CN102431989A - Method for obtaining large number of semi-conductive single-wall carbon nanometer tubes - Google Patents
Method for obtaining large number of semi-conductive single-wall carbon nanometer tubes Download PDFInfo
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- CN102431989A CN102431989A CN2010102961363A CN201010296136A CN102431989A CN 102431989 A CN102431989 A CN 102431989A CN 2010102961363 A CN2010102961363 A CN 2010102961363A CN 201010296136 A CN201010296136 A CN 201010296136A CN 102431989 A CN102431989 A CN 102431989A
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Abstract
The invention relates to the field of single-wall carbon nanometer tubes, in particular to a method for obtaining a large number of semi-conductive single-wall carbon nanometer tubes through combining post treatment oxidation with chemical gas-phase deposition in-situ weak oxidation. Trace oxygen is introduced in the process of chemical gas-phase deposition growth of the singe-wall carbon nanometer tubes, and then, the prepared single-wall carbon nanometer tubes are oxidized in the air at the proper temperature. Ferrocene is used as a catalysis precursor, hydrogen is used as carrying gas, sulfur powder is used as growth promoters, carbon source gas and trace oxygen are simultaneously introduced at a certain temperature for carrying out the growth and in-situ weak oxidation of single-wall carbon nanometer tubes, the obtained single-wall carbon nanometer tube samples are oxidized for a long time in the air atmosphere at the low temperature, and the oxidized samples are soaked into hydrochloric acid solution to remove catalyst particles, are cleaned and dried. The method realizes the mass preparation of the single conductive (semi-conductive) single-wall carbon nanometer tubes and solves the problems that the damage to the intrinsic structure of the single-wall carbon nanometer tubes in the existing chemical and physical method separation process is serious, and the like.
Description
Technical field
The present invention relates to single conductive properties (semiconductive) SWCN field, be specially a kind of chemical vapour deposition original position weak oxide a large amount of methods that obtain semi-conductive single-walled carbon nanotubes that combine with the aftertreatment oxidation.
Background technology
The conductive properties of SWCN and its structure are closely related; Because of the curling mode difference that constitutes its Graphene lamella can show as metallicity or semiconductive; And carbon nanotube has excellent transport property, so carbon nanotube is considered to make up the ideal material of nanometer electronic device.And the carbon nanotube that obtains the conductive properties homogeneous is to realize its important prerequisite of in fields such as nanometer electronic device, using and basis.But the carbon nanotube sample for preparing usually all is the mixture of metallicity and semiconductive carbon nano tube.Therefore, the preparation research of homogeneous conductive properties carbon nanotube receives much attention.
Semi-conductive single-walled carbon nanotubes is considered to make up the important constituent element of nano electron device of future generation because of its particular structure and performance.For realizing the stability and the homogeneity of device performance, the metallicity carbon pipe of how removing in the SWCN sample is particularly important.The method that obtains the semiconductor properties SWCN at present mainly is divided into two kinds: 1) direct growth; 2) aftertreatment separates (document 1, Ding L, Tselev A, Wang JY, Yuan, DN; Chu HB, McNicholas TP, Li Y, Liu J, Nano Lett.9,800-805 (2009); Document 2, Zhang GY, Qi PF, Wang XR, Lu YR, Li XL; Tu R, Bangsaruntip S, Mann D, Zhang L, Dai HJ.Science 314,974-977 (2006)).Thereby these methods or because will pass through the intrinsic structure that complicated chemistry or physical process are destroyed the carbon pipe, or purity is not high, productive rate is low excessively, the diameter Distribution scope is excessive etc., these performance studies that hindered carbon nanotube are explored with using.Present subject matter is: how under the prerequisite of not destroying SWCN intrinsic structure, obtain semi-conductive single-walled carbon nanotubes a large amount of, high-purity and that diameter Distribution is suitable.
Summary of the invention
The object of the present invention is to provide the method for the semiconductor properties SWCN that a kind of a large amount of acquisition is high-purity, diameter Distribution is suitable; Overcome complex steps in existing chemistry and the physical method for separation process, to problem such as the structure deteriorate of SWCN intrinsic is serious; When keeping semiconductor properties SWCN intrinsic structure, realized the magnanimity preparation of semi-conductive single-walled carbon nanotubes first.
