WO2015142077A1 - Conducteur transparent, son procédé de fabrication, et dispositif d'affichage optique comprenant ledit conducteur - Google Patents
Conducteur transparent, son procédé de fabrication, et dispositif d'affichage optique comprenant ledit conducteur Download PDFInfo
- Publication number
- WO2015142077A1 WO2015142077A1 PCT/KR2015/002678 KR2015002678W WO2015142077A1 WO 2015142077 A1 WO2015142077 A1 WO 2015142077A1 KR 2015002678 W KR2015002678 W KR 2015002678W WO 2015142077 A1 WO2015142077 A1 WO 2015142077A1
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- WO
- WIPO (PCT)
- Prior art keywords
- metal
- transparent conductor
- transparent
- layer
- nanowire dispersion
- Prior art date
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Classifications
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- H—ELECTRICITY
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- 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
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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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
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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
- H01L31/18—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
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- H—ELECTRICITY
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- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
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- H02S20/10—Supporting structures directly fixed to the ground
-
- 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
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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
Definitions
- the present invention relates to a transparent conductor, a method of manufacturing the same, and an optical display device including the same.
- the transparent conductor may be used in devices such as touch panels, display devices, e-papers, and solar cells.
- the devices include an X channel and a Y channel formed of transparent conductors.
- the X and Y channels must have uniform line resistance.
- the transparent conductor including the metal nanowires may be manufactured by a roll-to-roll method by wet thin coating of the metal nanowire dispersion liquid containing the metal nanowires on the substrate layer.
- a line resistance deviation may occur between a direction in which the metal nanowires are coated (MD, machine direction) and a direction perpendicular to the MD (TD).
- MD machine direction
- TD direction perpendicular to the MD
- the metal nanowire solution can be diluted or crude for roll-to-roll coating.
- an anti-bubble agent or an organic solvent may be blended to remove bubbles.
- an antifoaming agent or an organic solvent has a limit in improving the channel line resistance uniformity.
- the technical problem to be solved by the present invention is to provide a transparent conductor with improved channel resistance uniformity.
- Another technical problem to be solved by the present invention is to provide a transparent conductor having a low sheet resistance by lowering contact resistance between metal nanowires.
- Another technical problem to be solved by the present invention is to provide an optical display device including the transparent conductor.
- the transparent conductor of the present invention may include a base layer and a transparent conductive layer formed on the base layer, and the transparent conductive layer may include metal nanowires and metal particles.
- a metal nanowire dispersion liquid containing a metal nanowire, a viscosity modifier and a metal particle forming agent is coated on a base layer to form a metal nanowire dispersion layer, and the metal nanowire dispersion layer It may comprise the step of curing.
- the optical display device of the present invention may include the transparent conductor.
- the present invention provides a transparent conductor with improved channel resistance uniformity.
- the present invention provides a transparent conductor having low sheet resistance by lowering contact resistance between metal nanowires.
- the present invention provides an optical display device including the transparent conductor.
- FIG. 1 is a cross-sectional view of a transparent conductor according to an embodiment of the present invention.
- FIG. 2 is an enlarged view of a cross section of the transparent conductive layer of FIG. 1.
- FIG 3 is a cross-sectional view of a transparent conductor according to another embodiment of the present invention.
- FIG. 4 is a cross-sectional view of a transparent conductor according to still another embodiment of the present invention.
- FIG. 5 is a cross-sectional view of a transparent conductor according to still another embodiment of the present invention.
- FIG. 6 is a cross-sectional view of an optical display device according to an exemplary embodiment of the present invention.
- FIG. 7 is a cross-sectional view of an optical display device according to another exemplary embodiment of the present invention.
- FIG. 8 is a cross-sectional view of an optical display device according to still another embodiment of the present invention.
- FIG. 9 is a cross-sectional view of an optical display device according to still another embodiment of the present invention.
- FIG. 10 is a cross-sectional view of an optical display device according to still another embodiment of the present invention.
- 11 is a conceptual diagram of measurement of channel line resistance uniformity.
- spect ratio means the ratio (L / d) of the longest length L of the metal nanowire to the shortest diameter d of the cross section of the metal nanowire.
- channel wire resistance uniformity value refers to a value calculated by the following Equation 1 for the transparent conductor:
- R MD ' is the resistance (unit: kPa) of the rectangular first specimen 10 whose long side is the first direction among the transparent conductors, and R TD' is the second side of the transparent conductor in the second direction) Is the resistance of the second specimen 20 of rectangular shape, wherein the first direction and the second direction are orthogonal and R TD ' ? R MD' .
- the coating direction of the metal nanowire dispersion is MD (machine direction)
- TD transverse direction
- the second direction may or may not coincide.
- 11 illustrates a case where the MD and the first direction coincide with each other and the TD and the second direction coincide with each other.
- (meth) acryl refers to acrylic and / or methacryl.
- FIGS. 1 and 2 are cross-sectional views of a transparent conductor according to an embodiment of the present invention
- Figure 2 is an enlarged view of the cross section of the transparent conductive layer of the transparent conductor of FIG.
- the transparent conductor 100 may include a base layer 110 and a transparent conductive layer 120.
- the base layer 110 supports the transparent conductive layer 120 and may include a resin film having transparency.
- the substrate layer 110 may include a resin film having a transmittance of about 85% to about 100%, more specifically about 88% to about 99% at a wavelength of 550 nm. In this range, the optical properties of the transparent conductor can be improved.
- the base layer 110 is a polyester, polyolefin, polysulfone, polyimide, silicone, polystyrene, polyacryl, poly, including polycarbonate, cyclic olefin polymer, polyethylene terephthalate, polyethylene naphthalate, and the like. It may be a film formed of one or more of the vinyl chloride resins, but is not limited thereto.
