CN1802727A - Methods and apparatus for patterned deposition of nanostructure-containing materials by self-assembly and related articles - Google Patents
Methods and apparatus for patterned deposition of nanostructure-containing materials by self-assembly and related articles Download PDFInfo
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Abstract
Methods and apparatus are described for patterned deposition of nanostructure-containing materials by self-assembly and related articles. According to an exemplary embodiment self-assembly method for depositing nanostructure-containing materials includes forming a nanostructure-containing material. The nanostructure-containing material is chemically functionalized and dispersed in a liquid medium to form a suspension. At least a portion of a substrate having a surface that can attract the functionalized nanostructure-containing material is brought into contact with the suspension. The substrate is separated from the suspension. The nanostructure-containing material adheres to the portion of the substrate when separated from the suspension. According to another exemplary embodiment, hydrophilic and hydrophobic regions are formed on the surface of the substrate before bringing the substrate into contact with the suspension. The functionalized nanostructure-containing material is hydrophilic and adheres to the hydrophilic region of the substrate when separated from the suspension.
Description
Of the present invention is that according to the contract number N00014-98-1-05907 and NAG-1-01061 are supported to produce by government to the small part aspect.Government has certain right in the present invention.
Background
During background was below described, with reference to some structure and method, still, this class was with reference to not being considered to admit that these structures and method have the prior art qualification under suitable statutory provision.The applicant keeps any right that is not constituted prior art of the present invention by referenced subject matter of explanation.
Term " nanostructure " material is used to refer to the material that comprises nano particle, nano wire/nanometer rods or single wall or many walls nanotube, wherein nano particle such as C by those people that are familiar with this area
60Fullerene, the concentric graphite granule of fullerene type, metal, compound semiconductor such as CdSe, InP, nano wire/nanometer rods such as Si, Ge, SiO
x, GeO
x, single wall or many walls nanotube are by single or multiple element such as carbon, B
xN
y, C
xB
yN
z, MoS
2And WS
2Form.A common trait of nano structural material is their basic structural unit.Single nano particle or carbon nano-tube have at least one direction the size less than 500nm.The material that has shown these types can show the special properties that promotes interest in various application and technology.
People's such as Zhou United States Patent (USP) 6280697 and 6422450 (exercise question all is " Nanotube-Based High Energy Material and Method ") discloses the manufacturing and they application as battery electrode material of carbon-based nano tube material, and this paper introduces its full text content as a reference.
U.S. Patent No. _ _ _ _ (sequence number 09/296572, exercise question is " DeviceComprising Carbon Nanotube Field Emitter Structure andProcess for Forming Device ") carbon nanotube-based electron emitter structure is disclosed, this paper introduces its full text content as a reference.
U.S. Patent No. _ _ _ _ (sequence number 09/351537, exercise question is " DeviceComprising Thin Film Carbon Nanotube Electron Field EmitterStructure ") the field emission body of Nano carbon tube structure with high emission current density is disclosed, this paper introduces its full text content as a reference.
People's such as Bower United States Patent (USP) 6277318 (exercise question is " Method for Fabricationof Patterned Carbon Nanotube Films ") discloses the method for making the patterned carbon nano-tube film of adhesion on substrate, and this paper introduces its full text content as a reference.
United States Patent (USP) 6334939 (exercise question is " Nanostructure-Based High EnergyMaterial and Method ") discloses the nano structured alloy of alkali metal as a kind of component, and this paper introduces its full text content as a reference.This material is described to can be used for some battery applications.
U.S. Patent No. _ _ _ _ _ (sequence number 09/679303, exercise question is " X-RayGenerating Mechanism Using Electron Field Emission Cathode ") the X-ray generation device in conjunction with nanostructure-containing materials is disclosed, this paper introduces its full text content as a reference.
U.S. published patent application No.US2002/0140336 (exercise question is " CoatedElectrode With Enhanced Electron Emission And IgnitionCharacteristics ") discloses a kind of electrode and in conjunction with the relevant apparatus of kind electrode, electrode comprises first electrode material, adhesion promoter and is arranged in the material of the carbon nanotubes on adhesion promoter layer at least a portion that this paper introduces its full text content as a reference.
U.S. Patent No. _ _ _ _ (sequence number 09/881684, exercise question is " Method ofMaking Nanotube-Based Material With Enhanced FieldEmission ") disclose introduce exterior materials in the nano tube based material to improve the technology of its performance, this paper introduces its full text content as a reference.
U.S. Patent No. _ _ _ _ (sequence number 10/051183, exercise question is " Large-AreaIndividually Addressable Multi-Beam X-Ray System and Methodof Forming Same ") structure that produces the x-ray disclosed, it has a large amount of fixing electrical addressing field emitting electronic sources separately, as carbon nano-tube, this paper introduces its full text content as a reference.
U.S. Patent No. _ _ _ _ (sequence number 10/103803, exercise question is " Method forAssembling Nanoobjects ") technology with preformed nano object self assembly macrostructure disclosed, wherein nano object can processedly have required draw ratio and chemical functional, and this paper introduces its full text content as a reference.
U.S. Patent No. _ _ _ _ (act on behalf of case numbering 032566-043) (exercise question is " Methods for Assembly of Nanostructure-Containing Materialsand Related Articles ") described various assemblings and adhered to the electrophoretype method of nanostructure-containing materials to the various objects, and this paper introduces it, and content is as a reference in full.