Technical scheme of the present invention is:
A kind of chemical vapour deposition original position weak oxide combines with the aftertreatment oxidation and obtains the methods of semi-conductive single-walled carbon nanotubes in a large number, adopts chemical vapour deposition original position weak oxide to combine with the aftertreatment oxidation; At first; Prepare the oxygen that adds trace in the process of SWCN in chemical vapour deposition; Oxygen flow is: the 0.1-0.2 ml/min; Preferential and higher metallic carbon nanotubes and the effect of small dia SWCN of reactive behavior of oxygen increases its surface imperfection, thereby the resistance of oxidation of these carbon pipes is reduced; Then; With the SWCN sample for preparing low temperature, long-time oxidation under air atmosphere; Temperature is: 370-410 ℃; Oxidization time is: 5-20 hour, air flow quantity was: the 10-500 ml/min, remove metallic single-wall carbon nano-tube, small dia SWCN and amorphous carbon impurity; At last, repeatedly clean and vacuum-drying through hydrochloric acid soln (concentration is 15-35wt%) immersion removal metal catalyst particles and with deionized water; Thereby, under the prerequisite of not destroying SWCN intrinsic structure, obtain high purity, a large amount of, the narrower semi-conductive single-walled carbon nanotubes of diameter Distribution.
Said chemical vapour deposition original position weak oxide combines with the aftertreatment oxidation and obtains the methods of semi-conductive single-walled carbon nanotubes in a large number; The concrete steps of chemical vapour deposition original position weak oxide are following: with organic gas hydrocarbon (as: methane, acetylene, ethene or propylene etc.) is carbon-source gas; With hydrogen is carrier gas, and ferrocene is a catalyst precursor; Under hydrogen shield, the chemical gas phase furnace temperature is risen to 900-1200 ℃; Feed the oxygen of carbon-source gas and trace again, and shift ferrocene onto furnace temperature simultaneously and be 50-80 ℃ and locate, carry out the chemical vapor deposition growth SWCN and it is carried out the original position weak oxide; Flow rate of carrier gas is the 200-1000 ml/min, and the weight ratio of sulphur powder and ferrocene is 1: 40-1: 200, and the flow of carbon-source gas is the 1-10 ml/min, and oxygen flow is the 0.1-0.2 ml/min, and the time is 10-120 minute.
The specification of medium-small diameter SWCN of the present invention is: diameter is less than the SWCN of 1.3 nanometers.
Among the present invention; The SWCN sample for preparing through the original position weak oxide shows the oxidation peak of two separations: the oxidation peak at lesser temps place corresponding higher metallic single-wall carbon nano-tube and the small dia SWCN of reactive behavior, and the oxidation peak at comparatively high temps place correspondence larger-diameter semi-conductive single-walled carbon nanotubes.
Adopt in the resultant product of the inventive method; The content of SWCN (purity 1, >=99wt%), and the content of semiconductor properties SWCN (purity 2 in the SWCN; >=95wt%); Purity 1 is according to thermogravimetric/differential thermal curve quantitative Analysis, and purity 2 obtains according to absorption spectrum and Raman spectrum quantitative Analysis, and the intrinsic structural integrity of carbon nanotube also is to obtain (the oxidation peak invariant position of SWCN before and after purifying) according to thermogravimetric/differential thermal curve is qualitative.
Different according to chemical vapour deposition reduction furnace (CVD stove) size; Can realize the acquisition (5mg-1g) of the semi-conductive single-walled carbon nanotubes of every batch of milligram-Ke magnitude in a large number; Its diameter Distribution scope is 1.5-2.0nm (obtaining according to the high-resolution-ration transmission electric-lens statistics); This diameter Distribution is the ideal diameter scope of SWCN as electronic device applications just, and the semi-conductive single-walled carbon nanotubes of this diameter range is considered to optimum and is used for nanometer electronic device, is expected to obtain practical application.
Advantage of the present invention is:
1, the inventive method is introduced the oxygen of trace in chemical vapor deposition growth SWCN process, again with the SWCN for preparing oxidation in air under proper temperature.In efficient removal amorphous carbon, catalyst particle, metallicity and small dia SWCN; Do not destroy the intrinsic structure of SWCN, overcome complex steps in existing chemistry and the physical method for separation process, problem such as the structure deteriorate of SWCN intrinsic is serious.This method can obtain the semiconductor properties SWCN that content is higher than 95wt%, and diameter Distribution is 1.5-2.0nm, has realized a large amount of acquisitions of the narrower single conductive properties SWCN of diameter Distribution.
