CN103928637B - The preparation method of carbon nano tube transparent combination electrode - Google Patents
The preparation method of carbon nano tube transparent combination electrode Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 28
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000002238 carbon nanotube film Substances 0.000 claims abstract description 25
- 239000002322 conducting polymer Substances 0.000 claims abstract description 20
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229920000307 polymer substrate Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 3
- 239000006184 cosolvent Substances 0.000 claims description 3
- 238000003698 laser cutting Methods 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- CTIFKKWVNGEOBU-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O CTIFKKWVNGEOBU-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001197 polyacetylene Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229920005601 base polymer Polymers 0.000 abstract 1
- 239000010408 film Substances 0.000 description 37
- 229920002521 macromolecule Polymers 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- -1 CNT compound Chemical class 0.000 description 1
- 241001181909 Gaura Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DEQLTFPCJRGSHW-UHFFFAOYSA-N hexadecylbenzene Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1 DEQLTFPCJRGSHW-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Theoretical Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electromagnetism (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Human Computer Interaction (AREA)
- Manufacturing & Machinery (AREA)
- Manufacturing Of Electric Cables (AREA)
- Non-Insulated Conductors (AREA)
- Carbon And Carbon Compounds (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to " preparation method of carbon nano tube transparent combination electrode ". The present invention is to surpass in-line arrangement carbon nano-tube film as conducting base, and conducting polymer is carrier, forms one or more layer structures. The transparent CNT electrode film forming demonstrates excellent electric conductivity, can be at ambient temperature, utilize mechanical technique to manufacture this transparent CNT combination electrode according to economic and simple mode large area, and this transparent CNT combination electrode can be applicable to flexible OLED display part, solar cell, liquid crystal display, the devices such as touch panel.
Description
Technical field
The present invention relates to a kind of transparent combination electrode, particularly relate to a kind of preparation side of carbon nano tube transparent combination electrodeMethod.
Background technology
Display device and the photovoltaic devices such as liquid crystal panel, oled panel, touch-screen, Electronic Paper, solar cell, transparent electricalThe utmost point is all indispensable part. Conventional transparent electrode performance requires mainly to comprise transmitance and resistivity, wherein requires to see throughRate reaches more than 80%, and resistivity is lower than below 500 Ω/sqm. But along with scientific and technological development and the increase of demand, transparency electrodeExcept the requirement of transmitance and resistivity, just towards the development of flexible, flexible aspect. Be oxidized thin tin (ITO) in substrate of glassForm ito thin film and demonstrate excellent light transmission and electric conductivity, current business-like ITO electrode is in the application of transparency electrodeIn occupy leading position. But along with the diversification of transparent electrode applications, transparency electrode must possess low square resistance, visible rayGood transmitance, flexibility in scope, can realize the requirement such as technique of the simple operations of large area precise dipping film forming, this makesIn the expansion application of ito thin film, there is the technical problem that is difficult to overcome, as the preparation process condition (evaporation of ITO electrode high temperatureMethod or sputtering method), easily broken, be difficult to reduce sheet resistance, lack of homogeneity, color yellowing, blue light and be difficult to transmission etc., and if willIto thin film coordinates low-melting flexible substrates, deposit at low temperatures, and prepared ITO conductive film resistivity is high, transparentIt is poor to spend, and poor adhesive force between flexible substrates, and in the time of bending, easy jackknifing, causes component failure. And conventional macromolecule is softProperty backing material contrary with the thermal coefficient of expansion of ITO, can cause ITO conductive film because of device fuel factor in device workCome off and lost efficacy. Moreover ito thin film indium scarcity of resources used, cause ito thin film preparation cost to increase, it is new that this also becomes exploitationThe motive force of type transparency conductive electrode material.