As top confirmation; nano structural material especially carbon nano-tube and other nano object with big L/D ratio (being that length is fully greater than its diameter) has and can make them to all attractive character likely of various application, those that application examples such as illumination component, feds such as flat-panel monitor, the gas discharge tube that is used for overvoltage protection, x-ray generation device, little lead, transducer, exciter and high-resolution probe such as flying-spot microscope use.
Nano structural material is subjected to the difficult obstruction that is in distress in the materials processing to the effective combination in the device.For example, can comprise formation nano structural materials such as laser ablation, arc discharge method, solution synthesize, chemical etching, molecular beam epitaxy (MBE), chemical vapor deposition (CVD) by technology.In these technology of assembling nanostructure material each all self is challenged to them.
Utilized formation method in back to comprise silk screen printing and be sprayed on to deposit preformed nano object on the substrate, as carbon nano-tube.Also there is defective in these technology.For example, silk screen printing may need to use adhesive material and activation step, and this causes the low relatively resolution deposition of material.Spray efficiency is not high, and often can not be actually used in extensive manufacturing.In addition, silk screen printing and spraying can cause nano structural material to be randomly dispersed on the substrate.
Used CVD technology direct growth carbon nano-tube on substrate.Referring to people such as for example J.Hafner, Nature, 398 volumes, 761 pages, 1999; United States Patent (USP) 6457350; With United States Patent (USP) 6401526.A kind of potential application of the present invention is to form the lead of being made by nano structural material, as comprises the circuit of carbon nano-tube.Can use CVD technology to form carbon nano-tube and can utilize the CVD technology to be attached to the electrode ad-hoc location then, form lead.The reaction environment of these specification requirements under higher temperature (for example about 600 ℃-1000 ℃), and use catalyst to make nanotube growth effectively.The requirement of all severe rugged environment conditions has seriously been limited the kind of spendable backing material.In addition, the CVD technology often produces multi-walled carbon nano-tubes.These multi-walled carbon nano-tubes do not have the perfect structure level identical with single-walled nanotube usually, thereby may have relatively poor electric emitting performance when comparing with Single Walled Carbon Nanotube.
Other manufacturing technology that relates to nano structural material comprise accurate control separately or microcommunity nano object such as carbon nano-tube deposit to and taper off to a point on the substrate or projection.Referring to for example Dai, Nature, 384 volumes, 147-150 page or leaf (1996); With people such as R.Stevens, Appl.Phys.Lett, 77 volumes, 3453 pages, 2000.These technology are expected to realize large-scale production or batch technology.
General introduction
Therefore, method and apparatus and the correlated product that utilizes self assembly to come patterned deposition of nanostructure-containing materials disclosed.According to exemplary embodiment, the self-assembling method that is used for deposition of nanostructure-containing materials comprises the formation nanostructure-containing materials.Nanostructure-containing materials is by chemical functionalization and be dispersed in and form suspension in the liquid medium.Make the surface can attract at least a portion of the substrate of functionalized nanostructure-containing material to contact with suspension.Separate substrate and suspension.When separating with suspension, nanostructure-containing materials is adhered on the substrate part.
According to another exemplary, form the material that comprises carbon nano-tube.Carbon nano-tube is by chemical functionalization and be dispersed in and form suspension in the liquid medium.On the surface of the substrate that can attract functionalized carbon nanotubes, form hydrophilic and hydrophobic region.At least a portion of substrate is contacted with suspension.Substrate is separated with suspension.When separating with suspension, carbon nano-tube is adhered on the hydrophilic region of substrate.
According to another exemplary, the device that is used for deposition of nanostructure-containing materials on substrate has been described, comprise the equipment that is used to form nanostructure-containing materials.This device comprises the equipment that is used for the chemical functionalization nanostructure-containing materials.Comprise and be used for functionalized nanostructure-containing material is dispersed in the optional equipment that liquid medium forms suspension.Device comprises the equipment that is used to make at least a portion with the substrate that can attract the functionalized nanostructure-containing material surface to contact with suspension.Comprise the equipment that is used for separate substrate and suspension in the device.
The accompanying drawing summary
But accompanying drawing provides the view that is used for more abundant description representative embodiment disclosed herein, and can be used for understanding better they and their intrinsic advantages by those skilled in the art.In these figure, identical reference numerals represent corresponding key element and:
Fig. 1 illustrates (A) mean beam length and is the transmission electron microscope picture of handling Single Walled Carbon Nanotube of about 1-2 μ m and (B) Raman spectrum of handling Single Walled Carbon Nanotube of display characteristic breathing and tangent line pattern;
Fig. 2 illustrates the low temperature manufacturing process according to typical embodiments;
Fig. 3 illustrates and thoroughly does away with typical embodiments and be deposited on (A) glass and (B) the light microscope figure of the lip-deep Single Walled Carbon Nanotube of aluminium;
Fig. 4 illustrates the gradual change that is deposited on the aligned carbon nanotube on the patterned substrate according to typical embodiments;
Fig. 5 illustrates the field emission characteristic of the film that comprises the carbon nano-tube that deposits according to typical embodiments;
Fig. 6 illustrates according to first kind of typical embodiments the thin film deposition of nanostructure-containing materials such as the carbon nano-tube method on (the ITO-coating) glass substrate of glass or indium-Xi-oxide coating;
Fig. 7 illustrates according to second kind of typical embodiments the thin film deposition of nanostructure-containing materials such as the carbon nano-tube method on the glass substrate of glass or ITO-coating;
Fig. 8 illustrates according to the third typical embodiments the thin film deposition of nanostructure-containing materials such as the carbon nano-tube method on the glass substrate of glass or ITO-coating; With
Fig. 9 illustrates according to typical embodiments the thin film deposition of nanostructure-containing materials such as the carbon nano-tube method on the glass substrate of glass or ITO-coating;
Describe in detail
Method consistent with principle of the present invention and that carry out according to preferred embodiment is described below, and corresponding structure and device.
