CN101612612A - Be used to assemble method and correlated product with the material of sorting of nanostructure-containing - Google Patents
Be used to assemble method and correlated product with the material of sorting of nanostructure-containing Download PDFInfo
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- CN101612612A CN101612612A CN200910164632A CN200910164632A CN101612612A CN 101612612 A CN101612612 A CN 101612612A CN 200910164632 A CN200910164632 A CN 200910164632A CN 200910164632 A CN200910164632 A CN 200910164632A CN 101612612 A CN101612612 A CN 101612612A
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Abstract
A kind of nanostructure-containing material is deposited into object or on-chip method, comprise one or more the following steps: (1) forms the solution or the suspension of nanostructure-containing material, (2) optionally in solution, add " charger ", (3) electrode is immersed in the solution, to need the substrate of material of depositing nano structure or object as one of them electrode, (4) between two electrodes, apply direct current and/or alternating current electric field and certain time, thereby make the material of the nanostructured in the solution move and be attached on the substrate electrod, and (5) randomly carry out subsequent treatment to the substrate that applies to substrate electrod.The present invention also provides object correlation and equipment.The present invention has also described based on the performance of nanostructured and/or the geometry method with its separation.
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 in full at this.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 in full at this.
About the research of federal government's subsidy or the statement of exploration project
At least some aspect of the present invention is to carry out under contract number is the government-funded of N00014-98-1-0597 and NAG-1-01061.Government can have some right to the present invention.
Technical field
The present invention relates to material with nanostructure-containing or nanotube and be deposited into 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.
Use term " nanostructured " material to represent to comprise to personnel well known in the art 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 class 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 in full at this, discloses the manufacture method 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 in full at this, 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 in full at this, 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 " manufacture method of patterning (patterned) carbon nano-tube film "),, its content is incorporated herein by reference in full at this, discloses a kind of method of making adhesive patterned carbon nano-tube film on substrate.
United States Patent (USP) 6,334,939 (name is called " nanostructure-based high energy material and method "),, its content is incorporated herein by reference in full at this, and disclosing a kind of is the nano structured alloy of one of component with alkali metal.This material it is said and can use in some cell apparatus.
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 in full at this, 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 in full at this, a kind of electrode is disclosed, this electrode comprises first electrode material, adhesion promotor, and be distributed in carbon nanotube-containing material at least a portion adhesion-promoting layer and the relevant apparatus that has adopted kind electrode.
U.S. Patent Publication US 2002/0193040 (name is called " adopting the enhanced field emission to make the method for nano tube based material "), its content is incorporated herein by reference in full at this, discloses a kind of foreign substance of introducing and has entered nanotube type material to improve the technology of its performance.
U.S. Patent Publication US2002/0094064 (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 in full at this, 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.
U.S. Patent Publication US 2003/0180472 (name is called " method of assemble nanometer level object "), its content is incorporated herein by reference in full at this, disclose and a kind ofly be self-assembled into the technology of macrostructure, it can have been handled the draw ratio (aspect ratio) and/or the chemical functionality that need to obtain with preform nanoscale object.
As can be seen; 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; light-emitting component for example; field emission apparatus such as flat-panel monitor; the gas-discharge tube that is used for 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 meets with in the process of these materials 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 form.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 to form the nanostructured of random distribution on substrate.
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 material manufacturing 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 for 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 by 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 combines often very weak with interface between the CNT.Be difficult to once make a plurality of tips.This method is not only complexity but also loaded down with trivial details undesirably, and therefore is impractical in large-scale production.
Another consideration in the art is that when the material that uses nanostructured is made electrical equipment, must adopt the material that has such as the same performance of same Electronic Performance usually.This does not also realize.For example, comprised in essence by 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, for using, a lot of devices are necessary to make being separated of metal 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 method on the tip of anything, the method comprises: the suspension that i) forms a kind of nanostructure-containing material in a kind of liquid medium; (ii) at least one electrode is immersed in this suspension; (iii) the tip is put into this suspension; 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: the 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 method on the tip of anything, the method comprises: the suspension that i) forms a kind of nanostructure-containing material in a kind of liquid medium, (ii) at least one electrode is immersed in this suspension, (iii) the tip is put into this suspension, 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 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 setting up between a plurality of assemblies is provided, this method comprises: the suspension that i) forms nanostructure-containing material in a kind of liquid medium, (ii) suspension is contacted and (iii) applies direct current or alternating current on assembly with assembly, 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, provide a kind of device, 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 provides electrical connection between the two.
