CN107089652A - Narrow band gap distribution, the preparation method of high-purity semi-conductive single-walled carbon nanotubes - Google Patents
Narrow band gap distribution, the preparation method of high-purity semi-conductive single-walled carbon nanotubes Download PDFInfo
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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
- B01J23/745—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
- 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
- B01J23/89—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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- B01J35/40—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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, the method for high-purity semi-conductive single-walled carbon nanotubes.Using Self-Assembling of Block Copolymer method, the copolymer film cladding anionic metal nanocluster of size uniform is prepared；By controlling solvent anneal, oxidation, reducing condition, single dispersing, the metal-catalyst nanoparticles of part carbon coating are obtained；Again using hydrogen as etching gas in situ, the distribution of direct growth narrow band gap, high-purity semi-conductive single-walled carbon nanotubes.Wherein the content of semi-conductive single-walled carbon nanotubes is more than 98%, the minimum 0.05eV of difference in band gap and adjustable.The present invention realizes narrow band gap distribution, the direct controllable growth of 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 building TFT.
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 coating
Metallic catalyst prepares narrow band gap distribution, the method for high-purity semi-conductive single-walled carbon nanotubes, embedding by regulating and controlling
Section copolymer self assembling process and post-treatment condition, prepare single dispersing, narrow particle diameter distribution, the gold of part carbon coating
Metal catalyst nano particle；Then the metallicity list of high activity is removed with etching property gas original position by carrier gas of hydrogen
Wall carbon nano tube, is directly realized by narrow band gap distribution and the control of band gap variable semiconductor single-walled carbon nanotube growth.
Background technology
Single-walled carbon nanotube can regard the one-dimensional hollow tubular structure crimped by single-layer graphene as, and it has
There are the metallicity related with helical angle to diameter or characteristic of semiconductor.Semi-conductive single-walled carbon nanotubes have very
High electron mobility and adjustable band gap, is the ideal material for building fieldistor channel, is expected to not
Carry out substituted single crystal silicon and build nanometer electronic device of future generation.Therefore, the semi-conductive single-walled carbon of high-purity is directly obtained to receive
Mitron, is the key for promoting the application of its nanometer electronic device.
In recent years, the control preparation work of semi-conductive single-walled carbon nanotubes has been achieved for remarkable progress, mainly
It is the high chemical reactivity using metallic carbon nanotubes, original position introduces etching agent and removed it, according to etching
The characteristics of agent, can be attributed to 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) cerium oxide that can slowly discharge oxygen is
Catalyst carrier (Qin, X.；Peng,F.；Li,Y.et al.Nano Letter 2014,14,512)；(3) decomposable asymmetric choice net goes out
The alcohols of 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 nanotubes purity is~95% at present, and band gap wider distribution, this
The homogeneity of its constructed device performance can be influenceed.Because the band gap of single-walled carbon nanotube is inversely proportional with its diameter,
The necessary condition for obtaining narrow band gap distribution CNT is to obtain the homogeneous CNT of diameter.Meanwhile, single wall carbon
The reactivity of nanotube not only has conductive properties dependency characteristic, also related to diameter.In order to obtain high-purity
Semi-conductive single-walled carbon nanotubes, it is necessary to control the diameter of CNT to be distributed and concentrate.It can be seen that, CNT
Diameter control is not only the key for preparing narrow gap semiconductor CNT, is also to prepare high-purity semiconductive
The key of single-walled carbon nanotube.Yet with the nanoscale of single-walled carbon nanotube, the nanometer of its growth is catalyzed
Grain high temperature (>600 DEG C) under easily reunite, thus be difficult to obtain size uniformity nano-catalyst particles.Together
When, single-walled carbon nanotube forming core from nano particle mainly follows both of which, one kind be carbon nanotube diameter with
Consistent " tangent line growth " pattern of nano-particle diameter, another is that carbon nanotube diameter is less than nanoparticle size
" vertical-growth " pattern.(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, it is also difficult to the homogeneous list of growth size
Wall carbon nano tube.
Current subject matter is：How the catalyst nano-particles of size uniformity are obtained, while controlling single wall carbon
The nucleating growth pattern of nanotube；And then, break through narrow band gap, the control of high-purity semi-conductive single-walled carbon nanotubes
Prepare bottleneck.
