CN107089652B - Narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes preparation method - Google Patents
Narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes preparation method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 claims abstract description 45
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- ZUKAEACKOFSRLB-UHFFFAOYSA-N [W].[Co].[Ru] Chemical compound [W].[Co].[Ru] ZUKAEACKOFSRLB-UHFFFAOYSA-N 0.000 description 2
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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Abstract
The present invention relates to the controllable preparation field of semi-conductive single-walled carbon nanotubes, specially a kind of part carbon-clad metal catalyst preparation narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes method.Using Self-Assembling of Block Copolymer method, copolymer film cladding anionic metal nanocluster of uniform size is prepared；By controlling solvent anneal, oxidation, reducing condition, monodisperse, the carbon-coated metal-catalyst nanoparticles in part are obtained；It is again etching gas in situ with hydrogen, the directly distribution of growth narrow band gap, high-purity semi-conductive single-walled carbon nanotubes.Wherein the content of semi-conductive single-walled carbon nanotubes is greater than 98%, the minimum 0.05eV of difference in band gap and adjustable.The present invention realizes the direct controllable growth of narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes, break through the bottleneck that at this stage prepared by high-purity, narrow band gap distribution semi-conductive single-walled carbon nanotubes control, it was demonstrated that it is the desired channel material for constructing thin film transistor.
Description
Technical field
The present invention relates to the controllable preparation field of semi-conductive single-walled carbon nanotubes, specially a kind of part carbon-clad metal
The distribution of catalyst preparation narrow band gap, high-purity semi-conductive single-walled carbon nanotubes method, by regulation block copolymer from group
Dress process and post-treatment condition prepare monodisperse, narrow particle diameter distribution, the carbon-coated metal-catalyst nanoparticles in part；Then
The metallic single-wall carbon nano-tube for removing high activity in situ using hydrogen as carrier gas and etching property gas is directly realized by narrow band gap distribution
And the control growth of band gap variable semiconductor single-walled carbon nanotube.
Background technique
Single-walled carbon nanotube can be regarded as crimped as single-layer graphene made of one-dimensional hollow tubular structure, it have with
Diameter and the relevant metallicity of helical angle or characteristic of semiconductor.Semi-conductive single-walled carbon nanotubes have very high electron transfer
Rate and adjustable band gap are the ideal materials for constructing fieldistor channel, are expected to construct in the following substituted single crystal silicon next
For nanometer electronic device.Therefore, high-purity semi-conductive single-walled carbon nanotubes are directly obtained, are that its nanometer electronic device is pushed to apply
It is crucial.
In recent years, the control preparation work of semi-conductive single-walled carbon nanotubes has been achieved for remarkable progress, mainly sharp
With the high chemical reactivity of metallic carbon nanotubes, the etching agent in situ that introduces removes it, can return according to the characteristics of etching agent
Become following three kinds: (1) etching such as vapor, oxygen, hydrogen property gas (document one: Zhang, G.；Qi,P.；Dai,H.et
al.Science 2006,314,5801；Document two: Yu, B.；Liu,C.；Hou,P.X.et al.Journal of the
American Chemical Society 20011,133,5232；Document three: Li, W.S.；Hou,P.X.；Liu,C.et
al.ACS Nano 2013,7,6831)；(2) can slow release oxygen cerium oxide be catalyst carrier (Qin, X.；Peng,F.；
Li,Y.et al.Nano Letter 2014,14,512)；(3) alcohols that can decompose hydroxyl is carbon source (Che, Y.C.；
Wang,C.；Zhou,C.W.；et al.ACS Nano 2012,6,7454)；Prepared semi-conductive single-walled carbon nanometer at present
Pipe purity is~95%, and band gap wider distribution, this will affect the homogeneity of its constructed device performance.Due to single
The band gap of pipe is inversely proportional with its diameter, and the necessary condition for obtaining narrow band gap distribution carbon nanotube is to obtain the uniform carbon nanometer of diameter
Pipe.Meanwhile the reactivity of single-walled carbon nanotube not only has conductive properties dependency characteristic, it is also related to diameter.In order to obtain
High-purity semi-conductive single-walled carbon nanotubes, it is necessary to which the diameter distribution for controlling carbon nanotube is concentrated.As it can be seen that the diameter of carbon nanotube
Control is not only to prepare the key of narrow gap semiconductor carbon nanotube, and preparation high-purity semi-conductive single-walled carbon nanotubes
Key.However due to the nanoscale of single-walled carbon nanotube, be catalyzed its growth nano particle under high temperature (> 600 DEG C) pole
It is easy to reunite, thus be difficult to obtain the nano-catalyst particles of size uniformity.Meanwhile single-walled carbon nanotube forming core from nano particle
Both of which mainly is followed, one is carbon nanotube diameters and consistent " tangent line growth " mode of nano-particle diameter, another
It is that carbon nanotube diameter is less than nanoparticle size " vertical-growth " mode.(Fiawoo,M.F.C.；Bonnot,A.M.；
Amara, H et al.Physical Review Letters 2012,108) thus, even if obtaining the catalyst of size uniformity,
Also it is difficult to the uniform single-walled carbon nanotube of growth size.