- FIG. 1 illustrates a transparent conductor in which a base layer 110 includes a film formed of the resin as a single layer.
- transparent conductors in which the base layer is a multilayer film in which two or more films formed of the resin are bonded by an adhesive or the like may also be included in the scope of the present invention.
- the base layer 110 may have a thickness of about 10 ⁇ m to about 200 ⁇ m, specifically about 50 ⁇ m to about 150 ⁇ m. In the above range, the base layer can be used for the transparent conductor.
- a functional layer may be further stacked on one or both surfaces of the substrate layer 110.
- the functional layer may be a hard coating layer, an anticorrosion layer, an anti-glare coating layer, an adhesion promoting layer, an oligomer elution prevention layer, or the like, but is not limited thereto.
- the transparent conductive layer 120 may be formed on the base layer 110 to provide conductivity to the transparent conductor 100.
- FIG. 1 illustrates a transparent conductor in which the transparent conductive layer 120 is formed only on one surface of the base layer 110.
- a transparent conductor formed on both sides of the base layer 110 by the transparent conductive layer 120 may also be included in the scope of the present invention.
- the transparent conductive layer 120 may include metal nanowires 121 and metal particles 122. Referring to FIG. 2, the transparent conductive layer 120 will be described in more detail.
- the transparent conductive layer 120 may include metal nanowires 121 and metal particles 122.
- the metal nanowires 121 may provide conductivity to the transparent conductive layer 120 by forming a conductive network. Since the metal nanowires 121 have a nanowire shape, the metal nanowires 121 may provide flexibility and flexibility to the transparent conductive layer 120.
- the metal nanowires 121 may have an aspect ratio of about 10 to about 5,000. Within the above aspect ratio range, a high conductive network may be realized even at a low metal nanowire density, and the sheet resistance of the transparent conductor may be lowered. Specifically, the metal nanowires 121 may have an aspect ratio of about 500 to about 1,000, and more specifically about 500 to about 700. The metal nanowires 121 may have a diameter of more than about 0 nm and about 100 nm or less, specifically about 10 nm to about 100 nm, and more specifically about 10 nm to about 30 nm. In the above range, it is possible to have a high aspect ratio to increase the conductivity of the transparent conductor and lower the sheet resistance.
- the metal nanowire 121 may have a longest length of about 20 ⁇ m or more, specifically about 20 ⁇ m to about 50 ⁇ m. In the above range, it is possible to have a high aspect ratio to increase the conductivity of the transparent conductor and lower the sheet resistance.
- the metal nanowires 121 may be included in about 40 wt% or more, specifically about 50 wt% to about 90 wt% of the transparent conductive layer 120. In the above range, the transparent conductor may have high conductivity by sufficiently forming a conductive network.
- the metal nanowires 121 may be formed of a metal including at least one of silver, copper, aluminum, nickel, and gold. Specifically, the metal nanowires 121 may be formed of silver nanowires or a mixture including the same.
- the metal particles 122 may significantly lower the contact resistance between the metal nanowires.
- the metal particles 122 may increase the uniformity of the channel wire resistance of the transparent conductor and increase the reliability of the transparent conductor 100 by lowering the orientation of the metal nanowires, compared to the case where the metal nanowires are coated alone.
- the "orientation” means the tendency of the metal nanowires to be oriented such that the longitudinal direction of the metal nanowires coincides with a predetermined direction.
- the MD machine direction
- the TD transverse direction
- the metal particles 122 Since the metal particles 122 have the same or significantly smaller particle diameters than the metal nanowires 121, the contact resistance of the conductive network formed of the metal nanowires 121 may be lowered. Therefore, the metal particles 122 may lower the contact resistance of the transparent conductor 100. Specifically, the ratio of the average particle diameter of the metal particles 122 to the diameter of the metal nanowires 121 may be about 1: 4 to about 1: 100. Within this range, the contact resistance of the transparent conductor can be reduced. Specifically, the ratio of the average particle diameter of the metal particles 122 to the diameter of the metal nanowires 121 may be about 1:20 to about 1:50.
- the metal particles 122 may have an average particle diameter of about 1 nm to about 5 nm. In the above range, the conductive network of the transparent conductive layer can be made high density to reduce the contact resistance, and the transparency of the transparent conductive layer can be increased.
- the metal particles 122 may include metal particles formed of the same or different types of metals from the metal nanowires 121. Specifically, the metal particles 122 may be formed of the same metal as the metal nanowires 121 to further lower the contact resistance of the metal nanowires 121. In detail, the metal particles 122 may be formed of a metal including at least one of silver, copper, aluminum, nickel, and gold.
- the metal particles 122 may include particles formed in the reduction of metal cations.
- the transparent conductive layer 120 may be formed of a metal nanowire dispersion including metal nanowires, a viscosity modifier, and a metal particle former, as described below.
- Metal particle formers include metal cations.
- Metal particle formers may produce metal cations.
- the transparent conductive layer is formed, the metal cations may be reduced by curing or the like to form metal particles.
- the transparent conductive layer 120 may include metal cations, specifically metal cations formed from metal particle formers.
- FIG. 1 illustrates a transparent conductor in which metal particles 122 are regularly included in the transparent conductive layer 120.
- a transparent conductor in which metal particles are irregularly included in the transparent conductive layer may also be included in the scope of the present invention.
- the transparent conductive layer 120 may further include one or more of a viscosity regulator and a material generated from the viscosity regulator.
- the resulting material from the viscosity modifier and the viscosity modifier can stabilize the conductive network of the metal nanowires to lower the sheet resistance.
- the viscosity modifier may include poly (styrenesulfonic acid).
- the material resulting from the viscosity modifier may comprise poly (styrenesulfonate) ions (PSS ⁇ ).
- Poly (styrenesulfonate) ions (PSS ⁇ ) are produced by neutralizing poly (styrenesulfonic acid) with a base or metal particle former upon formation of a transparent conductive layer.