CNT is a kind of material with carbon element with typical stratiform hollow structure feature, form CNT pipe shaft byHexagon graphite carbon ring construction unit composition is that one has special construction (radial dimension is nanometer scale, and axial dimension is micro-Rice magnitude) One-dimensional Quantum material. Its tube wall forms the coaxial pipe that is mainly several layers to tens of layers. Keep between layersFixing distance, is about 0.34nm, and diameter is generally 2～20nm. On CNT the P electronics of carbon atom form on a large scale fromTerritory π key, because conjugation is remarkable, CNT has some special electrical properties. Due to structure and the stone of CNTThe lamellar structure of China ink is identical, so have good electric property. Carbon nano-tube material is because of its high electron mobility, low resistanceRate and the high grade of transparency, regarded as the transparency electrode that can replace ITO by scientific research and industrial circle.
The method of preparing at present carbon nano tube transparent electrode is more, is roughly divided into wet method and dry process.
Wet method is synthetic mainly refers to that adopting carbon nanotube dust to be dispersed in solution carries out film preparation, comprises vacuum filtrationTransfer method [GreenAA, HersamMC.ColoredSemitransparentConductiveCoatingsConsistingofMonodisperseMetallicSingle-WalledCarbonNanotubes[J].NanoLett., 2008,8 (5): 1417-1422.], spraying process [KangSJ, SongY, YiY, etal.Work-FunctionEngineeringofCarbonNanotubeTransparentConductiveFilms[J].Carbon,2010,48(2): 520-524.], spin-coating method [MeitlMA, ZhouYX, GaurA, etal.SolutionCastingandTransferPrintingSingle-WalledCarbonNanotubeFilms[J].Nano.Lett.,2004,4(9): 1643-1647.], czochralski method [NgMHA, HartadiLT, TanH, etal.EfficientCoatingofTransparentandConductiveCarbonNanotubeThinFilmsonPlasticSubstrates[J] .Nanotechnology, 2008,19:205703.], LB method [LiXL, ZhangL, WangXR, etal.Langmuir-BlodgettAssemblyofDenselyAlignedSingle-WalledCarbonNanotubesfromBulkMaterials[J] .J.Am.Chem.Soc., 2007,129 (16): 4890-4891.], electrophoresisMethod [PeiSF, DuJH, ZengY, etal.TheFabricationofaCarbonNanotubeTransparentConductiveFilmbyElectrophoreticDepositionandHot-PressingTransfer[J] .Nanotechnology, 2009,20:235707.] etc.; Dry process comprises aerosol direct synthesis technique[FraserIS,MottaMS,SchmidtRK,etal.ContinuousProductionofFlexibleCarbonNanotube-BasedTransparentConductiveFilms[J].Sci.Technol.Adv.Mater.,2010,11 (4), 045004.], super array czochralski method [FengC, LiuK, WuJS, etal.Flexible,Stretchable,TransparentConductingFilmsMadefromSuperalignedCarbonNanotubes[J] .Adv.Funct.Mater., 2010,20 (6): 885-891.] etc.
Carbon nano tube transparent electrode prepared by employing wet method is owing to there being the inhomogeneous problem of carbon nanotube dispersed, preparedElectrode can cause electrode failure due to local defect, and current study limitation is in laboratory research, aspect large-area applicationsAlso there is very large technological challenge.
The technique that adopts dry method-aerosol direct synthesis technique carbon nano tube transparent electrode is in gaseous phase deposition stove, to generateCNT aerosol have after beating on transparent polymeric adhesive tape column to disintegrate as smooth membranaceous. Carbon nanometer prepared by the methodThe pattern of pipe transparency electrode and quality are subject to the impact of factors in course of reaction, as the temperature of chemical vapor deposition stove, carryThe flow velocity of gas hydrogen, the speed etc. that detours of flexible substrates. The width of deposited film is subject to the restriction of reacting furnace exit diameter, Jin EryeLimit preparation large area carbon nano tube transparent electrode.
Super array czochralski method utilizes the extensibility of CNT, CNT can be stretched as to the film of endless. SuperIn-line arrangement carbon nano-pipe array is listed in after annealed processing, and the array direction of CNT is from vertically becoming level. In the time stretching, putBetween flexible substrates and stretched film, compressed by two rollers. This super array czochralski method compared with wet method synthetic method, workSkill is simple, and CNT utilization rate is high, and expense is low, and quality of forming film is high, can be used for industrialized mass production. But CNT and flexible baseThe combination at the end is just attached to the surface of flexible substrates by the method for mechanical presses, comparatively speaking, and in its operational process of craftBecause the insecure meeting of CNT rete causes electrode quality limited. And this process is difficult for carrying out in same substrateMulti-pass operation.
