CN1206699C - Carbon nano tube/carbon niride nano tube with nano junction and preparation and use - Google Patents
Carbon nano tube/carbon niride nano tube with nano junction and preparation and use Download PDFInfo
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- CN1206699C CN1206699C CN 02160815 CN02160815A CN1206699C CN 1206699 C CN1206699 C CN 1206699C CN 02160815 CN02160815 CN 02160815 CN 02160815 A CN02160815 A CN 02160815A CN 1206699 C CN1206699 C CN 1206699C
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Abstract
The present invention relates to a carbon nanotube or a carbon nitride nanotube with nanometer junction. A half of the carbon nanotube or a carbon nitride nanotube with nanometer junction along a tube axle direction is composed of carbon element, and the other half is the carbon nitride nanotube. A carbon nanotube part is a straight hollow tubular structure, and a nitrogen adulterating part is a bamboo structure. A diameter of the present invention is 10 to 100 nanometers, and the length is 5 to 400 microns. The electronic properties of the present invention are non-linear rectifying effect. In a preparation method, hydrogen gas or ammonia gas is communicated into a heating furnace; metal phthalocyanine is put into a region with 500 to 600 DEG C to be decomposed, and growth temperature is 800 to 1200 DEG C; under a hydrogen gas or ammonia gas atmosphere, after 1 to 20 minutes of constant temperature, a reaction atmosphere is changed, and another ammonia gas or hydrogen gas are communicated; after 1 to 60 minutes of constant temperature, the heating furnace is stopped to heating, and the hydrogen gas is continuously communicated to refrigerate; the flow capacity of the hydrogen gas is more than 0 to 500 ml / minute, and the flow capacity of the ammonia gas is 0 to 500 ml / minute. The present invention can be used for constructing nanometer devices.
Description
Technical field
The present invention relates to a kind of nano-device, relate in particular to a kind of carbon nano-tube/azotized carbon nano pipe with nano junction.
The invention still further relates to the preparation method of above-mentioned nanotube.
The invention still further relates to the application of above-mentioned nanotube in the structure nano-device.
Background technology
Along with the continuous microminiaturization of device, nano electron device will replace microelectronic component, and human society will progressively march toward the nano-device epoch.The same with microelectronics, the nano-device expection will be to become structural unit with various nanometers, and the controlled preparation of various nano junction is the preconditions that realize nano-device.The preparation of nano junction is current research focus at present.Carbon nano-tube is because its unique electricity and mechanical property, and becomes the nano-device material that has potentiality.Theory shows with experimental study: different with helicity according to diameter, carbon nano-tube shows a series of electrical properties from the semiconductor to the metal.By in the graphite network, introducing five-membered ring or heptatomic ring, the carbon nano-tube of the linear structure of two different electrical properties can be linked together and produce a nano junction (1:Odom, T.W.; Huang, J.-L.; Kim, P.; Lieber, C.M.J.Phys.Chem.B, 2000,104,2794.2:Yao, Z.; Postma, H.W.C.; Balents, L.; Dekker, C.Nature, 1999,402,273).But because helicity that can not controlling carbon nanotube, this method is difficult to implement.In the graphite network configuration of carbon nano-tube, introduce the electric property that nitrogen-atoms can change nanotube effectively, the azotized carbon nano pipe is a kind of n type nano material with semiconductor property, its electrical properties and helicity are irrelevant, therefore can control its electric property by the composition of control nanotube, this method is easy to implement.If in carbon nano-tube, partly mix the nitrogen element, make that the electrical properties of different parts is inequality, thereby produce nano junction.At present, can control growing go out to have carbon nano-tube (Satishkumar, the B.C. of the various bifurcation structures of nano junction; Thomas, P.J.; Govindaraj, A; Rao, N.R.Appl.Phys.Lett., 2000,77,2530) and utilize the microwave chemical vapour deposition process to prepare the linear azotized carbon nano pipe/existing report of carbon nanotube knot (Ma, X.C.; Wang, E.G.Appl.Phys.Lett.2001,78,978), but still do not have the nanotube of the linear structure of utilizing phthalocyanine derivates to have nano junction as catalyst and carbon source control growing and the report of this nano junction electric property.
Summary of the invention
The object of the present invention is to provide a kind of nanotube-carbon nano-tube/azotized carbon nano pipe (C/CN with nano junction
X).
Another object of the present invention is to provide the preparation method of above-mentioned nanotube.
Above-mentioned nanotube itself with nano junction provided by the invention is exactly a nanotube diode, shows nonlinear rectifying effect, and this nanotube can be directly used in the structure nano-device.