According to a further aspect of the invention, provide a kind of component with nanostructure-containing material from method, this method comprises: (i) formation comprises the group of nanostructure-containing material to be separated and the mixture of liquid medium, (ii) introduces a plurality of electrodes in mixture; (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 comprising in the mixture and the method for second group of particle separation, wherein at least first and second the group particle one of them comprise nanostructure-containing material, this method comprises: the device that (i) forms electrode, (ii) apply alternating-current power supply to this device, (iii) that mixture and this device is close, (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 " is represented to comprise following material to small part: 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 schematic diagram 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 schematic diagram of the material that contains nanostructured as depicted in figs. 1 and 2 on the object by disclosed method.
Fig. 4 A and 4B are the schematic diagram of an embodiment of the method implemented according to disclosed method.
Fig. 5 A and 5B are the schematic diagram of another embodiment of the method implemented according to disclosed method.
Fig. 6 is the schematic diagram of an embodiment that is used to implement the equipment of this method.
Fig. 7 is the schematic diagram of another embodiment that is used to implement the equipment of this method.
Fig. 8 A and 8B are the schematic diagram 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 schematic diagram, shows the relation of the various orientations when being attached to most advanced and sophisticated going up.
Figure 11 is the schematic diagram according to the another kind of object of another embodiment of the invention formation.
Figure 12 is the schematic diagram of the another kind of object that forms according to an alternative embodiment of the present invention.
Figure 13 is the schematic diagram according to the another kind of object of another embodiment of the invention formation.
Figure 14 is the schematic diagram of a separation arrangement and.
Figure 15 is the schematic diagram according to another 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 schematic diagram of emission pattern.
Detailed Description Of The Invention
The method and corresponding structure and the equipment that carry out according to the principle of the invention and illustrative embodiment have hereinafter been described.
Generally speaking, the method for carrying out according to the principle of the invention 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) it is functionalized this to be contained the material of nanostructured; (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, will needs the substrate of material of depositing nano structure or object as one of them electrode; (7) continuing the regular period applies direct current and/or alternating current forming electric field between electrode, 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, the front surface of deposition materials and liquid are kept in touch so that the material successive sedimentation of nanostructured to substrate; And (9) randomly carry out subsequent treatment to the substrate that applies.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 described 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 description herein.
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 or at least a such as in the magnetic-particle of the Fe that is packaged in nanostructured inside, Co and Ni.According to preferred embodiment, the material of undressed carbon nanotubes comprises SWCN.CNT can be by 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 by any applicable technology such as above-mentioned arc-discharge technique.
Rough stock can divide described multiple different technologies manufacturing such as above-mentioned background technology department by technology well known to those skilled in the art.
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 several technology that form these magnetic-particles.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 to be shaped to raw material such as the nanotube of single wall or multiple wall carbon nano tube.Raw material are processed to open the end of nanotube then.By 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.U.S. Patent Publication US2003/0180472 has carried out more detailed description to these technology, and its content is incorporated herein by reference in full at this.
Fig. 2 is the schematic diagram of this magnetic-particle mentioned above.For example as shown in Figure 2, provide a kind of multiple wall carbon nano tube 200, 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 explaining and explanation herein,, can also or be attached on the tip such as the probe of AFM these magnetic-particles assemblings according to disclosed more detailed method hereinafter.By measuring as the magnetic tip of above-mentioned method manufacturing and need interaction force between the object of 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 technology of purification rough stock.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 example technique, 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 large power supersonic luffing bar 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 by 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, such as chemical etching or mill to shorten the length of nanotube and nanotube bundle.
