CN101617383A - The electrochemical deposition method of carbon nano-tube - Google Patents
The electrochemical deposition method of carbon nano-tube Download PDFInfo
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- CN101617383A CN101617383A CN200880005629A CN200880005629A CN101617383A CN 101617383 A CN101617383 A CN 101617383A CN 200880005629 A CN200880005629 A CN 200880005629A CN 200880005629 A CN200880005629 A CN 200880005629A CN 101617383 A CN101617383 A CN 101617383A
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- H01J2201/30469—Carbon nanotubes (CNTs)
Abstract
The present invention relates to use electrochemical cell that carbon nano-tube (CNT) is electrochemically-deposited in the substrate.In and the dispersion of the complex compound of CNT and anionic polymer, thereby make on its positive plate that is deposited on described battery.
Description
The present patent application requirement is filed in the priority of the U.S. Provisional Application 60/903,260 on February 24th, 2007, and this patent application is incorporated this paper as the part of this paper into way of reference in full, to be used for all purposes.
Technical field
The present invention relates in substrate, carry out the electrochemical deposition of carbon nano-tube (" CNT ").
Background of invention
United States Patent (USP) 6,902,658 have described a kind of electrophoretic deposition method, wherein before deposition CNT in the substrate, carry out earlier binder substance is deposited to suprabasil independent step.Therefore, need a kind ofly can simultaneously CNT and one or more auxiliary informations be deposited on suprabasil method.
Summary of the invention
In one embodiment, the invention provides the method for deposition of carbon nanotubes, this method comprises:
(a) provide electrochemical cell, this electrochemical cell comprises negative electrode, positive plate, negative electrode is connected to first conductive path of power supply and second conductive path that power supply is connected to positive plate;
(b) dispersion that complex compound is provided is as aqueous electrolyte, and this aqueous electrolyte is arranged between negative electrode and the anode, and this complex compound is formed by the carbon nano-tube and first anionic polymer; And
(c) apply voltage so that complex compound is deposited on the anode to electrochemical cell.
In another embodiment, the invention provides a kind of film, (b) complex compound that this film comprises substrate and is arranged on suprabasil (a) coagulating agent remnants and formed by the carbon nano-tube and first anionic polymer.
In another embodiment, the invention provides the cathode assembly of field emission apparatus, this cathode assembly comprises aforesaid film.
In another embodiment, the invention provides field emission apparatus, this field emission apparatus comprises aforesaid cathode assembly.
The accompanying drawing summary
Fig. 1 shows the schematic diagram of the sedimentation mechanism in the embodiment of method of the present invention.
Fig. 2 shows as the deposition materials on the film of preparation among the embodiment 1.
Fig. 3 shows the configuration as the electrochemical cell that uses among each embodiment.
Fig. 4 shows as the deposition materials on the film of preparation among the embodiment 2.
Fig. 5 shows the fluorescent material illumination image as the film of test among the embodiment 3.
Fig. 6 shows anode current and the anode voltage record value figure line that derives from embodiment 4.
Fig. 7 shows the fluorescent material illumination image of the film of test in embodiment 4.
Fig. 8 shows the fluorescent material illumination image of the film of test in embodiment 5.
Detailed Description Of The Invention
As everyone knows, CNT has unique and available electrical characteristics, and is usually used in making the negative electrode of field emission apparatus. Yet the employing of these materials is subjected to its expensive limitation. Therefore, a target of the present invention provides the method at the even CNT film of substrate preparation, for example prepares in the conductive substrates with good uniformity and low material consumption. Another target is patterning CNT film, with for the preparation of electronic application. So the CNT film of preparation can be used for being installed in the cathode assembly in the field emission apparatus.
Adopt method of the present invention to prepare the CNT film, the method is deposited on CNT in the substrate for the use electrochemical appliance, and in order to realize this purpose, the method for this paper relates to the use electrochemical cell. This battery comprises negative electrode, positive plate, negative electrode is connected to the first conductive path of power supply and the second conductive path that power supply is connected to positive plate. For battery provides aqueous electrolyte, and this aqueous electrolyte is arranged between negative electrode and the anode. Being included in the electrolyte is the dispersion of complex compound, and this complex compound is formed by CNT and the first anionic polymer and optional coagulating agent.
As used herein, CNT typically has a diameter from about 0.5-2nm, and wherein the ratio of length dimension and width dimensions is that aspect ratio is at least 5. In general, aspect ratio is between 10 and 2000. CNT mainly is made of carbon atom, yet can mix other elements, for example metal. CNT of the present invention both can be many walls nanotube (MWNT), also can be single-walled nanotube (SWNT). MWNT for example, it comprises several concentric nanotube, each nanotube has different diameters. Thereby the pipe of diameter minimum is by the larger pipe encapsulation of diameter, and the pipe that this diameter is larger then is again by the larger nanotube encapsulation of another diameter. On the other hand, SWNT only comprises a nanotube.
CNT can prepare by several different methods, also can be by commercially available. The synthetic method of CNT comprises the laser evaporation graphite method [people such as A.Thess, Science 273,483 (1996)], the arc discharge method [people such as C.Journet, Nature 388,756 (1997)] and HiPCo (high pressure carbon monoxide) method [people such as P.Nikolaev, Chem.Phys.Lett.313,91-97 (1999)]. Also can adopt chemical vapour deposition (CVD) (CVD) method [people such as J.Kong, Chem.Phys.Lett.292,567-574 (1998); The people such as J.Kong, Nature 395,878-879 (1998); The people such as A.Cassell, J.Phys.Chem.103,6484-6492 (1999); The people such as H.Dai, J.Phys.Chem. 103,11246-11255 (1999)] produce CNT. Also can generate by the catalysis process in solution and on solid substrate in addition the people such as CNT[Yan Li, Chem.Mater.; 2001; 13 (3); 1008-1014); N.Franklin and H.Dai, Adv.Mater.12,890 (2000); The people such as A.Cassell, J.Am.Chem.Soc.121,7975-7976 (1999)].