- the transparent conductive layer 120 may have a thickness of about 10 nm to about 1 ⁇ m, specifically about 20 nm to about 500 nm, and more specifically about 30 nm to about 150 nm. In the above range, it can be used as a transparent conductor.
- the transparent conductor 100 is optically transparent and can be used in an optical display device.
- the transparent conductor 100 may have a haze of about 1.5% or less, specifically about 0.01% to about 1.15% at a wavelength of about 400 nm to about 700 nm.
- the transparent conductor 100 may have a light transmittance of about 85% to about 100%, specifically about 88% to about 95% at a wavelength of about 400nm to about 700nm. In the above range, good transparency can be used as a transparent conductor.
- the transparent conductor 100 may have a thickness of about 10 ⁇ m to about 130 ⁇ m. It can be used as a transparent conductor in the above range.
- the transparent conductor 100 may have a low sheet resistance by containing the metal nanowires 121 and the metal particles 122. Specifically, the transparent conductor 100 may have a sheet resistance of about 60 k ⁇ / ⁇ or less, more specifically, about 45 k ⁇ / ⁇ to about 60 k ⁇ / ⁇ . In the above range, the sheet resistance of the transparent conductor is low, it can be used as an electrode film for a touch panel, it can be applied to a large area touch panel.
- a metal nanowire dispersion liquid including a metal nanowire, a viscosity modifier, and a metal particle forming agent is coated on a base layer to form a metal nanowire dispersion layer. Curing the metal nanowire dispersion layer.
- a metal nanowire dispersion is prepared.
- the metal nanowire dispersion may include metal nanowires, viscosity modifiers and metal particle formers.
- the metal nanowires may be added to the metal nanowire dispersion by itself, or may be added to the metal nanowire dispersion as a solution in which the metal nanowires are dispersed in the liquid.
- the solution in which the metal nanowires are dispersed may use a commercially available product such as Clearohm Ink (Cambrios), but is not limited thereto.
- the viscosity modifier By adjusting the viscosity of the metal nanowire dispersion, the viscosity modifier lowers the orientation of the metal nanowires and can increase the channel line resistance uniformity of the transparent conductor. Specifically, the viscosity modifier may cause the metal nanowire dispersion to have a viscosity of about 1 cps to about 10 cps at 25 ° C. In the above range, the coating property of the metal nanowire dispersion may be good, and the channel wire resistance uniformity of the transparent conductor may be high.
- the viscosity modifier may have a molecular weight or weight average molecular weight of about 200 g / mol to about 100,000 g / mol, specifically about 10,000 g / mol to about 100,000 g / mol, more specifically about 10,000 g / mol to about 50,000 g / mol Can be. In the above range, the viscosity can be adjusted when included in the metal nanowire dispersion, it may not increase the sheet resistance of the transparent conductor.
- the viscosity modifier may be an acid.
- the viscosity modifier may include polymeric acid, oligomeric acid, and the like. More specifically, the viscosity modifier may use at least one of poly (styrenesulfonic acid), polyethylenedioxythiophene (PEDOT) doped poly (styrenesulfonic acid) (PEDOT-PSS).
- Poly (styrenesulfonic acid) and poly (styrenesulfonic acid) in combination with polyethylenedioxythiophene may increase the reactivity of the metal nanowire dispersion and increase the conductivity of the transparent conductor.
- Viscosity modifiers may be included in an aqueous solution of about 0.1% to about 5% by weight acid. In this range, an excess viscosity modifier may be used to prevent the metal nanowires from oxidizing.
- Viscosity modifiers may be included from about 0.1% to about 3% by weight based on solids in the metal nanowire dispersion. In the above range, it is possible to lower the viscosity of the metal nanowire dispersion.
- Metal particle formers can include materials that contain or can produce metal cations.
- the metal cation is reduced by curing or the like to form metal particles, thereby lowering the contact resistance of the transparent conductor.
- the metal particle former may be Ag 2 O, AgNO 3 or a mixture thereof.
- Ag 2 O, AgNO 3 can produce Ag + ions.
- Ag 2 O may react with water in the metal nanowire dispersion to form Ag + ions and OH ⁇ ions, and OH ⁇ ions may neutralize the viscosity regulator, which is an acid.
- Ag 2 O can facilitate the manufacture of transparent conductors by preventing the metal nanowire dispersion from containing additional bases separately:
- the metal particle former may be included in an amount of about 0.1 wt% to about 5 wt% based on the solids content of the metal nanowire dispersion. In the above range, the conductivity of the transparent conductor can be improved.
- Metal nanowire dispersions can be prepared by mixing metal nanowires, viscosity modifiers and metal particle formers.
- the metal nanowire dispersion can be prepared by simultaneously adding a viscosity modifier and a metal particle former to the metal nanowires.
- the metal nanowire dispersion can be prepared by first mixing the viscosity modifier and the metal particle former, followed by sequentially mixing the metal nanowires. Sequential mixing of the metal nanowires can prevent the metal nanowires from being oxidized by the acidic viscosity regulator by reacting the viscosity modifier with the metal particle former first to modify the viscosity modifier.
- the modification of the viscosity modifier may be carried out by mixing the viscosity modifier with the metal particle forming agent and bringing the pH of the resulting mixture to about 4 to about 9 using a base.
- Bases may include, but are not limited to, one or more of sodium hydroxide (NaOH), potassium hydroxide (KOH).
- NaOH sodium hydroxide
- KOH potassium hydroxide
- the metal particle forming agent Ag 2 O may allow the pH of the mixed solution to be adjusted to about 4 to about 9 by the scheme 1 without the need to add a base.