2, the present invention combines original position weak oxide in the preparation process with the aftertreatment oxidation, has realized a large amount of preparations of single conductive properties (semiconductive) SWCN.This method has simply, a large amount of, be easy to the mass-producing characteristics, have favorable industrial application prospect.
3, the inventive method has realized the acquisition of the every stove of semiconductor properties SWCN on milligram-Ke magnitude, has broken through to only limit to the bottleneck (can't collect) of surface growth on amount among the existing direct preparation method.
4, the inventive method has not only realized the acquisition of high purity semiconductor properties SWCN, and it is narrower and be suitable for the semiconductor properties SWCN that nano electron device is used to have obtained the diameter Distribution scope simultaneously.
5, the inventive method has simply, low consumption, good reproducibility, is easy to characteristics such as amplification.
Description of drawings
Fig. 1. the DTG curve of three kinds of different samples.Wherein: (a) in-situ oxidation sample; (b) in-situ oxidation+aftertreatment oxidation sample; (c) in-situ oxidation is not handled sample.
Fig. 2. the diameter Distribution figure of the semiconductor properties SWCN that statistics obtains from transmission electron microscope photo.Wherein: (a) in-situ oxidation sample; (b) in-situ oxidation+aftertreatment oxidation sample.
Fig. 3. Raman spectrum.Wherein, a figure is wavelength 633nm; B figure is wavelength 514nm; C figure is wavelength 488nm; D figure is wavelength 785nm; In a-d figure, (a) curve is the in-situ oxidation sample; (b) curve is in-situ oxidation+aftertreatment oxidation sample.
Fig. 4. absorption spectrum.Wherein: (a) in-situ oxidation sample; (b) in-situ oxidation+aftertreatment oxidation sample.
Embodiment
Through embodiment the present invention is detailed below.
Embodiment 1.
The ferrocene (weight ratio of sulphur powder and ferrocene is 0.5: 99.5) that a slice is contained 0.5wt% sulphur powder is placed on chemical vapour deposition reduction furnace (CVD stove; Diameter is 25cm, and flat-temperature zone length is 4cm) cold zone, the temperature rise rate with 30 ℃/minute under the hydrogen atmosphere of 200ml/min is raised to 1100 ℃; Feed the methane of 3ml/min and the oxygen of 0.2ml/min; And shift ferrocene onto furnace temperature simultaneously and be 60 ℃ and locate that carry out original position weak oxide growing single-wall carbon nano tube, growth time is 30 minutes.Chemical vapour deposition is closed methane, oxygen after finishing, and drops to room temperature at hydrogen shield.It is 25cm that the SWCN 20mg for preparing under the above-mentioned condition is evenly placed diameter, and flat-temperature zone length is in the heating furnace tube of 4cm, feeds the air of 100ml/min, at 400 ℃ of following oxidation 10h.After treating the sample cool to room temperature, take out and be soaked in the hydrochloric acid soln (concentration is 15-35wt%), clean repeatedly down, until hydrochloric acid soln no longer till the variable color at 80 ℃.Using this sample of washed with de-ionized water is 7 until pH, and at 120 ℃ of these samples of following vacuum-drying, example weight is: 4.1mg.Sample before and after the later stage oxide treatment is carried out thermogravimetric, transmission electron microscope, Raman spectrum and absorption spectrum respectively to be characterized.Can calculate the content＞99wt% of SWCN in the final sample according to thermogravimetric curve.The concentrated oxidation peak number that difference formula thermogravimetric analysis result (Fig. 1) shows SWCN after the thermal treatment becomes one by original two; And peak position remains unchanged, and shows that the later stage oxide treatment does not have to destroy to the intrinsic structure of the corresponding SWCN of second oxidation peak position.Under transmission electron microscope, the diameter of the SWCN before and after 100 thermal treatments is measured and added up respectively; Statistics is as shown in Figure 2; The diameter Distribution of SWCN is narrowed 1.5-2.0nm by original 0.8-3.0nm after the thermal treatment; Raman (Fig. 3) and absorption spectrum (Fig. 4) show; The peak that metallic single-wall carbon nano-tube is corresponding after the thermal treatment disappears or significantly weakens, and carries out integration according to the peak area at metallicity and semi-conductive single-walled carbon nanotubes pairing peak in absorption spectrum, and the content of quantitatively calculating the semiconductor properties SWCN is higher than 95wt%.