Use the major obstacle of CNT to be the diversity of following factor: the state of aggregation of pipe diameter, chiral angle and the nanotube sample that obtains by various preparation methods. Gathering is distinct issues especially, because fullerene pipes highly polarizable, that the side is level and smooth is easy to by a large amount of Van der Waals in conjunction with forming bundle of parallel tubes or pipe rope. This tube bank can be upset the electronic structure of pipe, and nearly allly separates these pipes or disturbed by it trial of the independent macromolecular substances of these effective works by size or type.
The invention provides a kind of method of the CNT for scatter-gather, the method is the aqueous solution that makes the nanotube contact anionic polymer of gathering. Thereby form the complex compound that comprises anionic polymer and CNT, but the association in the complex compound between anionic polymer and the CNT is loose association, it is formed in conjunction with energy or some other non-covalent method by Van der Waals basically, rather than forms by particular functional group's reciprocation. The structural intergrity that has kept thus CNT, but the complex compound that CNT and anionic polymer form is suspended in the electrolyte with the dispersion form.
Because multiple anionic polymer is conducive to the formation of polymer/CNT complex compound, therefore can be used as the dispersant that in the aqueous solution, disperses the CNT purposes, but the preferred polymers that is used for this purposes is the stable solution of nucleic acid, especially nucleic acid molecules. Nucleic acid is very effective when disperseing CNT owing to can form based on the non-covalent interactive nanotube between nanotube and the nucleic acid molecules-nucleic acid complex compound. Therefore, method of the present invention comprises the method for the CNT of scatter-gather, and the method is that nanotube is contacted with the solution of anionic polymer (for example nucleic acid molecules).
Hereinafter discussed and used nucleic acid molecules to form and the complex compound of CNT and the method for disperseing CNT thus, used following term and abbreviation in the argumentation:
" cDNA " is meant complementary DNA
" PNA " is meant peptide nucleic acid
" SEM " is meant scanning electron microscopy
" ssDNA " is meant single stranded DNA
" tRNA " is meant transfer RNA
" CNT " is meant carbon nano-tube
" MWNT " is meant many walls nanotube
" SWNT " is meant single-walled nanotube
" TEM " is meant transmission electron microscope
" nucleic acid molecules " is defined as strand or two strands, comprises RNA, the DNA of synthetic, non-natural or the nucleotide base that changes or the polymer of peptide nucleic acid (PNA) alternatively.The nucleic acid molecules of DNA polymer form can be made of the segment of one or more cDNA, genomic DNA or synthetic DNA.
Relating under the situation of nucleic acid, letter " A ", " G ", " T ", " C " will represent purine base adenine (C respectively
5H
5N
5), guanine (C
5H
5N
5O), pyrimidine bases thymidine (C
5H
6N
2O
2) and cytimidine (C
4H
5N
3O).
Term " peptide nucleic acid " is meant to have by peptide and connects the material that base is linked at the extension of nucleic acid polymers together.
" stabilizing solution of nucleic acid molecules " is meant such nucleic acid molecules solution, and these nucleic acid molecules have dissolved and be in loose secondary conformation form.
" nanotube-nucleic acid complex compound " is meant a kind of like this composition, and said composition comprises the carbon nano-tube with the loose association of at least one nucleic acid molecules.Usually the association between nucleic acid and the nanotube forms by van der waals bond or some other non-covalent method.
Term " agitating device " is meant the device that helps nanotube and nucleic acid dispersion.The exemplary stir device is the ultrasonic degradation device.
Term " denaturant " is meant the material that works in DNA and other nucleic acid molecules degenerative processes.
Standard DNA reorganization used herein and Protocols in Molecular Biology are known in the art, and in following document, describe to some extent: Sambrook, J., Fritsch, E.F. and Maniatis, T. Molecular Cloning:A Laboratory Manual, second edition, Cold SpringHarbor Laboratory Press, Cold Spring Harbor, NY (1989) (hereinafter referred to as " Maniatis "); Silhavy, T.J., Bennan, M.L. and Enquist, the Experiments with Gene Fusions of L.W., Cold Spring Harbor Laboratory ColdPress Spring Harbor, NY (1984); And Ausubel, people's such as F.M. CurrentProtocols in Molecular Biology publishes (1987) by Greene Publishing Assoc.andWiley-Interscience.
The nucleic acid molecules that is used for the inventive method can be any type, and can include but not limited to DNA, RNA and peptide nucleic acid from any suitable source.Nucleic acid molecules used herein can be generated by synthetic method, or can separate from natural materials and make according to rules well known in the art (people's such as above-mentioned Sambrook document).Nucleic acid molecules can be strand or two strands, and can be functionalized by multiple reactive group, part or reagent in the arbitrfary point alternatively.Yet, just associate being used to disperse with regard to the purposes with CNT, nucleic acid functionalized and nonessential, and most of nucleic acid that this paper is used to disperse all lack functional group, so this paper is referred to as " not functionalized ".
