CN104649247A - Method for formation of nitrogen doped single-walled carbon nanotube - Google Patents
Method for formation of nitrogen doped single-walled carbon nanotube Download PDFInfo
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- CN104649247A CN104649247A CN201310596616.5A CN201310596616A CN104649247A CN 104649247 A CN104649247 A CN 104649247A CN 201310596616 A CN201310596616 A CN 201310596616A CN 104649247 A CN104649247 A CN 104649247A
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- walled carbon
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Abstract
The invention discloses a method for formation of a nitrogen doped single-walled carbon nanotube. The method includes: employing nitrogen containing plasmas to conduct exposure irradiation on single-walled carbon nanotube powder or the single-walled carbon nanotube distributed on a selected matrix, injecting nitrogen atoms into the single wall carbon nanotube so as to form the nitrogen doped single-walled carbon nanotube. Specifically, the exciting power of the nitrogen containing plasmas is more than 6.0W and less than 10W. The nitrogen doped single-walled carbon nanotube prepared by the method provided by the invention has a pyridine nitrogen content of more than 0.5at%, and does not introduce defects into the carbon nanotube structure while acquiring a high nitrogen doping concentration, maintains the structure and quality of the original carbon nanotube, can be applied to single-walled carbon nanotube based microelectronic devices or corresponding integrated circuit modules and other components, and also can be applied as a catalyst to oxygen reduction reactions in alkaline medium. At the same time, the method provided by the invention has no limit to the source and form of an initial single-walled carbon nanotube material, has flexible controllability, and the cost is also low.
Description
Technical field
The present invention relates to a kind of carbon nanotube aftertreatment technology, in particular, relate to a kind of preparation method of nitrogen-doped single-walled carbon nanotubes.
Background technology
Carbon nanotube is according to by sp
2the number of plies of the tube wall of the carbon atom formation of orbital hybridization can be divided into Single Walled Carbon Nanotube (SWNT) and multi-walled carbon nano-tubes (MWNT); multi-walled carbon nano-tubes is also subdivided into double-walled carbon nano-tube (DWNT), few-wall carbon nanotube (FWNT) etc. in recent years under study for action usually.Due to structure and the premium properties of its uniqueness, carbon nanotube has shown using value widely in matrix material, nano coating and film, microelectronic device, energy storage, environment and biotechnology field.
Wherein, Single Walled Carbon Nanotube can be regarded as by graphene layers around central shaft by the curling seamless open tube of certain helix angle, this helix angle is usually with chiral index (m, n) form describes, and theory in the past and experimental evidence show Single Walled Carbon Nanotube electricity, the character such as mechanics depend on chiral index (m, n) largely.In addition in recent years wall defects to carbon nanotube electricity, the impact of mechanical property also result in concern, especially nitrogen-doped carbon nanometer pipe is at microelectronics, and the application of cathodic oxygen reduction catalyzed reaction in fuel cell, stimulates the development of the preparation of nitrogen-doped carbon nanometer pipe greatly.
The preparation method of nitrogen-doped carbon nanometer pipe can simply be divided into two classes: the first kind is in-situ doped, namely in the preparation process of carbon nanotube, adds doped element simultaneously; Conventional method prepares in the process of carbon nanotube at chemical Vapor deposition process (CVD), adds various nitrogenous organic molecule reactant.By the impact of carbon nano tube growth mechanism, introduce nitrogen-atoms and can make on aerodynamic point, more easily to form closed bamboo joint structure in carbon nanotube growth process.Therefore, although in-situ doped method can obtain the very high Bamboo-shaped multi-walled carbon nano-tubes of nitrogen content, be difficult to prepare nitrogenous Single Walled Carbon Nanotube, especially the Single Walled Carbon Nanotube of high nitrogen content.Equations of The Second Kind method is aftertreatment doping, namely carries out aftertreatment to the carbon nanotube prepared and completes doping.The main advantage of post treatment method is to retain the original microcosmic of processed carbon nanotube and characteristics of macrostructure.Wherein a kind of typical post treatment method realizes by Plasma ion implantation technology, as, namely the people such as Xia Yang propose a kind of nitrogenous preparation method of carbon nano-tube based on this technology, its be compared to over based on thermal treatment reaction doping means, be expected to introduce other less textural defect while introducing foreign atom, but, the method also has many limitation, such as, it forms carbon nanotube (mainly multi-walled carbon nano-tubes) under first needing the prerequisite existed at catalytic materials such as Ni metals, could be adulterated under then needing the prerequisite existed at Ni metal etc. equally nitrogen in carbon nanotube.And for the direct multi-walled carbon nano-tubes obtained by commercially available approach or other approach, the N doping operating method in more difficult direct employing the method.Further, same, this method is also unsuitable for preparing nitrogenous Single Walled Carbon Nanotube, especially the Single Walled Carbon Nanotube of high nitrogen content.
