WO2007004758A1 - Method for manufacturing transparent electrode and transparent electrode man¬ ufactured thereby - Google Patents

Method for manufacturing transparent electrode and transparent electrode man¬ ufactured thereby Download PDF

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Publication number
WO2007004758A1
WO2007004758A1 PCT/KR2005/002134 KR2005002134W WO2007004758A1 WO 2007004758 A1 WO2007004758 A1 WO 2007004758A1 KR 2005002134 W KR2005002134 W KR 2005002134W WO 2007004758 A1 WO2007004758 A1 WO 2007004758A1
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Prior art keywords
carbon nanotube
thin film
substrate
transparent electrode
flexible transparent
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PCT/KR2005/002134
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French (fr)
Inventor
Sang-Geun Oh
Jae-Ho Kim
Young-Kwan Kim
Chang-Soo Han
Jin-Won Song
Jun-Ho Jeong
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Korea Institute Of Machinery And Materials
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Priority to PCT/KR2005/002134 priority Critical patent/WO2007004758A1/en
Publication of WO2007004758A1 publication Critical patent/WO2007004758A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/311—Flexible OLED
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/221—Carbon nanotubes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • 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
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention is directed to a method for manufacturing a transparent electrode and a transparent electrode manufactured thereby, more specifically, to a method for manufacturing a flexible transparent electrode with large area, which comprises the formation of a thin film of carbon nanotube on a flexible polymer substrate, and thus achieves excellent adhesion stability of the thin film to the substrate even after repeated bending and folding, and to a transparent electrode manufactured by the method.
  • Background Art
  • the flexibility of a display is one of the key functions basically required to an advanced display, since it makes the display portable by bending or folding it.
  • Flexible display is a display which is, like paper, bendable or rollable without making damages to the display properties, and excellent in impact resistance, therefore it can be an alternative of conventional displays using a rigid glass substrate and further can be applied to various emerging fields such as e-paper which have been impossible to achieve with conventional displays. Disclosure of Invention Technical Problem
  • ITO indium-tin oxide
  • a plastic substrate such as a polyimide, polyester or polycarbonate substrate by sputtering
  • ITO film has excellent conductivity and transparency, its intrinsic brittleness and deformation owing to differences in thermal expansion coefficient between the ITO film and a substrate cause a problem of exhibiting poor mechanical stability when being applied to a touch-screen display or being bent or folded.
  • expensive devices such as a vacuum device are required, and problems such as changes in sheet resistance owing to thermal deformation of a plastic substrate are generated since the manufacturing process includes processes conducted at high temperature.
  • the use of conducting polymers such as polyacetylene, polypyrrole, polyaniline, polythiophene and the like are vigorously researched for the purpose of finding an alternative of a transparent ITO electrode.
  • the conducting polymer electrode have advantages of better flexibility and less brittleness as compared to an ITO electrode, and accordingly, of excellent mechanical stability when being bent or folded.
  • the conducting polymer layer thick so as to obtain appropriate sheet resistance, it generates a problem of a rapid decreasing of the visible light transmittance of the electrode, since the conducting polymer itself absorbs light in the visible spectral region.
  • Carbon nanotube has a structure in which a graphene sheet, a kind of crystalline graphite, is rolled up in the shape of a tube, wherein the diameter of the tube has on the order of nanometers.
  • Carbon nanotube is a nearly flawless new material which has been researched extensively since it was found in 1991. Since the electric characteristics of carbon nanotube are sensitively changed depending on the shape and the diameter of the roll of graphite sheet, it has been reported that carbon nanotube can exhibit various properties of insulator, semiconductor, metal and the like. Specifically, metallic carbon nanotubes exhibit about 10 -10 " ⁇ cm of resistivity which means very good conductivity.
  • the present invention is to overcome those problems of prior arts, with purposes of providing a method for manufacturing a flexible transparent electrode and a flexible transparent electrode manufactured thereby, which has an excellent conductivity in spite of using very small amount of carbon nanotube, a very small percolation threshold value, and significantly improved adhesion stability owing to interdigitation at the interface between a thin film of carbon nanotube and a polymer substrate.
  • a method for manufacturing a flexible transparent electrode comprising the steps of: (1) forming a thin film of carbon nanotube on a solid substrate; (2) coating a precursor capable of forming a flexible transparent substrate on the thin film of carbon nanotube; (3) curing the precursor to make a flexible transparent substrate on which the thin film of carbon nanotube is fixed; and (4) removing the solid substrate.
  • the solid substrate used in the method of the present invention may be selected from the group consisting of a filter membrane, a metal substrate, an opaque inorganic substrate, a transparent inorganic substrate and a polymer substrate.
  • the filter membrane can be made of materials selected from the group consisting of aluminum oxide, polycarbonate, polyethylene terephthalate, cellulose esters such as cellulose nitrate or cellulose acetate, nylon, polypropylene and polyethersulphone, and the pore of the filter membrane suitably has a diameter of 0.01-10 D.
  • the carbon nanotube in the method of the present invention may be at least one selected from the group consisting of single- walled carbon nanotube, double- walled carbon nanotube, multi-walled carbon nanotube, carbon nanofiber and graphite.
  • the carbon nanotube is not specifically limited by its manufacturing method, as long as it does not obstruct the purpose of the present invention, and may be selected from those manufactured by for example, chemical vapor deposition, arc discharge or laser ablation. Commercially available carbon nanotubes can be also used in the method of the present invention.
  • the thin film of carbon nanotube is preferably formed to have a thickness of 1-100 nm.
  • the carbon nanotube also may be a carbon nanotube modified with nanoparticles of metal such as gold, silver, copper or the like, in order to improve the conductivity.