- the viscosity modifier is poly (styrenesulfonic acid) (PSS) and the metal particle forming agent is Ag 2 O
- PSS poly (styrenesulfonic acid)
- the metal particle forming agent is Ag 2 O
- an aqueous solution containing a PSS ⁇ / Ag + salt may be mixed with the metal nanowires to prepare a metal nanowire dispersion.
- PSS - / Ag + salt may be included as about 0.1% to about 3% by weight by weight based on solid content of the metal nanowires dispersion. In the above range, the viscosity control effect and the metal particle forming effect is excellent, it is possible to prevent the oxidation of the metal nanowire.
- the metal nanowire dispersion may further include a solvent to increase the coating property of the metal nanowire dispersion.
- Solvents may include water, alcohols, organic solvents, and the like, but are not limited thereto.
- the metal nanowire dispersion may further include a binder, an initiator, an additive, and the like.
- the additives can be dispersants, thickeners and the like.
- the binder may include one or more of a (meth) acrylate-based monofunctional monomer and a (meth) acrylate-based polyfunctional monomer.
- the dispersant can increase the dispersion of the metal nanowires and the binder.
- Thickeners can increase the viscosity of the metal nanowire dispersion.
- the binder, initiator, and additives as a whole can be included from about 0.1% to about 50% by weight, specifically from about 5% to about 45% by weight solids in the metal nanowire dispersion. In the above range, the optical properties of the transparent conductor may be improved, the contact resistance may be prevented from increasing, and the durability and chemical resistance may be improved.
- the metal nanowire dispersion may be coated on the substrate layer to form a metal nanowire dispersion layer, and the metal nanowire dispersion layer may be cured to form a transparent conductive layer.
- Coating may be performed by bar coating, slot die coating, gravure coating, roll-to-roll coating, but is not limited thereto.
- the coating thickness may be about 10 nm to about 1 ⁇ m, specifically about 20 nm to about 500 nm, more specifically about 30 nm to about 150 nm.
- Curing can form a transparent conductive layer and can raise the intensity
- Curing may include one or more of thermosetting, photocuring.
- Thermal curing may be performed for about 40 ° C to about 180 ° C, about 1 minute to about 48 hours. Photocuring may be carried out with a UV dose of about 50 mJ / cm 2 to about 1,000 mJ / cm 2 .
- the metal nanowire dispersion layer may be dried prior to curing the metal nanowire dispersion layer to shorten the curing time. Drying may be performed for about 40 ° C. to about 180 ° C., for about 1 minute to about 48 hours.
- the transparent conductor 100 ′ may include a base layer 110 and a transparent conductive layer 120 ′. It is substantially the same as the transparent conductor according to the embodiment of the present invention except that the transparent conductive layer 120 ′ is included instead of the transparent conductive layer 120. Thus, hereinafter, the transparent conductive layer 120 'will be described.
- the transparent conductive layer 120 ′ may include metal nanowires 121, metal particles 122, and a matrix 123.
- the metal nanowires 121 and the metal particles 122 are impregnated in the matrix 123.
- the matrix 123 may increase the mechanical strength of the transparent conductive layer 120 ′.
- the matrix 123 may prevent the sheet resistance of the transparent conductor 100 ′ from being increased by oxidizing the metal nanowires 121 and the metal particles 122 by external moisture and / or air. It is substantially the same as the transparent conductive layer of one embodiment of the present invention, including a matrix 123, except that the metal nanowires 121 and the metal particles 122 are impregnated in the matrix 123.
- the matrix 123 may be formed on the base layer 110 to strengthen the bond between the base layer 110 and the transparent conductive layer 120 ′.
- the matrix 123 impregnates the conductive network of the metal nanowires 121 and the metal particles 122 to support the transparent conductive layer 120 ′ and to oxidize the metal nanowires 121 and the metal particles 122. It can prevent the rise of the sheet resistance of the transparent conductor.
- a portion of the metal nanowire 121 and the metal nanoparticle 122 protrude from the matrix 123 to form a conductive network with another conductor formed on the transparent conductor 100 ′. It can be done.
- Matrix 123 may be optically transparent.
- the matrix 123 may have a light transmittance of about 85% or more, specifically about 85% to about 100%, more specifically about 90% to about 95%, at a wavelength of 400 nm to 700 nm. In the above range, it is optically transparent and can be used for the transparent conductor.
- the matrix 123 may have a thickness of about 10 nm to about 1 ⁇ m, specifically about 20 nm to about 500 nm, more specifically about 30 nm to about 150 nm. In the above range, it can be used for the transparent conductor.
- the matrix 123 may be formed of a matrix composition including a binder, an initiator, and the like.
- the binder may include at least one of an ultraviolet curable resin and an ultraviolet curable monomer.
- UV-curable resins include urethane (meth) acrylates, epoxy (meth) acrylates, poly (meth) acrylates, poly (meth) acrylonitriles, polyvinyl alcohols, polyesters, polycarbonates, phenols, polystyrenes, and polyvinyl toluene It may include, but is not limited to, one or more of polyvinylxylene, polyimide, and polyamide resin.
- the ultraviolet curable monomer may include one or more functional (meth) acrylic monomers.
- UV-curable monomers include monofunctional (meth) acrylic monomers, bifunctional (meth) acrylic monomers, trifunctional (meth) acrylic monomers, tetrafunctional (meth) acrylic monomers, and 5-functional (meth) acrylic monomers. It may include one or more of a monomer, a six-functional (meth) acrylic monomer.
- the ultraviolet curable monomer is a mono (meth) acrylate having a linear or branched alkyl group of 1-20 carbon atoms, a mono (meth) acrylate having a hydroxyl group, alicyclic having 3-20 carbon atoms
- Monofunctional (meth) acrylates including mono (meth) acrylate having a group, and the like; Hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, ethyleneglycol di (meth) acrylate Bifunctional (meth) acrylates, such as neopentylglycol di (meth) acrylate and cyclodecanedimethanol di (meth) acrylate; Trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate ), Dipentaerythritol tri (meth)
- the binder may be included alone or in mixture of two or more kinds in the matrix composition.