Current main problem is: how to obtain the catalyst nano-particles of size uniformity, while controlling single
The nucleating growth mode of pipe；In turn, narrow band gap is broken through, high-purity semi-conductive single-walled carbon nanotubes control prepares bottleneck.
Summary of the invention
The object of the present invention is to provide a kind of distributions of part carbon-clad metal catalyst preparation narrow band gap, high-purity semiconductor
Property single-walled carbon nanotube method, overcome existing single-walled carbon nanotube forming core mode on metallic catalyst it is uncertain caused by carbon
Tube diameters are distributed wide problem, while it is wide to overcome the easy caused diameter of reuniting of existing metallic catalyst high temperature to be distributed
Problem is etched, directly growth narrow band gap is distributed, is high-purity by designing catalyst size control and structure in conjunction with hydrogen in-situ
Degree, high-quality semiconductor single-walled carbon nanotube.
The technical scheme is that
A kind of distribution of narrow band gap, high-purity semi-conductive single-walled carbon nanotubes preparation method, using block copolymer from
Construction from part can prepare the characteristics of size uniformity nano particle, and by controlling solvent anneal, oxidation, reducing condition, it is equal to obtain size
One, monodisperse, the carbon-coated metal nanoparticle in part；Using it as catalyst, the weak etching and same diameter of hydrogen are utilized
The higher feature of metallic carbon nanotubes reactivity, direct in-situ etch metallic carbon nanotubes, obtain high-purity, narrow band gap
It is distributed semi-conductive single-walled carbon nanotubes.
The preparation method of the narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes, catalyst structure is portion
Divide carbon-coated nano particle, particle size is 2.0~4.5nm；Wherein, catalyst component is one of transition metal or two
Kind or more；Alternatively, catalyst component is one or more of refractory metal.
The preparation method of the narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes, using self assembly legal system
During standby Block Copolymer Thin Film, the solvent anneal time is 6~30 hours, and Block Copolymer Thin Film is in air plasma
The time of processing is 20~60 minutes.
The preparation method of the narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes, in growth carbon nanotube
Preceding to need to carry out the carbon-coated catalyst in part reduction treatment, reducing atmosphere is the mixed gas of hydrogen and argon gas, reduction temperature
Degree is 500~800 DEG C, and the recovery time is 2~25 minutes；Catalyst is with hydrogen at 700~900 DEG C after reduction treatment
Carrier gas chemical vapor deposition prepares narrow band gap distribution semi-conductive single-walled carbon nanotubes.
The preparation method of the narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes, the single wall carbon grown
Nanotube difference in band gap is only 0.05eV and adjustable, and semiconductive carbon nano tube content is greater than 98%.
The preparation method of the narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes, by regulating and controlling catalyst
Structure and reduction process regulation semiconductive carbon nano tube difference in band gap.
The preparation method of the narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes, utilizes wavelength Raman
Qualitative spectrometric estimates the content of semi-conductive single-walled carbon nanotubes, is excited according to Katarula plots to each wavelength laser
Breathing mould carry out the divisions of semiconductive and metallic carbon nanotubes, count the number in corresponding region internal respiration mould, partly lead
The content of body carbon nanotube is by the breathing mould number excited in semiconductive region and the ratio of all breathing mould numbers.
The preparation method of the narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes, semi-conductive single-walled carbon
The content of nanotube is calculated using absorption spectrum is qualitative, i.e., by S corresponding to the absorption curve after deduction back end22And M11
Integrating peak areas is calculated using following formula:
M11, metallic single-wall carbon nano-tube M11Peak area；
S22, semi-conductive single-walled carbon nanotubes S22Peak area；
F, absorption coefficient.