Summary of the invention
The object of the present invention is to provide a kind of method preparing nitrogen-doped single-walled carbon nanotubes, to overcome deficiency of the prior art.
For realizing object of the present invention, present invention employs following technical scheme:
A kind of method forming nitrogen-doped single-walled carbon nanotubes, comprise: to carry out exposure irradiation containing nitrogen plasma to Single Walled Carbon Nanotube powder or the Single Walled Carbon Nanotube be distributed on selected matrix, institute's nitrogen atom in plasma body is made to inject Single Walled Carbon Nanotube, form nitrogen-doped single-walled carbon nanotubes, wherein, nitrogenous plasma exciatiaon power at more than 6.0W, but is less than 10W.
Further, the method can comprise the steps:
(1) Single Walled Carbon Nanotube is placed in plasma processing apparatus, and this plasma processing apparatus inner chamber is vacuumized;
(2) in this plasma processing apparatus, pass into working gas, carry out plasma exciatiaon, formed containing nitrogen plasma, and exposure irradiation is carried out to Single Walled Carbon Nanotube, form nitrogen-doped single-walled carbon nanotubes.
As one of comparatively preferred embodiment, the operating pressure in step (2) in plasma processing apparatus inner chamber is 400mTorr ~ 600mTorr.
Further, described working gas is at least selected from air, any one in nitrogen and krypton, and is not limited thereto.
As one of comparatively preferred embodiment, in the method, with in the process of nitrogenous plasma radiation Single Walled Carbon Nanotube, the bias voltage put in Single Walled Carbon Nanotube is-200V ~+200V.
Further, the method also can comprise plasma body pretreatment process, and the pretreatment gas wherein adopted at least is selected from air, argon gas, any one in helium.
More specifically, the method can comprise:
(2) in plasma processing apparatus, pretreatment gas is injected, and pressure is adjusted to 400mTorr ~ 600mTorr, with the radio frequency power activated plasma of 6.8W ~ 13.5W and irradiation 5s ~ 10min, exhaust also vacuumizes rear injection working gas again, and pressure is adjusted to 400mTorr ~ 600mTorr, with more than 6.0W, but the radio frequency power being less than 10W excites containing nitrogen plasma and stops after irradiation 5s ~ 10min.
The Single Walled Carbon Nanotube that described Single Walled Carbon Nanotube can adopt any approach to obtain, such as, commercially available all kinds of Single Walled Carbon Nanotube.
Further, in the method, with the time of nitrogenous plasma radiation Single Walled Carbon Nanotube at more than 5s, preferably at 1min ~ 10min.
Compared with prior art, the present invention at least tool have the following advantages:
(1) in the nitrogen-doped single-walled carbon nanotubes prepared by the inventive method, pyridine nitrogen content can more than 0.5at%, and while the more high nitrogen doped concentration of acquisition, also defect be can not introduce in carbon nanotube structure, structure and the quality of original carbon nanotube maintained;
(2) the inventive method does not need to introduce some comparatively complicated nitrogenous compounds and at high temperature decomposes, and unrestricted to the source of initial single tube material and form, and have controllability comparatively flexibly, cost is also lower.