Usually, the technology that is used for low temperature manufacturing nanostructure-containing materials according to typical embodiments can comprise at least partly or entirely following steps: (1) forms nanostructure-containing materials, as comprises the material of Single Walled Carbon Nanotube; (2) chemical functionalization nanostructure-containing materials; (3) the dispersing functional nanostructure-containing materials forms suspension in liquid medium; (4) at least a portion with the substrate that can attract the functionalized nanostructure-containing material surface is contacted with suspension; (5) separate substrate and suspension; (6) before making substrate and suspension contacts, on substrate surface, form hydrophilic and hydrophobic region; (7) purifying nanostructure-containing materials; (8) annealing nanostructure-containing materials; (9) remove hydrophobic region from substrate.
Typical manufacture method begins with preformed undressed nanostructure-containing materials, preferably begins with the material with high length-diameter ratio or the material of material that contains nanotube such as carbon nanotubes.This rough stock can comprise at least a in following: Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, silicon, silica, germanium, germanium oxide, carbonitride, boron, boron nitride, chalcogenide (dichalcogenide), silver, gold, iron, titanium oxide, gallium oxide, indium phosphide or be wrapped in magnetic-particle such as Fe, Co and Ni in the nanostructure.According to embodiment preferred, the material of unprocessed carbon nanotubes comprises Single Walled Carbon Nanotube.Carbon nano-tube can be by following means, comprise formation such as device, arc discharge device and the method for carrying out laser ablation, solution synthetics, chemical etching instrument, molecular beam epitaxy (MBE) instrument, chemical vapor deposition (CVD) instrument.
Unprocessed nanostructure-containing materials can be and consists of B
xC
yN
zThe nano tube structure form of (B=boron, C=carbon and N=nitrogen) maybe can be used and consist of MS
2The nanotube of (M=tungsten, molybdenum or barium oxide) or concentric fullerene structure.Equally, these unprocessed materials can form by any suitable technique, as above-mentioned arc-discharge technique.
Can after formation, carry out purifying to unprocessed nanostructure-containing materials.The technology that is used for purified raw material is in a large number arranged.According to a kind of preferred embodiment, can be at suitable solvent such as peroxide (H
2O
2) and the combination of water in utilize the unprocessed material of back flow reaction purifying.H
2O
2Concentration can be 1-40 volume %, the H of preferred about 20 volume %
2O
2, subsequently at CS
2Middle flushing in methyl alcohol, is filtered then then.According to typical technology,, in medium, introduce the H of about 10-100ml for every 1-10mg nanotube in the medium
2O
2, back flow reaction under 20 ℃-100 ℃ temperature, carry out (referring to for example U.S. Patent No. _ _ _ _ (sequence number 09/679303)).
According to another typical embodiment, unprocessed nanostructure-containing materials can come purifying by this material is suspended in suitable liquid medium such as acid medium, organic solvent or the pure particular methanol.Can use the high-power ultrasonic loudspeaker that rough stock is suspended to remain in the liquid medium several hours, and make suspension pass through microporous barrier simultaneously.In another embodiment, can under about 200 ℃-700 ℃ temperature, come purified raw material by oxidation in air or in the oxygen environment.Impurity in the rough stock can be oxidized with the fast speed of ratio nano pipe in this environment.In another typical embodiments, the impurity that separates in nanotube (or nano wire) and the material by liquid chromatography comes purified raw material.
When nanostructure-containing materials comprises nanotube, go forward depositing to substrate, can further process to shorten the length of nanotube and nanotube bundle.For example, can use chemical etching or grinding technique to shorten nanotube.
The nanostructure-containing materials that can further process rough stock is to give the material hydrophily.For example, can use equipment to come the chemical functionalization nanostructure-containing materials as the reaction instrument that disposes with acid moieties oxidation nanostructure-containing materials.
According to another typical embodiments, the undressed nanostructure-containing materials of the purifying of can under for example about 100 ℃-1200 ℃ temperature of suitable temperature, annealing.According to a kind of preferred embodiment, annealing temperature can be about 100 ℃-600 ℃.Material can be annealed reasonable time, for example about 1-60 minute.According to another embodiment, material can be annealed about 1 hour.Material can be about 10
-2Be annealed in the vacuum environment of Torr, or can in addition higher vacuum pressure under be annealed.According to a kind of embodiment, vacuum pressure can be about 5 * 10
-7Torr.
Representative transmission electron microscope (TEM) according to the carbon nanotube bundles of above-mentioned each step process is illustrated in Figure 1A.Can find out that from figure treatment step comprises material is carried out chemical treatment to give the basic structure that its hydrophily does not change nanotube.In addition, Figure 1B shows that the Raman of nanotube is effectively breathed and the frequency of oscillation of tangent line pattern remains unchanged after this processing.Fourier-transform infrared (FTIR) spectrum shows that the flexible pattern of strong C=0 is at 1727cm
-1Show in the material of handling that contains nanotube to form defective, and dangling bonds are by the COOH group end capping in the place.
Above-mentioned pre-formation and functionalized nanostructure-containing materials can be dispersed in now and form suspension in the liquid medium.Can use the suspension deposition materials on object or substrate, and/or form goods such as lead and field-transmitting cathode, this will be described in more detail below.