The described narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes preparation method, using this high-purity,
Thin film transistor constructed by narrow gap semiconductor single-walled carbon nanotube has both high on-off ratio and high carrier migration
Rate shows potential application of this narrow gap semiconductor single-walled carbon nanotube in terms of nanometer electronic device.
Design philosophy of the invention is:
The present invention provides a kind of method of directly growth narrow gap semiconductor single-walled carbon nanotube, designs and is prepared for one
Kind monodisperse, part carbon-coated metallic nano-particles catalyst of uniform size, the part carbon coating structure inhibit nanometer
The high temperature of metallic particles is reunited, and the forming core mode for controlling single-walled carbon nanotube is vertical-growth, and then it is equal to prepare size
One single-walled carbon nanotube；It is on this basis, in situ to introduce hydrogen etching agent removal metallic carbon nanotubes or inhibit its growth,
And then directly obtain narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes.
The present invention directly grows narrow band gap distribution, high-purity in conjunction with etching in situ by the structure of design metallic catalyst
Semi-conductive single-walled carbon nanotubes are advantageous in that:
1, the present invention designs for the first time and is prepared for monodisperse, part carbon-coated metallic nano-particles structure of uniform size,
It solves the problems, such as the reunion of catalyst high temperature, also solves the control problem of carbon nanotube nucleating growth mode, and then realize
The preparation of size uniformity single-walled carbon nanotube.
2, the method for the present invention size uniformity single-walled carbon nanotube prepare on the basis of, using hydrogen as carrier gas and etch gas
Body realizes narrow band gap distribution (smallest bandgap difference is only 0.05eV) for the first time and band gap is adjustable, high-purity (98% or more) is partly led
It is prepared by the control of body single-walled carbon nanotube.
In short, the present invention is realized using controlling catalyst structure that the single-walled carbon nanotube forming core stage is relied on as starting point
Narrow band gap distribution, the direct growth of high-purity semi-conductive single-walled carbon nanotubes breach high-purity, narrow band gap point at this stage
The bottleneck of cloth semi-conductive single-walled carbon nanotubes control preparation, is the nucleating mechanism of specific structure semi-conductive single-walled carbon nanotubes
Provide new understanding, it was confirmed that it is the desired channel material for constructing thin film transistor.
Detailed description of the invention
The preparation of the part Fig. 1 carbon coating cobalt nano-particle and growth narrow band gap are distributed semi-conductive single-walled carbon nanotubes mistake
Journey schematic diagram.
The pattern of the part Fig. 2 carbon coating cobalt nano-particle.(a) atomic force microscope of part carbon coating cobalt nano-particle
Photo；(b) transmission electron microscope photo of part carbon coating cobalt nano-particle；(c) the particle size distribution column of transmission electron microscope statistics
Figure.
Fig. 3 part carbon coating cobalt nano-particle is the pattern of the carbon nanotube of catalyst preparation.(a) silicon substrate surface carbon
The stereoscan photograph of nanotube network；(b) transmission electron microscope photo of single-walled carbon nanotube；(c) vertical-growth is in part carbon packet
Cover the single-walled carbon nanotube transmission electron microscope photo of cobalt nano-particle；(d) it is distributed using the carbon nanotube diameter of transmission electron microscope statistics
Histogram.
Fig. 4 part carbon coating cobalt nano-particle is Raman spectrum D, G mould of the single-walled carbon nanotube of catalyst preparation.
Fig. 5 part carbon coating cobalt nano-particle is the wavelength Raman spectrum RBM of the single-walled carbon nanotube of catalyst preparation
Mould.(a) 532nm wavelength laser；(b) 633nm wavelength laser；(c) 785nm wavelength laser；(d) 488nm wavelength laser.
Fig. 6 part carbon coating cobalt nano-particle is the abosrption spectrogram of the single-walled carbon nanotube of catalyst preparation.
The thin film field-effect that Fig. 7 is constructed using the single-walled carbon nanotube of part carbon coating cobalt nano-particle catalyst preparation
The performance of transistor.(a) output characteristic curve of the single field effect transistor in -1V to -5V；(b) 10 thin film field-effect crystalline substances
The transfer characteristic curve of body pipe.