- the binder may be included in about 50% to about 91% by weight of the composition for the solid content matrix. Within this range, the metal nanowires and metal particles can be sufficiently impregnated.
- An initiator hardens a binder and can contain a normal photoinitiator.
- the initiator may include an alpha-hydroxyketone series including 1-hydroxycyclohexylphenyl ketone and the like.
- the initiator may be included in about 1% to about 40% by weight of the composition for the solid content matrix.
- the binder can be sufficiently cured, and a residual amount of initiator can remain to prevent the matrix from inferior in transparency.
- the composition for the matrix may further include a solvent for coating.
- the solvent may be included in the remaining amount in the composition for the matrix.
- the solvent may contain organic solvents such as water and propylene glycol monomethyl ether.
- the composition for the matrix may further include an additive to improve the performance of the matrix.
- the additive may include one or more of adhesion promoters and antioxidants.
- the additive may be included in about 0.01% by weight to about 10% by weight in the composition for a solid content matrix.
- the antioxidant may prevent oxidation of the metal nanowire network of the transparent conductive layer 120 '.
- Antioxidant is one of triazole antioxidant, triazine antioxidant, phosphorus antioxidant such as phosphite, HALS (Hinder amine light stabilizer) antioxidant, phenolic antioxidant It may contain the above.
- the phosphorus antioxidant is tris (2,4-di-tert-butylphenyl) phosphite
- the phenolic antioxidant is pentaerythritol tetrakis (3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate)
- HALS-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate), bis (2, 2,6,6-tetramethyl-4-piperidinyl) sebacate (bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate), bis (2,2,6,6-tetramethyl- 5-piperidinyl) sebacate (bis (2,2,6,6-tetra
- Antioxidants may comprise from about 0.01% to about 10% by weight of the solids based matrix composition. Within this range, oxidation of the metal nanowire network can be prevented.
- An adhesion promoter may enhance adhesion of the metal nanowire 121 to the base layer 110 and at the same time increase the reliability of the transparent conductor 100 ′.
- the adhesion promoter may use one or more of a silane coupling agent and mono- or tri-functional monomers.
- the silane coupling agent may use a conventionally known silane coupling agent, and when using a silane coupling agent having an amino group or an epoxy group, adhesion and chemical resistance may be good.
- 3-glycidoxypropyltrimethoxysilane 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
- Silicon compounds having an epoxy structure such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
- Polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and (meth) acryloxypropyltrimethoxysilane
- 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane
- N- (2 amino group-containing silicon compounds such as -aminoethyl) -3-aminopropyl
- the monofunctional to trifunctional monomers may include monofunctional to trifunctional (meth) acrylate monomers having a (meth) acrylate group.
- the monofunctional to trifunctional monomers are monofunctional to trifunctional monomers of polyhydric alcohols having 3 to 20 carbon atoms, more specifically methyl (meth) acrylate, isobornyl (meth) acrylate (isobornyl (meth) acrylate), cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylolpropane di (meth) acrylate (trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanuate tri (meth) Acrylate (tris (2-hydroxyethyl) isocyanuate tri (meth) Acrylate (tris (2-
- Adhesion promoters may be included from about 0.01% to about 10% by weight of the solid matrix composition. Within this range, adhesion can be promoted while maintaining the reliability and conductivity of the transparent conductor.
- the composition for the matrix will comprise from about 50% to 91% by weight of the binder, from about 1% to about 40% by weight of the binder, from about 0.01% to about 10% by weight of the additive, based on solids in the composition for the matrix. Can be.
- the transparent conductor 100 ′ may have a channel wire resistance uniformity value of about 20% or less. In the above range, the transparent conductor can be used, and when the transparent conductor is patterned and used in the optical display device, the device can be driven well because the variation of the channel resistance (line resistance) of the X and Y channels is low. The lower the channel wire resistance uniformity value, the better the channel wire resistance uniformity. Specifically, the transparent conductor 100 ′ may have a channel wire resistance uniformity value of about 0% to about 20%.
- the transparent conductor 100 ′ is optically transparent and can be used in an optical display device.
- the transparent conductor 100 ′ may have a haze of about 1.5% or less, specifically about 0.01% to about 1.15% at a wavelength of about 400 nm to about 700 nm.
- the transparent conductor 100 ′ may have a light transmittance of about 85% to about 100%, specifically about 88% to about 95% at a wavelength of about 400 nm to about 700 nm. In the above range, good transparency can be used as a transparent conductor.
- the transparent conductor 100 ′ may have a thickness of about 10 ⁇ m to about 100 ⁇ m. It can be used as a transparent conductor in the above range.
- the transparent conductor 100 ′ may have low sheet resistance by containing the metal nanowires 121 and the metal particles 122. Specifically, the transparent conductor 100 ′ may have a sheet resistance of about 60 k ⁇ / ⁇ or less, more specifically, about 45 k ⁇ / ⁇ to about 60 k ⁇ / ⁇ . In the above range, the sheet resistance of the transparent conductor is low, it can be used as an electrode film for a touch panel, it can be applied to a large area touch panel.
- a method of manufacturing a transparent conductor by coating a metal nanowire dispersion comprising a metal nanowire, a viscosity modifier, and a metal particle forming agent on a base layer to form a metal nanowire dispersion layer. Coating the composition for the matrix on the metal nanowire dispersion layer and curing the metal nanowire dispersion layer and the composition for the matrix.
- the metal nanowire dispersion is coated on a base layer to form a metal nanowire dispersion layer.
- the composition for the matrix is coated on the metal nanowire dispersion layer, and the metal nanowire dispersion layer and the composition for the matrix are simultaneously cured to form a transparent conductive layer.