The content of the invention
It is an object of the invention to provide a kind of distribution of part carbon-clad metal catalyst preparation narrow band gap, high-purity half
The method of conducting single-walled carbon nanotube, overcoming existing single-walled carbon nanotube, forming core pattern is not on metallic catalyst
It is determined that the problem of caused carbon nanotube diameter distribution width, while overcoming existing metallic catalyst high temperature easily to roll into a ball
The problem of diameter distribution is wide caused by poly-, by catalyst size control and structure design, with reference to hydrogen in-situ
Etching, the distribution of direct growth narrow band gap, high-purity, high-quality semiconductor single-walled carbon nanotube.
The technical scheme is that：
A kind of narrow band gap distribution, the preparation method of high-purity semi-conductive single-walled carbon nanotubes, utilize block copolymerization
The characteristics of thing self-assembly method can prepare size uniformity nano particle, by controlling solvent anneal, oxidation, reduction bar
Part, obtains size uniformity, single dispersing, the metal nanoparticle of part carbon coating；Using it as catalyst, utilize
The characteristics of weak etching and higher same diameter metallic carbon nanotubes reactivity of hydrogen, direct in-situ etching
Metallic carbon nanotubes, obtain high-purity, narrow band gap distribution semi-conductive single-walled carbon nanotubes.
Described narrow band gap is distributed, the preparation method of high-purity semi-conductive single-walled carbon nanotubes, catalyst structure
For the nano particle of part carbon coating, particle size is 2.0~4.5nm；Wherein, catalyst component is transition gold
It is more than one or both of category；Or, catalyst component is more than one or both of refractory metal.
Described narrow band gap is distributed, the preparation method of high-purity semi-conductive single-walled carbon nanotubes, using self assembly
During method prepares Block Copolymer Thin Film, the solvent anneal time is 6~30 hours, Block Copolymer Thin Film
The time handled in air plasma is 20~60 minutes.
Described narrow band gap is distributed, the preparation method of high-purity semi-conductive single-walled carbon nanotubes, is received in growth carbon
Need to carry out the catalyst of part carbon coating reduction treatment before mitron, reducing atmosphere is the mixing of hydrogen and argon gas
Gas, reduction temperature is 500~800 DEG C, and the recovery time is 2~25 minutes；Catalyst after reduction treatment,
The semi-conductive single-walled carbon of narrow band gap distribution is prepared at 700~900 DEG C by carrier gas chemical vapor deposition of hydrogen to receive
Mitron.
Described narrow band gap is distributed, the preparation method of high-purity semi-conductive single-walled carbon nanotubes, the list grown
Wall carbon nano tube difference in band gap is only 0.05eV and adjustable, and semiconductive carbon nano tube content is more than 98%.
Described narrow band gap is distributed, the preparation method of high-purity semi-conductive single-walled carbon nanotubes, is urged by regulation and control
The structure and reduction process of agent regulate and control the difference in band gap of semiconductive carbon nano tube.
Described narrow band gap is distributed, the preparation method of high-purity semi-conductive single-walled carbon nanotubes, utilizes multi-wavelength
Raman spectra qualitative estimates the content of semi-conductive single-walled carbon nanotubes, according to Katarula plots to each wavelength
The breathing mould that laser is excited carries out the division of semiconductive and metallic carbon nanotubes, counts in respective regions
Breathe the number of mould, the content of semiconductive carbon nano tube is by the breathing mould number that is excited in semiconductive region
With the ratio of all breathing mould numbers.
Described narrow band gap is distributed, the preparation method of high-purity semi-conductive single-walled carbon nanotubes, semiconductive list
The content of wall carbon nano tube is obtained using the qualitative calculating of absorption spectrum, will deduct the institute of the absorption curve after back end right
The S answered22And M11Integrating peak areas, is calculated using equation below：
M11, metallic single-wall carbon nano-tube M11Peak area；
S22, semi-conductive single-walled carbon nanotubes S22Peak area；
F, absorption coefficient.
Described narrow band gap is distributed, the preparation method of high-purity semi-conductive single-walled carbon nanotubes, utilizes this height
TFT constructed by purity, narrow gap semiconductor single-walled carbon nanotube have concurrently high on-off ratio and
High carrier mobility, shows that this narrow gap semiconductor single-walled carbon nanotube is latent in terms of nanometer electronic device
In application.