Fig. 8 part carbon coating cobalt nano-particle is that the multi-wavelength of the band gap adjustable single-wall carbon nano of catalyst preparation is drawn
Graceful spectrum RBM mould.(a) 532nm wavelength laser；(b) 633nm wavelength laser；(c) 785nm wavelength laser.
Fig. 9 cobalt nano-particle is the wavelength Raman spectrum RBM mould of the single-walled carbon nanotube of catalyst preparation.(a)
532nm wavelength laser；(b) 633nm wavelength laser；(c) the single-walled carbon nanotube conductive properties content that Raman spectrum is characterized point
Butut.
Specific embodiment
In the specific implementation process, part carbon-clad metal catalyst preparation narrow band gap distribution of the present invention, high-purity are partly led
The method of body single-walled carbon nanotube is controlled by the structure snd size to catalyst, is directly selected using the corrasion of hydrogen
Selecting property grows narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes, the specific steps are as follows:
Using the method for block copolymer chemistry self assembly, the film of self-assembled block copolymers on a silicon substrate；It should
Film carries out chemisorption catalyst precursor after solvent anneal in the mixed vapour of toluene and tetrahydrofuran, then is carried out
Air plasma (plasma) processing can get the metal oxide catalyst nanocluster coated by partial organic substances, 500
It carries out hydrogen reducing at~800 DEG C to handle to obtain the carbon-coated catalyst nano-particles in part, with hydrogen at 700~900 DEG C
Narrow band gap, which is prepared, for carrier gas chemical vapor deposition is distributed semi-conductive single-walled carbon nanotubes.Wherein:
(1) it is that (PS-b-P4VP refers to poly- to 0.2~0.5wt%PS-b-P4VP that the block copolymer of self assembly, which is concentration,
(styrene-block-4-vinylpyridine) block copolymer) toluene and tetrahydrofuran mixed solution (toluene and tetrahydro
Mass ratio 1:1~5:1 of furans), the silicon chip surface that hydrophilic treated is crossed is spun on 3000~5000rpm.
(2) Block Copolymer Thin Film of silicon chip surface is placed in toluene and the mixing of tetrahydrofuran (volume ratio 1:2~1:6) is steamed
Solvent anneal 6~30 hours in vapour, after to be impregnated in molar concentration be Catalyst precursor solutions 1~5 minute of 0.1~1mM, go
After ion water washing is dry, air plasma is handled 20~60 minutes.
(3) solution of Block Copolymer Thin Film chemisorption catalyst precursor is that the hydrochloric acid of 41.5~166.2g/L is molten
Liquid, catalyst precursor are as follows: K3[Co(CN)6]、K3[Fe(CN)6]、K2RuCl5、(NH4)10W12O41、H2[PtCl6] in one
Kind is two or more, and must wherein contain K3[Co(CN)6]、K2RuCl5、K3[Fe(CN)6One of].
(4) catalyst reduction condition is to handle 2~25 minutes for 500~800 DEG C in 100~200sccm hydrogen.
(5) carbon source used in chemical vapor deposition is the small organic molecule alcohol vapor that argon gas is loaded into, and is passed through the argon of carbonaceous sources
The volume ratio of gas and carrier gas hydrogen is 1:1~1:5, and total gas flow rate is maintained at 100~600sccm, and growth time is 1~15
Minute.
(6) carbon-coated metallic nano-particles diameter in part obtained is distributed between 2.0~4.5nm, catalyst
It can be Co, Fe, Ru, CoPt, CoRu, CoW, FeRu, FeW, FePt, CoPtW, FePtW, CoRuW or FeRuW.The present invention
In, the carbon-coated concrete meaning in part and structure be metallic particles outer surface part coated to be formed similar to acorn by carbon-coating
Structure.That is metallic particles outer surface part is exposed, and other parts are coated by carbon-coating.
The diameter of single-wall carbon nano tube distribution grown is concentrated, the minimum 0.05eV of difference in band gap and adjustable, semiconductive carbon
Nanotube content is greater than 98%, and Raman spectrum is respectively adopted in the content of semi-conductive single-walled carbon nanotubes and absorption spectrum is determined
Property estimation and quantitative calculate.
The present invention is described in further detail below by embodiment.
The preparation of 1. part carbon coating cobalt nano-particle of embodiment and its distribution of catalytic growth narrow band gap, high-purity semiconductor
Property single-walled carbon nanotube
Specific preparation is as shown in Figure 1 with growth course.