With regard to dispersion, peptide nucleic acid (PNA) is particularly useful in this article, because they have the bifunctionality of nucleic acid and peptide.Method synthetic and use PNA is known in the art, referring to for example Antsypovitch, and S.I., Peptide nucleic acids:Structure, RussianChemical Reviews (2002), 71 (1), 71-83.
Nucleic acid molecules used herein can have any composition of base, and even can constitute by the extension of same base (for example polyA or polyT), and do not weaken the ability of the CNT of nucleic acid molecules scatter-gather.Nucleic acid molecules preferably has less than about 2000 bases, more preferably has less than 1000 bases, and most preferably has from about 5 bases to about 1000 bases.Usually, it is irrelevant that nucleic acid disperses the ability of CNT to show as with sequence or base composition, yet some evidences show, the reciprocation of G-C and T-A base-pair is few more in the sequence, then dispersion efficiency is high more, and RNA and modification thereof are especially effective in dispersion process, is preferred at this paper therefore.Be applicable to that the nucleic acid molecules of this paper includes but not limited to have the nucleic acid molecules of following general formula:
1.An, n=1-2000 wherein;
2.Tn, n=1-2000 wherein;
3.Cn, n=1-2000 wherein;
4.Gn, n=1-2000 wherein;
5.Rn, n=1-2000 wherein, and wherein R can be A or G;
6.Yn, n=1-2000 wherein, and wherein Y can be C or T;
7.Mn, n=1-2000 wherein, and wherein M can be A or C;
8.Kn, n=1-2000 wherein, and wherein K can be G or T;
9.Sn, n=1-2000 wherein, and wherein S can be C or G;
10.Wn, n=1-2000 wherein, and wherein W can be A or T;
11.Hn, n=1-2000 wherein, and wherein H can be A or C or T;
12.Bn, n=1-2000 wherein, and wherein B can be C or G or T;
13.Vn, n=1-2000 wherein, and wherein V can be A or C or G;
14.Dn, n=1-2000 wherein, and wherein D can be A or G or T; And
15.Nn, n=1-2000 wherein, and wherein N can be A or C or T or G.
Except the combination of listing above, in these sequences any one all can be substituted by ribonucleotide (being RNA or RNA/DNA heterozygosis) by one or more deoxynucleotides, perhaps has one or more phosphoric acid sugar to connect base and substituted by peptide bond (being PNA or PNA/RNA/DNA heterozygosis).
As used herein, nucleic acid molecules can be stabilized in suitable solution.Nucleic acid molecules is preferably loose secondary conformation form, and only loose each other association, thereby realizes that each chain farthest contacts with CNT.The stabilizing solution of nucleic acid is common and (referring to people's such as above-mentioned Sambrook the document) known in the art, and comprise salt and buffer usually, for example sodium salt and sylvite, and TRIS (three (2-amino-ethyl) amine), HEPES (N-(2-hydroxyethyl) piperazine-N '-(2-ethanesulfonic acid) and MES (2-(N-morpholinyl) ethyl sulfonic acid).The preferred solvent of stable nucleus acid solution is a water-soluble solvent, and wherein water is highly preferred.Optionally in solution, add the nucleic acid denaturation material and can improve process for dispersing.Denaturant commonly used includes but not limited to formamide, urea and guanidine.The non-limiting tabulation of suitable denaturant is found in people's such as above-mentioned Sambrook document.
For the method according to this paper prepares dispersion, one or more nucleic acid molecules can be contacted with one group of carbon nano-tube of assembling.Preferably (but and nonessential) contacts under the situation that adopts certain class agitating device.Usually, agitating device adopts the ultrasonic degradation device, but also can comprise the device that forms nucleic acid and CNT high shear mixing (being homogenizing), or their any combination.After stirring, CNT will disperse and form nanotube-nucleic acid complex compound, and this complex compound comprises at least one nucleic acid molecules by hydrogen bond or some other non-covalent method and the loose association of CNT.
CNT may be influenced dispersion effect to some extent with temperature in the process that nucleic acid contacts.If when mixing under room temperature or higher temperature, it is found that needs long jitter time, and when mixing (23 ℃) under being lower than the temperature of room temperature, then showing as needs short jitter time, and about 4 ℃ temperature is preferred.Also described by contact the dispersion that realizes CNT with nucleic acid molecules in United States Patent (USP) 2004/0132072 and United States Patent (USP) 2004/0146904, these two full patent texts are incorporated this paper as the part of this paper into way of reference, to be used for all purposes.
Except above-mentioned nucleic acid molecules, one or more other anionic polymers can be used to prepare the purposes of the aqueous dispersion of CNT.Other examples of having found to can be used for to prepare the anionic polymer of CNT dispersion include but not limited to poly-(acrylic acid) (" PAA ") of ionization or ethene/(methyl) acrylic copolymer (" EAA " or " EMAA ") of ionization, and any one in these copolymers is all available such as Na
+, K
+, NH
4 +Or Cr
+And so on cation neutralization; Styrene ionomer, for example styrene/Sodium styrene sulfonate copolymer (PSS) or styrene/styrene Sodium methacrylate copolymer; And the tetrafluoroethene/sulfonic acid copolymer of ionization, for example Nafion
TMCopolymer (deriving from Du Pont), wherein the sulfonic group in the tetrafluoroethylene/perfluoro vinyl ether copolymers can be neutralized by sodium.Described with respect to nucleic acid molecules as mentioned, can use ultrasonic degradation or other mixing arrangements to promote the dispersion of CNT in the aqueous solution of one or more anionic polymers of this section discussion.