The present invention design philosophy be：
The present invention provides a kind of method of direct growth narrow gap semiconductor single-walled carbon nanotube, designs and prepares
A kind of single dispersing, the part carbon-coated metallic nano-particles catalyst of size uniform, the part carbon coating structure
The high temperature of nano-metal particle is inhibited to reunite, it is vertical life that the forming core pattern of single-walled carbon nanotube is controlled again
It is long, and then the single-walled carbon nanotube of size uniformity can be prepared；On this basis, the hydrogen etching agent in situ that introduces is gone
Except metallic carbon nanotubes or suppress its growth, and then directly obtain narrow band gap distribution, high-purity semiconductive list
Wall carbon nano tube.
Structure of the invention by designing metallic catalyst, with reference to original position etching direct growth narrow band gap distribution, height
Purity semiconductor single-walled carbon nanotube, it is advantageous in that：
1st, the present invention design first and be prepared for single dispersing, the part carbon-coated metallic nano-particles knot of size uniform
Structure, that is, solve the problem of catalyst high temperature is reunited, and the control for also solving CNT nucleating growth pattern is asked
Topic, and then realize the preparation of size uniformity single-walled carbon nanotube.
2nd, the inventive method is used as carrier gas and quarter on the basis of the preparation of size uniformity single-walled carbon nanotube using hydrogen
Gas is lost, narrow band gap distribution (smallest bandgap difference be only 0.05eV) is realized first and band gap is adjustable, high-purity
It is prepared by the control of (more than 98%) semi-conductive single-walled carbon nanotubes.
In a word, the present invention is to control catalyst structure that the single-walled carbon nanotube forming core stage relied on as starting point,
Narrow band gap distribution, the direct growth of high-purity semi-conductive single-walled carbon nanotubes are realized, is breached high at this stage
Bottleneck prepared by purity, narrow band gap distribution semi-conductive single-walled carbon nanotubes control, is specific structure semiconductive
The nucleating mechanism of single-walled carbon nanotube provides new understanding, it was confirmed that it is to build TFT
Desired channel material.
Brief description of the drawings
The preparation of Fig. 1 parts carbon coating cobalt nano-particle and growth narrow band gap are distributed semi-conductive single-walled carbon nanometer
Pipe process schematic.
The pattern of Fig. 2 parts carbon coating cobalt nano-particle.(a) atomic force of part carbon coating cobalt nano-particle shows
Micro mirror photo；(b) transmission electron microscope photo of part carbon coating cobalt nano-particle；(c) particle of transmission electron microscope statistics
Size Distribution block diagram.
Fig. 3 parts carbon coating cobalt nano-particle is the pattern of the CNT of catalyst preparation.(a) silicon chip table
The stereoscan photograph of face carbon nano tube network；(b) transmission electron microscope photo of single-walled carbon nanotube；(c) it is vertical raw
It is longer than the single-walled carbon nanotube transmission electron microscope photo of part carbon coating cobalt nano-particle；(d) united using transmission electron microscope
The carbon nanotube diameter distribution histogram of meter.
Fig. 4 parts carbon coating cobalt nano-particle is Raman spectrum D, G of the single-walled carbon nanotube of catalyst preparation
Mould.
Fig. 5 parts carbon coating cobalt nano-particle is the wavelength Raman light of the single-walled carbon nanotube of catalyst preparation
Compose RBM moulds.(a) 532nm wavelength lasers；(b) 633nm wavelength lasers；(c) 785nm wavelength lasers；(d)
488nm wavelength lasers.
Fig. 6 parts carbon coating cobalt nano-particle is the abosrption spectrogram of the single-walled carbon nanotube of catalyst preparation.
The thin film field that Fig. 7 are constructed using the single-walled carbon nanotube of part carbon coating cobalt nano-particle catalyst preparation
The performance of effect transistor.(a) output characteristic curve of the single field-effect transistor in -1V to -5V；(b)10
The transfer characteristic curve of individual TFT.
Fig. 8 parts carbon coating cobalt nano-particle is many ripples of the band gap adjustable single-wall carbon nano of catalyst preparation
Long Raman spectrum RBM moulds.(a) 532nm wavelength lasers；(b) 633nm wavelength lasers；(c) 785nm ripples
Long laser.
Fig. 9 cobalt nano-particles are the wavelength Raman spectrum RBM moulds of the single-walled carbon nanotube of catalyst preparation.