(1) preparation of part carbon coating Co metal nanoparticle
By the toluene containing 0.3wt% block copolymer and tetrahydrofuran solution (mass ratio 2 of toluene and tetrahydrofuran:
1) silicon chip surface that hydrophilic treated is crossed is spun on 4000rpm, is subsequently placed in toluene and tetrahydrofuran solution (volume ratio 1:3)
Solvent anneal 20 hours in steam, then the silicon wafer is placed in 1mM K3[Co(CN)6] 3 minutes absorption [Co (CN) are impregnated in solution6]3-
Anion is washed with deionized after taking-up, 30 minutes dry at 60 DEG C, is finally placed in air plsama (power 20W)
Processing 20 minutes.Above-mentioned processed silicon wafer is placed in tube furnace, 0.5MPa or less is evacuated to and is passed through argon gas recovery again often
Pressure, is then switched to 200sccm hydrogen for argon gas, and silicon wafer is pushed into flat-temperature zone, with 20 DEG C/min of heating rate by constant temperature
Area's temperature rises to 700 DEG C from 500 DEG C and keeps the temperature 5min.Atomic force microscopy (Fig. 2 (a)) shows that nano particle uniformly divides
It is dispersed in silicon substrate surface.Transmission electron microscope photo (Fig. 2 (b)) shows that all nano grain surfaces all parts are coated by carbon-coating,
And particle size is uniform.The random statistical diameter of 130 particles, shown in result such as Fig. 2 (c), the partial size of nano particle
It is distributed in 2.0~4.5nm.
(2) narrow band gap distribution, the growth and characterization of high-purity semi-conductive single-walled carbon nanotubes
On the basis of step 1, it is further passed through the argon gas containing alcohol vapour, the volume ratio with carrier gas hydrogen is 1:
2, total gas flow rate remains 300sccm, carries out chemical vapor deposition growth single-walled carbon nanotube, and growth time is 10 minutes.
After growth, carbon source is closed, is cooled to room temperature taking-up sample under protection of argon gas.The scanning electricity of prepared single-walled carbon nanotube
It is uniform carbon nano tube network shown in mirror photo such as Fig. 3 (a).It is single high-quality shown in its transmission electron microscope photo such as Fig. 3 (b)
Single-walled carbon nanotube is measured, diameter is uniform.And it is vertical with part carbon-coated nano particle to observe directly single-walled carbon nanotube
Relationship, be shown in Fig. 3 (c), its vertical growth mode of indirect proof.The random statistical diameter of 150 carbon nanotubes, diameter point
Shown in cloth such as Fig. 3 (d), it is seen that diameter distribution is very narrow, concentrates on 1.6~1.9nm.It is straight according to semi-conductive single-walled carbon nanotubes
The corresponding relationship of diameter and band gap, difference in band gap are only 0.08ev.Drawing of the single-walled carbon nanotube in 1200~1800 wave-number ranges
Graceful spectrum as shown in figure 4, single-walled carbon nanotube in 1590cm-1There is the very strong peak G at place, illustrates carbon nanotube good crystallinity.It is more
Shown in wavelength (532nm, 633nm, 785nm, 488nm laser) Raman RBM peak such as Fig. 5 (a)-(d), according to katarula plots
Figure and the corresponding qualitative estimation semiconductor single-walled carbon content of the peak section RBM number are 98wt%.The suction of single-walled carbon nanotube
Spectrum is received as shown in Figure 6 (lower curve), using deducting back end (top curve) S afterwards22And M11The integral area at peak quantitatively calculates
The content for obtaining semi-conductive single-walled carbon nanotubes is 99wt%.
(3) narrow band gap distribution, the building and performance of high-purity semi-conductive single-walled carbon nanotubes film transistor device
Using the distribution of narrow band gap prepared by step 2, high-purity semi-conductive single-walled carbon nanotubes as channel material, structure
Bottom gate thin film field effect transistor is built.Shown in the output characteristic curve of field effect transistor such as Fig. 7 (a), show carbon nanometer
Good Ohmic contact is formd between pipe and electrode.Fig. 7 (b) is the transfer characteristic curve of same size, 10 devices.According to
The on-off ratio that thin film transistor is calculated in these curves is 3.1 × 103~3.6 × 106, carrier mobility 36
~143cm2v-1s-1.Compared with existing literature reports result, thin-film transistor performance is at the leading level.