In one embodiment, in the time will being dispersed in the electrolyte solution that comprises in the battery by the complex compound that CNT and anionic polymer molecule form, can promote the deposition of this complex compound on the galvanic anode plate by adding optional coagulating agent within it.Coagulating agent is with the negative electrical charge on the anionic polymer in the neutralized complex.Because anionic polymer/CNT complex compound group is mainly repelled (or by the repulsion around two layers of the positively charged of complex compound) mutually by electronegative complex compound and is kept dispersity, therefore, use coagulating agent these negative electrical charges (or compressing this two layers) that neutralize, make the complex compound group in electrolyte solution, keep the power of dispersity removal.Because the position of very pressing close to positive plate that is reflected at of coagulating agent neutralized complex takes place, therefore, complex compound (no longer disperseing) will change solid phase into from solution mutually with different degree, assemble and agglomeration state (being similar to the formation of floccule and flocculate) thereby be gradually, assemble then and be deposited on the surface of positive plate.Except the CNT complex compound, deposition material onboard also can comprise coagulating agent remnants.
If in electrolyte solution, there are first and second anionic polymers, for example form first polymer of complex compound with CNT, and with first polymer phase than second polymer looser with the association of CNT or that do not associate with CNT, then they can begin deposition simultaneously on anode surface.First polymer can for example be deposited in the matrix of second polymer.Additional materials for example exists conductivity or functionalized particulate with the validity and the performance of positive plate in the enhanced field emitter in electrolyte solution if desired, then itself and anionic polymer/CNT complex compound can be deposited on the positive plate simultaneously.Fig. 2 shows by carrying out the representative instance of the film type that this type of deposition forms on positive plate, and film has good homogeneous owing to material uniform deposition and good adhesion on its whole surface.
Be adapted at being used for herein and the coagulating agent of anionic polymer/CNT complex compound purposes comprises inorganic coagulant, the Tricationic that forms by metal for example, these metals comprise VIII/VIIIA family metal, for example iron, cobalt, ruthenium or osmium.Because the effect maximum of Tricationic neutralized complex can be ten times of bivalent cation, therefore provides the method easily of coagulating agent to be: in electrolyte solution, provide bivalent cation, terpyridyl ruthenic chloride (II) for example, wherein 2
+Cation is oxidized to 3 owing to having been captured electronics by positive plate
+Valency.Fig. 1 shows this machine-processed representative schematic diagram.
Yet in alternative embodiment, do not use coagulating agent, wherein positive plate is formed by metal (for example silver or nickel).In this case, the dissolving metal on the plate is in electrolyte solution, and the cation neutralization that formed by metallic atom of the electric charge on anionic polymer/CNT complex compound, and these metallic atoms enter the solution from the solid metal that forms plate.
The method of this paper is carried out under the situation than electronegative potential work at battery usually, for example less than about 5 volts, or from about 2 volts to less than about 5 volts, or from about 2 volts to about 3 volts.The thickness of deposit film is directly related with the length of sedimentation time to a great extent.Available sedimentation time is about 1 to about 10 minutes scope, or about 1 to about 2 minutes scope.On positive plate, keep positive potential with respect to cell cathode.
The method of this paper can be used for film former, and wherein deposition materials deposits with predetermined pattern.This can realize by using traditional photoimaging technology to carry out patterning as the surface of the plate of anode.Therefore, can activate photoresist by mask it is developed, provide pattern such as the array of circle hole with surface at anode.Since anionic polymer/CNT complex compound be assemble and from solution, be precipitated out, therefore, they only are deposited in the hole, and photoresist can be removed.This method provides patterning CNT film, and wherein positive plate is as the substrate of film, by being installed in the field emission apparatus for use.
On the positive plate of battery, finish after the deposition of CNT complex compound, can from battery, this plate be removed, clean, dry and under this condition, it is installed in and is used as the wherein part of cathode assembly in the field emission apparatus, so that the electronics emission to be provided.Yet, alternatively, before being installed on this plate in the field emission apparatus, it can being baked and banked up with earth and/or toasts, polymer with fusion sediment, and the polymer that uses this state is as adhesive, more firmly CNT is fixed on the surface of plate, make the film that contains CNT have excellent abrasive.
In the field emission apparatus of the above-mentioned plate that is coated with deposition materials of can packing into, on negative electrode, deposited electronic emission material, this material is used the electron bombard anode when being subjected to exciting.Electronic emission material can be acicular substance, for example carbon, semiconductor, metal or their mixture.As used herein, " needle-like " is meant that the aspect ratio of particulate is 10 or bigger.Usually use frit, metal dust or metallic paint or their mixture that electronic emission material is connected in the substrate in the cathode assembly.
Needle-like carbon as electronic emission material can be all kinds, but carbon nano-tube is preferred needle-like carbon, and single wall CNT is especially preferred.The carbon fiber that obtains by the catalytic decomposition of carbonaceous gas on little metal particle also can be used as needle-like carbon, and other examples of needle-like carbon are polyacrylonitrile-radical (PAN-yl) carbon fiber and asphalt base carbon fiber.
Can make ins all sorts of ways is connected to electronic emission material in the substrate.Method of attachment must be able to be born the condition of manufacturing equipment when being placed with field-transmitting cathode in it, and can bear the test of service condition and keep its integrality, for example typical vacuum condition and the highest about 450 ℃ temperature conditions.Preferable methods is: will be screen-printed in the substrate with required pattern by electronic emission material and frit, metal dust or metallic paint or their paste that mixture constituted, then the dry patterning paste of baking.For wider various application, for example need the more application of fine-resolution for those, preferable methods comprises that the paste that will further comprise light trigger and photocurable monomer carries out silk screen printing, and the paste of drying is carried out photo-patterned, toasts the paste of patterning then.
