CN107082412A - A kind of method for preparing high density electron level purity semiconductor ultra-long horizontal nano-tube array - Google Patents
A kind of method for preparing high density electron level purity semiconductor ultra-long horizontal nano-tube array Download PDFInfo
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Abstract
The invention provides a kind of method for preparing high density electron level purity semiconductor ultra-long horizontal nano-tube array, including supported catalyst and place substrate, temperature reaction and prepare the steps such as overlength carbon nano pipe, repeated growth and sampling excision.In the inventive method, pass through fine optimization CNT preparation technology and length, result in high density, the horizontal carbon nano pipe array of superelevation semiconductor purity, high-purity semiconductive horizontal array carbon nano tube preparation problem for the current carbon-based integrated circuit development core the most of restriction provides a kind of simple and reliable method, with wide commercial applications prospect.
Description
Technical field
The present invention relates to nano material preparation and application field, high density electron level is prepared in particular to one kind pure
The method of semiconductive ultra-long horizontal nano-tube array is spent, so as to be the height of the current carbon-based integrated circuit development of restriction core the most
Purity semiconductor CNT prepares problem and provides a kind of simple and reliable technology path.
Background technology
Reduction chip size, raising chip performance are to promote computer industry development many decades " Moore's Law " correctness
Crucial embodiment.According to described in Moore's Law, new chip fabrication techniques will every two years upgrade, and it has been helped computer
It is sent on our desk, in pocket and in wrist.But during electronic component reduces to atomic scale, but it is faced with
Severe engineering challenge, causes silicon substrate " Moore's Law " ultimate failure.In numerous materials in current " rear silicon epoch ", carbon nanometer
Pipe is the unique dirac carbon material of a class, due to its linear or almost linear energy and momentum low energy dispersion relation, electronics with
Hole can make it have excellent electronics, hole high mobility and very high current with 1/300 massless high-speed transfer of the light velocity
The characteristics such as density, the ideal candidates material as high-speed semiconductor of future generation.
In January, 2017, the world's minimum dimension 5nm transistors constructed based on carbon nano-tube material of Chinese independent research
Achievement in research is published in《Science》Magazine, fully presents CNT and promotes computing power to continue surely under rear mole of epoch
Surely the unlimited potentiality developed.Therefore, the international semiconductor route map committee (ITRS) determines that it is what future was most possibly applied
New device material, IBM Corporation also invest substantial contribution be used for develop next generation computer chip based on CNT,
And assert that the chip for fast 5 times of the existing chip of ratio being made up of CNT will be molded before the year two thousand twenty.
However, realize CNT, particularly high density electron level purity semiconductor ultra-long horizontal carbon nano pipe array
Controllable preparation be its application key and premise, while be also restricting current CNT research and its in the carbon-based electricity of high-performance
The bottleneck of sub- aspect application.
CNT can be regarded as the hollow cylinder crimped by graphite flake layer along a direction, according to rolled fashion
The difference of (commonly referred to as " chirality "), can embody metallicity and the adjustable semiconductive of band gap.Abundant atomic structure is real
Its existing diversification, flexibility, which are applied, provides considerable advantage, but also determines that the controllable preparation of specific structure is its development of restriction
Critical bottleneck and challenge.IBM is pointed out, wants really to realize the scale application of high-performance carbon nanotube base integrated circuit, high
Density, the controllable preparation of electron level pure carbon nanotubes array are the application problems of core.
Around this key problem, international research person is broadly divided into two technology paths, and one of them is desirable to using original
Method prepared by position obtains high density, high semiconductor pure carbon nanotubes array.The advantage of this method is that direct growth goes out
The CNT come can show the intrinsic performance advantage of material, and be can be achieved by optimizing catalyst structure design to carbon nanometer
The coarse adjustment of pipe caliber, density and chirality, but the highest semiconductor purity hitherto reached is only 98%, single chiral control
Highest purity processed is only 92%, and the realization of high-density carbon nano-tube array is still needed to by substrate lattice guide effect, it is difficult to straight
Connect for building high-performance carbon nanotube base electron device.And another technology path is then the CNT to prepare with scale
Powder is purified, and can obtain the CNT of more high density and semiconductor purity although with the technology path, but due to
The physical operations such as doping and mechanical agitation of a variety of chemical substances to CNT, vibration is made to CNT in purge process
Into structural damage, CNT has lost material intrinsic perfect atomic structure when for electronic device and superelevation is moved
Shifting rate, and the CNT orientation obtained using this kind of method is random, easily forms the structure of overlap joint or tube bank, applies in electricity
High conduction contact is hardly formed in sub- device, so as to cause electrical conductivity and switching current than declining, is unfavorable for giving full play to carbon and receives
The performance advantage of mitron in integrated circuits.