- the coating impregnates the metal nanowires in the composition for the matrix. Coating may be performed by bar coating, slot die coating, gravure coating, roll-to-roll coating, but is not limited thereto.
- the coating thickness may be about 10 nm to about 1 ⁇ m, specifically about 20 nm to about 500 nm, more specifically about 30 nm to about 150 nm. Curing can form a transparent conductive layer and can raise the intensity
- Curing can cure the dispersion layer of the metal nanowires and the composition for the matrix.
- Curing may include one or more of thermosetting, photocuring. Thermal curing may be performed for about 40 ° C to about 180 ° C, about 1 minute to about 48 hours. Photocuring may be carried out with a UV radiation of about 50 mJ / cm 2 to about 1000 mJ / cm 2 .
- the metal nanowire dispersion layer may be dried. Drying may be performed for about 40 ° C. to about 180 ° C., for about 1 minute to about 48 hours.
- FIG. 4 is a cross-sectional view of a transparent conductor according to still another embodiment of the present invention.
- the transparent conductor 100 ′′ may include a base layer 110 and a transparent conductive layer 120 ′′. It is substantially the same as a transparent conductor according to another embodiment of the present invention except that a transparent conductive layer 120 "is formed instead of the transparent conductive layer 120 '.
- a transparent conductive layer 120 will be described.
- the transparent conductive layer 120 ′′ may include the metal nanowires 121, the metal particles 122, and the matrix 123.
- the metal nanowires 121 and the metal particles 122 may be completely in the matrix 123. It is impregnated and formed only in a part of the matrix 123.
- the transparent conductive layer 120 "further includes a matrix on the conductive network formed of the metal nanowires 121 and the metal particles 122 in the thickness direction. Formed. Accordingly, the matrix 123 may prevent the sheet resistance of the transparent conductor from being increased by completely suppressing oxidation of the metal nanowire 121 and the metal particles 122 by moisture and / or air.
- metal nanowires 121 and the metal particles 122 are completely impregnated in the matrix 123 and there are no exposed metal nanowires 121 and the metal particles 122. It is substantially the same as the transparent conductor according to the example.
- FIG. 5 is a cross-sectional view of a transparent conductor according to still another embodiment of the present invention.
- the transparent conductor 100 ′′ ′ may include a base layer 110 and a transparent conductive layer 120 ′′ ′. It is substantially the same as a transparent conductor according to another embodiment of the present invention except that it includes a transparent conductive layer 120 "'instead of the transparent conductive layer 120'. Hereinafter, the transparent conductive layer 120 will be described. "') Only.
- the transparent conductive layer 120 "' may include the conductive layer 120a and the non-conductive layer 120b.
- the transparent conductive layer 120"' may be patterned by the conductive layer 120a and the non-conductive layer 120b. It is mad.
- the conductive layer 120a includes a matrix 123 and metal nanowires 121 and metal particles 122 impregnated in the matrix 123.
- Non-conductive layer 120b includes only matrix 123.
- the transparent conductive layer 120 "' may be formed by patterning the transparent conductive layer 120' according to another embodiment of the present invention. Patterning may be performed by a conventional method. Specifically, patterning Forms a transparent conductive layer 120 ', forms a photoresist layer on the transparent conductive layer 120', places a patterned mask on the photoresist layer, UV exposure, develops, Baking and etching.
- FIG. 6 is a cross-sectional view of an optical display device according to an exemplary embodiment of the present invention.
- an optical display device 200 may include a display unit 210, a polarizer 220, a transparent electrode body 230, a window film 240, and an adhesive layer 250. It includes, the transparent electrode body 230 may be formed of a transparent conductor according to embodiments of the present invention.
- the display unit 210 is for driving the optical display device 200 and may include an optical element including a substrate and an OLED, an LED, or an LCD element formed on the substrate.
- the display unit 210 may include a lower substrate, a thin film transistor, an organic light emitting diode, a planarization layer, a protective film, an insulating film.
- the display unit 210 may include an upper substrate, a lower substrate, a liquid crystal layer positioned between the upper substrate and the lower substrate, and a color filter formed on at least one of the upper substrate and the lower substrate.
- the polarizing plate 220 may be formed on the display unit 210 to implement polarization of internal light or prevent reflection of external light to implement a display or improve contrast ratio of the display.
- the polarizer 220 may be a polarizer alone.
- the polarizing plate 220 may include a polarizer and a protective film formed on one or both sides of the polarizer.
- the polarizing plate 220 may include a polarizer and a protective coating layer formed on one or both surfaces of the polarizer.
- the polarizer, the protective film, and the protective coating layer may use a conventional one known to those skilled in the art.
- a polarizer may be further formed below the display unit 210 to further improve the contrast ratio of the display.
- the polarizer may be formed on the display unit 210 by an adhesive layer.
- the transparent electrode body 230 may be formed on the polarizing plate 220, and may generate an electrical signal by detecting a change in capacitance generated when the transparent electrode body 230 is touched by contact or the like.
- the electrical signal may drive the display unit 210.
- the transparent electrode body 230 may include a base electrode 110, a first electrode 231 formed on one surface of the base layer 110, a second electrode 232, and a third electrode formed on the other side of the base layer 110 ( 233 and the fourth electrode 234.
- the first electrode 231 and the second electrode 232 may each be an Rx electrode
- the third electrode 233 and the fourth electrode 234 may each be a Tx electrode.
- an optical display device including a transparent electrode body in which the first electrode and the second electrode are each a Tx electrode and the third electrode and the fourth electrode are each an Rx electrode may also be included in the scope of the present invention.
- the window film 240 may be formed on the outermost side of the optical display device 200 to protect the optical display device 200.
- the window film 240 may be formed of a glass substrate or a flexible plastic substrate.