(a) 532nm wavelength lasers；(b) 633nm wavelength lasers；(c) single-walled carbon nanotube that Raman spectrum is characterized
Conductive properties content distribution figure.
Embodiment
In specific implementation process, part carbon-clad metal catalyst preparation narrow band gap distribution of the present invention, high-purity
The method of semi-conductive single-walled carbon nanotubes, is controlled by the structure snd size to catalyst, utilizes the quarter of hydrogen
The distribution of erosion effect directly selecting property growth narrow band gap, high-purity semi-conductive single-walled carbon nanotubes, specific steps are such as
Under：
Utilize the film of the method for block copolymer chemistry self assembly, on a silicon substrate self-assembled block copolymers；
The film is subjected to chemisorbed complex catalyst precursor after solvent anneal in the mixed vapour of toluene and tetrahydrofuran
Body, then carried out air plasma (plasma) processing and can obtain the metal oxidation coated by partial organic substances
Thing catalyst nano cluster, carries out the catalysis that hydrogen reducing processing obtains part carbon coating at 500~800 DEG C
Agent nano particle, narrow band gap distribution is prepared by carrier gas chemical vapor deposition of hydrogen at 700~900 DEG C and is partly led
Body single-walled carbon nanotube.Wherein：
(1) block copolymer of self assembly is that concentration is that (PS-b-P4VP is 0.2~0.5wt%PS-b-P4VP
Refer to poly- (styrene-block-4-vinylpyridine) block copolymer) toluene and tetrahydrofuran mixed solution (first
The mass ratio 1 of benzene and tetrahydrofuran:1~5:1) silicon chip that hydrophilic treated is crossed, is spun on 3000~5000rpm
Surface.
(2) Block Copolymer Thin Film of silicon chip surface is placed in toluene and tetrahydrofuran (volume ratio 1:2~1:6)
Solvent anneal 6~30 hours in mixed vapour, after be impregnated in molar concentration be 0.1~1mM complex catalyst precursor
Liquid solution 1~5 minute, after deionized water washing is dried, air plasma is handled 20~60 minutes.
(3) solution of Block Copolymer Thin Film chemisorbed catalyst precursor is 41.5~166.2g/L salt
Acid solution, its catalyst precursor is：K3[Co(CN)6]、K3[Fe(CN)6]、K2RuCl5、(NH4)10W12O41、
H2[PtCl6] in one or two kinds of more than, and must wherein contain K3[Co(CN)6]、K2RuCl5、
K3[Fe(CN)6] in one kind.
(4) catalyst reduction condition is handled 2~25 minutes for 500~800 DEG C in 100~200sccm hydrogen.
(5) carbon source used in chemical vapor deposition is the organic molecule alcohol vapor that argon gas is loaded into, and is passed through carbonaceous sources
The volume ratio of argon gas and carrier gas hydrogen be 1:1~1:5, total gas flow rate is maintained at 100~600sccm, raw
It is 1~15 minute for a long time.
(6) the part carbon-coated metallic nano-particles diameter obtained is distributed between 2.0~4.5nm,
Catalyst can for Co, Fe, Ru, CoPt, CoRu, CoW, FeRu, FeW, FePt, CoPtW,
FePtW, CoRuW or FeRuW.In the present invention, the concrete meaning and structure of part carbon coating are metals
Particle exterior surface partly coats to be formed similar to Oak Tree fruit structure by carbon-coating.That is metallic particles outer surface part is naked
Dew, other parts are coated by carbon-coating.
The diameter of single-wall carbon nano tube distribution grown is concentrated, and the minimum 0.05eV of difference in band gap and adjustable is partly led
Body content of carbon nanotubes is more than 98%, the contents of semi-conductive single-walled carbon nanotubes be respectively adopted Raman spectrum and
Absorption spectrum carries out qualitative estimation and quantitative calculating.
The present invention is described in further detail below by embodiment.
The preparation of the part carbon coating cobalt nano-particle of embodiment 1. and its distribution of catalytic growth narrow band gap, high-purity half
Conducting single-walled carbon nanotube
Specific preparation is as shown in Figure 1 with growth course.
