CN101612612B - Methods for assembly and sorting of nanostructure-containing materials and related articles - Google Patents
Methods for assembly and sorting of nanostructure-containing materials and related articles Download PDFInfo
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- CN101612612B CN101612612B CN2009101646320A CN200910164632A CN101612612B CN 101612612 B CN101612612 B CN 101612612B CN 2009101646320 A CN2009101646320 A CN 2009101646320A CN 200910164632 A CN200910164632 A CN 200910164632A CN 101612612 B CN101612612 B CN 101612612B
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Abstract
A method for depositing a nanostructure-containing material onto an object or substrate includes one or more of the following: (1) forming a solution or suspension of nanostructure-containing material, (2) selectively adding 'chargers' to the solution, (3) immersing electrodes in the solution, the substrate or object upon which the nanostructure material is to be deposited acting as one of the electrodes, (4) applying a direct and/or alternating current electrical field between the two electrodes for a certain period of time thereby causing the nanostructure materials in the solution to migrate toward and attach themselves to the substrate electrode, and (5) subsequent optional processing of the coated substrate. Associated objects and devices are also provided. A method for separating nanostructures based on their properties and/or geometry is also described.
Description
The application divides an application, and its female case is to be that to be 200380109509.X, denomination of invention be the application of " being used to assemble method and correlated product with the material of sorting of nanostructure-containing " for December 8, application number in 2003 applying date.
The application requires interim U.S. Patent application No.60/431 according to 35U.S.C. § 119,719 priority, and its content is incorporated herein by reference at this in full.The application also requires interim U.S. Patent application No.60/461 according to 35U.S.C. § 119,401 priority, and its content is incorporated herein by reference at this in full.
About the research of federal government's subsidy or the statement of exploration project
At least some aspect of the present invention is under contract number is the government-funded of N00014-98-1-0597 and NAG-1-01061, to carry out.Government can have some right to the present invention.
Technical field
The present invention relates to the material of nanostructure-containing or nanotube is deposited into the method on the object; The material of nanostructure-containing or nanotube is carried out the method for sorting; Form the method for goods with the material of nanostructure-containing or nanotube; The method that the material of nanostructure-containing or nanotube is carried out sorting, and dependency structure and equipment.
Background technology
During hereinafter background is described, with reference to some structure and method, still, these with reference to should not necessarily be construed as admit these structures and method under suitable legal provisions as prior art.The applicant keeps the prior art of the right any referenced subject matter of confirmation does not constitute to(for) the present invention.
Personnel well known in the art " nanostructured " material that uses a technical term is represented to comprise such as C
60Fullerene, the concentric graphite granule of fullerene type, metal is such as the material of the nano particle of the compound semiconductor of CdSe, InP; Comprise such as Si, Ge, SiO
x, GeO
xThe material of nano wire/nanometer rods, perhaps by one or more elements, such as carbon, B
xN
y, C
xB
yN
z, MoS
2And WS
2The material of the nanotube of forming.A common trait of the material of nanostructured is their basic building block.Single nanoparticle or single CNT size at least in one direction are less than 500nm.This type material has demonstrated some performance, and these performances cause that people are to its interest in various application and method.
People's such as week United States Patent (USP) 6,280,697 and 6; 422; 450 (both titles all are " nano tube based high energy material and methods "), their content is incorporated herein by reference at this in full, discloses the manufacturing approach of carbon-based nano tube material and as the application of battery electrode material.
United States Patent (USP)----(sequence number 09/296572, title are " contain the device of field emission body of Nano carbon tube structure and make the method for this device "), its content is incorporated herein by reference at this in full, discloses a kind of carbon nanotube-based electron emitter structure.
People's such as Bower United States Patent (USP) 6; 630; 772 (name is called " device that contains film carbon nano electronic field emission body structure "),, its content is incorporated herein by reference at this in full, discloses a kind of field emission body of Nano carbon tube structure with high emission current density.
People's such as Bower United States Patent (USP) 6; 277; 318 (name is called " manufacturing approach of patterning (patterned) carbon nano-tube film "),, its content is incorporated herein by reference at this in full, discloses a kind of method of on substrate, making adhesive patterned carbon nano-tube film.
United States Patent (USP) 6,334,939 (name is called " nanostructure-based high energy material and method "),, its content is incorporated herein by reference at this in full, and disclosing a kind of is the nano structured alloy of one of component with alkali metal.This material it is said and can in some cell apparatus, use.
People's such as week United States Patent (USP) 6,553,096 (name is called " using electron field emission cathode to produce the mechanism of X ray "), its content is incorporated herein by reference at this in full, discloses the X ray generation device that adopts a kind of nanostructure-containing material.
The U.S. is publication application US 2002/0140336 (name is called " having the coated electrode that strengthens electronics emission and firing characteristic "); Its content is incorporated herein by reference at this in full; Disclose a kind of electrode, this electrode comprises first electrode material, adhesion promotor; And be distributed in the carbon nanotube-containing material at least a portion adhesion-promoting layer, and the relevant apparatus that has adopted kind electrode.
The open US 2002/0193040 of United States Patent (USP) (name is called " adopting the enhanced field emission to make the method for nano tube based material "); Its content is incorporated herein by reference at this in full, discloses a kind of foreign substance of introducing and has got into nanotube type material to improve the technology of its performance.
The open US2002/0094064 of United States Patent (USP) (name is called " multi beam x-ray system that large tracts of land can single addressing and forming process thereof "); Its content is incorporated herein by reference at this in full, discloses a kind of structure that produces a plurality of static and field emitting electronic source such as the CNTs that can single electrical addressing of having of X ray.
The open US 2003/0180472 of United States Patent (USP) (name is called " method of assemble nanometer level object "); Its content is incorporated herein by reference at this in full; Disclose and a kind ofly be self-assembled into the technology of macrostructure, can it have been handled draw ratio (aspect ratio) and/or the chemical functionality who needs to obtain with preform nanoscale object.
Can find out, the material of nanostructured, particularly those have up-and-coming performance such as the CNT with big draw ratio (that is to say-more than the much bigger length of its diameter) and other nanoscale object; These performances make it for various application scenarios; For example light-emitting component such as the field emission apparatus of flat-panel monitor, is used for the gas-discharge tube of overload protection; X-ray generator; Little lead, sensor, actuator and attractive especially such as the high-resolution probe that is used for flying-spot microscope.
The difficulty that in the process of these materials, meets with has hindered effectively introduces this kind device with these materials.For example the material of nanostructured can pass through such as laser ablation, and arc discharge method, and solution is synthetic, chemical etching, and molecular beam epitaxy, chemical vapor deposition, technology such as laser ablation forms.But the treatment technology of assembling the material of these nanostructureds has run into some difficulty.
Used such as aftershaping methods such as serigraphy and sprayings and will deposit on the substrate such as the preformed nanoscale object of CNT.But these technology have some defective.For example screen printing technique need utilize binder material and activation step.Spray technique not only inefficiency but also impracticable for large-scale manufacturing.In addition, usually these technology can cause the material of nanostructured on substrate, to form the nanostructured of random.