Substrate can be any material, as long as paste composition can be adhered thereto.If paste is dielectric, and has used non-conductive substrate, then need the film of electric conductor, the film of electric conductor is used as cathode electrode, and the means that apply voltage to electronic emission material are provided.Silicon, glass, metal or refractory material (for example alumina) can be used as substrate.For display application, preferred substrate is a glass, and preferred bases soda lime glass especially.For in realization best electrical conductivity on glass, can in air or nitrogen, preferably in air, under 500-550 ℃, silver-colored paste be baked in advance on glass.Can on the conductive layer that so forms, print emitter paste then.
The paste that is used for silk screen printing comprises electronic emission material, organic media, solvent, surfactant and low softening point frit, metal dust or metallic paint or their mixture usually.The effect of medium and solvent is that suspension and disperse particles component are solid.Solid in the paste has suitable rheology, to be used for typical patterning method, for example silk screen printing.Numerous organic medias that become known for this purposes are arranged, comprise celluosic resin, for example the alkyd resins of ethyl cellulose and various molecular weight.The example of useable solvents is butyl carbitol ester, butyl carbitol acetate ester, dibutyl carbitol (DBC), dibutyl phthalate and terpineol.These and other solvent is prepared, to reach required viscosity and volatility requirement.
Also used frit, this frit can be fully softening under baking temperature, with adhere in the substrate and electronic emission material on.Can use lead glass material or bismuth glass material, and other has the glass of low softening point, for example calcium borosilicate and zinc borosilicate.But have the more composition of the silk screen printing of high conductivity if desired, then described paste also can comprise metal, for example silver or golden.Paste comprises the solid to about 80 weight % by the about 40 weight % of the total weight of paste usually.These solids comprise electronic emission material and frit and/or metal component.Can use the modification of composition to adjust the final thickness of viscosity and printing material.
Emitter paste is carried out triple-roller mill by the mixture to following material usually and is prepared: electronic emission material, organic media, surfactant, solvent and low softening point frit, metal dust or metallic paint or their mixture.For example can using, 165-400 order stainless steel cloth comes the silk screen printing paste mixture.Paste can be deposited as the form of continuous film or required pattern.If substrate is a glass,, preferably to about 525 ℃ temperature, in nitrogen, toasted paste about 10 minutes at about 450 ℃ then at about 350 ℃ to about 550 ℃.The higher baking temperature that can use substrate to bear, precondition are oxygen-free gas in the curing environment.Yet the organic component in the paste can effectively volatilize down at 350-450 ℃, thereby stays the composite layer of electronic emission material and glass and/or metallic conductor.During the baking, electronic emission material seems not take place observable oxidation or other chemistry or physical change under nitrogen.
If make the paste photo-patterned of silk screen printing, then paste also can comprise light trigger, ductile adhesive and photocurable monomer, but this photocurable monomer comprises the ethylene linkage unsaturated compound of for example at least a addition polymerization, and this compound has at least a polymerisable vinyl.Usually, to comprise CNT by the about 0.01-6.0 weight of the total weight of paste %, the frit of the silver of about 40-75 weight % (form is the fine silver particulate) and about 3-15 weight % by the paste of electronic emission material (for example carbon nano-tube, silver and frit) preparation.
The anode of field emission apparatus is the electrode that is coated with conductive layer.When using field emission apparatus in display unit, wherein negative electrode has the pel array of the thick-film paste of deposition as mentioned above, and the anode in the display unit can comprise the fluorescent material that incident electron is converted to light.Also the substrate of anode can be chosen as transparent substrates, so that the light of transmissive gained.Cathode assembly and anode have constituted sealing unit, and wherein cathode assembly and anode are separated by dividing plate, and have the space of finding time between anode and negative electrode.Needing this space of finding time is partial vacuum, so that can be transferred to anode from the electronics of cathode emission, has only a spot of collision with gas molecule simultaneously.Usually, this is found time space is pumped to less than 10
-5The pressure of holder.
This class field emission apparatus can be used for various electronic application, for example the backlight of vacuum electronic device, flat computer and television display screen, LCDs, emission gate amplifier, klystron and lighting device.For example, proposed to have the panel display screen of negative electrode, this negative electrode adopts field emitting electronic source, i.e. field emmision material or field emission body, and fluorescent material, and this fluorescent material can be luminous under the bombardment by the field emission body electrons emitted.This class display screen had both had the visual display advantage of conventional cathode ray tube, also had the advantage of other panel display screens on the degree of depth, weight and energy consumption.Panel display screen can be the plane or crooked.United States Patent (USP) 4,857,799 and 5,015,912 disclose the matrix addressing panel display screen, and this display screen has used little tip cathode, and this negative electrode is formed by tungsten, molybdenum or silicon structure.WO 94-15352, WO 94-15350 and WO 94-28571 disclose the panel display screen that negative electrode has the emitting surface of relatively flat.These devices are also described in United States Patent (USP) 2002/0074932 to some extent, and this patent application is incorporated this paper as the part of this paper into way of reference in full, to be used for all purposes.
Material used in this paper method can be made by methods known in the art, perhaps can be from supplier such as Alfa Aesar (Ward Hill, Massachusetts), City Chemical (WestHaven, Connecticut), Fisher Scientific (Fairlawn, New Jersey), Sigma-Aldrich (St.Louis, Missouri) or Stanford Materials (AlisoViejo, California) locate commercially available.