  • the precursor capable of forming a flexible transparent substrate in the method of the present invention is a precursor of a transparent and flexible polymeric materials such as polydimethylsiloxane (PDMS), polyepoxide, polyacrylate, polyimide, polyester, polycarbonate, cellulose acetate, polystyrene, polyolefin, polymethacrylate, polysulphone, polyethersulphone, polyvinyl acetate or the like, or a precursor being capable of forming a flexible glass material such as an ultra thin glass.
  • PDMS polydimethylsiloxane
  • polyepoxide polyacrylate
  • polyimide polyester
  • polyester polycarbonate
  • cellulose acetate polystyrene
  • polyolefin polymethacrylate
  • polysulphone polyethersulphone
  • polyvinyl acetate or the like or a precursor being capable of forming a flexible glass material such as an ultra thin glass.
  • the precursor is preferably a monomer capable of forming thermosetting, photocurable, or thermoplastic polymers such as PDMS, poly epoxide, polyacrylate, polyimide, polyester, polycarbonate, cellulose acetate, polystyrene, polyolefin, polymethacrylate, polysulphone, polyethersulphone or polyvinyl acetate.
  • PDMS poly epoxide, polyacrylate, polyimide, polyester, polycarbonate, cellulose acetate, polystyrene, polyolefin, polymethacrylate, polysulphone, polyethersulphone or polyvinyl acetate.
  • (1) in the method of the present invention may be conducted by using a method selected from the group consisting of vacuum filtration, self-assembly, Langmuir- Blodgett deposition, solution casting, bar coating, dip coating, spin coating, spray coating and roll-to-roll methods.
  • the coating of the precursor capable of a flexible transparent substrate on the thin film of carbon nanotube in the step (2) in the method of the present invention may be conducted by using a method selected from the group consisting of bar coating, dip coating, spin coating, spray coating and roll-to-roll methods.
  • the curing of the precursor in the step (3) in the method of the present invention may be conducted by, for example, cooling, a curing agent, heating, UV irradiation or solvent evaporation.
  • the removal of the solid substrate in the step (4) in the present invention may be carried out by mechanical peeling or dissolving the solid substrate with a suitable solvent.
  • the manufacture of the flexible transparent electrode is conducted as follows, provided that an aluminum oxide filter membrane is used as the solid substrate in the step (1) and monomer of PDMS is used as the precursor of a flexible transparent substrate.
  • carbon nanotube is added to an aqueous solution in which one or more surfactants such as Triton X-100, a sodium salt of dodecylbenzenesulphonic acid(Na-DDBS), cetyl trimethyl ammonium bromide(CTAB) or sodium dodecyl sulfate(SDS) or the like is dissolved, and to the resulting solution, ultrasonication is applied to prepare an aqueous suspension containing 0.001-0. lwt% of carbon nanotube which maintains the stable dispersion state.
  • one or more surfactants such as Triton X-100, a sodium salt of dodecylbenzenesulphonic acid(Na-DDBS), cetyl trimethyl ammonium bromide(CTAB) or sodium dodecyl sulfate(SDS) or the like is dissolved, and to the resulting solution, ultrasonication is applied to prepare an aqueous suspension containing 0.001-0. lwt% of carbon nanotube
  • organic solvents such as N- methylpyrrolidone (NMP), o-dichlorobenzene, dichloroethane, dimethylformamide (DMF), chloroform or the like, may be used for the same method to prepare an organic solution of carbon nanotube dispersed therein stably without being flocculated.
  • NMP N- methylpyrrolidone
  • DMF dimethylformamide
  • the resulting aqueous solution or organic solution of carbon nanotube dispersed therein as obtained from the above method is subjected to a vacuum filtration using a vacuum filtering device equipped with an aluminum oxide filter membrane(l) as a solid substrate, and then, a thin film(2) of carbon nanotube is uniformly formed on the filter membrane(l).
  • the thickness of the thin film(2) being formed is readily adjustable by controlling the amount of a suspension of carbon nanotube being filtered.
  • the thin film(2) formed on the filter membrane(l) is additionally washed with a sufficient amount of water to remove the residual surfactants on the thin film(2) of carbon nanotube.
  • the membrane having a thin film of carbon nanotube formed thereon is dried in a dry oven and the like.
  • the PDMS substrate the upper part of the thin film of carbon nanotube formed on the dried membrane is coated with thermally curable monomers(3) of PDMS by bar coating, and then the resultant is cured in an oven, wherein the PDMS substrate may be manufactured by any conventionally known method(for example, a method disclosed in Langmuir 1994, 10, 1498.).
  • the method of the present invention may further comprises, between the step (1) and the step (2), a step of growing a thin layer of a conducting polymer such as polyacetylene, polypyrrole, polyaniline, polythiophene or the like on the upper part of the thin film of carbon nanotube formed on a solid substrate, by using an electrochemical method.
  • a conducting polymer such as polyacetylene, polypyrrole, polyaniline, polythiophene or the like
  • the thin film of carbon nanotube which has the thin layer of conducting polymer grown on upper part thereof as described above is fixed to the flexible transparent substrate in later step.
  • a transparent electrode in which a thin film of carbon nanotube is fixed to a flexible transparent substrate, manufactured by firstly forming the thin film of carbon nanotube on a solid substrate, coating the upper part of the thin film of carbon nanotube with a precursor capable of forming a flexible transparent substrate and curing it, and then peeling the solid substrate or dissolving the solid substrate with an adequate solvent.
  • a precursor capable of forming a flexible transparent substrate and curing it, and then peeling the solid substrate or dissolving the solid substrate with an adequate solvent.