Used directly carbon nano-tube on substrate of chemical vapor deposition (CVD) technology.Referring to, J.Hafner etc. for example, Nature, the 398th volume, the 761st page, 1999 and United States Patent (USP) 6,457,350 and 6,401526.A potential application of this technology is made lead and the circuit of using such as the nanostructured of CNT.The CVD method can be used to form lead, and these leads utilize the CVD technology to be attached to ad-hoc location on the electrode so that form lead.But higher relatively temperature of these Technology Needs (for example 600-1,000 ℃) and reactive environments, and need to use catalyst with growing nano-tube effectively.The requirement of these severe rugged environment conditions has seriously been limited the type of the base material that can use.In addition, the CVD technology usually forms multiple wall carbon nano tube.Generally speaking, compare with SWCN, this multiple wall carbon nano tube does not have the structural perfection of same level, and therefore has relatively poor electron emission capability.And, use these technology directly on substrate growing nano-tube make the length of the nanotube of deposition, orientation and quantity are difficult to control.
Other technology comprises that accurate control with single or group's nanoscale object, is deposited into substrate such as CNT, such as the work of aspect on tip or the protrusion.Referring to for example Dai, Nature, the 384th volume, 147-150 page or leaf (1996); And people such as R.Stevens, Appl.Phys.Lett., the 77th volume, the 3453rd page.But these technology efforts are time-consuming, and can not carry out effective large-scale production or batch process.For example, United States Patent (USP) 6,528,785 have described and a kind of plate electrode have been placed electrophoresis solution, and with the method on nanotube deposition at least one electrode.Electrode is taken out from solution, in subsequent process steps, the nanotube that deposits on the electrode is transferred on the tip.Then through another can comprise with a kind of coating be deposited at least this be attached to processing step on the nanotube part on the tip with nanotube " melting welding " to the tip.This method is very slow and can not be orientated control.Most advanced and sophisticated each tip usually that forms thus comprises a CNT (CNT).The tip often combines very with interface between the CNT a little less than.Be difficult to once make a plurality of tips.This method is not only complicacy but also loaded down with trivial details undesirably, and therefore is impractical in large-scale production.
Another consideration in the art is that when using the made electrical equipment of nanostructured, must adopt usually to have material such as the same performance of same Electronic Performance.This does not also realize.For example, comprised in essence through laser ablation methods synthetic SWCN material and not only have metalline and but also have a material of semiconductor property.At present, the effective ways that also do not separate nanotube according to performance.For example,, a lot of devices are necessary to make being separated of metal for using with semiconductive nanotube.
Summary of the invention
Having developed can be efficiently under gentle relatively condition and assemble nanostructure-containing material effectively, and nanostructure-containing material is separated and method therefor is suitable for the technology and the correlated product thereof of batch process based on material property.
According to an aspect of the present invention, be a kind of nanostructure-containing material to be attached to the method on the tip of anything, the method comprises: the suspension that i) in a kind of liquid medium, forms a kind of nanostructure-containing material; (ii) at least one electrode is immersed in this suspension; (iii) this suspension is put at the tip; And (iv) on the electrode of submergence and tip, apply direct current or alternating current, make at least a portion nanostructure-containing material in the suspension be attached to object and approach the tip place most.
According to another aspect of the present invention, it is .5nm-100 μ m that a kind of diameter is provided, and length is 10 nanometers (nm)-greater than the line that comprises nanostructure-containing material of 1 centimetre (cm).
According to another aspect of the present invention, provide a kind of have be coated with single CNT, carbon nano-tube bundle; The perhaps object at the tip of nano wire, this object comprises following at least a: point-like electron field emission source, the probe of AFM (AFM); The probe of PSTM (STM), the electron source of transmission electron microscope (TEM), the electron source of SEM (SEM); The probe of magnetic force microscopy (MFM), perhaps profilograpy.
According to an aspect of the present invention; Provide a kind of nanostructure-containing material is attached to the method on the tip of anything; The method comprises: the suspension that i) in a kind of liquid medium, forms a kind of nanostructure-containing material; (ii) at least one electrode is immersed in this suspension; (iii) this suspension is put at the tip, and (iv) on the electrode of submergence and tip, applied direct current or alternating current, make at least a portion nanostructure-containing material in the suspension be attached to object and approach most advanced and sophisticated place, summit most.
According to another aspect of the present invention; A kind of device is provided; This device comprises having the conical tip of being essentially of a cone axis; And comprising the fibrillation that is attached to the most advanced and sophisticated material that contains nanostructured of going up and aliging with most advanced and sophisticated cone axis basically, fibriilar diameter is 0.5nm-10 μ m.
According to a further aspect of the invention; A kind of method that is electrically connected of between a plurality of assemblies, setting up is provided; This method comprises: the suspension that i) in a kind of liquid medium, forms nanostructure-containing material; (ii) suspension is contacted with assembly and (iii) on assembly, apply direct current or alternating current, thereby between assembly, form electric field, thereby make the nanostructure-containing material by coupling assembling form lead.
According to another aspect of the present invention, a kind of device is provided, this device comprises one first assembly; One second assembly; And first lead that comprises nanostructure-containing material, this lead is attached to first and second assembly, and between the two electrical connection is provided.
According to a further aspect of the invention; A kind of method that the component of nanostructure-containing material is left is provided; This method comprises: (i) formation comprises the group of nanostructure-containing material to be separated and the mixture of liquid medium, (ii) in mixture, introduces a plurality of electrodes; (iii) set up an asymmetric electric field in mixture inside; (iv) the group with nanostructure-containing material in the mixture polarizes; Thereby make at least the first group migrate to first electrode, make second group to migrate to second electrode, and (v) first electrode from liquid medium reclaims at least the first group.
According to a further aspect of the invention; Provide a kind of with the first group of particle that comprises in the mixture and the method for second group of particle separation; Wherein one of them of first and second group particle comprises nanostructure-containing material at least, and this method comprises: (i) form the device of electrode, (ii) apply alternating-current power supply to this device; (iii) with mixture and this device near; (iv) first group of particle and second group of particle are carried out polarization in various degree, (difference that v) relies on polarity is first group of particle and second group of particle separation, and (vi) reclaims at least a in first or second group of particle.
When using in this article then, term " nanostructure-containing material " expression part at least comprises following material: such as C
60Fullerene, the concentric graphite granule of fullerene type, metal is such as the nano particle of the compound semiconductor of CdSe, InP; Such as Si, Ge, SiO
x, GeO
xNano wire/nanometer rods, perhaps comprise such as carbon, B
xN
y, C
xB
yN
z, MoS
2And WS
2The nanotube of one or more elements.
Term " is essentially conical " and comprises it mainly being conical geometry in essence, but also can comprise the various structures that develop out from pure taper shape.The scope of these changes can be observed in the process that forms used tip usually; For example in the forming process of various probes, can observe; These probes are used for AFM, scanning probe microscopy, magnetic force microscopy, profilograpy, transmission electron microscope, SEM or the like, and they use traditional technology to form this type of tip.