In CNT prepared by numerous distinct methods, the ultra-long horizontal array carbon nano tube tool of " top pattern " growth
There is faint CNT-substrate to interact and intervalve coupling Van der Waals force.This almost entirely free on his growth pattern makes
It, which possesses, realizes that probability is only 1/60000000000th overlength, chiral consistent perfect structure, can most show CNT theoretical
On ultimate attainment performance.Such class overlength carbon nano pipe is used to construct electronic device, CNT can be more given full play to and exist
Limit advantage in integrated circuit.On the one hand, perfect atomic structure reduces carrier transmitting procedure in CNT
Scattering, is conducive to obtaining superelevation mobility and realizes ballistic transport in small-sized crystals tube device；On the other hand, using single
The electronic device that overlength carbon nano pipe is constructed has more preferable device architecture and consistency of performance, is shaken especially for ring type is improved
Swing device response frequency significant.In addition, perfect atomic structure and macro length are adjusted to carry out fine electronic structure
Control provides excellent easily platform, is the ideal candidates material for constructing the full carbon integrated circuit of function adjustable type of new generation.
However, the key issue for restricting its current development is, the highest semiconductor of ultra-long horizontal carbon nano pipe array is pure
Degree is only 92%, and from electron level purity (99.9999%), also there is a big difference, and density is also unable to reach high current and exports carbon-based
The ideal indicator of electronic device.It can be seen that, want to promote the fast development of high performance carbon base IC industry of new generation, prepare high
Density of electronic level purity semiconductor ultra-long horizontal carbon nano pipe array is extremely necessary.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is that providing one kind prepares high density electron level purity semiconductor ultra-long horizontal nanometer
The method of pipe array, the inventive method obtains high for being difficult to encountered in current development high performance carbon base integrated circuit process
The technical barrier of semiconductor purity, high-density carbon nano-tube horizontal array, it is proposed that one kind is by fine optimization and intercepts 15cm
The method that above length areas prepares electron level purity semiconductor ultra-long horizontal carbon nano pipe array, and can be by being repeated several times
Growth improves the density of carbon nano pipe array, and one is provided effectively reliably to break the material bottleneck of carbon-based Application of integrated circuit
Technology path.
The second object of the present invention is to provide a kind of high density electron level purity half prepared by the method for the invention
Conducting ultra-long horizontal nano-tube array, has high density, height as the ultra-long horizontal nano-tube array prepared by the inventive method
The advantages of semiconductor purity.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of method for preparing high density electron level purity semiconductor ultra-long horizontal nano-tube array, methods described includes
Following steps：
(a) substrate is placed in the reactor for be loaded with catalyst；And/or, it will have at least and be loaded with urging in a substrate
The multi-disc substrate of agent is placed in reactor；
(b) reaction temperature is warming up under the conditions of gas shield, the gaseous mixture for being passed through carbon source and carrier is reacted；
(c) after reaction time t1, it is passed through gas and switches to protection gas, and duration t2；Then, gas is passed through to cut
It is changed to the gaseous mixture of carbon source and carrier, and duration t3；
(d) repeat step (c) 5~100 times, are passed through gas and switch to protection gas, and are cooled to room temperature, take out substrate；
(e) substrate where length to be less than to 15cm overlength nanotubes is cut off, the product in residual substrate be high density,
With narrow diameter and chiral distribution, the semiconductive ultra-long horizontal carbon nano pipe array of electron level purity.
Optionally, the present invention in, the catalyst for transition metal simple substance or compound, and by solid-state, liquid or
Gaseous form is loaded；
It is preferred that the transition metal be Fe, Co, Ni, Cu, Zn, Cr, Ti, Pd, Pt, or at least one of Au.