For example, selection can make unprocessed nanostructure-containing materials form the suitable liquid medium of stable suspension therein.According to embodiment preferred, liquid medium comprises water.When adding rough stock in liquid medium the time, the stirring that mixture can randomly be subjected to ultrasonic energy or use magnetic stirring bar for example is to help the formation of stable suspension.The time quantum that applies ultrasonic energy can change, but finds at room temperature to stir can produce acceptable result in about 2 hours.The concentration of rough stock is transformable in the liquid medium, as long as can keep steady suspension.For example, the concentration of the carbon nano-tube that comprises in the suspension can be in the scope of the every premium on currency of about 0.0001-1 gram nanotube.
In case form, use suspension to help the deposition of nanostructure-containing materials on suitable substrate.Fig. 2 illustrates the low temperature manufacturing process of deposition of nanostructure-containing materials on substrate.Preferably, at least a portion substrate possess hydrophilic property matter.Substrate can comprise glass, plastics or the pottery of glass, metal such as the aluminium of silicon, glass, indium-Xi-oxide (ITO) coating or chromium, metal coat.In step (1), for example photoresist such as Shiplcy1813 make hydrophilic substrate such as glass substrate patterning with hydrophobic polymer.Can use other known method of photoetching technique and those skilled in the art to make the photoresist patterning.According to a kind of typical embodiments, use the self assembling process shown in step (2a) that nanostructure-containing materials such as Single Walled Carbon Nanotube are deposited on the hydrophilic region (for example glass surface of Bao Luing) of substrate.Preferably in step (3a), remove the hydrophobic polymer coating, for example by in acetone, washing the substrate of band coating.
In optional embodiment, patterned substrate can be metallized in step (2b), for example thermal evaporation and photoresist " (lift-off) moves " process by metal such as chromium and aluminium.In step (3b), can on hydrophilic (hydroxy-end capped) surface of glass substrate, form octadecyl trichlorosilane (OTS) molecule, make this part surface hydrophobicity.Nanostructure-containing materials can be deposited on the metalized portion of substrate surface then, shown in step (4).
As shown in Figure 2, the patternable substrate makes it have hydrophobic and hydrophilic region to limit nanostructure-containing materials with the substrate part that is deposited.These zones can change on length and/or width according to application requirements.For example, made the control line width that between 10 μ m and 100 μ m, changes, but can obtain other size if desired.Dissimilar substrates shows in each embodiment shown in the figure.In the first kind of embodiment that in step (2a), shows, use standard photolithographic methods for example use the printed polymeric paper tinsel as photomask at hydrophilic substrate such as formation pattern on glass.
In the second kind of embodiment that in step (2b), shows, before deposition of nanostructure-containing materials, use thermal evaporation and the photoresist process metallization hydrophilic glass substrate of " moving ".Metallized substrates capable of washing is then for example used ultraviolet (UV) ozone clean, and this is described in more detail below.After the cleaning, can in step (3b), in dried case, use for example expose portion of the suitable 1mM OTS mixed solvent solution silanized glass substrate of hexadecane and tetrachloro carbon.The silanization of glass substrate expose portion makes these parts hydrophobic.Before deposition of nanostructure-containing materials, can be in for example chloroform and ethanol the substrate of sonicated preparation.
As mentioned above, nanostructure-containing materials for example comprises that the unit for uniform suspension of Single Walled Carbon Nanotube can be stabilized in liquid medium such as the deionized water with the concentrations of nanotubes up to about 1.0g/L.At least a portion with the substrate that can attract functionalized nanostructure-containing materials surface is contacted with suspension.For example, can use equipment, the device that if can the submergence patterned substrate vertically enters into suspension at room temperature makes the part substrate contact with suspension.
After making the part substrate and suspension contact, for example by submergence, substrate is separated with suspension, on the hydrophilic region of substrate, assemble along water/substrate/air triple line (see figure 4) to allow nanotube.The equipment of separate substrate and suspension can comprise the device of pulling out substrate at a predetermined velocity from suspension and the device such as the hot plate that keep at substrate with evaporating liquid when suspension contacts.Do not find that nanotube assembles on the hydrophobic region of substrate.From water, pull out or water when evaporating gradually when for example substrate,, in the hydrophilic region of substrate, form the single-wall continuous nano carbon tube film along with triple line moves down.
Nanotube firmly is adhered on the hydrophilic substrate, can not be removed because of washing in solvent such as methyl alcohol, ethanol and buffering hydrofluoric acid.Therefore, can after deposition, use these solvents to remove photoresist.Single Walled Carbon Nanotube is attributable to exist on the glass substrate with combining of substrate-interaction between the functional group of OH group and end-blocking nanotube defective bit.
Fig. 3 A and 3B illustrate the light microscope figure of the Single Walled Carbon Nanotube pattern of the sharp outline of using the said method deposition.Image shows that use above-mentioned " dip-coating " technology can obtain little line width to 10 μ m.The line width of the Single Walled Carbon Nanotube bar shown in Fig. 3 A is respectively 100 μ m, 40 μ m and 10 μ m.Shade shown in Fig. 3 A can be in the result who gets when resembling from the reflection of glass substrate lower surface.Deposition velocity with about 1cm/ days obtains single wall carbon nano-tube film.At present, think that line width is subjected to the restriction of printed polymeric photomask resolution, rather than limit by deposition process.The Single Walled Carbon Nanotube bar is showing staged point limit at the interface, and is level and smooth and continuous.Measuring the conductivity that is deposited on the self-assembled film on the insulating surface under the room temperature is 0.2S/cm.In order to compare, the conductivity with " stand alone type (freestanding) " single-wall carbon nanotube membrane of comparativity is shown as about 0.3S/cm.