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.
Above-mentioned " undressed " or preformed material can be introduced solution now, it is deposited on object or the substrate and/or the goods of formation 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 the material introducing H of the nanostructured that will purify
2SO
4And HNO
3Solution in 10-24 hour, be subjected to the effect of ultrasonic energy simultaneously.Perhaps, can chemical substance be attached on the outer surface of nanostructured by 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 can provide steady suspension.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 can provide steady suspension.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 by 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 ultrasonic processing 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 by select material that the charger material controls nanostructured to the special electrodes (that is to say anode or negative electrode) of migration.For example, by 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 by 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 special electrodes 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.May preferably carry out such annealing operation, because remove electricity between material that impurity such as the residual suspension medium can improve nanostructured and object and thermo-contact and combine situation.For example, the substrate that applies can 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 by 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 by 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, add adhesive such as polymer adhesive to the suspension of nanostructure-containing material, then with its stirring or carry out ultrasonic processing to obtain unit for uniform suspension.The suitable polymers adhesive comprises poly-(vinyl butyral-vinyl alcohol-vinyl acetate) and poly-(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 tight mixed 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 that metal particle and nanostructured are closely mixed.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.These methods also can be used for the bigger or giant molecule 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 preparing the electrically connecting of material of using nanostructured at circuit 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 a suitable optics 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 by 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 when being removed suspension 420 gradually, tip 430 continue to apply voltage, 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 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 ultrasonic processing 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 by 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 is 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.By regulating nanostructure concentration and sedimentation time, single nanostructured or groups of nanostructures can 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, by 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, it is polarized and be aligned in field direction to be dispersed in nanostructured 450,550 in the liquid or CNT.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 more nanometer structures 450,550 are pulled and adhere to the outermost surface that accompanying outermost layer nanostructured 450,550 or CNT become electrode.Can form the long continuous conductors (referring to, Fig. 9 for example) of the material of nanostructured by above method.By 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.By 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 by 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 can pass fiber a bath that comprises such as the different kind of material of polymer melt or polymer solution.The fiber of material by at first extracting nanostructured out from liquid is then by 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 from medium 630, extract the continuous lines or the rope of nanostructure-containing material 640 with the following method 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 describe in detail herein, the nanostructure-containing material that contains in the medium 630 is attached on the counterelectrode 650, be attached to each other then, and can form continuous line or restrict 640.The line of nanostructure-containing material or restrict 640 can be randomly by 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 by various additional treatment step.For example, as shown in Figure 6, line or restrict 640 can by 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 be directly form one group most advanced and sophisticated 710 by etching or 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.Afterwards, tip 710 and suspension 730 are separated in one period fixing time of staying (such as 1 second-10 seconds).By 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 into by in four assemblies 810,820,830 and 840 zones that limit, these four assemblies can be the assemblies in the circuit board.At first at the electric field of setting up such as two inter-modules of 810 and 830 such as the AC fields, form and be communicated with 810 and 830 up to the lead that contains nano object or nanotube.Between 820 and 840, set up then up to the lead that contains described nano object and form and be communicated with 820 and 840.As a result, having set up a kind of intersection between four assembly 810-840 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 is SEM (SEM) image that contains the lead of SWCN (SWNT) bundle that with good grounds the inventive method is attached to the tungsten tip.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 schematic diagram 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 tip 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 will be divided into two subgroups 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 suitable technology.In liquid, set up an asymmetric AC field by 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 the electrical property difference, metal will have different frequency dependences with polarization semi-conductive CNT.Under optimal frequency, metal carbon nanotube will move to the electrode with ledge quickly than semiconductor carbon nanometer tube.In another case, 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 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 may be applied in, and the electric field positive polarization that second type of particle 1418 may be applied in.Therefore, because the polarity difference, second type of particle 1418 is held and is trapped in the electric field region 1408 with high relatively intensity, and may 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 °.Device 1500 can 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, as 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 may 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 by the tungsten of chemical etching method preparation, little metallic plate or ring are used as counterelectrode.Be installed in them on separately the translation stage and be 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 by 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 between nanotube and the metal tip and the nanotube.