Embodiment 2.
The ferrocene (weight ratio of sulphur powder and ferrocene is 0.5: 99.5) that a slice is contained 0.5wt% sulphur powder is placed on chemical vapour deposition reduction furnace (CVD stove; Diameter is 25cm, and flat-temperature zone length is 4cm) cold zone, the temperature rise rate with 30 ℃/minute under the hydrogen atmosphere of 200ml/min is raised to 1100 ℃; Feed the methane of 3ml/min and the oxygen of 0.15ml/min; And shift ferrocene onto furnace temperature simultaneously and be 60 ℃ and locate that carry out the growth of SWCN, growth time is 30 minutes.Chemical vapour deposition is closed methane, is dropped to room temperature at hydrogen shield after finishing.It is 25cm that the SWCN 20mg for preparing under the above-mentioned condition is evenly placed diameter, and flat-temperature zone length is in the heating furnace tube of 4cm, feeds the air of 100ml/min, at 400 ℃ of following oxidation 10h.After treating the sample cool to room temperature, take out and be soaked in the hydrochloric acid soln (concentration is 15-35wt%), clean repeatedly down, until hydrochloric acid soln no longer till the variable color at 80 ℃.Using this sample of washed with de-ionized water is 7 until pH, and at 120 ℃ of these samples of following vacuum-drying, example weight is: 6mg.Sample before and after the later stage oxide treatment is carried out thermogravimetric, transmission electron microscope, Raman spectrum and absorption spectrum respectively to be characterized.Can calculate the content＞99wt% of SWCN in the final sample according to thermogravimetric curve.Difference formula thermogravimetric analysis result shows that the concentrated oxidation peak number of SWCN is one before and after the thermal treatment, and the oxidation peak position remains unchanged, and shows that the later stage oxide treatment do not destroy the intrinsic structure of SWCN.Under transmission electron microscope, the diameter of the SWCN before and after 100 above thermal treatments is measured and added up respectively; It is less that statistics shows that the diameter Distribution of SWCN after the thermal treatment changes, and Raman and absorption spectrum show that the intensity at the peak that metallic single-wall carbon nano-tube is corresponding after the thermal treatment does not have variation basically.
The original position weak oxide that embodiment 1 and 2 is illustrated in the preparation SWCN process can effectively increase semi-conductive single-walled carbon nanotubes and metallicity and the difference of small dia SWCN on oxidation-resistance; Thereby just can small dia and metallic single-wall carbon nano-tube be removed through simple later stage oxide treatment, and not destroy the intrinsic structure of the semiconductor properties SWCN of appropriate diameter.
Embodiment 3.
The ferrocene that a slice is contained 0.5wt% sulphur powder (weight ratio of sulphur powder and ferrocene is 0.5: 99.5) is placed on chemical vapour deposition reduction furnace (CVD stove; Diameter is 25cm, and flat-temperature zone length is 4cm) cold zone, the temperature rise rate with 30 ℃/minute under the hydrogen atmosphere of 200ml/min is raised to 1100 ℃; Feed the methane of 3ml/min and the oxygen of 1.5ml/min; And shift ferrocene onto furnace temperature simultaneously and be 60 ℃ and locate that carry out the in-situ oxidation growing single-wall carbon nano tube, growth time is 30 minutes.Chemical vapour deposition is closed methane, oxygen after finishing, and drops to room temperature at hydrogen shield.Above-mentioned sample is directly carried out transmission electron microscope and Raman spectrum to be characterized.Characterization result shows with this understanding can not growing single-wall carbon nano tube, shows in conjunction with embodiment 1 and 2, and suitable weak oxide is preparation and increase the prerequisite that metallicity and semi-conductive single-walled carbon nanotubes oxidation-resistance are distinguished.
Embodiment 4.