Film thickness and uniformity can be depending on the concentration of suspension and pull out the speed of substrate or the evaporation rate of suspension from suspension.Use is uphang supernatant liquid concentration (for example about 1.0g/L) and can be obtained relative thick film with lower pulling out/evaporation rate.When suspension comprised water, the thickness of single wall carbon nano-tube film can raise with temperature and reduce.When temperature raise above about 40 ℃, it is discontinuous that film can become.When water is replaced by rapid evaporation solvent such as ethanol, can be observed similar discontinuity in suspension.Temperature fluctuation in the deposition process also can cause the variation of film thickness, is considered to the result that evaporation rate of solvent changes.In addition, comprise that the film of short Single Walled Carbon Nanotube is comparable and comprise more evenly that this is considered to relevant with the difference of the quality/stability of suspension than those of long tube.In some cases, can on deposit film, observe the striped that extends in parallel with deposition direction.This is considered to withdraw from owing to the three phase boundary place unsteadiness of fluid.
The carbon nano-tube film of assembling on chemical homogeneous texture of report before being similar to, the carbon nanotube bundles that deposits in each striped is arranged along water/substrate/air triple line direction " in face ".For patterned substrate, triple line can be from changing in each striped hydrophilic region center perpendicular to deposition direction, from being parallel to deposition direction between hydrophobic and hydrophilic region at the interface as shown in Figure 4.Therefore, the orientation of carbon nanotube bundles can taper to perpendicular to deposition direction from parallel between each stripe edge and mid point.This can confirm by the TEM image of the single wall carbon nano-tube film that obtains removing from substrate.The overall orientation of Single Walled Carbon Nanotube can be depending on width of fringe.For bigger striped, the striped of for example about 100 μ m, preferred orientations is perpendicular to deposition direction.
Can use above-mentioned self-assembling method to be manufactured on the field-transmitting cathode that uses in the various application, use those that use as light-emitting component, feds such as flat-panel monitor, the gas discharge tube that is used for overvoltage protection, x-ray generation device, little lead, transducer, exciter and high-resolution probe such as ESEM.Use the emissive material of the nanostructure-containing of self-assembling technique manufacturing described herein can produce the feds that has superiority than device with other method such as silk screen printing or electrophoresis production.For example, use screen printing technique produce the used thickener of feds can comprise can limiting device in emitter density and reduce the impurity of performance.In addition, the comparable use of the characteristic size self-assembling technique described herein of the emitting structural of producing by silk screen printing produce those are much bigger.In addition, the feds that produces by electrophoresis must be produced on conductive substrates.The used substrate of self-assembling technique described herein can be conduction or the insulation, depend on application requirements.
Can be for example 5 * 10 in vacuum chamber
-7Measure the electronic field emission characteristic of this self assembly single wall carbon nano-tube film under the Torr reference pressure.In order to provide and the electrically contacting of Single Walled Carbon Nanotube, can on the edge of Single Walled Carbon Nanotube striped, evaporate two chromium stripeds.Fig. 5 has shown emission current-voltage (I-V) characteristic with the patterned film (100 μ m line widths, 300 μ m pitches) of the long carbon nanotube bundles deposition of 5 μ m.The figure that shows in the illustration is the Fowler-Nordheim figure of identical data.Can use hemispherical tip (for example having the 5mm radius) to collect data as anode, cathode-anode spacing is about 168 μ m.Shown in first kind of measurement in, produce 10mA/cm
2The threshold field that current density needs can be about 11V/ μ m.
Make electricity consumption regulate technology and can further reduce threshold field greatly.For example, after processing, can reduce the about 6V/ μ of threshold field m (seeing the block curve among the figure).10A/cm for the free-standing films of growing carbon nanotube bundles
2, this threshold electric is close with the threshold field of the 4-7V/ μ m of previous report.
In the self assembly negative electrode that the method for stating is in the use made, Single Walled Carbon Nanotube can planar be arranged on the surface of substrate.What be similar to isolated Single Walled Carbon Nanotube induces arrangement, thinks when making the electric field that applies enough big, and carbon nanotube bundles is at first crooked and give prominence to along the direction of field, then from their most advanced and sophisticated emitting electrons.Therefore, threshold field can be depending on the aspect ratio of nanotube and the interaction between carbon nano-tube and the substrate.Activation is considered to remove so-called high spot on the negative electrode, and it is outstanding to reduce threshold field that nanotube is easier to along field direction.Activation can be included in the deposition back and remove excess stock from substrate surface, for example uses sonicated and/or machinery to remove technology.
The electronic field emission characteristic of the self-assembled structures of making according to said method can be advantageously with the structure of using the CVD-carbon nano-tube to make and use negative electrode that method for printing screen makes relatively.Those obtain than the much higher emitting cathode of those pixel resolutions that uses so-called " thick film " technology to obtain as described herein can to use self-assembling method.In addition, can use self-assembling method from being in control similar result at various substrate deposition single walls and multi-wall carbon nano-tube, substrate comprises glass, aluminium and the chromium of silicon, glass, ITO-coating.Can use described self-assembling method to obtain to be used for device application and comprise the assembling of nano structural material of Field Emission Display and integrated.
After stating the self-assembling method deposition of nanostructure-containing materials in the use, can further handle the substrate of coating, as annealing.For example, the substrate of the coating of can annealing to be removing the liquid medium residue pull out the evaporation of substrate or suspension from suspension after, improving the electricity and the hot property of nanostructure-containing materials, and promotes the combination between material layer and the substrate.According to a kind of typical embodiments, the substrate that can heat coating is to about 100 ℃-1200 ℃ temperature and kept about 1 hour, further about 2 hours of annealing under about 800 ℃ temperature then.Twice annealing all can be about 5 * 10
-7Carry out under the vacuum pressure of Torr.