Favourable attribute of the present invention and effect are found among a series of embodiment as described below (embodiment 1-5).Embodiment based on these embodiments only be representational, and select those embodiments to come example the present invention, material, condition, specification, component, reactant, technology and the rules not representing not describe in these embodiments just are not suitable for enforcement the present invention, do not represent that the theme of not describing in these embodiments just is not included among the category of claims and equivalent thereof yet.
Embodiment
At the 1X of 15mL TBE[tris boric acid (ethylenediamine tetra-acetic acid)] in the buffer (deriving from SigmaAldrich), (derive from CNI, Houston Texas) mixes with 30mg yeast rna (deriving from Sigma Aldrich) with the CNT of 150mg laser ablation.Use the probe supersonic generator under the power stage of 20W with mixture ultrasonic degradation 30 minutes.According to following table (table 1) two kinds of components of dispersion and other of gained are mixed, make the deposit solution of 100mL.Used Ru in the deposit solution
2+(bipyridine)
3For terpyridyl ruthenic chloride (II), derive from Sigma Aldrich.EMMA is the ethylene/methacrylic acid ionomer, with trade name Surlyn
TMIonomer derives from Du Pont.
Table 1
The composition of deposit solution
| Component | Original liquid concentration | Addition | Ultimate density |
| The CNT dispersion | ??10mg/mL | ??4mL | ??0.04％ |
| ??EMMA | ??10mg/mL | ??2mL | ??0.02％ |
| ??Ru 2+(bipyridine) 3 | ??10mM | ??2mL | ??0.2mM |
| Water | ??92mL |
With parallel mode 2 ' * 2 ' stainless-steel sheet (as negative electrode) and 2 ' * 2 ' indium tin oxide (" ITO ") plate (as anode) are inserted in the rectangle electrochemical cell (configuration as shown in Figure 3).The deposit solution of 15mL is packed in the battery as electrolyte.Between two electrodes, apply the electrical potential difference of 3.2V.After 1 minute, stop deposition, from battery, take out the ITO plate, with washed with de-ionized water and at air drying.Obtain the material of uniform deposition onboard, as shown in Figure 2.
Indium tin oxide (ITO) substrate (2 ' * 2 ') of photoresist (PR) patterning is used as anode.The PR layer defines the round hole array of diameter 20 μ m.These holes come out the surface of ITO plate to carry out the CNT deposition.Before electro-deposition, the ITO plate that applies PR immersed in 0.01% the Triton X-100 solution, take out then and carry out drying by nitrogen blowing.This helps to apply thin hydrophilic layer to hydrophobicity PR layer, and is better moistening to carry out.After this is handled, with 2 ' * 2 ' stainless-steel sheet (as negative electrode) and the ITO plate (being used as anode) that applies PR with parallel mode be inserted into embodiment 1 in the electrochemical cell of used same type.The deposit solution of 15mL is packed in the battery.Between two electrodes, apply ac potential (100Hz square wave) with 0 to 3.5V peak-to-peak voltage and 50% duty ratio.After 1 minute, stop deposition, from battery, take out the ITO plate, with washed with de-ionized water and at air drying.By handling the PR layer is removed with acetone solvent.Obtain the excellent homogeneity of the CNT material deposition in the hole that exposes, as shown in Figure 4.
Embodiment 3
To derive from then embodiment 1 and dry shown in figure 2 plate in nitrogen in 420 ℃ of bakings 10 minutes down.Then an adhesive tape is laminated on the CNT film, subsequently it is removed.This method is commonly referred to " activation ", becomes known for making the film surface failure of rock, thereby the CNT long filament is exposed and perk from substrate surface, with remarkable enhancing electronic field emission.Assemble the diode field emission apparatus by the ITO substrate that will apply the CNT film as negative electrode then.In the mode relative with this " activation " negative electrode positive plate is installed, this positive plate is made of the substrate of glass that applies ITO, and this substrate of glass has the fluorescent material coating.Use the thick electric insulation baffle of 1mm to keep the distance between negative electrode and the anode substrate.Use silver coating and copper strip to realize and the electrically contacting of negative electrode and anode electrode, thereby finish diode apparatus.Device is installed in the vacuum chamber, and this vacuum chamber is sucked up to pressure and is lower than 1 * 10
-5Holder.With repetition rate is that 60Hz and pulse duration are that the pulse square wave of 60 μ s is applied on the anode electrode.Make cathode electrode remain on earth potential.Under the anode voltage of 2kV, obtain the anode current of 200 μ A.Fig. 5 shows the fluorescent material illumination image that obtains by this device emitting electrons.
Then as described in the embodiment 3, with the plate that derives from embodiment 2 and drying shown in Figure 4 in nitrogen in 420 ℃ of bakings 10 minutes down.As described in embodiment 3, use an adhesive tape to activate CNT point surface.Then by ITO substrate that CNT point is covered as negative electrode, and the substrate of glass that will have a coating ITO of fluorescent material coating is used as anode, assembles the diode field emission apparatus.Adopt the thick glass partition of 0.22mm to keep distance between negative electrode and the anode substrate in this embodiment.Device is installed in the vacuum chamber, and this vacuum chamber is sucked up to pressure and is lower than 1 * 10
-5Holder.With repetition rate is that 60Hz and pulse duration are that the pulse square wave of 60 μ s is applied on the anode electrode.Make cathode electrode remain on earth potential.When pulsed anode voltage reached 800V, recording average anode current was 5 μ A.Measured anode current increases with the increase of pulsed anode voltage.Under the anode voltage of 925V, obtain the anode current of 40 μ A.Fig. 6 shows anode current and the anode voltage record value figure line that derives from this field emission apparatus.Fig. 7 shows the fluorescent material illumination image that obtains by this device emitting electrons, and this device is worked under the anode current of the anode voltage of 975V and 80 μ A.The pixel of each rectangular illumination is generated by a plurality of CNT lattice arrays on the negative electrode on the anode.