The ferrocene (weight ratio of sulphur powder and ferrocene is 2: 98) that a slice is contained 2wt% sulphur powder is placed on chemical vapour deposition reduction furnace (CVD stove; Diameter is 25cm, and flat-temperature zone length is 4cm) cold zone, the temperature rise rate with 30 ℃/minute under the hydrogen atmosphere of 500ml/min is raised to 900 ℃; Feed the ethene of 5ml/min and the oxygen of 0.1ml/min; And shift ferrocene onto furnace temperature simultaneously and be 70 ℃ and locate that carry out original position weak oxide growing single-wall carbon nano tube, growth time is 60 minutes.Chemical vapour deposition is closed ethene, oxygen after finishing, and drops to room temperature at hydrogen shield.It is 25cm that the SWCN 20mg for preparing under the above-mentioned condition is evenly placed diameter, and flat-temperature zone length is in the heating furnace tube of 4cm, feeds the air of 100ml/min, at 380 ℃ of following oxidation 20h.After treating the sample cool to room temperature, take out and be soaked in the hydrochloric acid soln (concentration is 15-35wt%) at 80 ℃ and clean repeatedly down, until hydrochloric acid soln no longer till the variable color.Using this sample of washed with de-ionized water is 7 until pH, and at 120 ℃ of these samples of following vacuum-drying, example weight is: 3.9mg.Sample before and after the later stage oxide treatment is carried out thermogravimetric, transmission electron microscope, Raman spectrum and absorption spectrum respectively to be characterized.Can calculate the content＞99wt% of SWCN in the final sample according to thermogravimetric curve.The concentrated oxidation peak number that difference formula thermogravimetric analysis result shows SWCN after the thermal treatment becomes one by original two; And peak position remains unchanged, and shows that the later stage oxide treatment does not have to destroy to the intrinsic structure of the corresponding SWCN of second oxidation peak position.Under transmission electron microscope, the diameter of the SWCN before and after 100 thermal treatments is measured and added up respectively; The diameter Distribution of SWCN is narrowed 1.5-2.0nm after the thermal treatment; Raman and absorption spectrum show that metallic single-wall carbon nano-tube is corresponding after the thermal treatment peak disappears or significantly weakens; Peak area according to metallicity and semi-conductive single-walled carbon nanotubes pairing peak in absorption spectrum carries out integration, and the content of quantitatively calculating the semiconductor properties SWCN is higher than 95wt%.
Embodiment result shows; The present invention can combine with the later stage oxide treatment through the original position weak oxide in preparation SWCN process, and a large amount of preparations are high-purity, the semiconductor properties SWCN of appropriate diameter, and do not break the structure of the semi-conductive single-walled carbon nanotubes that ring finally obtains.Key of the present invention is in the SWCN process of growth, to introduce the oxygen of trace; Increased the difference of semi-conductive single-walled carbon nanotubes on oxidation-resistance of metallicity and small dia SWCN and appropriate diameter, thereby can obtain high-purity semi-conductive single-walled carbon nanotubes through simple later stage oxide treatment.
Claims (5)
1. an a large amount of method that obtains semi-conductive single-walled carbon nanotubes is characterized in that, adopts chemical vapour deposition original position weak oxide to combine with the aftertreatment oxidation; At first; Prepare the oxygen that adds trace in the process of SWCN in chemical vapour deposition; Oxygen flow is: the 0.1-0.2 ml/min; Preferential and higher metallic carbon nanotubes and the effect of small dia SWCN of reactive behavior of oxygen increases its surface imperfection, thereby the resistance of oxidation of these carbon pipes is reduced; Then; With the SWCN sample for preparing long-time oxidation under proper temperature, temperature is: 370-410 ℃, oxidization time is: 5-20 hour; Air flow quantity is: the 10-500 ml/min, remove metallic carbon nanotubes, small dia SWCN and amorphous carbon impurity; At last, after the salt soak is removed metal catalyst particles, obtain the semiconductor properties SWCN.