Summary of the invention
The present invention has developed a kind of process of preparing of novel transparent carbon nanotube combination electrode. The present invention is with super suitableRow's carbon nano-tube film [FengC, LiuK, WuJS, etal.Flexible, Stretchable, TransparentConductingFilmsMadefromSuperalignedCarbonNanotubes[J].Adv.Funct.Mater.,2010,20 (6): 885-891.] be conducting base, conducting polymer is carrier, forms one or more layer structures, and institute formsTransparent CNT electrode film demonstrate excellent electric conductivity, can be at ambient temperature, utilize mechanical technique according to economical andSimple mode large area is manufactured this transparent CNT combination electrode, and this transparent CNT combination electrode to can be applicable to flexible OLED aobviousShow device, solar cell, liquid crystal display, the devices such as touch panel.
The preparation method of carbon nano tube transparent combination electrode, described combination electrode comprises transparent polymer substrate and transparentThe CNT laminated film forming on the surface of substrate, described CNT laminated film is made up of CNT film and conducting polymer film, comprisesFollowing steps: (1) carbon nano-tube film of the super in-line arrangement of lay in transparent polymer substrate, film part grows on Si sheet by drawingThe CNT rete of certain width is extracted at the edge of super in-line arrangement CNT out, then this rete is laid in to transparent polymer baseBasal surface, to being paved with desired zone, adopts laser cutting method or adopts the method that ethanol shrinks to cut off carbon nano-tube film;(2) substrate that is covered with carbon nano-tube film is passed through, between a pair of counterrotating roller, to make on the surface of carbon nano-tube filmAdhere to one deck conducting polymer film, one or two roller surface is coated with and is brushed with the conducting polymer aqueous solution.
Described roller surface roughness Ra 0.01-0.02 μ m.
Crack minimum range between described roller is substrate thickness.
The viscosity of the described conducting polymer aqueous solution is 1-10 × 10-3PaS。
The constituent of the described conducting polymer aqueous solution is: 1) polyaniline, poly-3,4-ethylene dioxythiophene, polyacetyleneOr/and polypyrrole, 2) cosolvent: poly styrene sulfonate, camphorsulfonic acid, DBSA and salt, cetyl benzene sulphurAcid and salt is or/and naphthalene sulfonic acids and salt, and 3) modified additive: propane diols, sorbierite, ethylene glycol, dimethyl sulfoxide (DMSO) is or/and N-N diformazanBase formamide, 4) all the other are water.
The described conducting polymer aqueous solution is the 1.8%PEDOT:PSS aqueous solution, and it is specifically composed as follows:
Described roller inside is provided with heater block.
The invention discloses one and utilize the method for the electrically conducting transparent combination electrode of CNT (CNT) film preparation. ShouldThe CNT laminated film that transparent CNT membrane electrode comprises transparent polymer substrate and forms on the surface of transparent substrates, wherein,CNT conductive film forms by comprising CNT film and conducting polymer film. The present invention adopts the carbon good with substrate adhesion to receiveThe conducting polymer of mitron array film and liquid phase forms a CNT laminated film in the time of mechanical presses. This transparent CNT compound electricThe utmost point demonstrates excellent electric conductivity, can utilize at ambient temperature the wet processing of mechanical presses to prepare transparent CNT compoundElectrode. Macromolecule conductive film is to adopt the form of solution to stick to carbon nano-tube film surface, and macromolecule conductive film and carbon are receivedBetween mitron stretched film and substrate, there is good adhesion, be suitable for multilayer technology operation. The present invention form film be one deck orMulti-layer compound film. Because CNT rete is originally thinner, individual layer CNT thicknesses of layers is several or tens nanometers, and rete exists like thisIn the process of lay, there will be local failure, in order to ensure plane or the three-dimensional electric conductivity of CNT conductive layer, can paved in multi-layers.This process preparation cost is cheap, can realize the preparation of large-area transparent electrode. This transparent CNT electrode can be applicable to manufacture and needsThere are the various devices of light transmission and electric conductivity as flexible organic electro-luminescence display device (OLED), solar cell, liquidLCD, plasma display apparatus (PDP), imageing sensor, touch panel etc.