The preparation of 2. part carbon-encapsulated iron nano particle of embodiment and its distribution of catalytic growth narrow band gap, high-purity semiconductor
Property single-walled carbon nanotube
(1) preparation of part carbon-encapsulated iron metal nanoparticle
Catalyst preparation step is consistent with embodiment 1, the difference is that catalyst precursor is 1mM K3[Fe(CN)6] solution.
Atomic force microscope shows that nano particle is dispersed in silicon substrate surface.Transmission electron microscope observing shows all nanometers
Grain surface all parts are coated by carbon-coating, and particle size is uniform.125 particle diameter distributions of random statistical 2.5~
4.0nm。
(2) narrow band gap distribution, the growth and characterization of high-purity semi-conductive single-walled carbon nanotubes
Single-walled carbon nanotube growth and characterization are consistent with embodiment 1.The diameter of single-wall carbon nano tube collection of transmission electron microscope statistics
In be distributed in 1.8~2.1nm.According to the corresponding relationship of semi-conductive single-walled carbon nanotubes diameter and band gap, difference in band gap is only
0.08ev.It is 98wt% according to the qualitative estimation semiconductor single-walled carbon content in the peak wavelength Raman RBM.After button back end
Absorption spectrum quantitatively calculate semi-conductive single-walled carbon nanotubes content be 98wt%.
(3) narrow band gap distribution, the building and performance of high-purity semi-conductive single-walled carbon nanotubes film transistor device
The building of thin film transistor device and performance test process are the same as embodiment 1, constructed thin film field-effect
The on-off ratio of transistor is 4.0 × 104~2.5 × 105, carrier mobility is 50~110cm2v-1s-1。
The preparation of 3. part carbon coating ferrotungsten nano particle of embodiment and its distribution of catalytic growth narrow band gap, high-purity are partly led
Body single-walled carbon nanotube
(1) preparation of part carbon coating ferrotungsten metal nanoparticle
Catalyst preparation step is consistent with embodiment 1, the difference is that catalyst precursor is 0.5mM K3[Fe(CN)6] with
0.5mM(NH4)10W12O41Mixed solution.Atomic force microscope shows that nano particle is dispersed in silicon substrate surface.
Transmission electron microscope observing shows that all nano grain surfaces all parts are coated by carbon-coating, and particle size is uniform.Random system
135 particle diameter distributions of meter are in 3.0~4.5nm.
(2) narrow band gap distribution, the growth and characterization of high-purity semi-conductive single-walled carbon nanotubes
Single-walled carbon nanotube growth and characterization are consistent with embodiment 1.The diameter of single-wall carbon nano tube collection of transmission electron microscope statistics
In be distributed in 1.9~2.2nm.According to the corresponding relationship of semi-conductive single-walled carbon nanotubes diameter and band gap, difference in band gap is only
0.06ev.It is 98wt% according to the qualitative estimation semiconductor single-walled carbon content in the peak wavelength Raman RBM.After button back end
Absorption spectrum quantitatively calculate semi-conductive single-walled carbon nanotubes content be 99wt%.
(3) narrow band gap distribution, the building and performance of high-purity semi-conductive single-walled carbon nanotubes film transistor device
The building of thin film transistor device and performance test process are the same as embodiment 1, constructed thin film field-effect
The on-off ratio of transistor is 5.7 × 104~7.3 × 105, carrier mobility is 45~131cm2v-1s-1。
The preparation of 4. part carbon coating cobalt tungsten ruthenium nano-particle of embodiment and its distribution of catalytic growth narrow band gap, high-purity half
Conducting single-walled carbon nanotube
(1) preparation of part carbon coating cobalt tungsten ruthenium metal nanoparticle
The method that catalyst preparation uses embodiment 1, the difference is that catalyst precursor is 0.3mM K3[Co(CN)6],
0.3mM(NH4)10W12O41With 0.3mM K2RuCl5Mixed solution.Atomic force microscope shows that nano particle is evenly dispersed
In silicon substrate surface.Transmission electron microscope observing shows that all nano grain surfaces all parts are coated by carbon-coating, and particle ruler
It is very little uniform.125 particle diameter distributions of random statistical are in 3.5~5.0nm.