2. according to the method for the described a large amount of acquisition semi-conductive single-walled carbon nanotubes of claim 1, it is characterized in that the concrete steps of chemical vapour deposition original position weak oxide are following: with hydrogen is carrier gas, and ferrocene is a catalyst precursor, and the sulphur powder is a growth stimulant; Under hydrogen shield, the chemical gas phase furnace temperature is risen to 900-1200 ℃; Feed the oxygen of carbon-source gas and trace again, and shift ferrocene onto furnace temperature simultaneously and be 50-80 ℃ and locate, carry out the chemical vapor deposition growth SWCN and it is carried out the original position weak oxide; Flow rate of carrier gas is the 200-1000 ml/min, and the weight ratio of sulphur powder and ferrocene is 1: 40-1: 200, and the flow of carbon-source gas is the 1-10 ml/min, and oxygen flow is the 0.1-0.2 ml/min, and the time is 10-120 minute.
3. according to the method for the described a large amount of acquisition semi-conductive single-walled carbon nanotubes of claim 2, it is characterized in that carbon-source gas is the organic gas hydrocarbon.
4. according to the method for claim 1 or 2 described a large amount of acquisition semi-conductive single-walled carbon nanotubes; It is characterized in that; The SWCN sample for preparing through the original position weak oxide shows the oxidation peak of two separations: the oxidation peak at lesser temps place corresponding higher metallic single-wall carbon nano-tube and the small dia SWCN of reactive behavior, and the oxidation peak at comparatively high temps place correspondence larger-diameter semi-conductive single-walled carbon nanotubes.
5. according to the method for the described a large amount of acquisition semi-conductive single-walled carbon nanotubes of claim 1; It is characterized in that; In the resultant product, the content of SWCN is more than 99wt%, and the content of semiconductor properties SWCN is more than 95wt%; Every batch of semiconductor properties SWCN that obtains 5mg-1g, the diameter Distribution of the prepared semi-conductive single-walled carbon nanotubes that obtains is 1.5-2.0nm; This diameter Distribution is the ideal diameter scope of SWCN as electronic device applications just.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103466597A (en) * | 2013-09-02 | 2013-12-25 | 中国科学院金属研究所 | Method for growing metallic single-walled carbon nanotubes by less doping nitrogen onto carbon lattices |
| CN108101025A (en) * | 2017-11-29 | 2018-06-01 | 航天材料及工艺研究所 | A kind of reinforcement of carbon nanotubes structural pipe wall |
| CN109592669A (en) * | 2018-10-18 | 2019-04-09 | 中国科学院福建物质结构研究所 | A kind of method of semi-conductor type single-walled carbon nano tube separation and concentration |
| CN110040720A (en) * | 2019-04-22 | 2019-07-23 | 中国科学院金属研究所 | High-purity, narrow diameter distribution, minor diameter double-walled carbon nano-tube preparation method |
-
2010
- 2010-09-29 CN CN2010102961363A patent/CN102431989A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| BING YU ET AL.: "Selective removal of metallic single-walled carbon nanotubes by combined in situ and post-synthesis oxidation", 《CARBON》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103466597A (en) * | 2013-09-02 | 2013-12-25 | 中国科学院金属研究所 | Method for growing metallic single-walled carbon nanotubes by less doping nitrogen onto carbon lattices |
| CN103466597B (en) * | 2013-09-02 | 2016-01-13 | 中国科学院金属研究所 | The method of a small amount of doped growing metallic single-wall carbon nano-tube of nitrogen on carbon grid |
| CN108101025A (en) * | 2017-11-29 | 2018-06-01 | 航天材料及工艺研究所 | A kind of reinforcement of carbon nanotubes structural pipe wall |
| CN109592669A (en) * | 2018-10-18 | 2019-04-09 | 中国科学院福建物质结构研究所 | A kind of method of semi-conductor type single-walled carbon nano tube separation and concentration |
| CN109592669B (en) * | 2018-10-18 | 2021-12-14 | 中国科学院福建物质结构研究所 | Method for separating and enriching semiconductor type single-walled carbon nanotubes |
| CN110040720A (en) * | 2019-04-22 | 2019-07-23 | 中国科学院金属研究所 | High-purity, narrow diameter distribution, minor diameter double-walled carbon nano-tube preparation method |
| CN110040720B (en) * | 2019-04-22 | 2022-05-31 | 中国科学院金属研究所 | Preparation method of high-purity narrow-diameter-distribution small-diameter double-wall carbon nano tube |
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Application publication date: 20120502 |