Optionally, in the present invention, catalyst can be carried in reactor by deposition；Or, can be by base
Basal surface spin coating, coining or evaporation, so that catalyst is carried in substrate.
Optionally, in the present invention, the substrate is silicon, silica, the quartz acted on without crystal lattice orientation, or blue precious
At least one of stone.
Optionally, in the present invention, carbon source described in step (b) is methane, ethane, propane, butane, methanol, ethanol, second
Alkene, propylene, or at least one of carbon monoxide, it is preferred that the volume ratio of carrier gas and carbon source is 1~5, and containing 0.3~
0.6% water；
And/or, the gas shield is inert gas-hydrogen mixed gas gas shield, it is preferred that inert gas and hydrogen
Volume ratio be 1.5~4；At least one of it is furthermore preferred that the inert gas is helium, neon, or argon gas.
Optionally, in the present invention, reaction temperature described in step (b) is 700~2000 DEG C, and the ripple of controlling reaction temperature
Move as ± 0.5 DEG C；
It is preferred that, programming rate is 10~60 DEG C/min.
Optionally, in the present invention, in step (c) flow of protection gas be gaseous mixture volume flow in step (b) 1/4~
1/2；It is preferred that, the protection gas is the gaseous mixture of inert gas and hydrogen；It is furthermore preferred that protecting inert gas and hydrogen in gas
Volume ratio be 1.5~4.
Optionally, in the present invention, in step (c), t1 is 20~120min, and t2 is 3~5min, and t3 is the 1/10 of t1 durations
~1/2.
Optionally, in the present invention, the reactor, which is positioned in high temperature reaction stove, carries out heating response；It is preferred that, it is described
High temperature reaction stove is tube furnace or Muffle furnace.
Meanwhile, present invention also offers the high density electron level purity semiconductor according to prepared by the method for the invention
Ultra-long horizontal nano-tube array；It is preferred that, the length of the high density electron level purity semiconductor ultra-long horizontal nano-tube array
Spend for 15~100cm, density is 1~200 piece/micron, wall number is single wall, double-walled and/or many walls, a diameter of 1.8~2.1nm
And/or 2.9~3.2nm, semiconductor purity ＞ 99.9999%；It is furthermore preferred that the high density electron level purity semiconductor is super
The chirality of long horizontal nanotube array is (9,7), (14,13), (16,6), (22,11), (18,16), (19,18), (24,23)
At least one of.
Compared with prior art, beneficial effects of the present invention are：
Compared with the prior art, the technology of the present invention provides one kind by growth in situ, fine optimization length of carbon nanotube and cut
Length is taken to exceed the method that 15cm region prepares electron level purity semiconductor ultra-long horizontal carbon nano pipe array, can be in silicon substrate
CNT is directly prepared on bottom and construct high performance device, it is to avoid in the prior art using later stage separation and electrical selectivity
The method blown improves the material structure defect problem that semiconductor purity is brought, with wide commercial applications prospect.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described.
Fig. 1 is the overlength carbon nano pipe sample that multi-disc large area silicon sheet substrate surface is grown in described in the embodiment of the present invention 1
Product.
Fig. 2 is that substrate surface carbon is received using liquid nitrogen cooling steam assistant visualizing method described in the embodiment of the present invention 1
The morphology characterization result of mitron.
Fig. 3 is that the Raman G peaks of target sample random areas characterize knot after 15cm before excision described in the embodiment of the present invention 1
Really.
Fig. 4 is that the Raman RBM peaks of target sample random areas characterize knot after 15cm before excision described in the embodiment of the present invention 1
Really.
Fig. 5 is to the morphology characterization result of overlength carbon nano pipe and straight in the embodiment of the present invention 1 using AFM
Footpath distribution statisticses.
Fig. 6 is to point out sign to the chiral parameter of CNT using electron diffraction described in the embodiment of the present invention 1 to tie
Really.
Fig. 7 is the large area crystal made described in the embodiment of the present invention 2 of the high-purity semiconductive carbon nano tube preparing
Tube device and transfer curve test result.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, be
The conventional products that can be obtained by commercially available purchase.