  • the present invention has an advantage that the adhesion stability of the thin film of carbon nanotube is significantly improved by interdigitation at the interface between the carbon nanotube and the flexible transparent substrate. Therefore, according to the present invention, it is possible to minimize the amount of carbon nanotube used in manufacture of a transparent carbon nanotube electrode and to prevent decrease in conductivity which occurs when carbon nanotubes are dispersed inside a polymer, thereby achieving good conductivity, even though additional coating with a conducting polymer is not carried out.
  • FIG. 1 is a schematic view showing a method for manufacturing a transparent electrode according to one embodiment of the present invention.
  • Fig. 2 is a photograph showing that the transparency of the transparent electrode can be easily adjusted by controlling the amount of a suspension of carbon nanotube.
  • FIG. 3 is a photograph showing the flexibility of the transparent electrode obtained from Example 1 of the present invention.
  • Fig. 4 is a photograph showing the patterns of carbon nanotube on the transparent electrode obtained from Example 4 of the present invention.
  • a 0.00 lwt% aqueous suspension of carbon nanotube in stable dispersion state was prepared by adding 10 mg of single- walled carbon nanotube (manufactured by Iljin Nanotech) to a IL aqueous solution in which Ig of Triton X-100 was dissolved as a surfactant, and sonicating at 60Hz.
  • PDMS were applied to the upper part of the thin film of carbon nanotube formed on the dried membrane by using a bar coating method, and then the coated membrane was cured in an oven at 65°C.
  • the aluminum oxide filter membrane was removed in 3M of an aqueous NaOH solution, and accordingly a transparent electrode in which the thin film of carbon nanotube is formed on the flexible transparent PDMS substrate was obtained.
  • the amount of carbon nanotube per unit area was 1 D/cm
  • the transparent electrode manufactured as above showed about 90% of transmittance measured by a UV- visible spectrometer.
  • the sheet resistance of the transparent electrode measured by a four point probe was less than lOO ⁇ /sq.
  • the transparent electrode manufactured by the present example is excellent in transparency, conductivity, flexibility, and adhesion stability of the thin film of carbon nanotube.
  • a transparent electrode, in which the thin film of carbon nanotube was formed, was manufactured by using the same method as in Example 1, except that the thin film of carbon nanotube was formed by the Langmuir-Blodgett method, which comprises preparing a chloroform suspension containing 0.00 lwt% of carbon nanotube dispersed therein, spreading the solution on the water surface of a Langmuir-Blodgett trough, evaporating the solvent, gradually compressing the carbon nanotube film by pushing two movable barriers to obtain a Langmuir film of carbon nanotube, and transferring the Langmuir film to a silicone or glass substrate to obtain the thin film of carbon nanotube.
  • the thin film of carbon nanotube was about 30 nm in thickness.
  • a transparent electrode, in which the thin film of carbon nanotube was formed, was manufactured by using the same method as in Example 1, except that monomers of polyacrylate were coated to the upper part of the thin film of carbon nanotube formed on the membrane by spin coating, and cured by UV light.
  • the amount of carbon nanotube per unit area of the thin film was about 1 D/cm
  • a transparent electrode, in which the thin film of carbon nanotube was formed, was manufactured by using the same method as in Example 1, except that polymethacrylate dissolved in chloroform was coated to the upper part of the thin film of carbon nanotube formed on the membrane by spin coating, and cured by solvent evaporation.
  • the amount of carbon nanotube per unit area of the thin film was about 1 D/cm
  • a transparent electrode, in which the thin film of carbon nanotube was formed, was manufactured by using the same method as in Example 1, except that the filtration of a suspension of carbon nanotube was carried out through the aluminum oxide filter membrane on which a patterned 300 mesh TEM grid was placed, for obtaining a patterned thin film of carbon nanotube on the filter membrane.
  • a transparent electrode, in which the thin film of carbon nanotube was formed, was manufactured by using the same method as in Example 1, except that a conducting polymer film of polyaniline was additionally grown, according to an electrochemical method disclosed in Diamond and Related Materials, 2004, 13, 256, on the upper part of the thin film of carbon nanotube formed on the filter membrane, and then dried.
  • a transparent electrode, in which the thin film of carbon nanotube was formed, was manufactured by using the same method as in Example 3 except that a conducting polymer film of polyaniline was additionally grown, according to an electrochemical method disclosed in Diamond and Related Materials, 2004, 13, 256, on the upper part of the thin film of carbon nanotube formed by the Langmuir-Blodgett method, and dried.
  • Carbon nanotubes were modified with gold nanoparticles by using a method disclosed in Langmuir 2000, 18, 3569.
  • the shape of the carbon nanotubes and the distribution of the nanoparticles were observed by Atomic Force Microscope (AFM).
  • AFM Atomic Force Microscope
  • a transparent electrode in which the thin film of carbon nanotube modified with metal particles was formed, was manufactured by using the same method as in Example 1.
  • Carbon nanotubes were modified with gold nanoparticles by using a method disclosed in Langmuir 2000, 18, 3569. The shape of the carbon nanotubes and the distribution of the nanoparticles were observed by AFM. By using the gold nanoparticle- modified carbon nanotubes, a transparent electrode, in which the thin film of carbon nanotube modified with metal particles was formed, was manufactured by using the same method as in Example 2.
  • the present invention can provide a flexible transparent electrode with large area and excellent optical characteristics.
  • the flexible transparent electrode according to the present invention can be advantageously used in various applications, for example, displays such as LCD, PDP, OELD, FED and the like; electronic devices such as electrostatic recording substrate, photodiode, register, thin film composite circuit and the like; sensors such as photo-sensor, IR-sensor, pressure- sensor, biochemical-sensor and the like; memory devices such as FRAM, thermoplastic recording and the like; and others including antistatic devices, electromagnetic shielding devices, battery electrodes and the like.

