CN101671001B - Preparation method for semiconductor single wall carbon nano tube - Google Patents
Preparation method for semiconductor single wall carbon nano tube Download PDFInfo
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- CN101671001B CN101671001B CN200910308291XA CN200910308291A CN101671001B CN 101671001 B CN101671001 B CN 101671001B CN 200910308291X A CN200910308291X A CN 200910308291XA CN 200910308291 A CN200910308291 A CN 200910308291A CN 101671001 B CN101671001 B CN 101671001B
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Abstract
The invention discloses a preparation method for a semiconductor single wall carbon nano tube, which comprises the following steps: taking a transition element as a catalytic agent, fully blending catalytic agent, sulphur powder and graphite powder with 99.99% purity to obtain an anode graphite rod, and putting the prepared anode graphite rod in an arc chamber charged with buffer gas to be over against the graphite cathode. Discharge voltage and discharge current between the cathode and anode are controlled to lead the cathode and anode in the arc chamber to generate arc discharge, thus obtaining the semiconductor single wall carbon nano tube. The preparation method directly prepares the semiconductor single wall carbon nano tube by adopting the arc method and doping sulphur powder, and has simple technique and high yield; and the prepared semiconductor single wall carbon nano tube has few flaws and increases the electron mobility of a CNT based transistor.
Description
Technical field
The present invention relates to a kind of method of technical field of material, specifically is a kind of preparation method of semi-conductive single-walled carbon nanotubes.
Background technology
Because CNT (CNT) has accurate one-dimentional structure and unique electric property; So it has just caused the extensive concern of scientific circles after coming to light in 1991, extensively carried out the research work that CNT is applied to numerous areas such as nanometer electronic device, a lift-off technology, biological medicine carrying, hydrogen storage technology at present.CNT can be divided into SWCN (SWNT), double-walled carbon nano-tube (DWNT) and multi-walled carbon nano-tubes (MWNT); Wherein SWCN is as good monodimension nanometer material; Be used as nanometer electronic devices such as making field-effect transistor, thin film transistor (TFT) because of it has higher carrier mobility, be expected to replace silicon materials and the critical material that becomes microelectronic component of future generation.Different according to diameter of single-wall carbon nano tube with chirality; SWNT shows as metallicity and semiconductive; And metallic carbon nanotubes can have a strong impact on the performance of CNT based transistor, and therefore preparing the pure semiconductor conductive single-walled carbon nanotubes is to solve to adopt CNT to make one of key technology of CNT based transistor on a large scale.
Through existing literature search is found; People such as Z Xu, W Lu and W Wang have delivered on Adv.Mater (advanced material) in 2008 and have been entitled as " Converting Metallic Single-Walled Carbon Nanotubes intoSemiconductors by Boron/Nitrogen Co-Doping (changing metallic single-wall carbon pipe into semi-conductive single-walled carbon pipe through the B/N codope) "; This article adopts chemical vapour deposition technique (CVD) to prepare semiconductor single-walled carbon through the mode of B/N codope; But this technology adopts the CVD method; Complex process, productive rate are low; There is more fault of construction in the CNT of preparation, has limited the generation of the mobility of high carrier on the CNT.
Summary of the invention
The objective of the invention is to overcome the deficiency and the defective that exist in the prior art, a kind of preparation method of semi-conductive single-walled carbon nanotubes is provided.The present invention adopts the semi-conductive single-walled carbon nanotubes of arc discharge method (Arc discharging) preparation to have the less relatively characteristics of fault of construction, has improved the electron mobility of CNT based transistor.
The present invention realizes through following technical scheme; The concrete grammar of preparation is: be catalyst with the transition metal; With catalyst, sulphur (S) powder and purity is to make graphite anode rod after 99.99% graphite powder fully mixes in proportion, with the graphite anode rod that makes be placed on dash in the arc chamber that buffer gas is arranged with graphite cathode over against.Through the discharge voltage and the discharge current of control negative and positive two interpolars, negative and positive the two poles of the earth of arc chamber are taken place and arc discharge, can make semi-conductive single-walled carbon nanotubes.
Described catalyst, sulphur (S) powder and purity are that 99.99% graphite powder mixes in proportion; Its ratio is meant: the content molar percentage of catalyst is: 1%～6%; The content molar percentage of sulphur powder is: 0.1%～2%, and surplus is that purity is 99.99% graphite powder.
Described catalyst is one or more in iron (Fe), cobalt (Co), nickel (Ni), the yttrium (Y).