Term " substantial alignment " comprises that being up to 15 spends or bigger a little alignment error.
Term " fibrillation " comprises single nano-structured particles, nano wire or nanotube; A plurality of such particles, nano wire or nanotube; The Dan Shu of these objects; Perhaps a plurality of bundles of these objects.
The accompanying drawing summary
Fig. 1 is the sketch map that contains the material of nanostructured.
Fig. 2 is the TEM image that contains the material of nanostructured.
Fig. 3 is for being assembled in the sketch map of the material that contains nanostructured as depicted in figs. 1 and 2 on the object through disclosed method.
Fig. 4 A and 4B are the sketch map of an embodiment of the method implemented according to disclosed method.
Fig. 5 A and 5B are the sketch map of another embodiment of the method implemented according to disclosed method.
Fig. 6 is the sketch map of an embodiment that is used to implement the equipment of this method.
Fig. 7 is the sketch map of another embodiment that is used to implement the equipment of this method.
Fig. 8 A and 8B are the sketch map of another embodiment of a process conducted according to the principles of the present invention.
Fig. 9 A-9E is the SEM image of amplification that has the fibriilar tip of the CNT that adheres to or nano wire.
Figure 10 is fibriilar sketch map, shows the relation of the various orientations that are attached to most advanced and sophisticated last time.
Figure 11 is the sketch map according to the another kind of object of another embodiment of the invention formation.
Figure 12 is the sketch map of the another kind of object that forms according to an alternative embodiment of the present invention.
Figure 13 is the sketch map according to the another kind of object of another embodiment of the invention formation.
Figure 14 is the sketch map of a separation arrangement and.
Figure 15 is the sketch map according to other a kind of separator of the present invention and/or technology.
Figure 16 is institute's flow of emitted electrons and alive curve map of device formed according to the present invention.
Figure 17 is institute's flow of emitted electrons of device formed according to the present invention and the curve map of time.
Figure 18 is the point-like electron field emission source of device formed according to the present invention and the sketch map of emission pattern.
Detailed Description Of The Invention
Hereinafter has been described method and corresponding structure and the equipment that carries out according to the principle of the invention and illustrative embodiment.
The method of carrying out according to the principle of the invention generally speaking, can comprise the combination of part or all of the following step: (1) forms a kind of suitable nanostructure-containing material; (2) this nanostructure-containing material of purifying; (3) this material that contains nanostructured is functionalized; (4) formation contains the solution or the suspension of the material of this nanostructured; (5) optionally in this solution, add " charger "; (6) electrode is immersed in the solution, with the substrate of the material that needs the depositing nano structure or object as one of them electrode; (7) continuing the regular period applies direct current and/or alternating current between electrode, forming electric field, thereby the material that makes the nanostructured in the solution is to the substrate electrod migration and be attached on the substrate; (8) gradually object is removed liquid, front surface and the liquid that makes deposition materials simultaneously keep in touch so that the material successive sedimentation of nanostructured to substrate; And subsequent treatment is randomly carried out to the substrate that applies in (9).Just also within the scope of the invention with the method that partly or entirely makes up of these general steps.But, be to be further appreciated that other step and method also can be included in.Should be appreciated that simultaneously the method that the combination of the said step of part or Overall Steps are carried out with particular order also within the scope of the invention.Perhaps, the order of step can be different from the description here.
The method starts from preformed, and " undressed " nanostructure-containing material of preferred high length-diameter ratio is perhaps such as the material that contains nanotube of carbon nanotube-containing material.This rough stock can comprise SWCN, multiple wall carbon nano tube, silicon, silica, germanium, germanium oxide, carbonitride, boron, boron nitride, two chalcogenides (dichalcogenide), silver, gold, iron, titanium dioxide, gallium oxide, indium phosphide, perhaps at least a such as in the magnetic-particle of the Fe, Co and the Ni that are packaged in nanostructured inside.According to preferred embodiment, the material of undressed carbon nanotubes comprises SWCN.CNT can be through any applicable technology, and such as above-mentioned arc discharge, laser ablation and chemical vapor deposition method form.
The present invention has also been contained and has been consisted of B
xC
yN
zThe nano tube structure form of (B=boron, C=carbon, and N=nitrogen) perhaps consists of MS
2The rough stock of the nanotube of (M=tungsten, molybdenum, the perhaps oxide of vanadium) or concentric fullerene structure form.These rough stocks can form through any applicable technology such as above-mentioned arc-discharge technique.
The technology that rough stock can be known is by one of skill in the art divided described multiple different technologies manufacturing such as above-mentioned background technology department.
According to a further embodiment of the present invention, magnetic tube or nano wire can be used as raw material.For example, as shown in Figure 1, can contain magnetic-particle 110 such as the material 100 of the nanostructured of CNT.Can expect that several kinds of forming these magnetic-particles are technological.Such technology comprises chemical gas-phase deposition method.Magnetic-particle such as Fe, Co and/or Ni is used as catalyst in the CVD technology.Hydrocarbon is as carbon source.Under appropriate condition, magnetic-particle plays the effect of the nucleating point of nanotube formation.Magnetic-particle 110 is retained in the end or the most advanced and sophisticated place of nanotube.Perhaps, use proper technology will such as single wall or again the nanotube of wall carbon nano tube be shaped to raw material.Then raw material are processed to open the end of nanotube.Through solution, electrochemistry, vapor phase or solid-state treatment technology magnetic-particle is inserted in the nanometer die then.Can use then such as the proper method end-blocking that forms passivation layer.The open US2003/0180472 of United States Patent (USP) has carried out more detailed description to these technology, and its content is incorporated herein by reference at this in full.
Fig. 2 is the sketch map of this magnetic-particle mentioned above.For example as shown in Figure 2, a kind of multiple wall carbon nano tube 200 is provided, it comprises a kind of Co particle 210 that is placed in one.As shown in Figure 3, according to more detailed method disclosed herein, can also or be attached on the tip such as the probe of AFM magnetic-particle 310 assembling.
As further explain and explanation, according to the disclosed more detailed method of hereinafter, can also or be attached on the tip such as the probe of AFM these magnetic-particles assemblings. hereThrough measuring magnetic tip of making like above-mentioned method and the interaction force between the object that needs imaging, can be with the magnetic texure imaging of object.This kind object comprises magnetic data storage medium.Because above-mentioned magnetic-particle size is little, can expect to obtain much higher resolution.
Unprocessed nanostructure-containing material can be purified.Can expect several kinds of purification rough stock technology.According to a preferred embodiment, can be with rough stock in appropriate solvent, such as H
2O
2Volumetric concentration be 1-40%, preferred H
2O
2Volumetric concentration is about 20% peroxide (H
2O
2) and the mixture of water in reflux, then at CS
2Middle rinsing, then rinsing in methyl alcohol is again filtered then and is purified.According to exemplary techniques, in medium, introduce the peroxide of about 10-100ml for the nanotube of every 1-10mg in the medium, and back flow reaction under 20-100 ℃ of temperature, carry out (referring to, for example United States Patent (USP) 6,553,096 (sequence number 09/679,303)).