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 by 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
By the monitoring under fixed voltage, DC pattern in continuous 10 hours emission current measure launch stability over time.Figure 17 has shown the data at the tip of measuring continuously (diameter is about 50nm) under three different voltages.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.As 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, is comparable to the value that single SWCN write down from no ballast.
As 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, shows at 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 by the scope and spirit of appended claims.
Claims (49)
1. one kind is attached to method on the tip of anything with nanostructure-containing material, and this method comprises:
(i) suspension of formation nanostructure-containing material in liquid medium;
(ii) at least one electrode is immersed in this suspension;
(iii) the tip is put into this suspension; 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 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 before that nanostructure-containing material is the functionalized step of step (i).
4. method according to claim 1, wherein step (iii) moves the tip up to being electrically connected setting up between tip and the suspension to suspension surface with (iv) comprising further, keep being electrically connected one period scheduled time, and the tip is taken out from suspension.
5. method according to claim 4, wherein nanostructure-containing material comprises CNT, and wherein step (iv) comprises further adhere to single CNT on the tip, 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 tip diameter of convergent end 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 (iii) is included in and places a plurality of tips in the suspension.
12. method according to claim 1, wherein step (iv) comprises and applies the alternating current that frequency is 10Hz-10GHz.
13. method according to claim 1, wherein step (iv) comprises and applies direct current.
14. method according to claim 13, wherein step (i) comprises that further 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, wherein nanostructure-containing material 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 magnetic-particle of nanotube inside; Consist of B
xC
yN
zNanotube; Consist of MS
2The nanotube of (M=tungsten, molybdenum, the perhaps oxide of vanadium) or concentric at least a in the fullerene.
16. method according to claim 4, wherein gradually the tip is pulled out from suspension surface while applying electric current, at first nanostructure-containing material 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, wherein the diameter of wire of Xing Chenging is 0.5nm-100 μ m.
18. method according to claim 1 is included in step further (iv) afterwards with tip and nanostructure-containing material annealing.
19. a lead, its diameter are 0.5nm-100 μ m, comprise nanostructure-containing material.
20. lead according to claim 19, wherein nanostructure-containing material comprises CNT.
21. lead according to claim 19, it is formed by the described method of claim 16.
22. method according to claim 1, wherein step (iv) comprises a CNT is attached on the tip, and 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.
23. method according to claim 22, wherein the tip is the probe of AFM.
24. method according to claim 22, wherein magnetic-particle is encapsulated by CNT.
25. an equipment comprises:
Have the conical tip of being essentially of a cone axis, and
Comprise the fibrillation that is attached to the most advanced and sophisticated material that contains nanostructured of going up and aliging with the cone axis at tip basically, fibriilar diameter is 0.5nm-1.0 μ m.
26. equipment according to claim 25, wherein this equipment comprises the point-like electron field emission source.
27. equipment according to claim 25, wherein this equipment comprises AFM, scanning probe microscopy, transmission electron microscope, SEM, magnetic force microscopy, or the probe of profilograpy.
28. equipment according to claim 25, wherein nanostructure-containing material 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 magnetic-particle of nanotube inside; Consist of B
xC
yN
zNanotube; Consist of MS
2The nanotube of (M=tungsten, molybdenum, the perhaps oxide of vanadium) or concentric at least a in the fullerene.
29. equipment according to claim 25, wherein fibrillation comprises: single CNT, a plurality of CNTs, single carbon nano-tube bundle, or a plurality of carbon nano-tube bundle.
30. set up the method that is electrically connected for one kind between a plurality of assemblies, this method comprises:
(i) suspension of formation nanostructure-containing material in liquid medium,
(ii) suspension is contacted with assembly; And
(iii) on assembly, apply direct current or alternating current, thereby form an electric field, thereby make the nanostructure-containing material by coupling assembling form lead between the two.
31. method according to claim 30, wherein a plurality of assemblies comprise two assemblies.
