sulfur-bearing powder is placed on chemical vapour deposition reactor furnace, and (diameter is 50mm, flat-temperature zone length is 10cm) cold zone, temperature rise rate with 22 ℃/minute under hydrogen atmosphere is raised to 1100 ℃, pass into the methane of 30ml/min, and hydrogen flowing quantity is adjusted to 2000ml/min, simultaneously ferrocene being shifted onto furnace temperature is 80 ℃ and locates, carry out the growth of Single Walled Carbon Nanotube, growth time is 30 minutes.Chemical vapour deposition is closed methane and is turned down hydrogen flowing quantity to 400ml/min after finishing, and allows Reaktionsofen drop to room temperature in the mode of naturally cooling.
(2) (Fig. 2 a), Raman spectrum and absorption spectrum characterize the resulting sample of step (1) to be carried out respectively transmission electron microscope.Under transmission electron microscope 150 Single Walled Carbon Nanotube have been carried out diameter measurement and statistics, statistics is shown in Fig. 2 b, and the diameter Distribution of Single Walled Carbon Nanotube is 1.5-2.5nm, and the carbon-coating structural integrity is good, I G/ I DRatio is 81.6, Raman (Fig. 3,3#) show with absorption spectrum, the Single Walled Carbon Nanotube for preparing under this condition is that semiconductive is dominant, according to metallicity and semi-conductive single-walled carbon nanotubes in absorption spectrum the peak area at corresponding peak carry out integration, quantitatively calculate the content 91wt% of semiconductor properties Single Walled Carbon Nanotube, contact resistance is 60 Ω/.
Among the present invention, the high quality of magnanimity Single Walled Carbon Nanotube sample characterizes by thermal analysis experiment, to the oxidation 5 hours under 360 ℃, air atmosphere of the resulting sample of step (1); Use again hydrochloric acid soln (concentration is 20wt%) to soak above-mentioned sample to remove metal catalyst particles and repeatedly to clean and vacuum-drying with deionized water.Get dried sample 5mg and carry out thermogravimetric analysis experiment under the air atmosphere, its thermogravimetric/differential thermogravimetric curve as shown in Figure 4, sample is weightless 600 ℃ of beginnings, begins to concentrate oxidation at 800 ℃ of samples.The oxidation resistance temperature that this is high only has Single Walled Carbon Nanotube or the Single Walled Carbon Nanotube after greying of arc process preparation just can reach at present.
Comparative example 1.
(1) (diameter is 50mm the ferrocene (weight ratio of sulphur powder and ferrocene is 1:200) of a slice sulfur-bearing powder to be placed on chemical vapour deposition reactor furnace, flat-temperature zone length is 10cm) cold zone, temperature rise rate with 22 ℃/minute under hydrogen atmosphere is raised to 950 ℃, pass into the methane of 30ml/min, and hydrogen flowing quantity is adjusted to 500ml/min, simultaneously ferrocene being shifted onto furnace temperature is 80 ℃ and locates, and carry out the growth of Single Walled Carbon Nanotube, growth time is 30 minutes.Chemical vapour deposition is closed methane and is turned down hydrogen flowing quantity after finishing, and allows Reaktionsofen drop to room temperature in the mode of naturally cooling.
(2) the resulting sample of step (1) being carried out respectively transmission electron microscope, Raman spectrum and absorption spectrum characterizes.Under transmission electron microscope to the carrying out of 124 Single Walled Carbon Nanotube diameter measurement and statistics, the diameter Distribution that records Single Walled Carbon Nanotube is 0.8-2.5nm, Raman (Fig. 3,1#) show with absorption spectrum, the Single Walled Carbon Nanotube for preparing under this condition there is no selectivity aspect conductive properties, according to metallicity and semi-conductive single-walled carbon nanotubes in absorption spectrum the peak area at corresponding peak carry out integration, the content of quantitatively calculating the semiconductor properties Single Walled Carbon Nanotube is 69wt%.Behind embodiment 1 described Methods For Purification, the concentrated oxidation resistance temperature of sample is 700 ℃.