(1) preparation of part carbon coating Co metal nanoparticles
By the toluene containing 0.3wt% block copolymers and the tetrahydrofuran solution (mass ratio of toluene and tetrahydrofuran
2:1) 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 chip is placed in 1mM K3[Co(CN)6]
3 minutes absorption [Co (CN) are impregnated in solution6]3-It is washed with deionized after anion, taking-up, at 60 DEG C
Dry 30 minutes, be finally placed in processing 20 minutes in air plsama (power 20W).Will be above-mentioned treated
Silicon chip is placed in tube furnace, is evacuated to below 0.5MPa and is passed through argon gas recovery normal pressure again, then cuts argon gas
200sccm hydrogen is changed to, and silicon chip is pushed into flat-temperature zone, with 20 DEG C/min of heating rate by flat-temperature zone temperature
Degree rises to 700 DEG C from 500 DEG C and is incubated 5min.Atomic force microscopy (Fig. 2 (a)) shows, nanometer
Even particulate dispersion is in silicon substrate surface.Transmission electron microscope photo (Fig. 2 (b)) shows all nano grain surfaces
All part is coated by carbon-coating, and particle size is homogeneous.The random statistical diameter of 130 particles, it is tied
Fruit is as shown in Fig. 2 (c), and the particle diameter distribution of nano particle is in 2.0~4.5nm.
(2) narrow band gap distribution, the growth of high-purity semi-conductive single-walled carbon nanotubes and sign
On the basis of step one, the argon gas containing alcohol vapour is further passed through, its volume ratio with carrier gas hydrogen
For 1:2, total gas flow rate remains 300sccm, carries out chemical vapor deposition growth single-walled carbon nanotube, raw
It is 10 minutes for a long time.After growth terminates, carbon source is closed, sample is taken out after argon gas protection drops to room temperature.
It is uniform carbon nano tube network shown in the stereoscan photograph of prepared single-walled carbon nanotube such as Fig. 3 (a).Its
It is single high-quality single-walled carbon nanotube, diameter is homogeneous shown in transmission electron microscope photo such as Fig. 3 (b).And can be direct
It was observed that the vertical relation of single-walled carbon nanotube and part carbon-coated nano particle, is shown in Fig. 3 (c), indirect proof
Its vertical growth mode.The random statistical diameter of 150 CNTs, the distribution of its diameter as shown in Fig. 3 (d),
It can be seen that diameter distribution is very narrow, 1.6~1.9nm is concentrated on.According to semi-conductive single-walled carbon nanotubes diameter and band
The corresponding relation of gap, its difference in band gap is only 0.08ev.Single-walled carbon nanotube is in 1200~1800 wave-number ranges
Raman spectrum as shown in figure 4, single-walled carbon nanotube is in 1590cm-1There are very strong G peaks at place, illustrates carbon
Nanotube good crystallinity.Multi-wavelength (532nm, 633nm, 785nm, 488nm laser) Raman RBM peaks
As shown in Fig. 5 (a)-(d), schemed according to katarula plots and the qualitative estimation semiconductor of correspondence interval RBM peaks number
Single-walled carbon nanotube content is 98wt%.The absorption spectrum of single-walled carbon nanotube is (lower curve) as shown in Figure 6,
Using deducting back end (top curve) S afterwards22And M11The integral area at peak, which is quantitatively calculated, obtains semi-conductive single-walled
The content of CNT is 99wt%.
(3) narrow band gap distribution, the structure of high-purity semi-conductive single-walled carbon nanotubes film transistor device and property
Energy
Raceway groove material is used as by the use of the narrow band gap distribution prepared by step 2, high-purity semi-conductive single-walled carbon nanotubes
Material, constructs bottom gate thin film field-effect transistor.The output characteristic curve of field-effect transistor such as Fig. 7 (a) institutes
Show, show to form good Ohmic contact between CNT and electrode.Fig. 7 (b) be same size, 10
The transfer characteristic curve of device.It is according to the on-off ratio that the calculating of these curves obtains TFT
3.1×103~3.6 × 106, carrier mobility is 36~143cm2v-1s-1.Compared with existing literature report result,
Its thin-film transistor performance is in a leading position level.