A kind of nanotube provided by the invention with nano junction since in the same nanotube along two parts chemical composition difference of tube axial direction, and show tangible structure and electric property difference, the pipe diameter is 10～100 nanometers, pipe range is 5～400 microns.
The present invention is used to prepare C/CN
XThe device of nanotube adopts popular response equipment, mainly is made up of reactor, air distribution system, temperature-controlling system three parts.(1) reactor: form by quartz ampoule and electric tube furnace; (2) air distribution system: form by gas circuit and mass-flow gas meter, can control flow, ratio and the kind of carrier gas; (3) temperature-controlling system: form by programmed temperature control instrument, owing to be in the heating of the central area of body of heater, thereby a temperature gradient is arranged from the body of heater center to fire door.
The preparation method of a kind of nanotube with nano junction provided by the invention is as follows:
Utilize phthalocyanine derivates to make raw material, connect air distribution system, feed hydrogen or ammonia, it is 500～600 ℃ Region Decomposition that the quartz boat that fills the metal phthalocyanine of quartz boat volume 1/50-2/3 is put into the fire door temperature, the center growth temperature is 800～1200 ℃ in the stove, under a kind of gas (hydrogen or ammonia) atmosphere, behind the constant temperature 1～20 minute, change reaction atmosphere, feed another kind of gas (ammonia or hydrogen), behind the constant temperature 1～60 minute, stop heating, continue logical hydrogen refrigeration, the palpulus of hydrogen flowing quantity is greater than 0 ml/min, be 500 ml/min to the maximum and get final product, ammonia is 0～500 ml/min.Getting product is the C/CN with nano junction
XNanotube.Described metal phthalocyanine comprises: FePC, phthalocyanine nickel or phthalocyanine cobalt.
The C/CN of the present invention's preparation
XNanotube has following characteristics and advantage:
1, a kind of two parts chemical composition difference provided by the invention with nanotube of nano junction along tube axial direction, half is made up of carbon, is pure nano-carbon tube, and second half nitrogen that mixed is the carbonization nitride nanotubes.
2, a kind of nanotube with nano junction provided by the invention is formed difference because of two parts, and its two-part structure has notable difference: pure nano-carbon tube partly is straight hollow tubular structures, and doping nitrogen partly has tangible bamboo knot shaped structure.
3, a kind of nanotube provided by the invention with nano junction, its diameter is 10～100 nanometers, length is 5～400 microns.
4, a kind of nanotube with nano junction provided by the invention is because of its two parts are formed the different intramolecular heterojunction that have.
5, a kind of nanotube with nano junction provided by the invention, its electric property shows as non-linear preferably rectifying effect.
6, a kind of nanotube with nano junction provided by the invention itself is exactly a kind of nanotube diode.
7, a kind of novel uniqueness of nano tube structure with nano junction provided by the invention has special electricity and mechanical property, is a kind of nano-device desirable material of constructing.
8, the inventive method preparation manipulation is easy, and technology is simple, and is with low cost, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1: the C/CN that transmission electron microscope photographs
XThe nanotube photo.
Fig. 2: the ESEM picture of carbon nano tube device.
Fig. 3: adopt the two end electrodes method to record C/CN
xThe current-voltage curve of nanotube has tangible rectification behavior.
Embodiment
The present invention is described in detail below in conjunction with drawings and Examples.
Embodiment 1: connect air distribution system, feed hydrogen, when the body of heater central temperature reaches 800～1200 ℃, it is 500～600 ℃ zone that the quartz boat that fills 0.02 gram FePC is put into the fire door temperature, under hydrogen atmosphere, constant temperature changed reaction atmosphere after 1 minute, feed another kind of gas ammonia, behind the constant temperature 2 minutes, stop heating, continue logical hydrogen refrigeration, the flow of every kind of gas is 40 milliliters of per minutes, and products therefrom is the C/CN with nano junction
XNanotube.Fig. 1 is the C/CN of gained
XThe transmission electron microscope photo of nanotube, Fig. 2 is for measuring C/CN
XThe current-voltage curve of nanotube.
Embodiment 2: they according to the preparation method of embodiment 1, are earlier logical ammonia, and promptly first doping nitrogen element, the back feeds hydrogen, and 40% is the C/CN with nano junction in the products therefrom
XNanotube.
Embodiment 3: according to the preparation method of embodiment 1, just the quantitative change with FePC is 0.05 gram, and 35% is the C/CN with nano junction in the products therefrom
XNanotube.
Embodiment 4: according to the preparation method of embodiment 1, instead of phthalocyanine nickel, 50% is the C/CN with nano junction in the products therefrom with FePC
XNanotube.