This transparent CNT combination electrode can be applicable to manufacture the various devices need to light transmission and electric conductivity to be had as flexibilityOrganic electro luminescent display device (OLED), solar cell, liquid crystal display device, plasma display apparatus (PDP), image sensingThe electrode material of device, touch panel etc.
Brief description of the drawings
The preparation of carbon nano-tube film on Fig. 1 Si sheet,
Carbon nano-tube film schematic diagram on Fig. 2 transparent base,
Fig. 3 CNT macromolecule laminated film prepare schematic diagram,
Fig. 4 CNT macromolecule laminated film schematic diagram,
Fig. 5 multilayer carbon nanotube macromolecule laminated film schematic diagram,
Wherein each label lists as follows:
1-transparent substrates, 2-carbon nano-tube film, 3-carbon nano-tube coextruded film, 4-be covered with carbon nano-tube filmTransparent substrates, 5-roller, 6-silicon chip, 7-draw film part.
Detailed description of the invention
The major technique of the preparation of transparent carbon nanotube combination electrode is divided into two parts: (1) carbon nano-tube film and baseAdhering at the end is to be combined by power between the surface molecular between carbon nano-tube film 2 surfaces and transparent substrates 1. Concrete one-tenthFig. 1 is shown in by film schematic diagram. For ensureing adhesive force between carbon nano-tube film 2 and transparent substrates 1, can be by shape as the CNT of Fig. 2Film 2 lies against in the environment of ethanol spraying and shrinks. The carbon nano-tube film 2 forming after single membrane is at the steam of ethanolIn environment, the structure that the automatic carbon nano-tube bundle that shrinks the stable wire of formation of meeting forms. Ethanol molecule can be adsorbed on its tableFace, modifies its surface polarity, has also strengthened the adhesion of carbon nano-tube film 2 with transparent base 1 substrate simultaneously, gained carbon nanometerPipe film 2 can not destroy easily in environment transport and put procedure. The transparent base of carbon nano-tube film will be covered with shown in Fig. 2The end 4, is by a pair of counterrotating roller 5. Require roller 5 surface roughness Ra 0.01-0.02 μ m. Crack between roller 5Small distance is transparent substrates 1 thickness. In roller 5 external coating viscosity in 1-10 × 10-3The macromolecule aqueous solution of PaS. If neededWant can add certain heating annex to realize the control of roller temperature, to guarantee the viscosity of polymer body. Go out from roller 5 topsCarry out substrate surface and formed the conducting polymer laminated film 3 with CNT, Fig. 3 is the schematic diagram of preparing of laminated film.The membrane structure forming is as Fig. 4. Can as required the CNT macromolecule membrane in Fig. 4 be repeated to spread to carbon nano-tube film one timeThen adhere to afterwards electroconductive polymer layer, can also multi-pass operation.
Conducting polymer aqueous solution composition: 1) polyaniline, poly-3,4-ethylene dioxythiophene, polyacetylene be or/and polypyrrole, 2)Cosolvent: poly styrene sulfonate, camphorsulfonic acid, DBSA and salt, cetyl benzene sulfonic acid and salt are or/and naphthalene sulphurAcid and salt, 3) modified additive: propane diols, sorbierite, dimethyl sulfoxide (DMSO) is or/and N-N dimethyl formamide, ethylene glycol, 4) all the otherFor water.
Preparation method: be that mixed dissolution is in certain solvent in proportion by all components, its concentration can be by adding waterOr corresponding solvent is adjusted.
As: the conducting polymer aqueous solution is the 1.8%PEDOT:PSS aqueous solution.