The preparation of the part carbon-encapsulated iron nano particle of embodiment 2. and its distribution of catalytic growth narrow band gap, high-purity half
Conducting single-walled carbon nanotube
(1) preparation of part carbon-encapsulated iron metal nanoparticle
Catalyst preparation step be the same as Example 1 is consistent, the difference is that catalyst precursor is 1mM K3[Fe(CN)6] solution.AFM shows that nano particle is dispersed in silicon substrate surface.Transmission electron microscope observing
Show that all nano grain surfaces all parts are coated by carbon-coating, and particle size is homogeneous.Random statistical
125 particle diameter distributions are in 2.5~4.0nm.
(2) narrow band gap distribution, the growth of high-purity semi-conductive single-walled carbon nanotubes and sign
Single-walled carbon nanotube grows and characterized consistent with embodiment 1.The single-walled carbon nanotube of transmission electron microscope statistics is straight
Footpath integrated distribution is in 1.8~2.1nm.According to semi-conductive single-walled carbon nanotubes diameter and the corresponding relation of band gap,
Its difference in band gap is only 0.08ev.Contained according to the qualitative estimation semiconductor single-walled carbon in wavelength Raman RBM peaks
Measure as 98wt%.The content for quantitatively calculating semi-conductive single-walled carbon nanotubes using the absorption spectrum behind buckle back bottom is
98wt%.
(3) narrow band gap distribution, the structure of high-purity semi-conductive single-walled carbon nanotubes film transistor device and property
Energy
The structure and performance test process be the same as Example 1 of TFT device, constructed thin film field
The on-off ratio of effect transistor is 4.0 × 104~2.5 × 105, carrier mobility is 50~110cm2v-1s-1。
The preparation of the part carbon coating ferrotungsten nano particle of embodiment 3. and its distribution of catalytic growth narrow band gap, high-purity
Semi-conductive single-walled carbon nanotubes
(1) preparation of part carbon coating ferrotungsten metal nanoparticle
Catalyst preparation step be the same as Example 1 is consistent, the difference is that catalyst precursor is 0.5mM K3[Fe(CN)6] and 0.5mM (NH4)10W12O41Mixed solution.AFM 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
And particle size is homogeneous.135 particle diameter distributions of random statistical are in 3.0~4.5nm.
(2) narrow band gap distribution, the growth of high-purity semi-conductive single-walled carbon nanotubes and sign
Single-walled carbon nanotube grows and characterized consistent with embodiment 1.The single-walled carbon nanotube of transmission electron microscope statistics is straight
Footpath integrated distribution is in 1.9~2.2nm.According to semi-conductive single-walled carbon nanotubes diameter and the corresponding relation of band gap,
Its difference in band gap is only 0.06ev.Contained according to the qualitative estimation semiconductor single-walled carbon in wavelength Raman RBM peaks
Measure as 98wt%.The content for quantitatively calculating semi-conductive single-walled carbon nanotubes using the absorption spectrum behind buckle back bottom is
99wt%.
(3) narrow band gap distribution, the structure of high-purity semi-conductive single-walled carbon nanotubes film transistor device and property
Energy
The structure and performance test process be the same as Example 1 of TFT device, constructed thin film field
The on-off ratio of effect transistor is 5.7 × 104~7.3 × 105, carrier mobility is 45~131cm2v-1s-1。
The preparation of the part carbon coating cobalt tungsten ruthenium nano-particle of embodiment 4. and its catalytic growth narrow band gap distribution, it is high-purity
Spend semi-conductive single-walled carbon nanotubes
(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 shows
Micro mirror 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 homogeneous.125 particle diameters of random statistical point
Cloth is in 3.5~5.0nm.
(2) narrow band gap distribution, the growth of high-purity semi-conductive single-walled carbon nanotubes and sign
Single-walled carbon nanotube grows and characterized consistent with embodiment 1.The single-walled carbon nanotube of transmission electron microscope statistics is straight
Footpath integrated distribution is in 1.9~2.2nm.According to semi-conductive single-walled carbon nanotubes diameter and the corresponding relation of band gap,
Its difference in band gap is only 0.07ev.Contained according to the qualitative estimation semiconductor single-walled carbon in wavelength Raman RBM peaks
Measure as 98wt%.The content for quantitatively calculating semi-conductive single-walled carbon nanotubes using the absorption spectrum behind buckle back bottom is
98wt%.