Abstract

The present invention relates to a method for manufacturing a flexible transparent electrode, comprising the steps of: (1) forming a thin film of carbon nanotube on a solid substrate; (2) coating a precursor capable of forming a flexible transparent substrate on the thin film of carbon nanotube; (3) curing the precursor to make a flexible transparent substrate on which the thin film of carbon nanotube is fixed; and (4) removing the solid substrate, and to the flexible transparent electrode manufactured thereby. Using the method of the present invention, a flexible transparent electrode with large area can be obtained, which maintains stable adhesiveness of the carbon nanotube film to the substrate even after repeated bending and folding. The flexible transparent electrode according to the invention can be advantageously used in various applications such as displays, electronic devices, sensors, memory devices or the like.

Description

Description
METHODFORMANUFACTURING TRANSPARENT ELECTRODE AND TRANSPARENT ELECTRODE MANUFACTURED THEREBY
Technical Field
[1] The present invention is directed to a method for manufacturing a transparent electrode and a transparent electrode manufactured thereby, more specifically, to a method for manufacturing a flexible transparent electrode with large area, which comprises the formation of a thin film of carbon nanotube on a flexible polymer substrate, and thus achieves excellent adhesion stability of the thin film to the substrate even after repeated bending and folding, and to a transparent electrode manufactured by the method. Background Art
[2] In recent years, as the Age of Information based on digital technology emerges, the development of a novel advanced display becomes increasingly important. Particularly, based on the researches in high performance of flat panel displays which have been commercialized at present such as TFT-LCD(thin film transistor-liquid crystal display), PDP(plasma display panel), OLED(organic light emitting diode), the development of advanced displays has been proceeded vigorously.
[3] The flexibility of a display is one of the key functions basically required to an advanced display, since it makes the display portable by bending or folding it. Flexible display is a display which is, like paper, bendable or rollable without making damages to the display properties, and excellent in impact resistance, therefore it can be an alternative of conventional displays using a rigid glass substrate and further can be applied to various emerging fields such as e-paper which have been impossible to achieve with conventional displays. Disclosure of Invention Technical Problem
[4] As for a method for manufacturing a flexible transparent electrode for embodying a flexible display, a method of forming an indium-tin oxide (ITO) film on a plastic substrate such as a polyimide, polyester or polycarbonate substrate by sputtering, is well known in this field. However, although the ITO film has excellent conductivity and transparency, its intrinsic brittleness and deformation owing to differences in thermal expansion coefficient between the ITO film and a substrate cause a problem of exhibiting poor mechanical stability when being applied to a touch-screen display or being bent or folded. Additionally, for a manufacture of the ITO film, expensive devices such as a vacuum device are required, and problems such as changes in sheet resistance owing to thermal deformation of a plastic substrate are generated since the manufacturing process includes processes conducted at high temperature.
[5] Because of the above-mentioned problems of the ITO film, the use of conducting polymers such as polyacetylene, polypyrrole, polyaniline, polythiophene and the like are vigorously researched for the purpose of finding an alternative of a transparent ITO electrode. The conducting polymer electrode have advantages of better flexibility and less brittleness as compared to an ITO electrode, and accordingly, of excellent mechanical stability when being bent or folded. However, when coating the conducting polymer layer thick so as to obtain appropriate sheet resistance, it generates a problem of a rapid decreasing of the visible light transmittance of the electrode, since the conducting polymer itself absorbs light in the visible spectral region.
[6] Recently, another method for manufacturing a flexible and transparent electrode has been suggested by using a carbon nanotube which has both excellent conductivity and mechanical properties at the same time.
[7] Carbon nanotube has a structure in which a graphene sheet, a kind of crystalline graphite, is rolled up in the shape of a tube, wherein the diameter of the tube has on the order of nanometers. Carbon nanotube is a nearly flawless new material which has been researched extensively since it was found in 1991. Since the electric characteristics of carbon nanotube are sensitively changed depending on the shape and the diameter of the roll of graphite sheet, it has been reported that carbon nanotube can exhibit various properties of insulator, semiconductor, metal and the like. Specifically, metallic carbon nanotubes exhibit about 10 -10" Ωcm of resistivity which means very good conductivity. Other than such electric characteristics, carbon nanotubes are excellent in mechanical properties, chemically stable, transparent in visible spectral region when being a thin film, therefore researches have been reported in which carbon nanotube is used as a material for a transparent electrode. For example, Korean laid- open patent publication No. 2005-0001589 discloses a method for manufacturing a transparent electrode by preparing a copolymer containing carbon nanotubes and then coating the polymer composite onto a polyester substrate. However, the method as above has some problems such that a relatively large amount of carbon nanotube is required to obtain an appropriate sheet resistance value since the carbon nanotubes are dispersed in a polymer film, and that additional coating onto the polyester substrate with a conductive film is required. Technical Solution
[8] The present invention is to overcome those problems of prior arts, with purposes of providing a method for manufacturing a flexible transparent electrode and a flexible transparent electrode manufactured thereby, which has an excellent conductivity in spite of using very small amount of carbon nanotube, a very small percolation threshold value, and significantly improved adhesion stability owing to interdigitation at the interface between a thin film of carbon nanotube and a polymer substrate.
[9] According to the present invention, provided is a method for manufacturing a flexible transparent electrode, comprising the steps of: (1) forming a thin film of carbon nanotube on a solid substrate; (2) coating a precursor capable of forming a flexible transparent substrate on the thin film of carbon nanotube; (3) curing the precursor to make a flexible transparent substrate on which the thin film of carbon nanotube is fixed; and (4) removing the solid substrate.