According to another alternative, undressed nanostructure-containing material is put into suitable liquid medium, such as acid medium, organic solvent, perhaps alcohol is preferably among the methyl alcohol.Use the large power supersonic horn that rough stock is retained in several hrs in the liquid medium with suspension, simultaneously suspension is passed through microporous barrier.In another embodiment, can in air or oxygen atmosphere, under 200-700 ℃ of temperature, rough stock be purified through oxidation.Impurity in the rough stock is with the fast speed oxidation of a kind of ratio nano pipe.
In yet another embodiment, can nanowires/nanotubes be separated with impurity and rough stock is purified with liquid chromatogram.
Randomly raw material is further processed then, perhaps milled to shorten the length of nanotube and nanotube bundle such as chemical etching.
No matter whether carry out above-mentioned shortening and handle, the rough stock of purification can randomly be annealed under such as 100-1200 ℃ suitable temperature.According to preferred embodiment, annealing temperature is 100 ℃-600 ℃.Material carries out the annealing in process such as about 1-60 minute appropriate time.According to preferred embodiment, the anneal of material time is approximately 1 hour.Material is being about 10
-2Anneal in the vacuum of torr or higher vacuum.According to preferred embodiment, vacuum is approximately 5 * 10
-7Torr.
Can above-mentioned " undressed " or preformed material be introduced solution now, it be deposited on object or the substrate and/or form goods such as lead.
According to an alternative embodiment, before the nanostructure-containing material of purifying is put into above-mentioned solution or suspension, that it is functionalized.For example, can be in strong acid with the nanostructure-containing material oxidation of purifying so that the material possess hydrophilic property.An illustrative methods of this way comprises introduces H with the material of the nanostructured of purifying
2SO
4And HNO
3Solution in 10-24 hour, receive the effect of ultrasonic energy simultaneously.Perhaps, can chemical substance be attached on the outer surface of nanostructured through chemical method or physical method the nanostructure-containing material of purifying is functionalized so that nanostructured is solvable or promote steady suspension to form.
Select suitable liquid medium so that in this liquid, can form the stable suspension of the material of unprocessed nanostructured.According to preferred embodiment, liquid medium comprises water, methyl alcohol, ethanol, alcohols, and at least a in dimethyl formamide (DMF) and the glycerine.When in liquid medium, adding rough stock, can randomly apply ultrasonic energy or use and stir the mixture, form to promote stable suspension such as magnetic stirring bar.Can change the time that applies ultrasonic energy, but we find at room temperature about two hours just enough.
Can change the concentration of rough stock in the liquid medium, as long as formed steady suspension.For example, adopt the liquid medium that comprises methyl alcohol, the rough stock such as SWCN of about 0.01mg (0.01mg/ml) can be arranged in every milliliters of liquid medium, just steady suspension can be provided.When liquid medium comprises DMF, the rough stock such as SWCN of about 0.4-0.5mg (0.4-0.5mg/ml) can be arranged in every milliliters of liquid medium, just steady suspension can be provided.When using the CNT of brachymemma, can obtain the stable suspension of higher concentration.For example, can form the stable dispersion of the shortened nanotubes of the about 0.1mg/ml in the water.Among another embodiment, will be through chemical treatment the carbon nanotube bundles of possess hydrophilic property be dispersed in the water.Deposition is as required regulated the concentration of nanotube.
According to an embodiment, in suspension, add charger to promote electrophoretic deposition.A kind of preferred charger is MgCl
2Other possible charger comprises Mg (NO
3)
2, La (NO
3)
3, Y (NO
3)
3, AlCl
3And NaOH.Can use any suitable amount.With respect to the amount of nanostructure-containing material, all be feasible from being lower than the amount that 1 weight % is up to 50 weight %.According to preferred embodiment, suspension can contain the charger less than 1%.
According to another embodiment of the invention, small amount of carbon nanotubes is dispersed in the water.Suspension is carried out sonicated to obtain the homogeneous dispersion of CNT.Need not to apply any charger to suspension.Use the alternating current dielectrophoresis technology that CNT is deposited on the object that needs.At AC after the match, CNT polarizes and moves to certain field direction, and this direction depends on field concentration, AC field frequencies range, and the dielectric constant of liquid and CNT.
In suspension, introduce a plurality of electrodes then.According to preferred embodiment, use two electrodes.Electrode comprises on it object of material that will the depositing nano structure.Can expect and use any suitable object or substrate material, as long as it has the conductance of necessary degree.According to preferred embodiment, object can be the silicon of metal or doping.According to another preferred embodiment, at least one electrode comprises one or more tips.
On electrode, apply alternating current or direct current, make and form electric field between electrode.This material that causes the nanostructured in the suspension moves and is attached on the substrate electrod to substrate electrod.According to an embodiment, being applied to interelectrode electric field is 0.1-1000V/cm, and applies 0.1-200mA/cm
2Direct current 1 second-1 hour.According to another embodiment, apply the alternating current that frequency is 10Hz-10GHz.
According to preferred embodiment, above-mentioned electrophoretic deposition is at room temperature carried out.
Multiple factor can influence the structure and the pattern of material of the nanostructured of deposition and deposition.These factors comprise: the concentration of material of nanostructured in the suspension, (MgCl for example of charger material in the suspension if any
2) concentration, the object electrical conductivity, and power supply control (that is to say, when applying alternating current, the electric current that applies, voltage conditions and frequency).
For example, when applying direct current, can through select material that the charger material controls nanostructured to the specific electrode (that is to say anode or negative electrode) of migration.For example, through utilizing negative charger, apply negative electrical charge to the material of nanostructured, thereby make the trend of the material production of nanostructured to positive electrode (negative electrode) migration such as NaOH (NaOH).On the contrary, when using such as MgCl
2Positive charger material the time, apply positive charge to the material of nanostructured, thereby make the trend of the material production of nanostructured to negative electrode (anode) migration.
When using AC field, can be through selecting ac frequency, with respect to the liquid dielectric of the material of nanostructured, field concentration, and the geometry of the electrode material of controlling nanostructured to the specific electrode of migration.
Can randomly further process the band coating object that has deposited nanostructure-containing material on it.For example, can be with the annealing of band coating object to remove liquid medium.Possibly preferably carry out such annealing operation because remove between material that impurity such as the residual suspension medium can improve nanostructured and object electricity and thermo-contact with combine situation.For example, can the substrate that apply be heated to about 100-1200 ℃, keep about 1 hour, keep 2 hours at about 800 ℃ then, two processes are all about 5 * 10
-7Carry out under the vacuum of torr.
According to another embodiment, can be further through introducing such as binding agent, the adhesion promotion material and the high annealing of carbon dissolution or carbide-forming metal improve the bonding of CNT and substrate.These materials can be through introducing such as one of following technology: the particle codeposition of nanostructured and adhesion promotion material, sequential aggradation, pre-deposition of adhesion promotion material layer or the like.