(2) narrow band gap distribution, the growth and characterization of high-purity semi-conductive single-walled carbon nanotubes
Single-walled carbon nanotube growth and characterization are consistent with embodiment 1.The diameter of single-wall carbon nano tube collection of transmission electron microscope statistics
In be distributed in 1.9~2.2nm.According to the corresponding relationship of semi-conductive single-walled carbon nanotubes diameter and band gap, difference in band gap is only
0.07ev.It is 98wt% according to the qualitative estimation semiconductor single-walled carbon content in the peak wavelength Raman RBM.After button back end
Absorption spectrum quantitatively calculate semi-conductive single-walled carbon nanotubes content be 98wt%.
(3) narrow band gap distribution, the building and performance of high-purity semi-conductive single-walled carbon nanotubes film transistor device
The building of thin film transistor device and performance test process are the same as embodiment 1, constructed thin film field-effect
The on-off ratio of transistor is 9.7 × 103~8.1 × 105, carrier mobility is 51~124cm2v-1s-1。
The preparation of 5. part carbon coating cobalt nano-particle of embodiment and its catalytic growth band gap variable semiconductor single wall carbon
Nanotube
(1) catalyst preparation
Step is consistent with embodiment 1, the difference is that catalyst reduction process is 800 in 100sccm hydrogen and 100sccmAr
DEG C reduction 10 minutes.Atomic force microscope shows that nano particle is dispersed in silicon substrate surface.Transmission electron microscope observing table
Bright all nano grain surfaces all parts are coated by carbon-coating, and particle size is uniform.140 particles of random statistical are straight
Diameter is distributed in 2.5~4.5nm.
(2) narrow band gap distribution, the growth and characterization of high-purity semi-conductive single-walled carbon nanotubes
Single-walled carbon nanotube growth and characterization are consistent with embodiment 1.The diameter of single-wall carbon nano tube collection of transmission electron microscope statistics
In be distributed in 2.0~2.2nm, band gap difference is 0.05ev.According to the peak wavelength Raman RBM (Fig. 8 (a)-(c)) qualitative estimation
Semiconductor single-walled carbon content is 97wt%.Semi-conductive single-walled carbon is quantitatively calculated using the absorption spectrum after button back end to receive
The content of mitron is 99wt%.
(3) narrow band gap distribution, the building and performance of high-purity semi-conductive single-walled carbon nanotubes film transistor device
The building of thin film transistor device and performance test process are the same as embodiment 1, constructed thin film field-effect
The on-off ratio of transistor is 5.9 × 103~3.4 × 105, carrier mobility is 50~121cm2v-1s-1。
The preparation and its catalytic growth of single-wall carbon nanotube of the common cobalt nano-particle of comparative example
(1) catalyst preparation
Preparation step is consistent with embodiment 1, the difference is that solvent-free annealing process during Self-Assembling of Block Copolymer, and
And it is received with " being heat-treated 10 minutes for 700 DEG C in air " replacement " air plasama treatment process " with obtaining the metal being completely exposed
Rice grain.Atomic force microscope shows that nano particle is dispersed in silicon substrate surface.Transmission electron microscope observing shows own
Nano grain surface without carbon-coating coat.130 particle diameter distributions of random statistical are in 1.5~5.5nm.
(2) growth and characterization of single-walled carbon nanotube
Single-walled carbon nanotube growth and characterization are consistent with embodiment 1.The diameter of single-wall carbon nano tube collection of transmission electron microscope statistics
In be distributed in 1.1~2.2nm, band gap difference is 0.38ev.According to the qualitative estimation half in the peak wavelength Raman RBM (Fig. 9 (a)-(c))
Conductor single-walled carbon nanotube content is 67wt%.Semi-conductive single-walled carbon nanometer is quantitatively calculated using the absorption spectrum after button back end
The content of pipe is 69wt%.
(3) building and performance of single wall carbon nano-tube film transistor device
The building of thin film transistor device and performance test process are the same as embodiment 1, constructed thin film field-effect
The on-off ratio of transistor is 0.5 × 102~1.4 × 102, carrier mobility is 10~21cm2v-1s-1。
Embodiment the result shows that, the present invention can pass through the design control carbon nanotube of part carbon coating catalyst structure
Nucleation mode, it be obtain narrow diameter distribution single-walled carbon nanotube premise can directly be given birth to using the corrasion in situ of hydrogen
Long narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes.Moreover, the difference in band gap of semi-conductive single-walled carbon nanotubes can be with
Regulated and controled by regulation catalyst type, ingredient and reducing condition, narrow band gap distribution obtained, high-purity semiconductive list
Wall carbon nano tube has excellent field-effect transistor performance.