[10] The solid substrate used in the method of the present invention, may be selected from the group consisting of a filter membrane, a metal substrate, an opaque inorganic substrate, a transparent inorganic substrate and a polymer substrate. In particular, among these, the filter membrane can be made of materials selected from the group consisting of aluminum oxide, polycarbonate, polyethylene terephthalate, cellulose esters such as cellulose nitrate or cellulose acetate, nylon, polypropylene and polyethersulphone, and the pore of the filter membrane suitably has a diameter of 0.01-10 D.
[11] The carbon nanotube in the method of the present invention may be at least one selected from the group consisting of single- walled carbon nanotube, double- walled carbon nanotube, multi-walled carbon nanotube, carbon nanofiber and graphite. The carbon nanotube is not specifically limited by its manufacturing method, as long as it does not obstruct the purpose of the present invention, and may be selected from those manufactured by for example, chemical vapor deposition, arc discharge or laser ablation. Commercially available carbon nanotubes can be also used in the method of the present invention. The thin film of carbon nanotube is preferably formed to have a thickness of 1-100 nm. When the thickness is less than lnm, it is not sufficient to obtain desired conductivity, and when it is more than lOOnm, the light transmittance of the electrode is likely to be decreased. Additionally, the carbon nanotube also may be a carbon nanotube modified with nanoparticles of metal such as gold, silver, copper or the like, in order to improve the conductivity.
[12] The precursor capable of forming a flexible transparent substrate in the method of the present invention, is a precursor of a transparent and flexible polymeric materials such as polydimethylsiloxane (PDMS), polyepoxide, polyacrylate, polyimide, polyester, polycarbonate, cellulose acetate, polystyrene, polyolefin, polymethacrylate, polysulphone, polyethersulphone, polyvinyl acetate or the like, or a precursor being capable of forming a flexible glass material such as an ultra thin glass. The precursor is preferably a monomer capable of forming thermosetting, photocurable, or thermoplastic polymers such as PDMS, poly epoxide, polyacrylate, polyimide, polyester, polycarbonate, cellulose acetate, polystyrene, polyolefin, polymethacrylate, polysulphone, polyethersulphone or polyvinyl acetate.
[13] The formation of the thin film of carbon nanotube on the solid substrate in the step
(1) in the method of the present invention, may be conducted by using a method selected from the group consisting of vacuum filtration, self-assembly, Langmuir- Blodgett deposition, solution casting, bar coating, dip coating, spin coating, spray coating and roll-to-roll methods.
[14] The coating of the precursor capable of a flexible transparent substrate on the thin film of carbon nanotube in the step (2) in the method of the present invention, may be conducted by using a method selected from the group consisting of bar coating, dip coating, spin coating, spray coating and roll-to-roll methods.
[15] The curing of the precursor in the step (3) in the method of the present invention, may be conducted by, for example, cooling, a curing agent, heating, UV irradiation or solvent evaporation.
[16] The removal of the solid substrate in the step (4) in the present invention may be carried out by mechanical peeling or dissolving the solid substrate with a suitable solvent.
[17] According to one preferred embodiment of the present invention as shown in Fig. 1, the manufacture of the flexible transparent electrode is conducted as follows, provided that an aluminum oxide filter membrane is used as the solid substrate in the step (1) and monomer of PDMS is used as the precursor of a flexible transparent substrate.
[18] Firstly, carbon nanotube is added to an aqueous solution in which one or more surfactants such as Triton X-100, a sodium salt of dodecylbenzenesulphonic acid(Na-DDBS), cetyl trimethyl ammonium bromide(CTAB) or sodium dodecyl sulfate(SDS) or the like is dissolved, and to the resulting solution, ultrasonication is applied to prepare an aqueous suspension containing 0.001-0. lwt% of carbon nanotube which maintains the stable dispersion state. Alternatively, organic solvents such as N- methylpyrrolidone (NMP), o-dichlorobenzene, dichloroethane, dimethylformamide (DMF), chloroform or the like, may be used for the same method to prepare an organic solution of carbon nanotube dispersed therein stably without being flocculated.
[19] The resulting aqueous solution or organic solution of carbon nanotube dispersed therein as obtained from the above method, is subjected to a vacuum filtration using a vacuum filtering device equipped with an aluminum oxide filter membrane(l) as a solid substrate, and then, a thin film(2) of carbon nanotube is uniformly formed on the filter membrane(l). The thickness of the thin film(2) being formed is readily adjustable by controlling the amount of a suspension of carbon nanotube being filtered. On the while, when the filtration is carried out through an aluminum oxide filter membrane(l) on which a patterned object(for example, a TEM grid) is placed, the flow of the suspension may be blocked partially by the patterned object, and as a result, a patterned thin film of carbon nanotube can be obtained on the filter membrane.
[20] After completing the filtration, if it is the case that an aqueous suspension of carbon nanotube has been used, the thin film(2) formed on the filter membrane(l) is additionally washed with a sufficient amount of water to remove the residual surfactants on the thin film(2) of carbon nanotube. After the filtration, the membrane having a thin film of carbon nanotube formed thereon is dried in a dry oven and the like.
[21] Next, for transferring the thin film(2) of carbon nanotube to a flexible transparent
PDMS substrate, the upper part of the thin film of carbon nanotube formed on the dried membrane is coated with thermally curable monomers(3) of PDMS by bar coating, and then the resultant is cured in an oven, wherein the PDMS substrate may be manufactured by any conventionally known method(for example, a method disclosed in Langmuir 1994, 10, 1498.).
[22] After completing the curing of PDMS, followed by removing the aluminum oxide filter membrane(l) in an aqueous NaOH solution, a transparent electrode in which the thin film(2) of carbon nanotube is formed on the flexible transparent PDMS substrate(3), can be obtained.