In one embodiment, in the suspension of adhesive to the nanostructure-containing material of interpolation such as polymer adhesive, it is stirred perhaps carry out sonicated then to obtain unit for uniform suspension.The suitable polymers adhesive comprises and gathers (vinyl butyral-vinyl alcohol-vinyl acetate) and gather (vinylidene fluoride).Select suitable charger with under DC that applies or AC electric field, adhesive and nanostructured will be moved to identical electrodes, to form the intimate admixture coating of nanostructured and adhesive.
In another embodiment, such as titanium, iron, lead, tin, the little metal particle of cobalt is sneaked into the suspension of nanostructure-containing material.Select suitable charger with under the electric field that applies, metal particle and nanostructured will be to the electrode migrations of needs, to form the uniform coating of metal particle and nanostructured intimate admixture.After the deposition, 10
-3In the vacuum of torr or higher basic vacuum pressure with coating annealing in process 0.1-10 hour.Preferably, particle diameter is less than 1 micron.
Adhesive or adhesion promotion material can add with any suitable amount.The amount that can contain with respect to nanostructure-containing material is the amount of 0.1-20 weight %.
In another embodiment, need the object of coated with nano structure at first to apply at least one deck such as titanium, iron, lead, tin, cobalt, nickel, tantalum, tungsten, niobium, zirconium, vanadium, the layer of the adhesion promotion metal of chromium or hafnium.Layer like this can pass through such as electrochemical plating, thermal evaporation, and the technology of sputter or pulse laser deposition applies.After the electrophoretic deposition of nanostructured, 10
- 3In the vacuum of torr or higher basic vacuum pressure with film annealing in process 0.1-10 hour.
Said method advantageously is applicable in high output and the automation application.These methods also are very multiduty.Method of the present invention also is suitable for producing the goods that comprise nanostructure-containing material, and these nanostructure-containing material have makes it be suitable for the performance of multiple different application.The bigger or giant molecule that these methods also can be used for producing the goods of micron order or large-size and comprise DNA.
Generally speaking; Method of the present invention is particularly suitable for being provided at profilograpy and electron microscope probe, such as the nanotube and/or the nano-bar material that use in the electron field emission cathode in the equipment of X-ray generator, gas-discharge tube, lighting device, microwave power amplifier, ion gun, electron-beam lithography device, high energy acclerator, free electron laser and flat-panel monitor.For example, disclosed electrophoresis can be used for single or a branch of CNT or nano wire optionally are deposited on the tip.This tip can be for example to be used for such as comprising AFM (AFM), PSTM (STM), magnetic force microscopy (MFM), and the microscope tip of chemical force microscope (CFM).This method can also be used for the continuous fiber or the long stapled production of the material of CNT and other nanostructured.This method can also be used for being prepared in the electrically connecting of material that circuit uses nanostructured further.
Particular technology and the correlated product consistent with the principle of the invention of above-outlined will be described now for illustrative purposes.
Fig. 4 A and 4B show a kind of technology, wherein at first prepare a kind of diluted suspension of the nanostructure-containing material such as nanotube or nano wire.At first a counterelectrode 410 is immersed in the suspension 420.Metal tip 430 is used as second electrode.Can pass through, for example the standard metal silk of chemical method etching such as tungsten filament forms metal tip.At first with the 420 vertical placements in surface of metal tip 430 and suspension, make the tip of the material that needs deposition of nanostructure-containing be higher than the upper surface of suspension 420 a little.Gradually tip 430 is moved to suspension 420 surfaces then.Power supply 440 is electrically connected to electrode 410 and most advanced and sophisticated 430.Can use one such as the electric current between galvanometric gauge monitoring counterelectrode and the metal tip.In addition, can use the spacing of 420 of an appropriate optical multiplying arrangement monitoring metal tip 430 and suspension surface.When most advanced and sophisticated 430 touch suspension 420 surfaces, can detect the electric current that passes through between two electrodes.Most advanced and sophisticated 430 can keep in touch one period scheduled time, and this time is depended on the concentration and the used electric field of nanostructure-containing material in the suspension.Voltage is put between two electrodes through direct current or alternating current by power supply 440.Close voltage after the scheduled time, tip 430 is raised to the suspension top to stop deposition process.Perhaps, shown in Fig. 4 B, can, tip 430 continue to apply voltage when being removed suspension 420 gradually, on most advanced and sophisticated 430, to form the line or the rope of the nanotube 450 that adheres to.Can introducing device 460, it can be stand or roller, is used to make most advanced and sophisticated 430 rotation and/or linear movements.Most advanced and sophisticated speed is removed in sedimentation rate control according to the material 450 of nanostructured, contacts with suspension 420 with the outermost surface of the material that guarantees only to be attached to most advanced and sophisticated 430 nanostructured.The metal tip 430 that has CNT attached to it in a vacuum 450 or other nanostructured also can be annealed so that increase the combination between tip and the nanostructured.
With reference to figure 5A and 5B another embodiment of the invention is described.Will be such as any formerly disclosed material, the nanostructure-containing material of preferred CNT is dispersed in the appropriate solvent such as water, and concentration is about 0.01g/L.Suspension is carried out sonicated so that material is dispersed in the liquid.The drop of nanotube/water suspension 510 is applied on the metal-O-ring 520.Metal-O-ring 520 is mobilizable, for example is installed in (not shown) on the translation stage.Metal tip 530 is electrically connected to power supply 540, and power supply 540 also is connected in metal-O-ring 520.Metal tip 530 does not contact with drop 510 during beginning.In preferred embodiments, device is placed under the light microscope.Set up the AC signal of 20V and 10MHz through AC power supplies 540.At microscopically, tip 530 is moved to drop 510 gradually.After their physics contact, under electric field, make their keep static about 1-60 second.Gradually liquid is removed at tip 530 then.When metal tip 530 contacts with drop 510 physics, formed with metal tip 530 and the circuit of metal-O-ring as two electrodes.Shown in Fig. 5 B, at AC after the match, nanostructured 550 has been polarized.Because electrode is asymmetric, thus field and non-uniform Distribution, but mainly concentrate on around the tip.Shown in Fig. 5 B, thereby furthered most advanced and sophisticated 530 such as the nanostructured 550 of nanotube.Through regulating nanostructure concentration and sedimentation time, can single nanostructured or groups of nanostructures be attached on the metal tip such as single CNT or carbon nano-tube bundle.
As a possibility modification of above-mentioned operation, can between tip 530 and counterelectrode or O shape ring 520, set up a direct current electric field, but not AC field.Can add such as MgCl to suspension
2Suitable " charger ".Under electric field, nanostructured 550 or nanotube are to most advanced and sophisticated 530 migrations and be attached to tip end surface.