Comparative example 2.
(1) (diameter is 50mm the ferrocene (weight ratio of sulphur powder and ferrocene is 1:200) of a slice sulfur-bearing powder to be placed on chemical vapour deposition reactor furnace, flat-temperature zone length is 10cm) cold zone, temperature rise rate with 22 ℃/minute under helium atmosphere is raised to 1100 ℃, pass into the methane of 30ml/min, and helium gas flow is adjusted to 2000ml/min, simultaneously ferrocene being shifted onto furnace temperature is 80 ℃ and locates, and carry out the growth of Single Walled Carbon Nanotube, growth time is 30 minutes.After chemical vapour deposition finishes, close methane, also again reduce helium gas flow, allow Reaktionsofen drop to room temperature in the mode of naturally cooling.
(2) the resulting sample of step (1) being carried out respectively transmission electron microscope, Raman spectrum and absorption spectrum characterizes.Under transmission electron microscope to the carrying out of 90 Single Walled Carbon Nanotube diameter measurement and statistics, the diameter Distribution that records Single Walled Carbon Nanotube is 0.8-1.6nm, Raman (Fig. 3,2#) show with absorption spectrum, the Single Walled Carbon Nanotube for preparing under this condition does not have selectivity aspect conductive properties, according to metallicity and semi-conductive single-walled carbon nanotubes in absorption spectrum the peak area at corresponding peak carry out integration, the content of quantitatively calculating the semiconductor properties Single Walled Carbon Nanotube is 68wt%.Behind embodiment 1 described Methods For Purification, the concentrated oxidation resistance temperature of sample is 680 ℃.
Comparative example 1 and 2 result show at lower H 2Under the helium-atmosphere of flow (500ml/min) or same traffic, the growth of Single Walled Carbon Nanotube does not have selectivity, the diameter Distribution scope broadens, minor diameter carbon pipe ratio increases and its concentrated oxidation resistance temperature step-down, but this further specifies hydrogen and appropriate amount of hydrogen original position selective etch minor diameter, metallic single-wall carbon nano-tube, and has kept the structure of major diameter, semi-conductive single-walled carbon nanotubes.
Embodiment 2.
(1) (diameter is 50mm the nickelocene (weight ratio of sulphur powder and nickelocene is 1:100) of a slice sulfur-bearing powder to be placed on chemical vapour deposition reactor furnace, flat-temperature zone length is 10cm) cold zone, temperature rise rate with 22 ℃/minute under hydrogen atmosphere is raised to 1100 ℃, pass into the methane of 20ml/min, and hydrogen flowing quantity is adjusted to 2300ml/min, simultaneously nickelocene being shifted onto furnace temperature is 85 ℃ and locates, and carry out the growth of Single Walled Carbon Nanotube, growth time is 40 minutes.After chemical vapour deposition finishes, close methane, also again turn down hydrogen flowing quantity to 400ml/min, allow Reaktionsofen drop to room temperature in the mode of naturally cooling.
(2) the resulting sample of step (1) being carried out respectively transmission electron microscope, Raman spectrum and absorption spectrum characterizes.Under transmission electron microscope 146 Single Walled Carbon Nanotube have been carried out diameter measurement and statistics, statistics shows that the diameter Distribution of Single Walled Carbon Nanotube is 1.8-2.4nm, and the carbon-coating structural integrity is good, I G/ I DRatio is 80.2, Raman and absorption spectrum show, the Single Walled Carbon Nanotube for preparing under this condition is that semiconductive is dominant, according to metallicity and semi-conductive single-walled carbon nanotubes in absorption spectrum the peak area at corresponding peak carry out integration, quantitatively calculate the content 92wt% of semiconductor properties Single Walled Carbon Nanotube.
(3) to the oxidation 10 hours under 350 ℃, air atmosphere of the resulting sample of step (1); Use again hydrochloric acid soln (concentration is 35wt%) to soak above-mentioned sample to remove metal catalyst particles and repeatedly to clean and vacuum-drying with deionized water.Get dried sample 5mg and carry out thermogravimetric analysis experiment under the air atmosphere, sample is weightless 580 ℃ of beginnings, begins to concentrate oxidation at 780 ℃ of samples.