Prepare transparent carbon nanotube combination electrode: the CNT of the super in-line arrangement of lay in macromolecule transparent substrates 1Film 2, is extracted out the CNT rete of certain width by the edge that draws the super in-line arrangement CNT that film part 7 grows on silicon chip 6,Then this rete is laid in to macromolecule transparent substrates 1 surface to being paved with desired zone, adopts laser cutting method or employingThe method that ethanol shrinks is cut off carbon nano-tube film 2; (2) by the substrate 4 that is covered with carbon nano-tube film by a pair of relative rotationRoller (the conducting polymer aqueous solution is applied on roller) 5 between, make to adhere on the surface of carbon nano-tube film 2 one deck conduction highMolecular film, forms laminated film 3.
Claims (7)
1. the preparation method of carbon nano tube transparent combination electrode, described combination electrode comprises transparent polymer substrate and at transparent baseThe CNT laminated film forming on the surface at the end, described CNT laminated film is made up of CNT film and conducting polymer film, comprise asLower step: (1) carbon nano-tube film of the super in-line arrangement of lay in transparent polymer substrate, by drawing super that film part grows on Si sheetThe CNT rete of certain width is extracted at the edge of in-line arrangement CNT out, then this rete is laid in to transparent polymer substrateSurface, to being paved with desired zone, adopts laser cutting method or adopts the method that ethanol shrinks to cut off carbon nano-tube film; (2)The substrate that is covered with carbon nano-tube film, by between a pair of counterrotating roller, is made to adhere on the surface of carbon nano-tube filmOne deck conducting polymer film, one or two roller surface is coated with and is brushed with the conducting polymer aqueous solution.
2. the preparation method of carbon nano tube transparent combination electrode according to claim 1, described roller surface roughnessRa0.01-0.02μm。
3. the preparation method of carbon nano tube transparent combination electrode according to claim 1, the crack between described rollerSmall distance is substrate thickness.
4. the preparation method of carbon nano tube transparent combination electrode according to claim 1, the described conducting polymer aqueous solutionViscosity be 1-10 × 10-3PaS。
5. the preparation method of carbon nano tube transparent combination electrode according to claim 1, the described conducting polymer aqueous solutionConstituent is: 1) polyaniline, poly-3,4-ethylene dioxythiophene, polyacetylene be or/and polypyrrole, 2) and cosolvent: polystyrene sulphurHydrochlorate, camphorsulfonic acid, DBSA and salt, cetyl benzene sulfonic acid and salt is or/and naphthalene sulfonic acids and salt, 3) modification helpsAgent: propane diols, sorbierite, ethylene glycol, dimethyl sulfoxide (DMSO) is or/and N-N dimethyl formamide, and 4) all the other are water.
6. the preparation method of carbon nano tube transparent combination electrode according to claim 5, the described conducting polymer aqueous solutionFor the 1.8%PEDOT:PSS aqueous solution, it is specifically composed as follows:
7. the preparation method of carbon nano tube transparent combination electrode according to claim 1, described roller inside is provided with heatingParts.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310012106.9A CN103928637B (en) | 2013-01-14 | 2013-01-14 | The preparation method of carbon nano tube transparent combination electrode |
| PCT/CN2013/089463 WO2014108015A1 (en) | 2013-01-14 | 2013-12-14 | Preparation method for carbon nanotube transparent composite electrode |
| KR1020157017465A KR101693774B1 (en) | 2013-01-14 | 2013-12-14 | Preparation method for carbon nanotube transparent composite electrode |
| JP2015551963A JP5965554B2 (en) | 2013-01-14 | 2013-12-14 | Manufacturing method of carbon nanotube transparent composite electrode |