(3) narrow band gap distribution, the structure of high-purity semi-conductive single-walled carbon nanotubes film transistor device and property
Energy
The structure and performance test process be the same as Example 1 of TFT device, constructed thin film field
The on-off ratio of effect transistor is 9.7 × 103~8.1 × 105, carrier mobility is 51~124cm2v-1s-1。
The preparation of the part carbon coating cobalt nano-particle of embodiment 5. and its catalytic growth band gap variable semiconductor list
Wall carbon nano tube
(1) catalyst preparation
Step be the same as Example 1 is consistent, the difference is that catalyst reduction process is 100sccm hydrogen and 100sccmAr
In 800 DEG C reduce 10 minutes.AFM 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 homogeneous.
140 particle diameter distributions of random statistical are in 2.5~4.5nm.
(2) narrow band gap distribution, the growth of high-purity semi-conductive single-walled carbon nanotubes and sign
Single-walled carbon nanotube grows and characterized consistent with embodiment 1.The single-walled carbon nanotube of transmission electron microscope statistics is straight
Footpath integrated distribution is in 2.0~2.2nm, and its band gap difference is 0.05ev.According to wavelength Raman RBM peaks (figure
8 (a)-(c)) qualitative estimation semiconductor single-walled carbon content is 97wt%.Utilize the absorption spectrum behind buckle back bottom
The content for quantitatively calculating semi-conductive single-walled carbon nanotubes is 99wt%.
(3) narrow band gap distribution, the structure of high-purity semi-conductive single-walled carbon nanotubes film transistor device and property
Energy
The structure and performance test process be the same as Example 1 of TFT device, constructed thin film field
The on-off ratio of effect transistor is 5.9 × 103~3.4 × 105, carrier mobility is 50~121cm2v-1s-1。
The preparation of the common cobalt nano-particles of comparative example and its catalytic growth of single-wall CNT
(1) catalyst preparation
Preparation process be the same as Example 1 is consistent, the difference is that solvent-free annealed during Self-Assembling of Block Copolymer
Journey, and with " in air 700 DEG C be heat-treated 10 minutes " replacement " air plasama processing procedures " with
Obtain the metal nanoparticle being completely exposed.AFM shows that nano particle is dispersed in silicon substrate
Basal surface.Transmission electron microscope observing shows that all nano grain surfaces are coated without carbon-coating.The 130 of random statistical
Individual particle diameter distribution is in 1.5~5.5nm.
(2) growth of single-walled carbon nanotube and sign
Single-walled carbon nanotube grows and characterized consistent with embodiment 1.The single-walled carbon nanotube of transmission electron microscope statistics is straight
Footpath integrated distribution is in 1.1~2.2nm, and its band gap difference is 0.38ev.According to wavelength Raman RBM peaks (Fig. 9 (a)-
(c)) qualitative estimation semiconductor single-walled carbon content is 67wt%.Quantified using the absorption spectrum behind buckle back bottom
The content for calculating semi-conductive single-walled carbon nanotubes is 69wt%.
(3) structure and performance of single wall carbon nano-tube film transistor device
The structure and performance test process be the same as Example 1 of TFT device, constructed thin film field
The on-off ratio of effect transistor is 0.5 × 102~1.4 × 102, carrier mobility is 10~21cm2v-1s-1。
Embodiment result shows that the present invention can control carbon nanometer by the design of part carbon coating catalyst structure
The nucleation mode of pipe, it is to obtain the premise that narrow diameter is distributed single-walled carbon nanotube, is etched using the original position of hydrogen
Effect, can the distribution of direct growth narrow band gap, high-purity semi-conductive single-walled carbon nanotubes.Moreover, semiconductive
The difference in band gap of single-walled carbon nanotube can be regulated and controled by regulating and controlling catalyst type, composition and reducing condition, institute
The narrow band gap distribution of acquisition, high-purity semi-conductive single-walled carbon nanotubes have excellent field-effect transistor performance.
Claims (9)
1. a kind of narrow band gap distribution, the preparation method of high-purity semi-conductive single-walled carbon nanotubes, it is characterised in that
The characteristics of can preparing size uniformity nano particle using Self-Assembling of Block Copolymer method, by control solvent anneal,
Oxidation, reducing condition, obtain size uniformity, single dispersing, the metal nanoparticle of part carbon coating；Using its as
Catalyst, using hydrogen weak etching and higher same diameter metallic carbon nanotubes reactivity the characteristics of,
Direct in-situ etches metallic carbon nanotubes, obtains high-purity, narrow band gap distribution semi-conductive single-walled carbon nanotubes.