Embodiment 5: according to the preparation method of embodiment 1, instead of the phthalocyanine cobalt, 52% is the C/CN with nano junction in the products therefrom with FePC
XNanotube.
Embodiment 6: according to the preparation method of embodiment 1, just respectively the flow of two kinds of gases is changed into 80 milliliters of per minutes, 30% is the C/CN with nano junction in the products therefrom
XNanotube.
Embodiment 7: according to the preparation method of embodiment 4, just the quantitative change with phthalocyanine nickel is 0.05 gram, and 35% is the C/CN with nano junction in the products therefrom
XNanotube.
Embodiment 8: they according to the preparation method of embodiment 4, are earlier logical ammonia, and promptly first doping nitrogen element, the back feeds hydrogen, and 35% is the C/CN with nano junction in the products therefrom
XNanotube.
Embodiment 9: according to the preparation method of embodiment 5, just the quantitative change with the phthalocyanine cobalt is 0.05 gram, and 35% is the C/CN with nano junction in the products therefrom
XNanotube.
Embodiment 10: they according to the preparation method of embodiment 5, are earlier logical ammonia, and promptly first doping nitrogen element, the back feeds hydrogen, and 35% is the C/CN with nano junction in the products therefrom
XNanotube.
Embodiment 11: according to the preparation method of embodiment 5, just respectively the flow of two kinds of gases is changed into 80 milliliters of per minutes, 30% is the C/CN with nano junction in the products therefrom
xNanotube.
Claims (3)
1, a kind of carbon nano-tube/azotized carbon nano pipe with nano junction is made up of carbon along half of tube axial direction, and second half is the azotized carbon nano pipe;
Described carbon nano-tube partly is straight hollow tubular structures, and the part of the carbon nano-tube of nitrogenize has bamboo knot shaped structure;
The diameter of described carbon nano-tube/azotized carbon nano pipe is 10～100 nanometers, and length is 5～400 microns;
Its electric property has non-linear rectification effect.
2, a kind of method for preparing the described nanotube of claim 1, feed hydrogen or ammonia in the heating furnace, metal phthalocyanine is in 500～600 ℃ Region Decomposition, and 800～1200 ℃ of center growth temperatures are under hydrogen or ammonia atmosphere, behind the constant temperature 1～20 minute, change reaction atmosphere, feed another kind of gas ammonia or hydrogen, constant temperature is after 1～60 minute, stop heating, continue logical hydrogen refrigeration;
Wherein: the hydrogen flowing quantity minimum is greater than 0 ml/min, is 500 ml/min to the maximum; Ammonia flow is 0～500 ml/min.
3, method as claimed in claim 2 is characterized in that, described metal phthalocyanine is FePC, phthalocyanine nickel or phthalocyanine cobalt.
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| CN 02160815 CN1206699C (en) | 2002-12-30 | 2002-12-30 | Carbon nano tube/carbon niride nano tube with nano junction and preparation and use |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101616516A (en) * | 2008-06-27 | 2009-12-30 | 清华大学 | Line heat source |
| US8410676B2 (en) | 2007-09-28 | 2013-04-02 | Beijing Funate Innovation Technology Co., Ltd. | Sheet-shaped heat and light source, method for making the same and method for heating object adopting the same |
| US8450930B2 (en) | 2007-10-10 | 2013-05-28 | Tsinghua University | Sheet-shaped heat and light source |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254916B (en) * | 2008-04-11 | 2010-04-07 | 北京工业大学 | Method for in-situ synthesis of metal phthalocyanine/carbon nano-tube compound |
| CN102502573B (en) * | 2011-10-19 | 2014-05-14 | 沈阳建筑大学 | Templet assembling technique of carbon-base nanotube coaxial heterojunction |
| CN103293822B (en) * | 2013-05-16 | 2015-10-28 | 中北大学 | The preparation method of a kind of nonlinear optics carbon nano-particle and phthalocyanine-like compound hybrid material |
| CN104952631B (en) * | 2015-06-15 | 2017-10-17 | 四川环碳科技有限公司 | The method that Graphene/carbon nanotube composite material is prepared using solid phase cracking technique |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8410676B2 (en) | 2007-09-28 | 2013-04-02 | Beijing Funate Innovation Technology Co., Ltd. | Sheet-shaped heat and light source, method for making the same and method for heating object adopting the same |
| US8450930B2 (en) | 2007-10-10 | 2013-05-28 | Tsinghua University | Sheet-shaped heat and light source |
| CN101616516A (en) * | 2008-06-27 | 2009-12-30 | 清华大学 | Line heat source |
| CN101616516B (en) * | 2008-06-27 | 2013-04-24 | 清华大学 | Line heat source |
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