| DE112013006416.2T DE112013006416T5 (en) | 2013-01-14 | 2013-12-14 | Process of manufacturing a transparent composite electrode with carbon nanotubes |
| TW103100887A TWI553662B (en) | 2013-01-14 | 2014-01-10 | Preparation of Carbon Nanotube Transparent Composite Electrode |
| HK14110367.8A HK1196996A1 (en) | 2013-01-14 | 2014-10-16 | Preparation method for carbon nanotube transparent composite electrode |
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| KR (1) | KR101693774B1 (en) |
| CN (1) | CN103928637B (en) |
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| HK (1) | HK1196996A1 (en) |
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| CN105321592B (en) * | 2014-08-01 | 2017-03-22 | 广东阿格蕾雅光电材料有限公司 | CNT (carbon nanotube)-polymer laminated composite flexible transparent electrode and preparation method thereof |
| CN105361977B (en) * | 2014-08-26 | 2018-08-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Resistance-type flexible and transparent joint part electronic skin and its preparation method and application |
| CN104465993A (en) * | 2014-10-28 | 2015-03-25 | 南昌大学 | Carbon-based composite transparent electrode and manufacturing method thereof |
| CN104576321A (en) * | 2015-01-30 | 2015-04-29 | 京东方科技集团股份有限公司 | Electrode structure, manufacturing method thereof, display substrate and display device |
| CN104616838B (en) | 2015-02-10 | 2018-02-06 | 京东方科技集团股份有限公司 | The preparation method and electronic device of a kind of electronic device |
| KR102487673B1 (en) * | 2015-02-23 | 2023-01-11 | 린텍 오브 아메리카, 인크. | adhesive sheet |
| CN105024015B (en) * | 2015-06-24 | 2017-12-22 | 复旦大学 | A kind of sliceable perovskite solar cell and preparation method thereof |
| CN106601329B (en) * | 2016-08-18 | 2019-04-16 | 北京纳米能源与系统研究所 | A kind of flexible nano friction generator, preparation method and manufactured sensor |
| CN106782774A (en) * | 2017-01-10 | 2017-05-31 | 京东方科技集团股份有限公司 | Transparent conductive film, its preparation method and device |
| CN109427982B (en) * | 2017-08-30 | 2020-01-03 | 清华大学 | Organic light emitting diode |
| CN109428006B (en) | 2017-08-30 | 2020-01-07 | 清华大学 | Organic light emitting diode |
| CN109428009B (en) | 2017-08-30 | 2020-05-15 | 清华大学 | Preparation method of organic light emitting diode |
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| CN101923912A (en) * | 2010-06-18 | 2010-12-22 | 北京富纳特创新科技有限公司 | Carbon nanotube film and composite film based on same |
| CN102086035A (en) * | 2009-12-03 | 2011-06-08 | 北京富纳特创新科技有限公司 | Carbon-nano-tube film and preparation method thereof |
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| KR100992154B1 (en) * | 2008-09-19 | 2010-11-05 | 한국전자통신연구원 | Transparent Conductive Thin Film Using Carbon Nano Tube and Method for Preparation thereof |
| JP5554552B2 (en) * | 2009-12-09 | 2014-07-23 | アルプス電気株式会社 | Transparent conductive film and method for producing the same |
| KR101272483B1 (en) * | 2010-12-09 | 2013-06-10 | 한국과학기술원 | Manufacturing Method of Transparent Conducting Plate using Carbon Nanotubes-Conducting Polymer Hybrid Multilayer |
| CN102321323B (en) * | 2011-05-27 | 2013-08-28 | 清华大学 | Preparation method of transparent carbon nano tube composite membrane |
| JP2015067483A (en) * | 2013-09-30 | 2015-04-13 | 日立造船株式会社 | Manufacturing method of fibrous carbon material |
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| CN102086035A (en) * | 2009-12-03 | 2011-06-08 | 北京富纳特创新科技有限公司 | Carbon-nano-tube film and preparation method thereof |
| CN101923912A (en) * | 2010-06-18 | 2010-12-22 | 北京富纳特创新科技有限公司 | Carbon nanotube film and composite film based on same |
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| TW201432718A (en) | 2014-08-16 |
| WO2014108015A1 (en) | 2014-07-17 |
| KR101693774B1 (en) | 2017-01-06 |
| CN103928637A (en) | 2014-07-16 |
| JP5965554B2 (en) | 2016-08-10 |
| JP2016504738A (en) | 2016-02-12 |
| TWI553662B (en) | 2016-10-11 |
| HK1196996A1 (en) | 2014-12-24 |
| DE112013006416T5 (en) | 2015-10-15 |
| KR20150118583A (en) | 2015-10-22 |
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