It is involved in the present invention, a kind of high density electron level purity semiconductor ultra-long horizontal carbon nano pipe array for preparing
Method, specifically includes following steps：
(1) supported catalyst and substrate is placed：
The conventional at present catalyst for being used to preparing CNT in chemical gaseous phase depositing process include Fe, Co, Ni,
Cu, Zn, Cr, Ti, Pd, Pt, Au etc.；
It is dispersed in order to realize, typically can will containing a kind of salting liquid of metallic element of any of the above in advance in reactive group
Bottom, such as silicon, silica, quartz, the surface of the substrate such as the sapphire that lives form catalyst film, and specific adoptable method is rotation
Any one in painting, impressing, evaporation；Catalyst fines can also be subjected to thermal reduction in advance, be attached to metal particles deposition
Reactor wall, creates and is suitable to the reaction environment that overlength carbon nano pipe repeatedly continuously grows, for details, reference can be made to Xie et
al.Carbon 2016(98):157-161；
, can directly catalyst be carried on reactor wall by method as described above in the present invention；Or can also
By catalyst, method is carried at least one substrate as described above, and can be carried on catalyst preferably is passed through gas
On first substrate in direction；Or can also carry out catalyst while catalyst is carried out in reactor wall load
Load on substrate；
Further, in the method for the invention, the material of the reactor is in quartz, silicon nitride, or corundum
It is a kind of；It is shaped as the standard shapes such as cylindricality, cube, or can also be the irregular shape of other specific customizations.
(2) temperature reaction prepares overlength carbon nano pipe：
Before overlength carbon nano pipe is prepared, protection gas need to be first passed through, so that reactor is under gas shield state；
It is preferred that, the protection gas is the gaseous mixture of inert gas and hydrogen, the inert gas be in helium, neon, argon gas at least
One kind, and the volume content ratio of inert gas and hydrogen is 1.5~4；
Meanwhile, along with the temperature-rise period that programming rate is 10~60 DEG C/min, the hydrogen in protection gas will can also be urged
Metallic particles in agent salt is restored, the active material grown as catalyzing carbon nanotube；
Be warming up to after reaction temperature, can also further under the reaction temperature constant temperature keep a period of time so that
Reactor temperature reaches stabilization, and carbon source and carrier gas etc. are then passed through again and is reacted；
Further, the reaction time is relevant with the length of required CNT, due to the speed of growth of overlength carbon nano pipe
For 50~100 μm/s, to make length more than 15cm, growth time will be controlled in 25~50min.
(3) repeated growth：
Based on the SF regularities of distribution (Zhang et al.ACS Nano, 2013,7 (7):6156-6161), overlength carbon nano pipe
Density can be gradually reduced with length increase, so for improve length exceed 15cm carbon nanotube density, need to carry out repeatedly
Repeated growth, if using the method for being previously deposited catalyst, more than 50 times (Xie et of the stable growth of overlength carbon nano pipe can be made
al.Carbon 2016(98):157-161)；
However, after the complete CNT of each secondary growth, the surface of catalyst all can deposition fraction carbon, and then hinder carbon source
Molecule is combined with the active sites of catalyst surface and the stable of CNT grows；So, since the second secondary growth, every time
Needing first to be passed through the gaseous mixture of 3~5min low discharges indifferent gas and hydrogen before growth, (the volume content ratio of inert gas and hydrogen is
1.5~4), the carbon distribution for partly removing catalyst surface, meanwhile, using the 1/4~1/2 of stage of reaction gaseous mixture total flow
The gaseous mixture of indifferent gas and hydrogen is passed through, it is also possible that CNT of the previous growth phase minority in floating state is dropped back into
Substrate surface.
(4) sampling excision：
After the repeated growth stage of reaction terminates, switching gas is the gaseous mixture of indifferent gas and hydrogen and is cooled to room temperature, can
Taking out all growths has the substrate sample of overlength carbon nano pipe.Using precision laser cutting, resection length is less than 15cm overlength
Overlength carbon nano pipe in substrate where CNT, remaining substrate is high density, with narrow diameter and chiral distribution, electronics
The semiconductive ultra-long horizontal carbon nano pipe array of level purity.