The method of this paper is not used the flat glass substrate of the coating ITO for preparing and use in embodiment 4 in embodiment 2, but adopted top grid triode substrate to deposit the CNT point.Top grid triode substrate is made of two conductive layers usually, is provided with insulating barrier between these two conductive layers.In this embodiment, will apply of the substrate of the substrate of glass of ITO, use the ITO layer as negative electrode as top grid triode.Insulative dielectric is deposited upon the top of ITO layer.Metal gate electrode is deposited upon on the dielectric layer.In addition,, pass metal and dielectric layer etch and go out round hole array, make the surface of ITO be exposed by using photoresist (" PR ") and mask.As described in embodiment 2, circle hole array defines the pattern on the PR layer that covers the triode assembly.The opening diameter in hole is less than the diameter in the hole that extends through metal and dielectric layer among the PR, but than the circumference of duck eye with the hole is concentric greatly.Use and similar step described in the embodiment 2 and 4, the CNT spot deposition on the ITO surface, and is toasted and activates.
In the position relative with the triode negative electrode of this activation positive plate is installed, this positive plate is made of the substrate of glass that applies ITO, and this substrate of glass has the fluorescent material coating.The thick dividing plate of use 3mm keeps the distance between negative electrode and the anode substrate.Use silver coating and copper strip to realize and the electrically contacting of ITO cathode electrode, metal gate electrode and ito anode electrode, to finish top grid triode device.Device is installed in the vacuum chamber, and this vacuum chamber is sucked up to pressure and is lower than 1 * 10
-5Holder.The anode electrode applies the direct voltage of 3kV.With repetition rate is that 120Hz and pulse duration are that the pulse square wave of 30 μ s is applied on the gate electrode.Make cathode electrode remain on earth potential.When the pulse gate voltage reached 70V, recording average anode current density was 5.0 μ A/cm
2Fig. 8 shows the fluorescent material illumination image that obtains by this triode device emitting electrons.
This paper has described the feature of some device of the present invention in the context of one or more specific embodiments, described embodiment combines various these category features.Yet scope of the present invention is not limited to the description of independent certain the several feature in any specific embodiments, and the present invention comprises that also (1) is less than time combination of all features of any described embodiment, and described time combined feature is not exist formation time combination institute abridged feature; (2) each independently comprises the feature in the combination of what described embodiment in office; (3) can other locate disclosed further feature with this paper by optional, only the combination of the further feature that the selected feature classification in two or more described embodiments is formed.
In this manual, unless under the use situation, clearly indicate in addition or indicate on the contrary, wherein the embodiment of theme of the present invention is discussed or is described as to comprise, comprise, contain, have, contain or contains some features or key element, except clearly discuss or describe those one or more features or key element also can be present in the embodiment.Yet, an alternative embodiment of theme of the present invention can be discussed or be described as to be made up of some features or key element basically, and the embodiment feature or the key element that wherein will change operating principle or the remarkable characteristic of embodiment significantly are not present in herein.The alternative embodiment of another of theme of the present invention can be discussed or be described as to be made up of some features or key element basically, in described embodiment or its non-intrinsically safe modification, only has that institute is concrete to be discussed or the feature or the key element of description.
Claims (20)
1. the method for deposition of carbon nanotubes, described method comprises:
(a) provide electrochemical cell, described electrochemical cell comprises negative electrode, positive plate, described negative electrode is connected to first conductive path of power supply and second conductive path that described power supply is connected to described positive plate;
(b) dispersion that complex compound is provided is as aqueous electrolyte, and described aqueous electrolyte is arranged between described negative electrode and the described anode, and described complex compound is formed by the carbon nano-tube and first anionic polymer; And
(c) apply voltage so that described complex compound is deposited on the described anode to described electrochemical cell.
2. according to the process of claim 1 wherein that described aqueous electrolyte also comprises coagulating agent.
3. according to the method for claim 2, wherein coagulating agent remnants and described complex compound are deposited on the described anode together.
4. according to the process of claim 1 wherein that described first polymer comprises nucleic acid molecules.
5. according to the process of claim 1 wherein that described first polymer comprises RNA.
6. according to the process of claim 1 wherein that described electrolyte also comprises second anionic polymer.
7. according to the method for claim 6, wherein said second ionomer comprises ethene/(methyl) acrylic copolymer of styrene ionomer or ionization.
8. according to the method for claim 6, the described complex compound that wherein is deposited on the described anode is deposited in the matrix of described second anionic polymer.
9. according to the method for claim 7, wherein said first polymer comprises nucleic acid molecules.
10. according to the method for claim 7, wherein said first polymer comprises RNA.
11. according to the method for claim 1, described method also comprises from described battery and removes described positive plate, it is installed in step the field emission apparatus then.
12. the complex compound that film, described film comprise substrate and be arranged on described suprabasil (a) coagulating agent remnants and (b) formed by the carbon nano-tube and first anionic polymer.