Embodiment 3.
(1) (diameter is 50mm the dicyclopentadienylcobalt (weight ratio of sulphur powder and dicyclopentadienylcobalt is 1:150) of a slice sulfur-bearing powder to be placed on chemical vapour deposition reactor furnace, flat-temperature zone length is 10cm) cold zone, temperature rise rate with 22 ℃/minute under hydrogen atmosphere is raised to 1050 ℃, pass into the ethene of 25ml/min, and hydrogen flowing quantity is adjusted to 2500ml/min, simultaneously dicyclopentadienylcobalt being shifted onto furnace temperature is 90 ℃ and locates, and carry out the growth of Single Walled Carbon Nanotube, growth time is 50 minutes.Chemical vapour deposition is closed ethene, is turned down hydrogen flowing quantity to 400ml/min after finishing, and allows Reaktionsofen drop to room temperature in the mode of naturally cooling.
(2) the resulting sample of step (1) being carried out respectively transmission electron microscope, Raman spectrum and absorption spectrum characterizes.Under transmission electron microscope, 132 Single Walled Carbon Nanotube diameter measurement and statistics have been carried out, statistics can be found out, the diameter Distribution of Single Walled Carbon Nanotube is 2.0-2.4nm, and the carbon-coating structural integrity is good, IG/ID ratio is 78.6, Raman and absorption spectrum show, the Single Walled Carbon Nanotube for preparing under this condition is that semiconductive is dominant, according to metallicity and semi-conductive single-walled carbon nanotubes in absorption spectrum the peak area at corresponding peak carry out integration, quantitatively calculate the content 90wt% of semiconductor properties Single Walled Carbon Nanotube.
(3) to the oxidation 3 hours under 380 ℃, air atmosphere of the resulting sample of step (1); Use again hydrochloric acid soln (concentration is 15wt%) to soak above-mentioned sample to remove metal catalyst particles and repeatedly to clean and vacuum-drying with deionized water.Get dried sample 5mg and carry out thermogravimetric analysis experiment under the air atmosphere, sample is weightless 580 ℃ of beginnings, begins to concentrate oxidation at 740 ℃ of samples.
Embodiment 4.
(1) (diameter is 50mm the cuprocene (weight ratio of sulphur powder and cuprocene is 1:120) of a slice sulfur-bearing powder to be placed on chemical vapour deposition reactor furnace, flat-temperature zone length is 10cm) cold zone, temperature rise rate with 22 ℃/minute under hydrogen atmosphere is raised to 1100 ℃, pass into the propylene of 15ml/min, and hydrogen flowing quantity is adjusted to 3100ml/min, simultaneously cuprocene being shifted onto furnace temperature is 90 ℃ and locates, and carry out the growth of Single Walled Carbon Nanotube, growth time is 40 minutes.Chemical vapour deposition is closed propylene, is turned down hydrogen flowing quantity to 400ml/min after finishing, and allows Reaktionsofen drop to room temperature in the mode of naturally cooling.
(2) the resulting sample of step (1) being carried out respectively transmission electron microscope, Raman spectrum and absorption spectrum characterizes.Under transmission electron microscope 136 Single Walled Carbon Nanotube have been carried out diameter measurement and statistics, statistics shows that the diameter Distribution of Single Walled Carbon Nanotube is 2.0-2.5nm, and the carbon-coating structural integrity is good, I G/ I DRatio is 80.5, Raman and absorption spectrum show, the Single Walled Carbon Nanotube for preparing under this condition is that semiconductive is dominant, according to metallicity and semi-conductive single-walled carbon nanotubes in absorption spectrum the peak area at corresponding peak carry out integration, quantitatively calculate the content 90wt% of semiconductor properties Single Walled Carbon Nanotube.