Accompanying drawing explanation
Fig. 1 is the structural representation of a kind of plasma processing apparatus in one embodiment of this invention, and wherein each parts and Reference numeral thereof are respectively: 1-treatment chamber (silica glass), 2-RF(radio frequency) coil, 3-RF(radio frequency) power supply, 4-front panel (stainless steel), 5-inlet mouth, 6-venting port, 7-O RunddichtringO, 8-joint flange, 9-quartz observing window, 10-electricity feedthrough, 11-lead-in wire, 12-is with the sample table of PMMA burden copper net electrode.
Fig. 2 a-Fig. 2 b is respectively in order to the structural representation (Fig. 2 a-1,2a-2 are respectively vertical view and side-view) of the field-effect transistor based on Single Walled Carbon Nanotube (FET) device by nitrogenous plasma radiation and electron scanning micrograph in embodiment 1, and wherein each parts and Reference numeral thereof are respectively: 1-Single Walled Carbon Nanotube, 2-electrode, 3-layer-of-substrate silicon, 4-silicon dioxide insulating layer.
Fig. 3 is the change collection of illustrative plates of the electrical properties of FET device shown in Fig. 2 b before and after nitrogenous plasma radiation in embodiment 1.
Fig. 4 a-Fig. 4 b is the XPS collection of illustrative plates of Single Walled Carbon Nanotube powder before and after nitrogenous plasma radiation in embodiment 2.
Fig. 5 a-Fig. 5 b is the change of properties of the Single Walled Carbon Nanotube powder electrochemical catalysis redox reactions in alkaline medium in embodiment 2 before and after nitrogenous plasma radiation, wherein, Fig. 5 a is static volt-ampere curve, and Fig. 5 b is stable state volt-ampere curve, and rotating ring disk electrode (r.r.d.e) rotating speed is 1600 revs/min.
Fig. 6 is the change of properties of Single Walled Carbon Nanotube powder electrochemical catalysis redox reactions in alkaline medium after the ammonia plasma treatment irradiation being applied with different additional bias in embodiment 2.
Embodiment
As previously mentioned, in view of the deficiencies in the prior art, the present invention aims to provide a kind of method preparing the Single Walled Carbon Nanotube (N-SWCNT) of N doping, it is excite nitrogenous plasma body by electromagnetic radiation, and by Single Walled Carbon Nanotube sample being exposed in plasma body the regular hour so that some nitrogen of major general are by during ion implantation form is from plasma transferred to Single Walled Carbon Nanotube.
As the typical embodiment of one of the present invention, a kind of method forming nitrogen-doped single-walled carbon nanotubes wherein can comprise:
Be placed on the sample table in plasma processing apparatus by pending Single Walled Carbon Nanotube sample, wherein a kind of structure of classicalpiston treatment unit can consult Fig. 1;
Select suitable shooting conditions to excite nitrogenous plasma body, and sample is carried out exposing irradiation thus the nitrogen produced in plasma body be injected in sample.
Wherein, sample can be distributed in Single Walled Carbon Nanotube on selected matrix or Single Walled Carbon Nanotube powder.
Further, at least in the process of plasma radiation, in plasma processing apparatus operating pressure can be 400mTorr ~ 600mTorr.
Further, the RF power of plasma body controls at more than 6.0W, but is less than 10W.
Further, in the method, if using plasma pre-treatment, so pretreatment gas at least comprises the one in air, argon gas, helium, and is not limited thereto.
Further, in the method, working gas at least should comprise air, the one in nitrogen and krypton, and is not limited thereto.
Further, in the method, at least in the process of plasma radiation, the bias voltage putting on sample can be-200V ~+200V.
Further, in the method, according to the difference of processing sample characteristic, the time of Cement Composite Treated by Plasma also can be very different, and it can be several seconds (more than 5s, such as 5 ~ 7 seconds), can also be several minutes (preferably 1 ~ 10min).