The big measuring exemplary embodiment consistent with the principle of the invention will be described now.These embodiment are used for exemplary illustration, should not be considered to limit by any way.
Embodiment 1: at the deposition on glass carbon nano-tube film
At first clean the substrate of the glass that comprises various sizes and thickness, to eliminate the hydrophilic nmature of organic dirt and recovery glass surface.An example of cleaning method can be sonicated glass substrate in the sonicated of using solvent such as acetone, alcohol or deionized water is bathed.After the sonicated, can use filter nitrogen to dry up glass substrate.Can use other method that substrate is further cleaned, clean as " Piranha " solution, be about 4: 1 concentrated sulfuric acid and 30%H in ratio wherein
2O
2Middle about 30 minutes of substrate that expose.In addition, can use UV-ozone clean method to clean substrate, wherein substrate is exposed under the UV about 30 minutes in the oxygen environment.The glass surface available energy of Qing Xiing and the carboxyl that is attached to carbon nano-tube form the hydroxyl (OH) end-blocking of chemical bond fully.
Shifting carbon nano-tube is that the substrate that cleans of submergence at room temperature is in the suspension of carbon nano-tube and water to a kind of method on the glass surface.The concentration of carbon nano-tube/water slurry can be in the scope of the every premium on currency of about 0.0001-1 gram nanotube.The concentration of rough stock can change in the liquid medium, as long as can keep steady suspension.Nanotube can be assembled on the water-wetted surface of glass.When triple line because water gradually from substrate surface evaporation or owing to substrate is pulled out when moving down gradually, forms continuous carbon nanometer tube film on substrate surface from suspension.Be shown among Fig. 6 with above-mentioned consistent procedure chart.
Can be by various technological factors control film thicknesses, comprise that the speed of removing substrate from liquid or water are from the speed of substrate surface evaporation and the concentration of suspension.Film can be as thin as the carbon nano-tube individual layer, maybe can comprise thick extremely several microns carbon nanotube bundles.After the deposition, but annealing thin film is to remove the solvent that comprises in the suspension.Under some sedimentary conditions, the carbon nano-tube that is deposited on the substrate can be parallel to the alignment arrangement of triple line direction top.
Other method that carbon nano-tube is contacted with suspension with depositing nano pipe on glass substrate can comprise following equipment, as spin coating or Spray painting tool, electrophoretic apparatus and printing, casting and drippage instrument.An example of printing process comprises at first places the suspension that comprises carbon nano-tube on an end of substrate surface.Can move suspension across substrate surface then.When suspension moved across substrate surface, carbon nano-tube was settled out from suspension and is deposited on the substrate surface.
Embodiment 2: at deposition on glass patterned carbon nano tube structure
Available hydrophobic film covers the glass substrate of cleaning.But the example of suitable hydrophobic film comprises the sticky polymers of light forming pattern, as photoresist (Shipley 1813) with have the self-assembled monolayer of the organosilan of hydrophobic end group end-blocking, as the organosilan such as the OTS of ethyl capping.In step subsequently, can from the glass surface area of wanting carbon nano-tube film depositing, remove hydrophobic film.The method that is used to produce the patterning template comprises UV photoetching, electron beam lithography and UV-ozone treatment (described in top embodiment 1).
Described technology such as above-mentioned self assembly, spin coating, spraying, electrophoresis, printing, casting and drippage can carbon nano-tube be deposited on the surface of the glass substrate that comprises the patterning hydrophobic film by suitable technique.According to a special embodiment, can be by depositing in the suspension that at room temperature at least a portion of glass substrate is immersed into carbon nano-tube and water.Nanotube is preferably assembled on the hydrophilic region of glass.When water evaporates or substrate is pulled out and triple line when moving down gradually gradually, on the hydrophilic region of patterned substrate, form continuous carbon nanometer tube film from suspension.
After the deposition, can remove hydrophobic coating.When hydrophobic coating is photoresist, can by at first lower temperature as about 100 ℃ down about 2 minutes of the substrate of annealing coating remove photoresist to remove any moisture that remains on the substrate.Then, can be by applying acetone to resist and/or by removing photoresist in the ultra sonic bath that substrate is placed on acetone in about 5 minutes.Because the strong adhesion of carbon nano-tube and substrate, so carbon nano-tube film keeps being adhered on the hydrophilic region of substrate.
The consistent artwork that carries out with above-mentioned technology is shown in Fig. 7 and 8.
Embodiment 3: deposit patterned carbon nano tube structure on the ITO/ glass substrate
Can use alignment mask ITO coating patterns glass substrate.For example, can use a series of sonicated baths of acetone, pure and mild deionized water is the substrate that UV-ozone treatment (describing in conjunction with top embodiment 1) is cleaned the ITO-patterning then.But the hydrophobic film of light forming pattern can be added to then on the surface of ito glass of cleaning.For example, the self-assembled monolayer of photoresist (Shipley 1813) or organosilan can be added on the above-mentioned surface.Can use the pattern of ITO on the glass surface to aim at the photomask that is used for the patterning hydrophobic film then.Can carry out the UV photoetching by common mode, and can remove hydrophobic film from the ITO zone of substrate.Carbon nano-tube can be suspended in the liquid medium, and can use that disclosed any method deposits on substrate in embodiment 1 and 2.Can remove hydrophobic coating by disclosed method among the embodiment 2.
Be shown among Fig. 9 with above-mentioned consistent artwork.