(3) to the oxidation 10 hours under 350 ℃, air atmosphere of the resulting sample of step (1); Use again hydrochloric acid soln (concentration is 35wt%) to soak above-mentioned sample to remove metal catalyst particles and repeatedly to clean and vacuum-drying with deionized water.Get dried sample 5mg and carry out thermogravimetric analysis experiment under the air atmosphere, sample is weightless 590 ℃ of beginnings, begins to concentrate oxidation at 770 ℃ of samples.
Embodiment result shows, under the condition that high temperature and the granules of catalyst of Single Walled Carbon Nanotube growth exists, hydrogen has weak corrasion, and the power of its corrasion is relevant with the hydroperoxyl radical concentration of its decomposition; In the standby Single Walled Carbon Nanotube process of the weak etching floating catalytic agent legal system of hydrogen original position, the growth of Single Walled Carbon Nanotube and its original position etching are competitive relations.By being hydroperoxyl radical concentration at Single Walled Carbon Nanotube process of growth situ adjusting hydrogen flowing quantity, alternative metallicity and the minor diameter Single Walled Carbon Nanotube removed realizes the preparation of high quality, larger diameter, semi-conductive single-walled carbon nanotubes.In addition, the present invention adopts the metal at high temperature can hydrogen catalyzedly be dissociated into hydroperoxyl radical (such as Ni, Fe, Co, Cu etc.), all is applicable to the weak etching direct growth high-quality semiconductor conductive single-walled carbon nanotubes of hydrogen original position.The present invention compared with prior art maximum characteristics is: the quality of semi-conductive single-walled carbon nanotubes is high, and oxidation resistance temperature reaches 800 ℃, general method do not optionally single-walled pipe also be difficult to reach this temperature.

Claims (10)

1. the method for the weak etching growing high-quality semi-conductive single-walled carbon nanotubes of a hydrogen original position, it is characterized in that, with ferrocene, nickelocene, dicyclopentadienylcobalt or cuprocene are catalyst precursor, the sulphur powder is growth stimulant, hydrogen is carrier gas and etching gas, under temperature 1000-1100 ℃, pass into simultaneously carbon-source gas, and the regulation and control hydrogen flowing quantity carries out growth and the original position etching of Single Walled Carbon Nanotube, remove minor diameter semi-conductive single-walled carbon nanotubes and metallic single-wall carbon nano-tube, the final sample that semi-conductive single-walled carbon nanotubes is dominant, the semi-conductive single-walled carbon nanotubes content 〉=91wt% of obtaining.
2. according to the method for etching growing high-quality semi-conductive single-walled carbon nanotubes a little less than the hydrogen original position claimed in claim 1, it is characterized in that, first the Single Walled Carbon Nanotube sample for preparing is directly transferred on the quartz plate with transmittance 80%-90%, carried out infrared-visible-ultra-violet absorption spectrum test; Then measured curve is carried out background subtraction, and by the absorption spectrum quantitative Analysis of going after the back end, obtain in the Single Walled Carbon Nanotube sample of this method preparation semi-conductive single-walled carbon nanotubes content 〉=91wt%.
3. according to the method for etching growing high-quality semi-conductive single-walled carbon nanotubes a little less than the hydrogen original position claimed in claim 1, it is characterized in that the carbon nanotube diameter Distribution adopts transmission, Raman Characterization, the carbon nanotube diameter is between 1.5-2.5nm; Transmission, Raman spectrum also are used for characterizing the quality of micro-example, and high quality refers to that the carbon-coating structural integrity is good, I G/ I DRatio is higher than 78, I G/ I DRatio for G peak intensity and D peak intensity.