13. according to the method for claim 12, wherein said first polymer comprises nucleic acid molecules.
14. according to the method for claim 12, wherein said first polymer comprises RNA.
15., wherein in described substrate, also be provided with second anionic polymer according to the film of claim 12.
16. according to the method for claim 15, wherein said second ionomer comprises ethene/(methyl) acrylic copolymer of styrene ionomer or ionization.
17. according to the method for claim 15, wherein said first polymer comprises nucleic acid molecules.
18. according to the method for claim 15, wherein said first polymer comprises RNA.
19. be used for the cathode assembly of field emission apparatus, described cathode assembly comprises the film according to claim 1.
20. field emission apparatus, described field emission apparatus comprises the cathode assembly according to claim 19.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US90326007P | 2007-02-24 | 2007-02-24 | |
| US60/903,260 | 2007-02-24 |
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| CN101617383A true CN101617383A (en) | 2009-12-30 |
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| CN200880005629A Pending CN101617383A (en) | 2007-02-24 | 2008-02-22 | The electrochemical deposition method of carbon nano-tube |
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|---|---|
| US (1) | US20090314647A1 (en) |
| EP (1) | EP2113125A2 (en) |
| JP (1) | JP2010519416A (en) |
| KR (1) | KR20090113906A (en) |
| CN (1) | CN101617383A (en) |
| WO (1) | WO2008103439A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103043653A (en) * | 2013-01-17 | 2013-04-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method and device for preparing metal-nanoparticle functionalized carbon nanotube |
| TWI557767B (en) * | 2014-07-10 | 2016-11-11 | 鴻海精密工業股份有限公司 | Method of making field emission cathode |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009111290A2 (en) * | 2008-02-29 | 2009-09-11 | E. I. Du Pont De Nemours And Company | Method for the electrochemical deposition of carbon nanotubes |
| US8110976B2 (en) * | 2008-07-09 | 2012-02-07 | Samsung Electronics Co., Ltd. | Method of preparing field electron emitter and field electron emission device including field electron emitter prepared by the method |
| WO2010021629A1 (en) * | 2008-08-22 | 2010-02-25 | E. I. Du Pont De Nemours And Company | Method for the electrochemical deposition of carbon nanotubes |
| JP6159564B2 (en) * | 2013-04-23 | 2017-07-05 | 田中貴金属工業株式会社 | Sensor electrode and manufacturing method thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4857799A (en) * | 1986-07-30 | 1989-08-15 | Sri International | Matrix-addressed flat panel display |
| US5015912A (en) * | 1986-07-30 | 1991-05-14 | Sri International | Matrix-addressed flat panel display |
| US7449081B2 (en) * | 2000-06-21 | 2008-11-11 | E. I. Du Pont De Nemours And Company | Process for improving the emission of electron field emitters |
| US6902658B2 (en) * | 2001-12-18 | 2005-06-07 | Motorola, Inc. | FED cathode structure using electrophoretic deposition and method of fabrication |
| CN1998061B (en) * | 2002-07-03 | 2010-08-04 | 新泰科有限公司 | Fabrication and activation processes for nanostructure composite field emission cathodes |
| US7498423B2 (en) * | 2002-11-21 | 2009-03-03 | E.I. Du Pont De Nemours & Company | Carbon nanotube-nucleic acid complexes |
| US7365186B2 (en) * | 2002-11-22 | 2008-04-29 | Arborgen, Llc | Vascular-preferred promoter sequences and uses thereof |
| US20070058014A1 (en) * | 2003-10-15 | 2007-03-15 | Marc Burglin | Process for printing textile fibre materials in accordance with the ink-jet printing process |
| CN1875075A (en) * | 2003-10-31 | 2006-12-06 | 东亚合成株式会社 | Water base ink |
| JP3972107B2 (en) * | 2004-03-26 | 2007-09-05 | 国立大学法人信州大学 | Manufacturing method of electron emission source using carbon nanotube and polymer |
| US7947371B2 (en) * | 2004-11-05 | 2011-05-24 | E. I. Du Pont De Nemours And Company | Single-walled carbon nanotube composites |
| US20060124028A1 (en) * | 2004-12-09 | 2006-06-15 | Xueying Huang | Inkjet ink compositions comprising carbon nanotubes |
-
2008
- 2008-02-22 CN CN200880005629A patent/CN101617383A/en active Pending
- 2008-02-22 US US12/525,699 patent/US20090314647A1/en not_active Abandoned
- 2008-02-22 EP EP08725933A patent/EP2113125A2/en not_active Withdrawn
- 2008-02-22 WO PCT/US2008/002344 patent/WO2008103439A2/en active Application Filing
- 2008-02-22 KR KR1020097019849A patent/KR20090113906A/en not_active Application Discontinuation
- 2008-02-22 JP JP2009550923A patent/JP2010519416A/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103043653A (en) * | 2013-01-17 | 2013-04-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method and device for preparing metal-nanoparticle functionalized carbon nanotube |
| TWI557767B (en) * | 2014-07-10 | 2016-11-11 | 鴻海精密工業股份有限公司 | Method of making field emission cathode |
Also Published As
| Publication number | Publication date |
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| WO2008103439A2 (en) | 2008-08-28 |
| US20090314647A1 (en) | 2009-12-24 |
| JP2010519416A (en) | 2010-06-03 |
| EP2113125A2 (en) | 2009-11-04 |
| WO2008103439A3 (en) | 2008-12-11 |
| KR20090113906A (en) | 2009-11-02 |
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