Described graphite anode rod is to be to fill out rod after 99.99% graphite powder fully mixes in proportion to make with catalyst, sulphur powder and purity.
Described graphite anode rod is to be that 99.99% graphite powder fully mixes the back adding additives in proportion and is squeezed into rod with catalyst, sulphur powder and purity.
Described buffer gas is one or more in the inert gas.
The air pressure range of described buffer gas is 20KPa～90KPa.
Described discharge voltage range is 40V～80V, and the discharge current scope is 60A～120A.
Compared with prior art; The invention has the beneficial effects as follows: adopt arc process directly to prepare semi-conductive single-walled carbon nanotubes through doping sulphur powder; Technology is simple, productive rate is high, and the semi-conductive single-walled carbon nanotubes fault of construction of preparation is few, has improved the electron mobility of CNT based transistor.
Description of drawings
Fig. 1 is the stereoscan photograph of the semi-conductive single-walled carbon nanotubes prepared of embodiment 2;
Fig. 2 is the projection electromicroscopic photograph of the semi-conductive single-walled carbon nanotubes prepared of embodiment 2;
Fig. 3 is the radially breathing mould of the Raman spectrum of the semi-conductive single-walled carbon nanotubes prepared of embodiment 2;
Wherein: (a) be the radially breathing mould of the Raman spectrum that obtains under the 514nm laser; (b) be the radially breathing mould of the Raman spectrum that obtains under the 633nm laser.
The specific embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated; All embodiment are to be to implement under the prerequisite with technical scheme of the present invention; Provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
With purity 99.99% graphite powder, Ni powder, yittrium oxide (Y
2O
3) powder and sulphur powder be 94.7%: 4.2%: 1% according to mol ratio: after 0.1% ratio fully mixes, be filled in the graphite rod of 4mm * 4cm * 6mm and make graphite anode rod.Graphite anode rod placed in the arc chamber that is connected with the 30KPa helium with graphite cathode over against; The discharge current of control negative and positive two interpolars is 60A～70A; Discharge voltage is 40V～50V, and be 5 minutes discharge time, finally obtains the semi-conductive single-walled carbon nanotubes of 0.8g.
Embodiment 2
Be 99.99% graphite powder, Fe powder and sulphur powder with purity according to mol ratio be after 94%: 5%: 1% ratio fully mixes; Add the moulding of 25wt% coal tar mixing pressure bar again, 1000 ℃ of high temperature furnaces then this rod being put into nitrogen protection are handled and were made graphite anode rod in 3 hours.Graphite anode rod placed in the arc chamber that is connected with 12KPa hydrogen, 18KPa argon gas with graphite cathode over against; The discharge current of control negative and positive two interpolars is 90A～100A; Discharge voltage is 60V～70V, and be 8 minutes discharge time, the final semi-conductive single-walled carbon nanotubes that gets 1g.
The stereoscan photograph of the semi-conductive single-walled nanotube of preparation is as shown in Figure 1; The projection electromicroscopic photograph is as shown in Figure 2; The radially breathing mould of the Raman spectrum that under 514nm laser and 633nm laser, obtains respectively is shown in Fig. 3 (a) and Fig. 3 (b); Wherein: abscissa is for being the wavelength of unit with nm; Ordinate is to be the light intensity of unit with arb.unit (arbitrary unit), and M represents metallicity, and S represents semiconductive; Because the peak value of M is all less than the peak value of S, so metallic carbon nanotubes content reduction in the prepared CNT of present embodiment.
Embodiment 3
With purity is that 99.99% graphite powder, Ni powder, Co powder, Fe powder and sulphur powder are 94.8%: 3%: 0.6% according to mol ratio: 0.6%: 1% mixed evenly after; Add the moulding of 25wt% coal tar mixing pressure bar again, the high temperature furnace of then this rod being put into nitrogen protection made graphite anode rod in 3 hours 1000 ℃ of heating.Graphite anode rod placed in the arc chamber that is connected with 24KPa hydrogen, 36KPa argon gas with graphite cathode over against; The discharge current of control negative and positive two interpolars is 110A～120A; Discharge voltage is 60V～70V, and be 10 minutes discharge time, the final semi-conductive single-walled carbon nanotubes that gets 1.2g.
Embodiment 4
With purity 99.99% graphite powder, Ni powder, Y
2O
3Powder and sulphur powder are 92.8%: 4.2%: 1% according to mol ratio: 2% mixed evenly after, be filled in the graphite rod of 4mm * 4cm * 6mm and make graphite anode rod.Graphite anode rod placed in the arc chamber that is connected with the 30KPa helium with graphite cathode over against, the discharge current of control negative and positive two interpolars is 80A～90A, discharge voltage is 60V～70V, be 8 minutes discharge time, finally obtains the semi-conductive single-walled carbon nanotubes of 1g.