[23] In the meantime, according to another embodiment of the present invention, the method of the present invention may further comprises, between the step (1) and the step (2), a step of growing a thin layer of a conducting polymer such as polyacetylene, polypyrrole, polyaniline, polythiophene or the like on the upper part of the thin film of carbon nanotube formed on a solid substrate, by using an electrochemical method. In this embodiment, the thin film of carbon nanotube which has the thin layer of conducting polymer grown on upper part thereof as described above, is fixed to the flexible transparent substrate in later step.
[24] According to the present invention, in order to improve the electrical properties of the conventional transparent electrode using carbon nanotube, provided is a transparent electrode in which a thin film of carbon nanotube is fixed to a flexible transparent substrate, manufactured by firstly forming the thin film of carbon nanotube on a solid substrate, coating the upper part of the thin film of carbon nanotube with a precursor capable of forming a flexible transparent substrate and curing it, and then peeling the solid substrate or dissolving the solid substrate with an adequate solvent. In the present invention as such, since carbon nanotubes are present in the form of a film only on the surface of the transparent polymer substrate, it is possible to manufacture a transparent electrode having effective conductivity by using only very small amount of carbon nanotube. Moreover, as the precursor of the flexible transparent substrate is coated and cured in the state that the solid substrate supports the thin film of carbon nanotube, the present invention has an advantage that the adhesion stability of the thin film of carbon nanotube is significantly improved by interdigitation at the interface between the carbon nanotube and the flexible transparent substrate. Therefore, according to the present invention, it is possible to minimize the amount of carbon nanotube used in manufacture of a transparent carbon nanotube electrode and to prevent decrease in conductivity which occurs when carbon nanotubes are dispersed inside a polymer, thereby achieving good conductivity, even though additional coating with a conducting polymer is not carried out. Advantageous Effects
[25] The major difference between the method of the present invention and conventional techniques is as described below. A conventional method, in which a suspension of carbon nanotube is sprayed onto the a polymer substrate, has limitations such that it is impossible to manufacture an electrode substrate with large area owing to very poor adhesion stability and uniformity of the thin film. In the meantime, in the method of the present invention, the adhesion stability of the thin film to a substrate can be dramatically increased by firstly preparing a uniform thin film of carbon nanotube on the substrate through vacuum filtration or the Langmuir-Blodgett method, and then forming, for example, a transparent polymer substrate on the upper part of the thin film of carbon nanotube by curing. Furthermore, according to the present invention, since carbon nanotubes are present only on the surface of a transparent electrode, it is possible to manufacture a flexible transparent electrode having excellent conductivity with very small amount of carbon nanotube as much as about 1 D/cm Brief Description of the Drawings
[26] Fig. 1 is a schematic view showing a method for manufacturing a transparent electrode according to one embodiment of the present invention.
[27] Fig. 2 is a photograph showing that the transparency of the transparent electrode can be easily adjusted by controlling the amount of a suspension of carbon nanotube.
[28] Fig. 3 is a photograph showing the flexibility of the transparent electrode obtained from Example 1 of the present invention.
[29] Fig. 4 is a photograph showing the patterns of carbon nanotube on the transparent electrode obtained from Example 4 of the present invention.
[30] [Numbers used in the drawings]
[31] 1 : solid substrate
[32] 2: thin film of carbon nanotube
[33] 3: precursor being capable of forming a flexible transparent substrate
Mode for the Invention [34] Hereinafter, the present invention is described in more detail through examples according to the present invention with referring to the drawings attached to this specification. However, it should be understood that those examples are presented only for illustrative purposes without restricting the scope of the present invention.
[35] EXAMPLES
[36] [Example 1]
[37] A 0.00 lwt% aqueous suspension of carbon nanotube in stable dispersion state was prepared by adding 10 mg of single- walled carbon nanotube (manufactured by Iljin Nanotech) to a IL aqueous solution in which Ig of Triton X-100 was dissolved as a surfactant, and sonicating at 60Hz.
[38] 1 ml of the aqueous suspension of carbon nanotube as obtained from the above was filtered through a vacuum filtration device equipped with an aluminum oxide filter membrane to form a uniform thin film of carbon nanotube on the filter membrane. The thin film of carbon nanotube was then washed with sufficient amount of water, and the membrane having the thin film of carbon nanotube formed thereon was dried in an oven.
[39] Next, according to a method disclosed in Langmuir 1994, 10, 1498, monomers of
PDMS were applied to the upper part of the thin film of carbon nanotube formed on the dried membrane by using a bar coating method, and then the coated membrane was cured in an oven at 65°C.
[40] After curing PDMS, the aluminum oxide filter membrane was removed in 3M of an aqueous NaOH solution, and accordingly a transparent electrode in which the thin film of carbon nanotube is formed on the flexible transparent PDMS substrate was obtained. In the resulting thin film of carbon nanotube on the transparent electrode, the amount of carbon nanotube per unit area was 1 D/cm
[41] The transparent electrode manufactured as above showed about 90% of transmittance measured by a UV- visible spectrometer. The sheet resistance of the transparent electrode measured by a four point probe was less than lOOΩ/sq.
[42] In the meantime, for investigating the transparency of a transparent electrode upon changes in the thickness of the thin film of carbon nanotube, transparent electrodes were manufactured with 0.5, 1.0, 1.5, 2.0 and 2.5ml of aqueous suspensions of carbon nanotube respectively, by using the same method as above, and the results were represented by Fig. 2, in which the resulting transparent electrodes are arranged in order from the left to the right. From Fig. 2, it can be recognized that the thickness of the thin film of carbon nanotube is adjustable by controlling the amount of a suspension of carbon nanotube, and accordingly the transparency of the resulting electrode can be also conveniently adjusted.