And use the overlength carbon nano pipe array length prepared by method as described above to reach 15~100cm, density
For 1~200 piece/micron, wall number is single wall, double-walled and/or many walls, a diameter of 1.8~2.1nm and/or 2.9~3.2nm scope,
Semiconductor purity>99.9999%, chirality for (9,7), (14,13), (16,6), (22,11), (18,16), (19,18), (24,
23) it is at least one, with narrower diameter and chiral distribution, electronic-grade semiconductor carbon nano pipe purity and higher density,
Application demand of the carbon-based integrated circuit of new generation to CNT can be met.
Embodiment 1：The preparation of electron level purity semiconductor ultra-long horizontal carbon nano pipe array and sign
(1) the continuous Si/SiO for putting seven a diameter of 10cm in cube shaped quartz reactor2Wafer, total length is
70cm, as shown in figure 1, by 0.05mol/L FeCl3Ethanol solution is stamped in first Si/SiO2Substrate front end (101)；
(2) 220sccm argon gas and the gaseous mixture (Ar of hydrogen are passed through into reactor:H2=1:2, v/v) as protection
Property gas, and start to warm up, after temperature rises to 1010 DEG C, constant temperature 20min subsequently enters the stage of reaction, is passed through 160sccm first
Alkane and hydrogen mixed gas (H2：CH4=2.1:1, v/v), the reaction time continues to enter cooling stage after 30min；Change and be passed through
200sccm argon gas and the gaseous mixture (Ar of hydrogen:H2=1:2, v/v), anti-blocking pipe is ablated in temperature-fall period；
(3) when temperature is reduced to room temperature, whole Si/SiO is taken out2Wafer, dotted line cuts the second wafer along along Fig. 1
Open, the interior substrate surface overlength carbon nano pipe of rectangle frame scope (102) is target sample；
In order to determine whether pattern, purity, caliber and the chiral distribution of sample, following characterize is carried out：
1) morphology characterization of CNT helps to obtain CNT entire length, Density Distribution information, conventional shape
Looks characterizing method includes ESEM, transmission electron microscope, AFM etc., but is limited by cavity, and the image gathered every time is only
Can be the zonule of one piece of part, it is impossible to directly obtain overall topographic profile, we use document Zhu et here
al.Science Advances,2016,2:The liquid nitrogen cooling auxiliary steam visualization method reported in e1601572 judges super
The distribution of lengths of long CNT.
Fig. 2 is first, the 4th and the 7th wafer substrate surface overlength carbon nano pipe in Fig. 1 samples, after testing, is surpassed
The extreme length of long CNT reaches 65cm；
2) grab sample Raman sign is carried out to 102 scopes in Fig. 1.For CNT, it is located in Raman spectrum
1580cm-1Neighbouring G peaks are the characteristic peaks of carbonizable substance, and can occur the phenomenon that G peaks divide for achiral CNT,
Form the G positioned at lower wave number-The G at peak and high wave number+Peak, according to G-The peak type at peak can determine whether that corresponding CNT is metallicity
Or semiconductive, if metallic carbon nanotubes, G-Peak is wider BWF peaks, if semiconductive carbon nano tube, G-
Peak narrow Lorentz peak for point.