- the adhesive layer 250 is formed between the display unit 210 and the polarizing plate 220, between the polarizing plate 220 and the transparent electrode body 230, and between the transparent electrode body 230 and the window film 240.
- the bonding between the 210, the polarizing plate 220, the transparent electrode body 230, and the window film 240 may be strengthened.
- the adhesive layer 250 may be formed of a conventional optically transparent adhesive.
- the adhesive layer 250 may be formed of a composition including a (meth) acrylic copolymer, a curing agent, and a silane coupling agent, but is not limited thereto.
- the adhesive layer 250 may be omitted if the display unit 210, the polarizing plate 220, the transparent electrode body 230, and the window film 240 are self-adhesive, the adhesive layer 250 may be omitted.
- FIG. 7 is a cross-sectional view of an optical display device according to another exemplary embodiment of the present invention.
- the optical display device 300 may include a display unit 210, a polarizing plate 220, a transparent electrode body 230 ′, a window film 240 ′, and an adhesive layer ( 250, and the transparent electrode body 230 ′ may be formed of a transparent conductor according to embodiments of the present invention.
- the transparent electrode body 230 ′ includes the base layer 110 and the third electrode 233 and the fourth electrode 234 formed on one surface of the base layer 110, and the window film 240 ′ is the first electrode. It is substantially the same as the optical display device according to the exemplary embodiment of the present invention except that 231 and the second electrode 232 are further formed.
- the above-described polarizing plate may be further formed in the optical display device according to another exemplary embodiment of the present invention.
- FIG. 8 is a cross-sectional view of an optical display device according to still another embodiment of the present invention.
- an optical display device 400 may include a display unit 210, a polarizer 220, a transparent electrode body 230 ′′, a window film 240, and an adhesive layer ( 250, and the transparent electrode body 230 ′′ may be formed of a transparent conductor according to embodiments of the present invention.
- the transparent electrode body 230 ′′ will be described.
- the transparent electrode body 230 ′′ includes an adhesive layer formed between the first transparent electrode body 230a, the second transparent electrode body 230b, and the first transparent electrode body 230a and the second transparent electrode body 230b. 250).
- the first transparent electrode body 230a is formed under the window film 240, and forms the base layer 110 and the first electrode 231 and the second electrode 232 formed on one surface of the base layer 110. It may include.
- the second transparent electrode body 230b is formed on the polarizer 220, and includes a base layer 110 and a third electrode 233 and a fourth electrode 234 formed on one surface of the base layer 110. can do.
- the adhesive layer 250 may be formed between the first transparent electrode body 230a and the second transparent electrode body 230b to bond the first transparent electrode body 230a and the second transparent electrode body 230b. .
- the above-described polarizing plate may be further formed in the optical display device according to another exemplary embodiment of the present invention.
- FIG. 9 is a cross-sectional view of an optical display device according to still another embodiment of the present invention.
- the optical display device 500 may include a display unit 210, a transparent electrode body 230, a polarizer 220, a window film 240, and an adhesive layer 250. ), And the transparent electrode body 230 may be formed of a transparent conductor according to embodiments of the present invention. Except that the transparent electrode body 230 is formed between the display unit 210 and the polarizing plate 220 is substantially the same as the optical display device according to an embodiment of the present invention.
- FIG 9 illustrates an optical display device in which an adhesive layer 250 is formed between the transparent electrode body 230 and the display unit 210.
- the transparent electrode body 230 and the display unit 210 may be formed together without the adhesive layer 250.
- the above-described polarizing plate may be further formed in the optical display device according to another exemplary embodiment of the present invention.
- FIG. 10 is a cross-sectional view of an optical display device according to still another embodiment of the present invention.
- an optical display device 600 includes a display unit 210a, a polarizer 220, a window film 240, and an adhesive layer 250.
- 210a may include a transparent electrode body, and the transparent electrode body may be formed of a transparent conductor according to embodiments of the present invention.
- the transparent electrode body is substantially the same as the optical display device according to the exemplary embodiment except that the transparent electrode body is formed inside the display unit 210a.
- the above-described polarizing plate may be further formed in the optical display device according to another exemplary embodiment of the present invention.
- Poly (styrene sulfonic acid) was added to Ag 2 O 5g to 1% by weight aqueous solution of 100ml and stirred for poly (styrene sulfonate) anion and the salt of the cation to prepare an aqueous solution (pH 7) containing the (PSS / Ag + salt) It was. 0.135 g of the prepared aqueous solution was added to 10.97 g of a silver nanowire-containing solution (trade name: Clearohm ink) and stirred to prepare a silver nanowire dispersion. The silver nanowire dispersion contains 0.5% by weight of PSS ⁇ / Ag + salt on a solids basis.
- the prepared silver nanowire dispersion was coated on a substrate layer (polycarbonate film, thickness: 50 ⁇ m) by spin coating to form a silver nanowire dispersion layer.
- the silver nanowire dispersion layer was dried in an 80 ° C. oven for at least 2 minutes and cured at 500 mJ / cm 2 in a UV curing machine to prepare a transparent conductor. At this time, the average particle diameter of the produced silver particle was about 1 nm-5 nm.
- Poly (styrene sulfonic acid) was added to Ag 2 O 5g to 1% by weight aqueous solution of 100ml and stirred for poly (styrene sulfonate) anion and the salt of the cation to prepare an aqueous solution (pH 7) containing the (PSS / Ag + salt) It was. 0.135 g of the prepared aqueous solution was added to 10.97 g of a silver nanowire solution (product name: Clearohm ink) and stirred to prepare a silver nanowire dispersion. The silver nanowire dispersion contains 0.5% by weight of PSS ⁇ / Ag + salt on a solids basis.
- TMPTA trimethylolpropane triacrylate
- DPHA dipentaerythritol hexaacrylate
- Irganox 1010 and 1.5 g of an initiator Irgacure 184 (CIBA) were mixed to prepare a composition for a matrix.