4. according to the method for etching growing high-quality semi-conductive single-walled carbon nanotubes a little less than the hydrogen original position claimed in claim 1, it is characterized in that concrete steps are as follows:
Under hydrogen shield, first the chemical gas phase furnace temperature is risen to 1000-1100 ℃; The re-adjustment hydrogen flowing quantity is to analog value, and passes into carbon-source gas; Then with ferrocene; nickelocene; dicyclopentadienylcobalt or cuprocene and sulphur powder place simultaneously furnace temperature to be 80-90 ℃ and locate; ferrocene; nickelocene; dicyclopentadienylcobalt or cuprocene decomposite catalyst nano iron particle under described temperature; nano nickle granules; nano cobalt granule or nano copper particle; in the growth of catalysis Single Walled Carbon Nanotube; also hydrogen catalyzed decomposition hydroperoxyl radical; then metallicity and minor diameter Single Walled Carbon Nanotube are carried out the original position etching; hydrogen flowing quantity is the 500-4000 ml/min; ferrocene; nickelocene; the weight ratio of dicyclopentadienylcobalt or cuprocene and sulphur powder is 200-50; the flow of carbon-source gas is the 1-30 ml/min, and the time is 5-60 minute.
5. according to the method for etching growing high-quality semi-conductive single-walled carbon nanotubes a little less than the hydrogen original position claimed in claim 4, it is characterized in that, preferably, hydrogen flowing quantity is the 1700-3000 ml/min, the weight ratio of ferrocene, nickelocene, dicyclopentadienylcobalt or cuprocene and sulphur powder is 200-100, the flow of carbon-source gas is the 10-30 ml/min, and the time is 20-40 minute.
6. according to the method for etching growing high-quality semi-conductive single-walled carbon nanotubes a little less than the hydrogen original position claimed in claim 4, it is characterized in that, take organic low-carbon (LC) hydrocarbon gas: methane, acetylene, ethene or propylene are as carbon-source gas, and the Microamounts of Hydrogen free radical of organic low-carbon (LC) hydrocarbon gas Pintsch process and alkyl diradical also can etching metallicity and minor diameter Single Walled Carbon Nanotube.
7. according to the method for etching growing high-quality semi-conductive single-walled carbon nanotubes a little less than claim 1 or the 4 described hydrogen original positions; it is characterized in that; hydrogen is not only as carrier gas but also as etching gas; the etching of hydrogen comes under the high temperature more than 1000 ℃ and catalyst nano iron particle, nano nickle granules, nano cobalt granule or nano copper particle effect; the hydrogen catalyzed hydroperoxyl radical that is dissociated into, and react with carbon nanotube.
8. according to the method for etching growing high-quality semi-conductive single-walled carbon nanotubes a little less than claim 1 or the 4 described hydrogen original positions, it is characterized in that, the high-quality characteristics of magnanimity sample characterizes by thermal analysis experiment, and the concentrated oxidizing temperature of high-quality semiconductor conductive single-walled carbon nanotubes is higher than 720 ℃; Before thermal analysis experiment, semi-conductive single-walled carbon nanotubes adopts low-temperature oxidation to purify, step is: low temperature, long-time oxidation are to remove amorphous carbon impurity under air atmosphere with the Single Walled Carbon Nanotube sample for preparing, and temperature is 350-380 ℃, and oxidization time is 3-10 hour; Be that the hydrochloric acid soln of 15-35wt% soaks above-mentioned sample removing metal catalyst particles with concentration again, and clean up and vacuum-drying with deionized water.
9. according to the method for etching growing high-quality semi-conductive single-walled carbon nanotubes a little less than claim 1 or the 4 described hydrogen original positions, it is characterized in that, hydrogen flowing quantity during by the control carbon nano tube growth is realized high quality, semi-conductive single-walled carbon nanotubes control growth, reactivity ratio's major diameter semi-conductive single-walled carbon nanotubes of metallic single-wall carbon nano-tube and minor diameter Single Walled Carbon Nanotube is high, by the corrasion of hydrogen original position, preferential original position selective etch falls metallicity and minor diameter Single Walled Carbon Nanotube, thereby obtains high quality, large diameter semi-conductive single-walled carbon nanotubes.
10. according to the method for etching growing high-quality semi-conductive single-walled carbon nanotubes a little less than claim 1 or the 4 described hydrogen original positions, it is characterized in that, the content of every batch of high-quality semiconductor attribute Single Walled Carbon Nanotube that obtains is determined by the diameter of reaction boiler tube, be the reaction boiler tube of 50mm for diameter, every batch of sample size that obtains is 10-30mg.
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