And it is all for can be seen that samples taken according to the G peaks peak type of 6 sample areas of random measurement in Fig. 3
Semiconductive carbon nano tube, the purity with superelevation；
3) RBM peaks further in analysis Raman spectrum, as shown in figure 4, the equal position in sample CNT RBM peaks detected
In semiconductor chirality area, meanwhile, carbon nanotube diameter is calculated according to RBM peak positions, finds to be distributed with narrower diameter, only exists
Enrichment occurs near 1.8nm and 3.2nm；
4) pattern and diameter of CNT are analyzed using AFM, such as Fig. 5 a, in 15cm length fields
Substantially 1/100 microns of the density of CNT at domain, obtained caliber is tested and based on RBM peak positions by AFM
Calculate obtained caliber to be counted, such as Fig. 5 b, further the Diameter distribution of checking CNT is near 1.8nm and 3.2nm；
5) for the further chirality for precisely confirming CNT, each layer chirality ginseng of CNT is confirmed using electronic diffraction
Number, wherein such as Fig. 6, a figures are 18cm overlength carbon nano pipe, and chiral parameter is (14,13)@(24,14)@(29,19), b
Figure is 16cm overlength carbon nano pipe, and chiral parameter is (9,7)@(14,12)
Embodiment 2：Repeated growth improves electron level purity semiconductor ultra-long horizontal carbon nano pipe array density
(1) in cube shaped reactor air-flow upstream tiling 0.3g FeCl3Catalyst fines, is passed through into reactor
200sccm argon gas and the gaseous mixture (Ar of hydrogen:H2=1:2, v/v) as protective gas, and start to warm up, when temperature liter
To after 1000 DEG C, cooling stage is entered after constant temperature 20min, reactor is opened when being down to room temperature；
(2) Si/SiO that 6 specifications are 5 × 8cm is continuously put in the reactor2Substrate, the direction of growth of CNT
Along base widths direction, by 0.03mol/L FeCl3Ethanol solution is stamped in first Si/SiO2Substrate front end；
(3) 200sccm argon gas and the gaseous mixture (Ar of hydrogen are passed through into reactor:H2=1:2, v/v) as protection
Property gas, and start to warm up, after temperature rises to 1000 DEG C, constant temperature 20min subsequently enters the stage of reaction, is passed through 160sccm first
Alkane and hydrogen mixed gas (H2：CH4=2.1:1, v/v), the reaction time continues after 40min, and switching gas is 60sccm argon gas and hydrogen
Gaseous mixture (the Ar of gas:H2=1:2, v/v), it is continually fed into after 5min, switching gas is 160sccm methane and hydrogen mixed gas
(H2：CH4=2.1:1, v/v), the reaction time continues 15min, and switching gas is the gaseous mixture (Ar of 60sccm argon gas and hydrogen:H2
=1:2, v/v), it is continually fed into after 5min, then switches gas for 160sccm methane and hydrogen mixed gas (H2：CH4=2.1:1, v/
V), the reaction time continues 15min, and such circulating repetition enters cooling stage after growing 10 times.Change be passed through 200sccm argon gas and
Gaseous mixture (the Ar of hydrogen:H2=1:2, v/v), anti-blocking pipe is ablated in temperature-fall period；
(4) when temperature is reduced to room temperature, whole Si/SiO is taken out2Substrate, from the 4th substrate whole substrate tables backward
The CNT in face is target sample；
(5) large area Ti/Au metal electrodes are deposited with photolithography method in the 4th substrate, as shown in Figure 7a.Using electricity
Method is tested to the semiconductive of CNT, according to the maximum ON state current of transfer curve and minimum off-state current
Ratio determines the on-off ratio of transistor device, and the on-off ratio of general semiconductive carbon nano tube is more than 1000, and on-off ratio is got over
Height, shows that the semiconductor purity of CNT is higher.Such as the transfer curve that Fig. 7 b are single-root carbon nano-tube, on-off ratio is 107, figure
7c is the transfer curve for the transistor device being made up of 10 CNTs, and on-off ratio is 106, it can be seen that, carried using us
The semiconductive ultra-long horizontal carbon that the method for the fine optimization overlength carbon nano pipe length gone out can successfully prepare electron level purity is received
Mitron array.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of method for preparing high density electron level purity semiconductor ultra-long horizontal nano-tube array, it is characterised in that institute
The method of stating comprises the following steps：
(a) substrate is placed in the reactor for be loaded with catalyst；And/or, it will have at least in a substrate and be loaded with catalyst
Multi-disc substrate be placed in reactor；
(b) reaction temperature is warming up under the conditions of gas shield, the gaseous mixture for being passed through carbon source and carrier is reacted；
(c) after reaction time t1, it is passed through gas and switches to protection gas, and duration t2；Then, gas is passed through to switch to
The gaseous mixture of carbon source and carrier, and duration t3；
(d) repeat step (c) 5~100 times, are passed through gas and switch to protection gas, and are cooled to room temperature, take out substrate；
(e) substrate where length to be less than to 15cm overlength nanotubes is cut off, and the product in residual substrate is high density, had
Narrow diameter and chiral distribution, the semiconductive ultra-long horizontal carbon nano pipe array of electron level purity.
2. according to the method described in claim 1, it is characterised in that the catalyst is the simple substance or compound of transition metal,
And loaded by solid-state, liquid or gaseous form；
It is preferred that the transition metal be Fe, Co, Ni, Cu, Zn, Cr, Ti, Pd, Pt, or at least one of Au.