[43] On the other hand, a photograph showing the flexibility of the transparent electrode obtained from the present example was represented in Fig. 3. From Fig. 3, it can be known that the transparent electrode obtained from the present example exhibited excellent flexibility.
[44] As described so far, it can be known that the transparent electrode manufactured by the present example is excellent in transparency, conductivity, flexibility, and adhesion stability of the thin film of carbon nanotube.
[45] [Example 2]
[46] A transparent electrode, in which the thin film of carbon nanotube was formed, was manufactured by using the same method as in Example 1, except that the thin film of carbon nanotube was formed by the Langmuir-Blodgett method, which comprises preparing a chloroform suspension containing 0.00 lwt% of carbon nanotube dispersed therein, spreading the solution on the water surface of a Langmuir-Blodgett trough, evaporating the solvent, gradually compressing the carbon nanotube film by pushing two movable barriers to obtain a Langmuir film of carbon nanotube, and transferring the Langmuir film to a silicone or glass substrate to obtain the thin film of carbon nanotube. In the resulting transparent electrode, the thin film of carbon nanotube was about 30 nm in thickness.
[47] The transparency, conductivity and flexibility of the resulting electrode were determined by the same method as in Example 1. As a result, the transparency measured with a UV- visible spectrometer was about 95%, the sheet resistance was less than 200Ω/sq, and the flexibility was in the similar level with the electrode of Example 1.
[48] [Example 3]
[49] A transparent electrode, in which the thin film of carbon nanotube was formed, was manufactured by using the same method as in Example 1, except that monomers of polyacrylate were coated to the upper part of the thin film of carbon nanotube formed on the membrane by spin coating, and cured by UV light. In the resulting transparent electrode, the amount of carbon nanotube per unit area of the thin film was about 1 D/cm
[50] The transparency, conductivity and flexibility of the resulting electrode were determined by the same method as in Example 1. As a result, it was found that the transparency, conductivity and flexibility were in the similar level with the electrode of Example 1.
[51] [Example 4]
[52] A transparent electrode, in which the thin film of carbon nanotube was formed, was manufactured by using the same method as in Example 1, except that polymethacrylate dissolved in chloroform was coated to the upper part of the thin film of carbon nanotube formed on the membrane by spin coating, and cured by solvent evaporation. In the resulting transparent electrode, the amount of carbon nanotube per unit area of the thin film was about 1 D/cm
[53] The transparency, conductivity and flexibility of the resulting electrode were determined by the same method as in Example 1. As a result, it was found that the transparency, conductivity and flexibility were in the similar level with the electrode of Example 1.
[54] [Example 5]
[55] A transparent electrode, in which the thin film of carbon nanotube was formed, was manufactured by using the same method as in Example 1, except that the filtration of a suspension of carbon nanotube was carried out through the aluminum oxide filter membrane on which a patterned 300 mesh TEM grid was placed, for obtaining a patterned thin film of carbon nanotube on the filter membrane.
[56] The photograph of the patterned transparent electrode thus obtained was shown in
Fig. 4.
[57] [Example 6]
[58] A transparent electrode, in which the thin film of carbon nanotube was formed, was manufactured by using the same method as in Example 1, except that a conducting polymer film of polyaniline was additionally grown, according to an electrochemical method disclosed in Diamond and Related Materials, 2004, 13, 256, on the upper part of the thin film of carbon nanotube formed on the filter membrane, and then dried.
[59] The transparency, conductivity and flexibility of the resulting electrode were determined by the same method as in Example 1. As a result, the transparency measured with a UV- visible spectrometer was about 85%, the sheet resistance was less than 50 Ω/sq, and the flexibility was in the similar level with the electrode of Example 1. According to the present example, it is learned that, in case of the thin film of carbon nanotube additionally coated with conducting polyaniline, the conductivity can be improved without large decrease in transmittance.
[60] [Example 7]
[61] A transparent electrode, in which the thin film of carbon nanotube was formed, was manufactured by using the same method as in Example 3 except that a conducting polymer film of polyaniline was additionally grown, according to an electrochemical method disclosed in Diamond and Related Materials, 2004, 13, 256, on the upper part of the thin film of carbon nanotube formed by the Langmuir-Blodgett method, and dried.
[62] The transparency, conductivity and flexibility of the resulting electrode were determined by the same method as in Example 1. As a result, the transparency measured with a UV- visible spectrometer was about 85%, the sheet resistance was less than 50 Ω/sq, and the flexibility was in the similar level with the electrode of Example 1. According to the present example, it is learned that, in case of the thin film of carbon nanotube additionally coated with conducting polyaniline, the conductivity can be improved without large decrease in transmittance.
[63] [Example 8]
[64] Carbon nanotubes were modified with gold nanoparticles by using a method disclosed in Langmuir 2000, 18, 3569. The shape of the carbon nanotubes and the distribution of the nanoparticles were observed by Atomic Force Microscope (AFM). By using the gold nanoparticle-modified carbon nanotubes, a transparent electrode, in which the thin film of carbon nanotube modified with metal particles was formed, was manufactured by using the same method as in Example 1.
[65] The transparency, conductivity and flexibility of the resulting electrode were determined by the same method as in Example 1. As a result, it was found that the transparency, conductivity and flexibility were in the similar level with the electrode of Example 1.
[66] [Example 9]
[67] Carbon nanotubes were modified with gold nanoparticles by using a method disclosed in Langmuir 2000, 18, 3569. The shape of the carbon nanotubes and the distribution of the nanoparticles were observed by AFM. By using the gold nanoparticle- modified carbon nanotubes, a transparent electrode, in which the thin film of carbon nanotube modified with metal particles was formed, was manufactured by using the same method as in Example 2.