32. method according to claim 30, wherein a plurality of assemblies comprise four assemblies, step (ii) comprises suspension is contacted with whole four assemblies, and step comprises that (iii) applying direct current or alternating current to first pair of assembly connects to form first between the two, applies direct current or alternating current connects to form second between the two to second pair of assembly then.
33. method according to claim 30, wherein assembly comprises the assembly that is arranged on the circuit board.
34. method according to claim 30 is included in further and adheres to nanotube, behind nanotube bundle or the nano wire with spike anneal.
35. method according to claim 30, wherein step (iii) comprises and applies direct current.
36. method according to claim 35, wherein step (i) comprises that further at least a compound of interpolation is to give nanostructure-containing material a kind of charge characteristic in suspension.
37. method according to claim 30, wherein nanostructure-containing material 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 magnetic-particle Fe of nanotube inside, Co or Ni; Consist of B
xC
yN
zNanotube; Consist of MS
2The nanotube of (M=tungsten, molybdenum, the perhaps oxide of vanadium) or concentric at least a in the fullerene.
38. a device comprises:
First assembly;
Second assembly; And
First lead that comprises nanostructure-containing material, this lead are attached to first and second assembly, and provide electrical connection between the two.
39. according to the described device of claim 38, wherein lead is formed by method according to claim 30.
40., comprise further according to the described device of claim 38:
The 3rd assembly;
The 4th assembly; And
Second lead that comprises nanostructure-containing material, this lead are attached to first and second assembly and electrical connection are provided between the two.
41. according to the described method of claim 40, wherein second lead is formed by method according to claim 30.
42. according to the described device of claim 38, wherein arrangement of components is on circuit board.
43. one kind with first group of contained in the mixture particle 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) device of formation electrode;
(ii) apply alternating-current power supply to this device;
(iii) that mixture and this device is close;
(iv) first group of particle carried out different polarization with second group of particle;
(difference that v) relies on polarity is with first group of particle and second group of particle separation; And
(vi) reclaim at least a in first or second group of particle.
44. according to the described method of claim 43, wherein nanostructure-containing material comprises CNT.
45. according to the described method of claim 43, wherein mixture comprises liquid medium.
46. according to the described method of claim 43, wherein step (i) comprises that forming a plurality of relative to each other is the electrode of 90 ° of intersections.
47. according to the described method of claim 43, wherein step (i) comprises a plurality of coaxal electrodes of formation.
48. according to the described method of claim 47, wherein step (ii) comprises to each coaxal electrode and applies the alternating current that has 90 ° of phase differences with another coaxal electrode at least.
49. according to the described method of claim 43, wherein step (v) comprises and adhere at least one group of particle on electrode.
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| CN102030308A (en) * | 2010-10-27 | 2011-04-27 | 复旦大学 | Method for assembling particle ordered array in polarized way based on ferroelectric film electric domain |
| CN107551804A (en) * | 2017-09-13 | 2018-01-09 | 李庆 | Resolution element with filtering, catalysis |
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| US8308930B2 (en) | 2008-03-04 | 2012-11-13 | Snu R&Db Foundation | Manufacturing carbon nanotube ropes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3536288B2 (en) * | 2001-04-05 | 2004-06-07 | 関西ティー・エル・オー株式会社 | Method of manufacturing nanotube probe |
-
2003
- 2003-12-08 CN CNB200380109509XA patent/CN100537052C/en not_active Expired - Fee Related
- 2003-12-08 CN CN2009101646320A patent/CN101612612B/en not_active Expired - Fee Related
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| CN102030308A (en) * | 2010-10-27 | 2011-04-27 | 复旦大学 | Method for assembling particle ordered array in polarized way based on ferroelectric film electric domain |
| 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 |
| CN107551804A (en) * | 2017-09-13 | 2018-01-09 | 李庆 | Resolution element with filtering, catalysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1849181A (en) | 2006-10-18 |
| CN101612612B (en) | 2012-05-16 |
| CN100537052C (en) | 2009-09-09 |
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