In another embodiment of the invention, through with according to Fig. 4 A, 4B, the similar technique manufacturing that 5A and 5B describe comprises the lead of the nanostructured that is preferably CNT.Shown in Fig. 4 B and 5B, when setting up the AC field, be dispersed in nanostructured 450,550 or CNT in the liquid and polarized and be aligned in field direction.Under asymmetric electric field, nanostructured 450,550 is then to stronger sharp electrode tip 430,530 migrations in field.They are attached on most advanced and sophisticated 430,530 then, become the initial outermost surface of electrode.When Donna rice structure 450,550 more is pulled and adheres to, the outermost surface that outermost layer nanostructured 450,550 of being adhered to or CNT become electrode.Can form the long continuous conductors (referring to, Fig. 9 for example) of the material of nanostructured through above method.Through optimizing rotating speed, electric field, electric field frequency, and the concentration of liquid that is dispersed with the material of nanostructured can be made the continuous fiber of the material of a volume nanostructured.Through coming pilot length such as the parameters such as concentration of nanostructured in electric current and the used suspension.After the deposition, lead can increase mechanical strength or improve functionality through further handling such as annealing.
The further processing method to fiber that can be integrated in the aforesaid deposition process is also contained in the present invention.For example, can pass a stove that is placed between device 460 and the liquid, with a step fortifying fibre performance during forming processes from lead or the fiber that liquid is extracted out.The present invention has also been contained and can fiber have been passed a bath that comprises such as the different kind of material of polymer melt or polymer solution.The fiber of material through at first extracting nanostructured out from liquid is then through liquid, and polymer will flood and coated fiber, and so forms a kind of material of nanostructured and the composite of polymer.
The method that Fig. 6 shows as above to be summarized and/or the exemplary of type of device.According to shown in embodiment, electrode 610 is put into container 620.Container 620 has been full of the medium of the material 630 that contains nanostructured.Can use following method from medium 630, to extract the continuous lines or the rope of nanostructure-containing material 640 out.The counterelectrode that at first will be roller 650 forms is placed on the surperficial position contacting with medium 630.When power supply 660 provides the alternating current current potential between electrode 610 and counterelectrode 650 when; Counterelectrode 650 moves to the direction away from medium 630 upper surfaces; As detail here; The nanostructure-containing material that contains in the medium 630 is attached on the counterelectrode 650, is attached to each other then, and can forms continuous line or restrict 640.The line of nanostructure-containing material or restrict 640 can be randomly through being used for removing the firing equipment or the stove 670 of liquid of being included in the medium 630 etc.According to another alternative, can use a series of rollers 680 to come pipeline or restrict 640 through various additional treatment step.For example, as shown in Figure 6, line or restrict 640 can through contain need with second medium 690 of this nanostructure-containing line or 640 second materials that mix of restricting.For example, medium 690 can contain polymer melt, and this polymer melt can flood the nanostructure-containing material line or restrict 640, therefore forms a kind of composite fiber.Medium 690 is arranged in container 695.To restrict then and 690 pull out and be delivered to additional treatment step, perhaps be deposited on the last roller 680 from container 695.Nanostructure-containing material line or restrict 640 can comprise or be made up of SWCN basically.Replacedly, nanostructure-containing material can comprise or be made up of the above-mentioned any nanostructure-containing material of the present invention basically.
In yet another embodiment of the invention, contained the batch-type method of handling a plurality of tips simultaneously.As shown in Figure 7, can directly form one group most advanced and sophisticated 710 through etching and perhaps tip 710 is installed on the support 720 from raw material.To be placed in the container 740 such as the suspension of the nanostructured 730 of CNT.Flat metal electrode 750 is put into same container.Alternating-current power supply 760 is connected on support 720 and the flat electrode 750.Between tip 710 and flat electrode 750, set up the AC field.An example of frequency is 1KHz-10GHz.Rising container 740 (perhaps reducing most advanced and sophisticated 710) contacts with suspension 730 surfaces up to most advanced and sophisticated 710.One period fixing time of staying (such as 1 second-10 seconds) afterwards, tip 710 and suspension were opened in 730 minutes.Through the control electric current, the concentration of nanostructure-containing material in the suspension, and the time of staying might make a nanostructured or CNT or one group of nanostructured or carbon nano-tube bundle be attached on each tip.After the deposition, can further handle most advanced and sophisticated 710 to improve bond strength.The most advanced and sophisticated probe that can be used as AFM, STM or other scanning probe microscopy of band coating, the microelectrode of sensor or electrochemical cell.
In another embodiment, the lead that comprises nano object forms predetermined pattern according to assembling mode so that make the electrical connection between the different elements in the circuit.Fig. 8 A and 8B show a specific embodiment.To contain such as the liquid drop 850 of the nano object of CNT and put in the zone that is limited by four assemblies 810,820,830 and 840, these four assemblies can be the assemblies in the circuit board.At first set up electric field, form and be communicated with 810 and 830 up to the lead that contains nano object or nanotube such as the AC fields at two inter-modules such as 810 and 830.Between 820 and 840, set up then up to the lead that contains said nano object and form and be communicated with 820 and 840.As a result, between four assembly 810-840, having set up a kind of intersection is electrically connected.
Fig. 9 A to 9E is the SEM image that is attached with the sharp metal end 910 of CNT formed according to the present invention or nano wire 920.Fig. 9 C contains SEM (SEM) image that with good grounds the inventive method is attached to the lead of most advanced and sophisticated SWCN (SWNT) bundle of tungsten.According to exemplary, fibriilar diameter can be less than 1.0 microns, and preferred 0.5nm-10 micron is preferably less than 1 micron.Fibriilar length can be the 50nm-50 micron, preferably less than 30 microns.Tip constructed according to the invention can provide the stable electron emission current of 1-10 microampere magnitude.
Figure 10 is for having roughly axis A longitudinally
FThe sketch map of fibrillation F, it is attached on the tip T that is essentially taper with cone axis Ac, so that make fibrillation F align along cone axis Ac basically.That is to say axle A
FWith axle A
cRelative to each other define an angle [alpha], less than about 15 degree, preferably less than about 10 degree.
The tip that is attached with CNT constructed in accordance can be used for comprising AFM, PSTM, the microscopical scanning probe microscopy of magnetic force microscopy and chemical force.Because the material such as the nanostructured of CNT has big draw ratio and little diameter, thereby can obtain better image quality.For example, Figure 11 shows a kind of typical atomic force microscope probe 1110 with the nanostructured 1120 that is assembled on its tip.Figure 12 shows a kind of SEM most advanced and sophisticated 1210 that is furnished with nanostructured 1220 on it.Figure 13 is the Spindt type electronic field emission body 1310 that a kind of tip is assembled with nanostructured 1320.
According to another aspect of the present invention, providing with its performance difference is technology and the device that the material of nanostructured is separated on the basis.The material that can separate the mixture that contains one or more nanostructure-containing material.For example, can be with being divided into two sub-group with semi-conductive nanostructured such as the metal of CNT.For example, one is the subgroup of only containing metal carbon nanotube, and another is the subgroup of only containing semiconductor carbon nanometer tube.In a particular embodiment, prefabricated SWCN is dispersed in the water.More preferably at first SWCN is purified to remove the impurity phase with proper technique.In liquid, set up an asymmetric AC field through between two electrodes, applying alternating voltage.A kind of method of setting up asymmetric electric field is to use two electrodes with different geometries.For example, an electrode has plane geometric shape, and another has sharp-pointed ledge.Regulate the frequency of AC field.Because electrical property is different, metal will have different frequency dependences with polarization semi-conductive CNT.Under optimal frequency, metal carbon nanotube will move to the electrode with ledge than semiconductor carbon nanometer tube quickly.Under another kind of situation, might pass through regulating frequency and used liquid, metal carbon nanotube is moved and semiconductor carbon nanometer tube moves to opposite electrode to an electrode.After applying the electric field certain hour, can on the opposite electrode surface, from liquid, collect every group of material.Method described herein can also be used for CNT is separated with the magnetic-particle that is present in raw material.The method is not limited to CNT.It also can be used to separate other nano object according to electrical property and/or geometry.