[68] The transparency, conductivity and flexibility of the resulting electrode were determined by the same method as in Example 1. As a result, it was found that the transparency, conductivity and flexibility were in the similar level with the electrode of Example 2. Industrial Applicability
[69] As seen from above, the present invention can provide a flexible transparent electrode with large area and excellent optical characteristics. The flexible transparent electrode according to the present invention can be advantageously used in various applications, for example, displays such as LCD, PDP, OELD, FED and the like; electronic devices such as electrostatic recording substrate, photodiode, register, thin film composite circuit and the like; sensors such as photo-sensor, IR-sensor, pressure- sensor, biochemical-sensor and the like; memory devices such as FRAM, thermoplastic recording and the like; and others including antistatic devices, electromagnetic shielding devices, battery electrodes and the like.

Claims

Claims
[1] A method for manufacturing a flexible transparent electrode, comprising the steps of: (1) forming a thin film of carbon nanotube on a solid substrate; (2) coating a precursor capable of forming a flexible transparent substrate on the thin film of carbon nanotube; (3) curing the precursor to make a flexible transparent substrate on which the thin film of carbon nanotube is fixed; and (4) removing the solid substrate.
[2] The method according to claim 1, wherein the solid substrate is selected from the group consisting of a filter membrane, a metal substrate, an opaque inorganic substrate, a transparent inorganic substrate and a polymer substrate.
[3] The method according to claim 2, wherein the filter membrane is made of materials selected from the group consisting of aluminum oxide, polycarbonate, polyethylene terephthalate, cellulose esters, nylon, polypropylene and polyethersulphone, and the pore of the filter membrane has a diameter of 0.01-10 D.
[4] The method according to claim 1, wherein the carbon nanotube is at least one selected from the group consisting of single- walled carbon nanotube, double- walled carbon nanotube, multi-walled carbon nanotube, carbon nanofiber and graphite.
[5] The method according to claim 1, wherein the carbon nanotube is a carbon nanotube modified with nanoparticles of metal of gold, silver or copper.
[6] The method according to claim 1, wherein the precursor capable of forming a flexible transparent substrate is a monomer capable of forming poly- dimethylsiloxane, polyepoxide, polyacrylate, polyimide, polyester, polycarbonate, cellulose acetate, polystyrene, polyolefin, polymethacrylate, polysulphone, polyethersulphone or polyvinyl acetate.
[7] The method according to claim 1, wherein the formation of the thin film of carbon nanotube on the solid substrate in the step (1), is conducted by using a method selected from the group consisting of vacuum filtration, self-assembly, Langmuir-Blodgett deposition, solution casting, bar coating, dip coating, spin coating, spray coating and roll-to-roll methods.
[8] The method according to claim 1, wherein the formation of the thin film of carbon nanotube on the solid substrate in the step (1), is conducted by using an aqueous suspension which contains Triton X-100, a sodium salt of dodecylben- zenesulphonic acid, cetyl trimethyl ammonium bromide or sodium dodecyl sulfate as a surfactant, and contains 0.001-0. lwt% of carbon nanotube dispersed therein.
[9] The method according to claim 1, wherein the formation of the thin film of carbon nanotube on the solid substrate in the step (1), is conducted by using an organic suspension which contains N-methylpyrrolidone, o-dichlorobenzene, dichloroethane, dimethylformamide or chloroform as a solvent, and contains 0.001-0.1wt% of carbon nanotube dispersed therein.
[10] The method according to claim 1, wherein the coating of the precursor capable of forming a flexible transparent substrate on the thin film of carbon nanotube in the step (2), is conducted by using a method selected from the group consisting of bar coating, dip coating, spin coating, spray coating and roll-to-roll methods.
[11] The method according to claim 1, wherein the curing of the precursor in the step
(3) is conducted by cooling, a curing agent, heating, UV irradiation or solvent evaporation.
[12] The method according to claim 1, wherein the removal of the solid substrate in the step (4) is carried out by mechanical peeling or dissolving the solid substrate with a solvent.
[13] A flexible transparent electrode which is manufactured by the method according to any one of claims 1 to 12, for displays, electronic devices, sensors or memory devices.
PCT/KR2005/002134 2005-07-05 2005-07-05 Method for manufacturing transparent electrode and transparent electrode man¬ ufactured thereby WO2007004758A1 (en)

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CN105741918A (en) * 2016-04-29 2016-07-06 苏州巨邦新材料科技有限公司 Nano copper based conductive composite material and fabrication process thereof
CN107525832B (en) * 2017-08-29 2019-06-28 浙江理工大学 A kind of preparation method of the flexible fiber sensor electrode of silver nanowires modification
CN107525832A (en) * 2017-08-29 2017-12-29 浙江理工大学 A kind of preparation method of the flexible fiber sensor electrode of nano silver wire modification
CN109768164A (en) * 2018-12-18 2019-05-17 杭州电子科技大学 A kind of preparation method of flexible optical detector
CN109799012A (en) * 2019-01-23 2019-05-24 河南工程学院 A kind of class sandwich structure pressure sensor and preparation method thereof based on cellulose
CN109799012B (en) * 2019-01-23 2021-01-22 河南工程学院 Cellulose-based sandwich-like structure pressure sensor and preparation method thereof
CN110568050A (en) * 2019-06-27 2019-12-13 吉林化工学院 Preparation method of enzyme-free catalytic hydrogen peroxide electrochemical sensor based on flexible electrode
CN110568050B (en) * 2019-06-27 2023-06-20 吉林化工学院 Preparation method of enzyme-free catalytic hydrogen peroxide electrochemical sensor based on flexible electrode

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