Nitrogen-doped single-walled carbon nanotubes of the present invention can be applicable to based in the elements such as the microelectronic device of Single Walled Carbon Nanotube or corresponding integrated circuit modules, also can be used as catalyzer or catalyst precursor and is applied to redox reactions in alkaline medium.
Below in conjunction with some embodiments and accompanying drawing, technical scheme of the present invention is further described.
Embodiment 1
The Single Walled Carbon Nanotube that horizontal array is arranged is transferred to Si/SiO by shifting process
2substrate surface, then be made into the FET device as shown in Fig. 2 a-Fig. 2 b by the technique that photolithographic deposits;
Then, substrate (the i.e. aforementioned FET device) entirety being loaded with Single Walled Carbon Nanotube is placed in the sample table (structure can consult Fig. 1) of apparatus for processing plasma chamber, chamber vent is vacuumized rear injection working gas ammonia, and pressure is adjusted to 500mTorr, with the radio frequency power activated plasma of 6.8W and irradiation stop after 5 ~ 7 seconds.The Electric transport properties that FET device takes out front and back is shown in Fig. 3, and measuring result shows to obtain remarkable lifting based on FET device on-off ratio performance after plasma radiation of Single Walled Carbon Nanotube.And the mobility of the electronic transport data sheet funerary objects part obtained remains unchanged substantially and carrier concentration there occurs obvious reduction.
Mobility due to the FET device based on Single Walled Carbon Nanotube depends primarily on the scattering coming from defect, and carrier concentration derives from doping state, conclusion shows that plasma radiation can not bring larger damage for the structure of Single Walled Carbon Nanotube, greatly can change again the dopant states of Single Walled Carbon Nanotube simultaneously.
Embodiment 2
Commercially available Single Walled Carbon Nanotube powder is placed in lid plastic culture dish, and has been positioned in the sample table (structure can consult Fig. 1) in apparatus for processing plasma chamber, and chamber vent has been vacuumized, then adopt the following two kinds mode to operate:
(1) injecting working gas ammonia, and pressure is adjusted to 500mTorr, sample table applies the direct current (DC) bias that-100V ~ 0V does not wait, with being more than or equal to 6W, but being less than any radio frequency power activated plasma of 10W and irradiation stopped after 3 minutes.
(2) pretreatment gas argon gas is injected, and pressure is adjusted to 500mTorr, with the radio frequency power activated plasma of 13.5W and irradiation after 1 minute, exhaust again vacuumizes and injects working gas ammonia, and pressure is adjusted to 500mTorr, with being more than or equal to 6W, but be less than any radio frequency power activated plasma of 10W and irradiation stopped after 10 minutes.
Be the Single Walled Carbon Nanotube of intrinsic and the XPS collection of illustrative plates of Single Walled Carbon Nanotube crossed by aforementioned (1), (2) art breading respectively shown in Fig. 4 a-Fig. 4 b, therefrom measure and obtain its nitrogen content and be respectively 0.22at.%, 0.38at.%, 0.54at.%.
What the nitrogen content wherein in the Single Walled Carbon Nanotube that obtains of (1) kind mode and in-situ doped method obtained is on close level, and (2) plants technique then obtains and be obviously better than the general obtainable level of in-situ doped method.
Postscript, refer to again Fig. 5 a-Fig. 5 b to illustrate the Single Walled Carbon Nanotube of intrinsic and the present embodiment obtain CV in the redox reactions that nitrogenous Single Walled Carbon Nanotube is applied in alkaline medium and stable state volt-ampere curve, obviously, the better redox reactions catalytic performance that higher nitrogen content brings, again, consulting Fig. 6, illustrating by regulating additional bias to obtain preferred redox reactions catalytic performance.Further, also can see, this type of nitrogenous Single Walled Carbon Nanotube substitutes the potentiality of Pt as redox reactions catalyzer in a fuel cell.