Figure 14 shows the exemplary according to another separation technique/arrangement of the present invention.
Device 1400 comprises a plurality of electrodes of arranging according to a kind of specific pattern 1402,1404.According to exemplary, electrode 1402,1404 is relative to each other to be the angle of 90 degree.But, be to be appreciated that the present invention also contains a lot of other electrode patterns.Power supply 1406 is supplied with alternating current to electrode 1402,1404.Non-uniform electric field has appearred because alternating current flows through the edge effect that electrode 1402,1404 causes.In exemplary, produced electric field region 1408 with high relatively intensity.In addition, also produced zone 1410 with low relatively electric-field intensity.
Device 1400 can be placed in passage or the chamber, schematically is shown in 1412 places.Can in chamber or passage 1412, introduce the mixture that contains the first kind particle 1416 and second type of particle 1418.The mixture that contains at least two kinds of dissimilar particles can have various ways.For example, at least a in the particle 1416 and 1418 can comprise nanostructure-containing material.According to an embodiment, particle 1416 and 1418 is positioned over a kind of liquid medium inside.According to another embodiment, will comprise that the mixture of the first kind nanostructure-containing material-particle 1416 and the different second type nanostructure-containing material particle 1418 is positioned in the liquid medium.Can introduce liquid medium at an end of chamber or passage 1412, and liquid medium is for example flowed along the direction shown in the arrow F basically.Because the difference of performance, the electric field that particle 1416 and 1418 is applied in polarizes in a different manner or influences.For example, the electric field negative polarization that first kind particle 1416 possibly be applied in, and the electric field positive polarization that second type of particle 1418 possibly be applied in.Therefore, because polarity is different, second type of particle 1418 is held and is trapped in the electric field region 1408 with high relatively intensity, and maybe be attached on the electrode 1402,1404.On the contrary, first kind particle 1416 is because its polarity and do not attracted to the electric field 1408 with high relatively intensity, but can be in having low relatively strength electric field zone 1410 in Figure 14 the direction shown in the arrow F flow.Like this, first particle 1416 can be in chamber or passage 1412 flow further downstream, and can be collected in position away from electrode.Second type of particle 1418 is contained in the electric field 1408, and/or attached on the electrode 1402,1404, and therefore can reclaim from electrode.
Figure 15 comprises the exemplary according to another separation technique/arrangement of the present invention.Device 1500 comprises a plurality of patterned electrodes 1502,1504,1506 and 1508.Apply alternating current to these electrodes, the amount of the alternating current that applies to all these electrodes according to an embodiment equates.Yet the mode that applies of electric current can be so that its phase difference with respect to other electrode be 90 °.Can device 1500 be placed in the mixture that comprises the first and second type of particle 1510,1512 at least then.This mixture can comprise the mixture of any above-described those types.Owing to apply difference and the effect that electric field causes to 1510,1512 of first and second particles, between these particles and electrode 1502,1504,1506 and 1508, have such interaction, to such an extent as to all there is relative motion in every kind of particle.The special exercise direction depends in two kinds of dissimilar particles 1510,1512 polarizability of each.Like this, just cause a kind of particle, for example 1510 to device 1500 central motions, shown in figure 15, and cause that another kind of particle 1512 is to the direction motion away from device 1500 centers.Like this, in such a way that two groups of particles are separated from one another.First group of particle 1510 can be collected from installing 1500 centers, and in fact possibly be attached to electrode 1502,1504, on 1506 and 1508.Second group of particle 1512 moves to the direction away from device 1500, thereby can reclaim from position far away.
With reference now to following exemplary, non-limiting example, principle of the present invention is described further.
Embodiment
Will be most advanced and sophisticated as working electrode through the tungsten of chemical etching method preparation, little metallic plate is perhaps encircled as counterelectrode.They are installed on the translation stage separately and are placed under the light microscope.At first SWCN is purified, it is long to be etched to about 2 microns bundle, and carries out hydrophilicity-imparting treatment through the chemical oxidation effect.Then they are dispersed in the deionized water.The drop of nanotube suspension is placed in the becket.In order to begin deposition, at first between two electrodes, apply AC field (10V, 2MHz).Under electric field,, it is contacted with nanotube/water suspension, and little by little pull out, have the fibrillation that needs length up to formation point electrode translation flatly.
After the deposition, 10
-6Torr vacuum will be attached with the fibriilar metal tip annealing in process of nanotube 1 hour under 800 ℃ removing residual solvent, and improve combining between cohesive and the nanotube between nanotube and the metal tip.
Use has the tip that is installed on the micrometer head as negative electrode, and opposite metal plates is measured these most advanced and sophisticated electronic field emission characteristics as the point-face geometrical construction of anode.Regulate distance between the two and be fixed as about 200mm through the translation micrometer head.Device is placed on 5 * 10
-7The vacuum chamber the inside of Torr pressure of foundation.To be collected as the function of the voltage that applies from total emission current at tip.Figure 16 and illustration show the data of collecting for the tip of about 50nm from a tip diameter.Emission current-voltage characteristic presents classical Fowler-Nordheim type characteristic, at ln (I/V
2) and 1/V between have linear relationship.When applying voltage was lower than 1000V, emission current reached 5mA, and the current density of its generation is estimated as 2.5 * 10
5A/cm
2
Through the monitoring under fixed voltage, DC pattern in continuous 10 hours emission current measure launch stability over time.Figure 17 has shown continuously and has depressed the data at the tip (diameter is about 50nm) of mensuration three different electric.When applied voltage was fixed as 800V and 1000V respectively, emission current was stabilized in 1mA and 2.8mA, and overall decay does not appear in emission current.Use the steady resistance of connecting with negative electrode, then the local current fluctuation is calculated as 5% when 1mA, and is 2.5% when 2.8mA.When voltage further increased to 1200V, the emission current of same sample reached 5.5mA, but was reduced to zero after one hour suddenly.Even more also detecting under the high voltage less than electric current.Shown in figure 17, the SEM test demonstrates W thread breakage and whole most advanced and sophisticated disappear badly damaged.This ascribes in W and fibrillation resistance heated effect at the interface.In the tip of another preparation, obtained the electric current of stable 6.5mA.This is not about 12% with the current fluctuation of the sample of steady resistance, compares favourably with the value that single SWCN write down from no ballast.