3. according to the method described in claim 1, it is characterised in that catalyst can be carried in reactor by deposition；
Or, can be by substrate surface spin coating, coining or evaporation, so that catalyst is carried in substrate.
4. according to the method described in claim 1, it is characterised in that the substrate is silicon, silica, made without crystal lattice orientation
At least one of quartz, or sapphire.
5. according to the method described in claim 1, it is characterised in that carbon source described in step (b) is methane, ethane, propane, fourth
At least one of alkane, methanol, ethanol, ethene, propylene, or carbon monoxide, it is preferred that the volume ratio of carrier gas and carbon source is 1
~5, and contain 0.3~0.6% water；
And/or, the gas shield is inert gas-hydrogen mixed gas gas shield, it is preferred that the body of inert gas and hydrogen
Product is than being 1.5~4；At least one of it is furthermore preferred that the inert gas is helium, neon, or argon gas.
6. according to the method described in claim 1, it is characterised in that reaction temperature described in step (b) is 700~2000 DEG C,
And the fluctuation of controlling reaction temperature is ± 0.5 DEG C；
It is preferred that, programming rate is 10~60 DEG C/min.
7. according to the method described in claim 1, it is characterised in that the flow of protection gas is mixing in step (b) in step (c)
The 1/4~1/2 of gas volumetric flow；
It is preferred that, the protection gas is the gaseous mixture of inert gas and hydrogen；
It is furthermore preferred that the volume ratio of inert gas and hydrogen is 1.5~4 in protection gas.
8. according to the method described in claim 1, it is characterised in that in step (c), t1 be 20~120min, t2 be 3~
5min, t3 are the 1/10~1/2 of t1 durations.
9. the method according to any one of claim 1-8, it is characterised in that the reactor is positioned over high temperature reaction stove
Middle carry out heating response；
It is preferred that, the high temperature reaction stove is tube furnace or Muffle furnace.
10. the high density electron level purity semiconductor overlength water according to any one of claim 1-9 prepared by method
Flat nano-tube array；
It is preferred that, the length of the high density electron level purity semiconductor ultra-long horizontal nano-tube array is 15~100cm, close
Spend for 1~200 piece/micron, wall number is single wall, double-walled and/or many walls, a diameter of 1.8~2.1nm and/or 2.9~3.2nm, half
Conductor purity>99.9999%；
It is furthermore preferred that the chirality of the high density electron level purity semiconductor ultra-long horizontal nano-tube array be (9,7), (14,
13), at least one of (16,6), (22,11), (18,16), (19,18), (24,23).
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| CN111017906A (en) * | 2019-12-25 | 2020-04-17 | 清华大学 | Ultra-long chiral carbon nanotube, preparation method, application and high-performance photoelectric device |
| CN111170309A (en) * | 2020-02-11 | 2020-05-19 | 江西铜业技术研究院有限公司 | Preparation method of ultra-long few-wall carbon nanotube array |
| CN115724422A (en) * | 2021-08-26 | 2023-03-03 | 北京大学 | Method for selectively growing carbon nano-tube on wafer size substrate |
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| CN102001643A (en) * | 2010-12-08 | 2011-04-06 | 清华大学 | Overlong carbon nanotubes and preparation method thereof |
| CN104986753A (en) * | 2015-06-25 | 2015-10-21 | 清华大学 | Super-long carbon nano tube and preparing method and device thereof |
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| CN102001643A (en) * | 2010-12-08 | 2011-04-06 | 清华大学 | Overlong carbon nanotubes and preparation method thereof |
| CN104986753A (en) * | 2015-06-25 | 2015-10-21 | 清华大学 | Super-long carbon nano tube and preparing method and device thereof |
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| CN111017906A (en) * | 2019-12-25 | 2020-04-17 | 清华大学 | Ultra-long chiral carbon nanotube, preparation method, application and high-performance photoelectric device |
| CN111170309A (en) * | 2020-02-11 | 2020-05-19 | 江西铜业技术研究院有限公司 | Preparation method of ultra-long few-wall carbon nanotube array |
| CN115724422A (en) * | 2021-08-26 | 2023-03-03 | 北京大学 | Method for selectively growing carbon nano-tube on wafer size substrate |
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