- the silver nanowire dispersion liquid was coated on one surface of the substrate layer (polycarbonate film, thickness: 50 ⁇ m) by spin coating to form a silver nanowire dispersion layer, and dried in an 80 ° C. oven for 2 minutes or more.
- the dried silver nanowire dispersion layer was coated with the composition for matrix prepared by spin coating, and cured at 500 mJ / cm 2 in a UV curing machine to prepare a transparent conductor. At this time, the diameter of the silver particle formed was about 1 nm-5 nm.
- Example 2 In the PSS is based on solids of the nanowire dispersion-was prepared in a transparent conductor in the same manner except that the changes to the / Ag + to the salt content in Table 1. At this time, the diameter of the silver particle formed was about 1 nm-5 nm.
- a transparent conductor was prepared in the same manner as in Example 6 except that poly (styrenesulfonic acid) doped with poly (ethylenedioxythiophene) was used instead of poly (styrenesulfonic acid). At this time, the diameter of the silver particle formed was about 1 nm-5 nm.
- silver nanowire dispersion 30 g was prepared by adding distilled water and PGME (propylene glycol monomethyl ether) to 18.98 g of silver nanowire solution (product name: Clearohm ink).
- PGME propylene glycol monomethyl ether
- TMPTA trimethylol propane triacrylate
- DPHA dipentaerythritol hexaacrylate
- antioxidant Irganox 0.510 and 10 g of initiator Irgacure 184 (CIBA) were mixed to prepare a composition for a matrix.
- the silver nanowire dispersion liquid was coated on one surface of the substrate layer (polycarbonate film, thickness: 50 ⁇ m) by spin coating to form a silver nanowire dispersion layer, and dried in an 80 ° C. oven for 2 minutes or more.
- the dried silver nanowire dispersion layer was coated with the composition for matrix prepared by spin coating, and cured at 500 mJ / cm 2 in a UV curing machine to prepare a transparent conductor.
- TMPTA trimethylol propane triacrylate
- DPHA dipentaerythritol hexaacrylate
- antioxidant Irganox 0.510 and 10 g of initiator Irgacure 184 (CIBA) were mixed to prepare a composition for a matrix.
- the silver nanowire dispersion liquid was coated on one surface of the substrate layer (polycarbonate film, thickness: 50 ⁇ m) by spin coating to form a silver nanowire dispersion layer, and dried in an 80 ° C. oven for 2 minutes or more.
- the dried silver nanowire dispersion layer was coated with the composition for matrix prepared by spin coating, and cured at 500 mJ / cm 2 in a UV curing machine to prepare a transparent conductor.
- Haze and transmittance (%): The transparent conductor was disposed so that the transparent conductive layer faced the light source. Haze and transmittance were measured using a haze meter (NDH-2000) D65 light source at a wavelength of 400 nm to 700 nm.
- Channel wire resistance uniformity value The coating direction of the silver nanowire dispersion solution for the transparent conductor is called MD and the direction perpendicular to the MD is called TD.
- the channel wire resistance uniformity value was calculated according to Equation 1 above. The lower the channel line resistance uniformity value, the higher the channel line resistance uniformity.
- Silver particles include include include include include include include Without Without Silver particle average particle diameter (nm) 1 to 5 1 to 5 1 to 5 1 to 5 1 to 5 1 to 5 - -
- the transparent conductor of the present invention has a low haze and a high transmittance, is transparent, has a low sheet resistance, and has a significantly low channel resistance uniformity, so that resistance variation between MD and TD may be low even before patterning and patterning. have. Accordingly, the present invention provides a transparent conductor having low sheet resistance by improving channel resistance uniformity and lowering contact resistance between metal nanowires.
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Abstract
L'invention concerne un conducteur transparent, son procédé de fabrication, et un dispositif d'affichage optique comprenant ledit conducteur. Le conducteur transparent comprend : une couche substrat ; et une couche conductrice transparente formée sur la couche substrat et comprenant des nanofils métalliques et des particules métalliques.
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US10575370B2 (en) * | 2015-09-25 | 2020-02-25 | Samsung Electronics Co., Ltd. | Electrical conductors, electrically conductive structures, and electronic devices including the same |
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KR102234230B1 (ko) * | 2017-05-29 | 2021-04-01 | 주식회사 에스지플렉시오 | 나노와이어 투명 전극 및 이의 제조방법 |
CN110459341B (zh) * | 2019-07-10 | 2021-04-06 | 南京邮电大学 | 基于金属纳米复合结构的半透明电极 |
US11652051B2 (en) * | 2021-01-22 | 2023-05-16 | Tpk Advanced Solutions Inc. | Contact structure and electronic device having the same |
US11652052B2 (en) * | 2021-03-29 | 2023-05-16 | Tpk Advanced Solutions Inc. | Contact structure and electronic device having the same |
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KR20090112626A (ko) * | 2006-10-12 | 2009-10-28 | 캄브리오스 테크놀로지즈 코포레이션 | 나노와이어 기반의 투명 도전체 및 그의 응용 |
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JP2011009302A (ja) * | 2009-06-23 | 2011-01-13 | Komuratekku:Kk | 薄膜太陽電池用裏面電極の形成方法 |
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US9776209B2 (en) * | 2012-02-16 | 2017-10-03 | Okura Industrial Co., Ltd. | Transparent electrically conductive substrate and manufacturing method thereof |
JP5569607B2 (ja) * | 2013-02-01 | 2014-08-13 | コニカミノルタ株式会社 | 透明導電膜、透明導電性フィルム及びフレキシブル透明面電極 |
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KR20150109222A (ko) | 2015-10-01 |
CN106104706B (zh) | 2019-02-15 |
CN106104706A (zh) | 2016-11-09 |
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