Embodiment 4: use the template of photoresist as the carbon nano-tube patterned deposition
The photosensitive polymer (for example Shipley 1813 photoresists) of viscous liquid type can be applied to glass substrate or scribble on the clean surface of glass substrate of ITO.Then can to substrate carry out standard photolithography process with the design transfer that will comprise in the optical tool to the light actuating resisting corrosion film of coating.The optical tool that uses can be included in the chromium photomask on the soda lime glass plate, or can be and use high-resolution printing machine to be printed on thin polymer film on the substrate.
The substrate that has the patterning light actuating resisting corrosion film then with the carbon nano-tube deposition.According to a kind of typical embodiment, substrate can at room temperature be immersed in the suspension of carbon nano-tube and water.Nanotube is along water/substrate/air triple line assembling, preferably on the glass hydrophilic region that is not covered by photoresist.When water evaporates or substrate is pulled out and triple line when moving down gradually gradually, in the hydrophilic region of substrate, form continuous pattern carbon nano tube film from suspension.
After the deposition, can by substrate is placed on temperature be on the about 100 ℃ heating plate about 2 minutes annealed substrate to remove any residual moisture.Then, can be by applying acetone and/or by removing the photoresist coating in the ultra sonic bath that substrate is placed on acetone in about 5 minutes.Equally, because the strong adhesion of carbon nano-tube and substrate, so carbon nano-tube film keeps being adhered on the substrate after removing resist.
Embodiment 5: use the template of self-assembled monolayer as the carbon nano-tube patterned deposition
Can by solution mutually or vapour-phase reaction (technology that is called silanization) cleaning glass or and the surface of the substrate of ITO coating on form the self-assembled monolayer of silane molecule with hydrophobic functional group.An example of solution phase silanization technology (for example can be included in dried condition, feed the about 30 minutes dried case of filter nitrogen and produce about 5% humidity or lower environment) under the glass substrate of cleaning glass or ITO coating is immersed in the dilution OTS solution that substantially constant stirs (being about 1mM OTS in about 4: 1 mixed solvent in hexadecane and tetrachloro carbon ratio example for example).An example of vapour phase silanization technology can comprise the glass substrate that applies with the dense OTS of about 1mL sealing cleaning glass or ITO in glass container (for example, glass drier) about 12 hours.Then, before dry, all in the ultra sonic bath of chloroform and ethanol, cleaned substrate about 5 minutes at every turn.The glass substrate that applies as the glass or the ITO of silanization is exposed to the UV light time by for example chromium photomask (the patterning chromium thin film on the soda lime glass plate) or physical mask (laser cutting template mask) in atmosphere, the expose portion of substrate is endowed hydrophily by oxidation.
Perhaps, the glass substrate of available photoresist coating cleaning glass or ITO coating, and use photomask (maybe can use negative photoresist) to carry out the photoetching of UV light with transoid pattern.Can be in the glass drier with about 12 hours of the substrate of the dense OTS sealing of about 1mM usefulness photoresist patterning.Then with ethanol or with the acetone rinsing substrate with dissolving photoresist coating.Can in the ultra sonic bath of ethanol and deionized water, clean substrate respectively about 5 minutes then.The zone that photoresist is removed forms the substrate hydrophilic region that is suitable for deposition of carbon nanotubes.
Use disclosed any deposition process 1 and 2 at room temperature carbon nano-tube to be deposited on the glass substrate of the glass of organosilan self-assembled monolayer or ITO coating in conjunction with the embodiments then with patterning.
Embodiment 6: deposition amine or other functional group are to improve the interface combination between carbon nano-tube and the substrate
The glass substrate of glass capable of washing or ITO-coating is hydroxy-end capped to form on the surface of substrate.For example, as mentioned above, the ultra sonic bath that can carry out organic solvent to substrate is that UV-ozone treatment and/or Piranha solution clean then.Can use organosilan such as the functionalized substrate of aminopropyltriethoxywerene werene then with amine end groups end-blocking.A functionalized example of amido is included under about 60 ℃ and kept substrate about 5 minutes in the anhydrous toluene solution of about 1wt% aminopropyltriethoxywerene werene.Use toluene and alcohol flushing substrate then, be placed in the ultra sonic bath of ethanol about 5 minutes then.
Can at room temperature use disclosed any deposition process in embodiment 1 and 2 that carbon nano-tube is deposited on the glass substrate of the glass of the organosilan self-assembled monolayer with patterning or ITO coating then.
Those ordinarily skilled in the art can recognize that under the situation that does not break away from this paper essential characteristic, principle described herein and technology may be embodied in the various concrete forms.It is illustrative that embodiment disclosed herein all is considered in all respects, and nonrestrictive.Scope of the present invention is shown by appended claim, rather than by top specification, all changes in claim equivalent implication and scope all are intended to involved.
Claims (28)
1. self-assembling method that is used for deposition of nanostructure-containing materials, this method comprises:
Form nanostructure-containing materials;
The chemical functionalization nanostructure-containing materials;
The dispersing functional nanostructure-containing materials forms suspension in liquid medium;
At least a portion with the substrate that can attract the functionalized nanostructure-containing material surface is contacted with suspension; With
Separate substrate and suspension, wherein when separating with suspension, nanostructure-containing materials is adhered on the substrate part.
2. the method for claim 1 comprises:
Before making substrate and suspension contact, on substrate surface, form hydrophilic and hydrophobic region, wherein functionalized nanostructure-containing material is hydrophilic, and is adhered to when separating with suspension on the hydrophilic region of substrate.