It is pointed out that above explanation and the embodiment shown on drawing, the design philosophy surely of the present invention that is limited can not be resolved.Hold in technical field of the present invention identical know the knowledgeable can by technical thought of the present invention with various form improvement change, such improvement and change are interpreted as belonging in protection scope of the present invention.
Claims (9)
1. one kind forms the method for nitrogen-doped single-walled carbon nanotubes, it is characterized in that, comprise: to carry out exposure irradiation containing nitrogen plasma to Single Walled Carbon Nanotube powder or the Single Walled Carbon Nanotube be distributed on selected matrix, institute's nitrogen atom in plasma body is made to inject Single Walled Carbon Nanotube, form nitrogen-doped single-walled carbon nanotubes, wherein, nitrogenous plasma exciatiaon power at more than 6.0W, but is less than 10W.
2. form the method for nitrogen-doped single-walled carbon nanotubes according to claim 1, it is characterized in that, comprise the steps:
(1) Single Walled Carbon Nanotube is placed in plasma processing apparatus, and this plasma processing apparatus inner chamber is vacuumized;
(2) in this plasma processing apparatus, pass into working gas, carry out plasma exciatiaon, formed containing nitrogen plasma, and exposure irradiation is carried out to Single Walled Carbon Nanotube, form nitrogen-doped single-walled carbon nanotubes.
3. form the method for nitrogen-doped single-walled carbon nanotubes according to claim 2, it is characterized in that, in step (2), the operating pressure in plasma processing apparatus inner chamber is 400 mTorr ~ 600 mTorr.
4. form the method for nitrogen-doped single-walled carbon nanotubes according to claim 2, it is characterized in that, described working gas is at least selected from air, any one in nitrogen and krypton.
5. according to claim 1 or 2, form the method for nitrogen-doped single-walled carbon nanotubes, it is characterized in that, with in the process of nitrogenous plasma radiation Single Walled Carbon Nanotube, the bias voltage putting on sample is-200 V ~+200 V.
6. according to claim 1 or 3, form the method for nitrogen-doped single-walled carbon nanotubes, it is characterized in that, the method also comprises plasma body pretreatment process, and the pretreatment gas wherein adopted at least is selected from air, argon gas, any one in helium.
7. form the method for nitrogen-doped single-walled carbon nanotubes according to claim 1, it is characterized in that, described Single Walled Carbon Nanotube selects commercially available Single Walled Carbon Nanotube.
8. according to claim 1 or 3, form the method for nitrogen-doped single-walled carbon nanotubes, it is characterized in that, with the time of nitrogenous plasma radiation Single Walled Carbon Nanotube at more than 5s.
9. form the method for nitrogen-doped single-walled carbon nanotubes according to claim 8, it is characterized in that, with the time of nitrogenous plasma radiation Single Walled Carbon Nanotube at 1min ~ 10min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106348277A (en) * | 2016-08-23 | 2017-01-25 | 石河子大学 | Heteroatom-doped carbon material and preparation method thereof |
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| CN1653204A (en) * | 2002-05-08 | 2005-08-10 | 达纳公司 | Plasma-assisted nitrogen surface treatment |
| CN1994875A (en) * | 2006-01-05 | 2007-07-11 | 三星电子株式会社 | Method of forming nitrogen-doped single-walled carbon nanotubes |
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Patent Citations (2)
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| CN1653204A (en) * | 2002-05-08 | 2005-08-10 | 达纳公司 | Plasma-assisted nitrogen surface treatment |
| CN1994875A (en) * | 2006-01-05 | 2007-07-11 | 三星电子株式会社 | Method of forming nitrogen-doped single-walled carbon nanotubes |
Non-Patent Citations (2)
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| CHANGLUN CHEN ET AL.: "Amino group introduction onto multiwall carbon nanotubes by NH3/Ar plasma treatment", 《CARBON》, vol. 48, 29 October 2009 (2009-10-29) * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106348277A (en) * | 2016-08-23 | 2017-01-25 | 石河子大学 | Heteroatom-doped carbon material and preparation method thereof |
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