Claims (6)
1. the preparation method of a kind of narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes, which is characterized in that utilize block
Copolymer self-assembly method can prepare the characteristics of size uniformity nano particle, by controlling solvent anneal, oxidation, reducing condition, obtain
Obtain size uniformity, monodisperse, the carbon-coated metal nanoparticle in part；Using it as catalyst, using hydrogen weak etching and
The higher feature of same diameter metallic carbon nanotubes reactivity, direct in-situ etch metallic carbon nanotubes, obtain high-purity
Degree, narrow band gap are distributed semi-conductive single-walled carbon nanotubes；
Catalyst structure is the carbon-coated nano particle in part, and particle size is 2.0~4.5nm；
During preparing Block Copolymer Thin Film using self-assembly method, the block copolymer of self assembly be concentration be 0.2~
The toluene and tetrahydrofuran mixed solution of 0.3wt%PS-b-P4VP, mass ratio 1:1~5:1 of toluene and tetrahydrofuran, with
3000~5000rpm is spun on the silicon chip surface that hydrophilic treated is crossed；The Block Copolymer Thin Film of silicon chip surface is placed in toluene and four
Volume ratio 1:2~1:6 of solvent anneal 6~30 hours in the mixed vapour of hydrogen furans, toluene and tetrahydrofuran；After be impregnated in and rub
Your concentration is Catalyst precursor solutions 1~5 minute of 0.1~1mM, after deionized water washing is dry, Block Copolymer Thin Film
The time handled in air plasma is 20~60 minutes；The solution of Block Copolymer Thin Film chemisorption catalyst precursor
For the hydrochloric acid solution of 41.5~166.2g/L, catalyst precursor are as follows: K3[Co(CN)6]、K3[Fe(CN)6]、K2RuCl5、
(NH4)10W12O41、H2[PtCl6] one of or it is two or more, and must wherein contain K3[Co(CN)6]、K2RuCl5、K3
[Fe(CN)6One of]；
Need to carry out the carbon-coated catalyst in part reduction treatment before growing carbon nanotube, reducing atmosphere is hydrogen and argon gas
Mixed gas, reduction temperature be 500~800 DEG C, the recovery time be 2~25 minutes；Catalyst is after reduction treatment, 700
Narrow band gap is prepared as carrier gas chemical vapor deposition using hydrogen at~900 DEG C and is distributed semi-conductive single-walled carbon nanotubes.
2. the preparation method of narrow band gap distribution described in accordance with the claim 1, high-purity semi-conductive single-walled carbon nanotubes, special
Sign is: the single-walled carbon nanotube difference in band gap grown is only 0.05eV and adjustable, and semiconductive carbon nano tube content is greater than
98%.
3. the preparation method of narrow band gap distribution according to claim 1 or 2, high-purity semi-conductive single-walled carbon nanotubes,
It is characterized by: regulating and controlling the difference in band gap of semiconductive carbon nano tube by the structure and reduction process of regulation catalyst.
4. according to claim 2 narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes preparation method, it is special
Sign is: using the content of wavelength Raman qualitative spectrometric estimation semi-conductive single-walled carbon nanotubes, according to Katarula
The breathing mould that plots excites each wavelength laser carries out the division of semiconductive and metallic carbon nanotubes, counts in phase
Answer the number of region internal respiration mould, the content of semiconductive carbon nano tube is by the breathing mould number that excites in semiconductive region
With the ratio of all breathing mould numbers.
5. according to claim 2 narrow band gap distribution, high-purity semi-conductive single-walled carbon nanotubes preparation method, it is special
Sign is: the content of semi-conductive single-walled carbon nanotubes is calculated using absorption spectrum is qualitative, i.e., by the suction after deduction back end
Receive S corresponding to curve22And M11Integrating peak areas is calculated using following formula:
M11, metallic single-wall carbon nano-tube M11Peak area；
S22, semi-conductive single-walled carbon nanotubes S22Peak area；
F, absorption coefficient.
6. the preparation method of narrow band gap distribution described in accordance with the claim 1, high-purity semi-conductive single-walled carbon nanotubes, special
Sign is: being had both using thin film transistor constructed by this high-purity, narrow gap semiconductor single-walled carbon nanotube
High on-off ratio and high carrier mobility show this narrow gap semiconductor single-walled carbon nanotube in terms of nanometer electronic device
Potential application.
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