3. the method for claim 2 wherein forms hydrophilic and hydrophobic region comprises:
On substrate surface, form the self-assembled monolayer of organosilan with hydrophobic end group end-blocking; With
In the oxygen environment, expose the part of self-assembled monolayer to ultraviolet (UV) light; Wherein the expose portion of self-assembled monolayer forms the hydrophilic region of substrate, and the remainder of self-assembled monolayer forms the hydrophobic region of substrate.
4. the method for claim 2 wherein forms hydrophilic and hydrophobic region comprises:
The hydrophobic photoresist of deposition on substrate surface;
A part that exposes photoresist is to ultraviolet (UV) light; With
Remove a part of photoresist to expose the hydrophilic region of substrate, wherein remain the hydrophobic region that photoresist forms substrate.
5. the method for claim 4 comprises:
Remove hydrophobic photoresist in separate substrate and the after-applied solvent of suspension to substrate, wherein nanostructure-containing materials keeps being adhered on the substrate after applying solvent.
6. the method for claim 5 comprises:
Annealed substrate before removing hydrophobic photoresist.
7. the method for claim 2, wherein when substrate comprised glass, this method comprised:
Part with the functionalized glass substrate surface corresponding to the substrate hydrophilic region of the organosilan with amine end groups end-blocking.
8. the method for claim 1 comprises:
Separating the after annealing substrate with suspension.
9. the method for claim 1 comprises:
After separating, remove unnecessary nanostructure-containing materials from substrate with suspension.
10. the method for claim 1 comprises:
Before making part and suspension contacts, clean substrate.
11. the method for claim 10 wherein when substrate comprises glass, is cleaned substrate and is comprised following at least a:
Place substrate in ultra sonic bath with solvent;
Make substrate stand the mixture of sulfuric acid and hydrogen peroxide; With
In the oxygen environment, expose substrate to ultraviolet (UV) light.
12. the process of claim 1 wherein that substrate is contacted with suspension to be comprised:
The submergence substrate is in the suspension of nanostructure-containing.
13. the method for claim 12, wherein separate substrate and suspension comprise at least a in following:
From suspension, pull out the substrate of submergence; With
Evaporation suspension in the submergence substrate.
14. the process of claim 1 wherein that substrate is contacted with suspension to be comprised:
On the part of substrate surface, arrange suspension; With
Move suspension across substrate surface, the nanostructure-containing materials that wherein is dispersed in the suspension is adhered on the surface that can attract functionalised materials.
15. the process of claim 1 wherein at least a to the substrate of the suspension that substrate contacted comprise spin coating and spraying nanostructure-containing with suspension.
16. the process of claim 1 wherein that liquid medium comprises that water is to form the aqueous suspension of nanostructure-containing.
17. the process of claim 1 wherein that the material concentration that comprises in the suspension is between every liter of liquid medium of about 0.0001-1 gram nanostructure-containing materials.
18. the method for claim 1, wherein nanostructure-containing materials comprises at least a in following: Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, silicon, silica, germanium, germanium oxide, carbonitride, boron, boron nitride, chalcogenide, silver, gold, iron, titanium oxide, gallium oxide, indium phosphide or be wrapped in magnetic-particle in the nanostructure comprise at least a among Fe, Co and the Ni.
19. the process of claim 1 wherein that the chemical functionalization nanostructure-containing materials comprises:
By with acid reaction partial oxidation nanostructure-containing materials.
20. the process of claim 1 wherein that substrate comprises at least a in glass, plastics and the pottery of glass, metal, metal coat of silicon, glass, indium-Xi-oxide (ITO) coating.
21. the process of claim 1 wherein that the nanostructure-containing materials that is adhered on the substrate arranges substantially in one direction.
22. the method by self assembly manufacturing pattern carbon nano tube field-transmitting cathode, this method comprises:
Formation comprises the material of carbon nano-tube;
The chemical functionalization carbon nano-tube;
The material that disperses to comprise functionalized carbon nanotubes in liquid medium forms suspension;
On the substrate surface that can attract functionalized carbon nanotubes, form hydrophilic and hydrophobic region;
At least a portion of substrate is contacted with suspension; With
Separate substrate and suspension, wherein when separating with suspension, carbon nano-tube is adhered on the hydrophilic region of substrate.
23. the method for claim 22 comprises:
Separating the after annealing substrate with suspension; With
After separating, remove unnecessary carbon nano-tube from substrate with suspension.
24. the method for claim 22, wherein the chemical functionalization carbon nano-tube comprises:
By with acid reaction partial oxidation carbon nano-tube.
25. the field-transmitting cathode of producing according to the method for claim 1.
26. the field-transmitting cathode of producing according to the method for claim 22.
27. a device that is used for deposition of nanostructure-containing materials on substrate, this device comprises:
Be used to form the equipment of nanostructure-containing materials;
The equipment that is used for the chemical functionalization nanostructure-containing materials;
Be used for forming the equipment of suspension at liquid medium dispersing functional nanostructure-containing materials;
The equipment that is used to make at least a portion to contact with suspension with the substrate that can attract the functionalized nanostructure-containing material surface; With
The equipment that is used for separate substrate and suspension, wherein when separating with suspension, nanostructure-containing materials is adhered on the substrate part.
28. the device of claim 27 comprises:
Be used for forming on substrate surface before making substrate and suspension contacts the equipment of hydrophilic and hydrophobic region, wherein functionalized nanostructure-containing material is hydrophilic, and is adhered to when separating with suspension on the hydrophilic region of substrate.
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| US45625403P | 2003-03-21 | 2003-03-21 | |
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| US10/803,639 | 2004-03-18 |
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