Shown in figure 18, in order to write down the emission pattern at tip 1800, the metal anode that uses in the last planar survey is replaced with ITO (indium-Xi-oxide) glass 1810 that fluorescer applies.Launch the image 1820 that electronics forms with a ccd video camera record that is placed on the vacuum chamber outside on fluorescent screen.Emission image 1820 obtains from multiple wall nanotube/tip.All can both observe single launch point under the operating voltage, this is consistent with SEM result, is illustrated in closs packing CNT of each tungsten tip on grappling.The diameter of bright spot is approximately 200mm on the fluorescent screen under 1400V, and beam-divergence angle is 50 °.Big extended corner is a little-the face geometry because of Electric Field Distribution, but not from the intrinsic angle of divergence of the field emission electron of nanotube.
Although described the present invention with reference to above-mentioned embodiment, certain modifications and variations are conspicuous to those skilled in the art.Therefore, the present invention is only limited with spirit by the scope of appended claims.
Claims (21)
1. one kind is attached to the method on the tip of anything with nanostructure-containing material, and this method comprises:
(i) the nanostructure-containing raw material is provided;
(ii) adopt this nanostructure-containing raw material of shortening PROCESS FOR TREATMENT that is selected from chemical etching or mills;
(iii) in liquid medium, form the suspension that this handles the back nanostructure-containing material;
(iv) at least one electrode is immersed in this suspension;
(v) this suspension is put at the tip; And
(vi) on the electrode of submergence and tip, apply direct current or alternating current, the nanostructure-containing material after at least a portion in the suspension is handled is attached to object and approaches most advanced and sophisticated place, summit most.
2. method according to claim 1, object wherein comprises the point-like electron field emission source, the probe of AFM; The probe of PSTM, the electron source of transmission electron microscope, the electron source of SEM; The probe of magnetic force microscopy, perhaps profilograpy.
3. method according to claim 1 further is included in the functionalized step of material that step will contain the nanostructured after the processing before (iii).
4. method according to claim 1, wherein step (v) with (vi) comprise further the tip moved up to being electrically connected setting up between tip and the suspension to suspension surface, keep being electrically connected one period scheduled time, and the tip is taken out from suspension.
5. method according to claim 4; Wherein the raw material of nanostructure-containing comprises CNT; And wherein step (vi) comprises further and on the tip, adheres to single CNT, nanotube bundle, or nano wire; Perhaps adhere to and comprise many CNTs, the fibrillation of nanotube bundle or nano wire.
6. method according to claim 5, wherein single CNT, nanotube bundle, or the longitudinal axis of nano wire aligns with most advanced and sophisticated cone axis.
7. method according to claim 5, comprising nanotube, nanotube bundle, or the fibriilar longitudinal axis of nano wire aligns with most advanced and sophisticated cone axis.
8. method according to claim 5, the nanotube in fibrillation wherein, the longitudinal axis of nanotube bundle or nano wire aligns with the fibriilar longitudinal axis.
9. method according to claim 5; Wherein fibrillation has cylindrical body and two ends; Wherein fibriilar first end is attached to tip, and fibriilar second end has the convergent geometry, and wherein the terminal tip diameter of convergent is 0.5nm-100nm.
10. method according to claim 5 is included in further and adheres to nanotube, behind nanotube bundle or the nano wire with spike anneal.
11. method according to claim 1, wherein step (v) is included in and places a plurality of tips in the suspension.
12. method according to claim 1, wherein step (vi) comprises and applies the alternating current that frequency is 10Hz-10GHz.
13. method according to claim 1, wherein step (vi) comprises and applies direct current.
14. method according to claim 13, wherein step comprises further that (iii) at least a compound of interpolation is to give nanostructure-containing material a kind of charge characteristic in suspension.
15. method according to claim 5, the nanostructure-containing material after wherein handling comprises SWCN; Multiple wall carbon nano tube; Silicon; Silica; Germanium; Germanium oxide; Carbonitride; Boron; Boron nitride; Two chalcogenides; Silver; Gold; Iron; Titanium dioxide; Gallium oxide; Indium phosphide; Perhaps be packaged in the inner magnetic-particle of nanotube; Consist of MS
2, M=tungsten wherein, molybdenum, the perhaps oxide of vanadium, nanotube or at least a in the fullerene with one heart.
16. method according to claim 4; Wherein gradually the tip is pulled out from suspension surface while applying electric current; Nanostructure-containing material with after at first will handling is assembled near the tip part; And then be assembled on the nanostructure-containing material of having adhered to, thereby the lead of formation nanostructure-containing material.
17. method according to claim 16, the diameter of wire that wherein forms is 0.5nm-100 μ m.
18. method according to claim 1 is included in step further and (is vi) annealed in tip and nanostructure-containing material.
19. method according to claim 1, wherein step (comprises vi) a CNT is attached on the tip that wherein the CNT longitudinal axis aligns with most advanced and sophisticated cone axis, and wherein contains magnetic-particle away from the CNT end on summit.
20. method according to claim 19, wherein the tip is the probe of AFM.
21. method according to claim 19, wherein magnetic-particle is encapsulated by CNT.
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| US60/461401 | 2003-04-10 |
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| US8308930B2 (en) | 2008-03-04 | 2012-11-13 | Snu R&Db Foundation | Manufacturing carbon nanotube ropes |
| JP5559158B2 (en) | 2008-06-06 | 2014-07-23 | ユニバーシティー・オブ・ワシントン | Method and system for concentrating particles from solution |
| US8673258B2 (en) | 2008-08-14 | 2014-03-18 | Snu R&Db Foundation | Enhanced carbon nanotube |
| US8357346B2 (en) | 2008-08-20 | 2013-01-22 | Snu R&Db Foundation | Enhanced carbon nanotube wire |
| US7917966B2 (en) * | 2008-08-21 | 2011-03-29 | Snu R&Db Foundation | Aligned nanostructures on a tip |
| US8021640B2 (en) | 2008-08-26 | 2011-09-20 | Snu R&Db Foundation | Manufacturing carbon nanotube paper |
| CN102030308B (en) * | 2010-10-27 | 2012-08-01 | 复旦大学 | Method for assembling particle ordered array in polarized way based on ferroelectric film electric domain |
| CN102205944B (en) * | 2011-04-19 | 2013-01-23 | 北京化工大学 | Device and method for manufacturing micro-nano structure |
| AU2014307715B2 (en) * | 2013-08-13 | 2019-02-14 | United Kingdom Research And Innovation | Electron microscopy sample support comprising porous metal foil |
| CN103757675B (en) * | 2014-01-20 | 2016-05-11 | 厦门大学 | A kind of fine and close gold thin film method of AFM silicon needle point pulse plating nano thickness |
| CN107551804A (en) * | 2017-09-13 | 2018-01-09 | 李庆 | Resolution element with filtering, catalysis |
| CN110514877A (en) * | 2019-08-30 | 2019-11-29 | 西安交通大学 | A kind of assemble method of big L/D ratio probe |
| CN112974796B (en) * | 2021-02-07 | 2022-06-21 | 南京大学 | Composite structure of single silver nanowire and preparation method and application thereof |
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