2. according to narrow band gap distribution, the preparation of high-purity semi-conductive single-walled carbon nanotubes described in claim 1
Method, it is characterised in that：Catalyst structure is the nano particle of part carbon coating, and particle size is 2.0~4.5
nm；Wherein, catalyst component is more than one or both of transition metal；Or, catalyst component is height
It is more than one or both of melting point metals.
3. according to narrow band gap distribution, the preparation of high-purity semi-conductive single-walled carbon nanotubes described in claim 1
Method, it is characterised in that：During Block Copolymer Thin Film being prepared using self-assembly method, the solvent anneal time
For 6~30 hours, the time that Block Copolymer Thin Film is handled in air plasma was 20~60 minutes.
4. according to narrow band gap distribution, the preparation of high-purity semi-conductive single-walled carbon nanotubes described in claim 1
Method, it is characterised in that：Need to carry out reduction treatment to the catalyst of part carbon coating before growth CNT,
Reducing atmosphere is the mixed gas of hydrogen and argon gas, and reduction temperature is 500~800 DEG C, and the recovery time is 2~25
Minute；Catalyst is prepared after reduction treatment at 700~900 DEG C by carrier gas chemical vapor deposition of hydrogen
Narrow band gap is distributed semi-conductive single-walled carbon nanotubes.
5. according to narrow band gap distribution, the preparation of high-purity semi-conductive single-walled carbon nanotubes described in claim 1
Method, it is characterised in that：The single-walled carbon nanotube difference in band gap grown is only 0.05eV and adjustable, semiconductor
Property content of carbon nanotubes be more than 98%.
6. according to the narrow band gap distribution described in claim 1 or 5, high-purity semi-conductive single-walled carbon nanotubes
Preparation method, it is characterised in that：Regulate and control semiconductive carbon nanometer by regulating and controlling the structure and reduction process of catalyst
The difference in band gap of pipe.
7. according to narrow band gap distribution, the preparation of high-purity semi-conductive single-walled carbon nanotubes described in claim 5
Method, it is characterised in that：The content of semi-conductive single-walled carbon nanotubes is estimated using wavelength Raman qualitative spectrometric,
The breathing mould excited according to Katarula plots to each wavelength laser carries out semiconductive and metallicity carbon nanometer
The division of pipe, counts the number in respective regions internal respiration mould, the content of semiconductive carbon nano tube is semiconductor
Property region in excited breathing mould number with it is all breathing mould numbers ratios.
8. according to narrow band gap distribution, the preparation of high-purity semi-conductive single-walled carbon nanotubes described in claim 5
Method, it is characterised in that：The content of semi-conductive single-walled carbon nanotubes is obtained using the qualitative calculating of absorption spectrum,
The S corresponding to the absorption curve after back end will be deducted22And M11Integrating peak areas, is counted using equation below
Calculate：
<mrow>
<msub>
<mi>R</mi>
<mi>S</mi>
</msub>
<mo>=</mo>
<mfrac>
<msub>
<mi>n</mi>
<mi>S</mi>
</msub>
<mrow>
<msub>
<mi>n</mi>
<mi>M</mi>
</msub>
<mo>+</mo>
<msub>
<mi>n</mi>
<mi>S</mi>
</msub>
</mrow>
</mfrac>
<mo>=</mo>
<mfrac>
<mn>1</mn>
<mrow>
<mn>1</mn>
<mo>+</mo>
<mfrac>
<msub>
<mi>M</mi>
<mn>11</mn>
</msub>
<mrow>
<msub>
<mi>S</mi>
<mn>22</mn>
</msub>
<mi>f</mi>
</mrow>
</mfrac>
</mrow>
</mfrac>
</mrow>
M11, metallic single-wall carbon nano-tube M11Peak area；
S22, semi-conductive single-walled carbon nanotubes S22Peak area；
F, absorption coefficient.
9. according to narrow band gap distribution, the preparation of high-purity semi-conductive single-walled carbon nanotubes described in claim 1
Method, it is characterised in that：Using thin constructed by this high-purity, narrow gap semiconductor single-walled carbon nanotube
Film field-effect transistor has high on-off ratio and high carrier mobility concurrently, shows this narrow gap semiconductor single wall
Potential application of the CNT in terms of nanometer electronic device.
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