Claims (6)
1. the preparation method of a semi-conductive single-walled carbon nanotubes; It is characterized in that, be catalyst with the transition metal, is to make graphite anode rod after 99.99% graphite powder mixes in proportion with catalyst, sulphur powder and purity; With the graphite anode rod that makes be placed on dash in the arc chamber that buffer gas is arranged with graphite cathode over against; Through the discharge voltage and the discharge current of control negative and positive two interpolars, make negative and positive the two poles of the earth of arc chamber that arc discharge take place, can make semi-conductive single-walled carbon nanotubes;
Described catalyst, sulphur powder and purity are that 99.99% graphite powder mixes in proportion; Its ratio is: the content molar percentage of catalyst is: 1%～6%; The content molar percentage of sulphur powder is: 0.1%～2%, and surplus is that purity is 99.99% graphite powder;
Described graphite anode rod is to be that 99.99% graphite powder fully mixes the back adding additives in proportion and is squeezed into rod with catalyst, sulphur powder and purity.
2. the preparation method of semi-conductive single-walled carbon nanotubes according to claim 1 is characterized in that, described catalyst is one or more in iron, cobalt, nickel, the yttrium.
3. the preparation method of semi-conductive single-walled carbon nanotubes according to claim 1 is characterized in that, described buffer gas is one or more in the inert gas.
4. the preparation method of semi-conductive single-walled carbon nanotubes according to claim 1 is characterized in that, the air pressure range of described buffer gas is 20KPa～90KPa.
5. the preparation method of semi-conductive single-walled carbon nanotubes according to claim 1 is characterized in that, described discharge voltage range is 40V～80V.
6. the preparation method of semi-conductive single-walled carbon nanotubes according to claim 1 is characterized in that, described discharge current scope is 60A～120A.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101905880B (en) * | 2010-07-23 | 2012-08-22 | 上海交通大学 | Method for preparing diameter-controllable single-walled carbon nanotube |
| CN102351171B (en) * | 2011-09-15 | 2014-01-01 | 上海交通大学 | Method for selectively preparing single-walled carbon nanotube in magnetic field |
| CN102502571B (en) * | 2011-10-11 | 2013-05-29 | 上海交通大学 | Method for manufacturing single-walled carbon nanotube aligned film by magnetically induced arc discharge |
| CN102602911A (en) * | 2012-03-07 | 2012-07-25 | 上海交通大学 | Method for preparing single-walled carbon nanotube by adopting controllability of low-pressure reactant gas |
| CN108220997B (en) * | 2018-01-31 | 2019-06-18 | 中国科学院福建物质结构研究所 | A kind of carbon containing nickel coat single-walled carbon nanotube composite material and preparation method and purposes |
| CN108212194B (en) * | 2018-01-31 | 2020-06-30 | 中国科学院福建物质结构研究所 | Nitrogen-doped carbon-coated nickel composite nano carbon water electrolysis catalyst and preparation method thereof |
| CN109714941B (en) * | 2018-11-22 | 2021-02-09 | 谢春艳 | Single-walled carbon nanotube embedded magnetic metal carbon onion nanocomposite and application and preparation method thereof |
| CN114558604A (en) * | 2022-03-09 | 2022-05-31 | 昆明理工大学 | Method for loading platinum on heteroatom-doped carbon nanohorn, catalyst and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235121A (en) * | 1999-06-04 | 1999-11-17 | 北京大学 | Method for preparing mono-layer nano-pipe |
| CN1579931A (en) * | 2004-05-17 | 2005-02-16 | 西安交通大学 | Method for batch type production of single-wall nano carbon tube suing temperature-controlled electric arc furnace |
| CN1887701A (en) | 2006-07-21 | 2007-01-03 | 太原理工大学 | Process of preparing single-wall carbon nanotube |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235121A (en) * | 1999-06-04 | 1999-11-17 | 北京大学 | Method for preparing mono-layer nano-pipe |
| CN1579931A (en) * | 2004-05-17 | 2005-02-16 | 西安交通大学 | Method for batch type production of single-wall nano carbon tube suing temperature-controlled electric arc furnace |
| CN1887701A (en) | 2006-07-21 | 2007-01-03 | 太原理工大学 | Process of preparing single-wall carbon nanotube |
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