CN109390104A - Transparent electrode having high transmittance and low resistance characteristics and method for manufacturing same - Google Patents
Transparent electrode having high transmittance and low resistance characteristics and method for manufacturing same Download PDFInfo
- Publication number
- CN109390104A CN109390104A CN201810369624.9A CN201810369624A CN109390104A CN 109390104 A CN109390104 A CN 109390104A CN 201810369624 A CN201810369624 A CN 201810369624A CN 109390104 A CN109390104 A CN 109390104A
- Authority
- CN
- China
- Prior art keywords
- transparent electrode
- transmittance
- low resistance
- resistance characteristic
- manufacturing
- Prior art date
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- 239000007769 metal material Substances 0.000 description 1
- RCYSGAYIEFAJTG-UHFFFAOYSA-N methyl acetate;propanoic acid Chemical compound CCC(O)=O.COC(C)=O RCYSGAYIEFAJTG-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacturing Of Electric Cables (AREA)
- Non-Insulated Conductors (AREA)
- Nonwoven Fabrics (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention relates to a method for manufacturing a transparent electrode having high transmittance and low resistance characteristics and a transparent electrode having high transmittance and low resistance characteristics manufactured by the same, the method for manufacturing a transparent electrode having high transmittance and low resistance characteristics according to an embodiment of the present invention includes: a step of forming polymer fibers on a substrate by spraying a polymer substance on the substrate by an electric spraying method; heat-treating the polymer fiber; a stage of Ultraviolet (UV) treatment of the heat-treated polymer fiber; forming a metal layer on the ultraviolet-treated polymer fiber; and removing the polymer fibers to form a transparent electrode containing nanofibers.
Description
[technical field]
The present invention relates to the manufacturing method with high-transmittance and the transparent electrode of low resistance characteristic and utilize party's legal system
The transparent electrode with high-transmittance and low resistance characteristic made.
[background technique]
Recently, it because of the development of intelligent electronic device, carries out for replacing the flexible of previous firm display device
Show the research of (flexible display) device or stretchable display (stretchable display) device.Display
Device requires the transparent electrode of the transparency, routinely uses indium tin oxide (indium tin oxide, ITO).
But such ITO is difficult to be suitable for display device flexible because flexibility or retractility are low.In order to overcome such ITO
Limitation, the transparent electrode comprising other substances, for example, there is the transparency, conductibility, the graphene of all advantages such as flexibility, silver
Nano wire, using the transparent electrode of conducting polymer in industrial circle, educational circles etc. is much concerned about.But using graphene,
Nano wire, the transparent electrode complex procedures of conducting polymer, particularly since graphene is to induce every 1 layer of (mono-
Layer) the substance that about 2.3% light transmittance reduces is not available certain to obtain effective light transmittance as transparent electrode
The graphene more than number of plies, to be unable to get sufficient sheet resistance.
[content of invention]
[technical problems to be solved by the inivention]
Present invention seek to address that above-mentioned problem, the present invention is intended to provide can simple method manufacture high light transmission, low electricity
It is the transparent electrode with high-transmittance and low resistance characteristic of resistance, transparent electrode with high-transmittance and low resistance characteristic
Manufacturing method and the transparent electrode with high-transmittance and low resistance characteristic manufactured using this method.
But the technical problem to be solved in the present invention is not limited to project as mentioned above, those skilled in the art can be under
Record in text is expressly understood that unmentioned other technologies problem.
[solution of technical problem]
The manufacturing method for having the transparent electrode of high-transmittance and low resistance characteristic is provided in one embodiment comprising:
Polymer substance is sprayed on substrate using electrojet method and forms the stage of macromolecular fibre on the substrate；To the height
The stage that molecular fiber is heat-treated；The stage of ultraviolet light (UV) processing is carried out to the macromolecular fibre of the heat treatment；?
The stage of metal layer is formed on the macromolecular fibre of the UV treatment；And it removes the macromolecular fibre and is formed comprising receiving
The stage of the transparent electrode of rice fiber.
On the one hand, the stage being heat-treated to the macromolecular fibre can be in Glass Transition (glass
Transition) temperature is implemented 30 minutes~3 hours.
On the one hand, the stage for carrying out ultraviolet light (UV) processing to the macromolecular fibre of the heat treatment can be will have
The ultraviolet light of the wavelength of 150nm~370nm was with intensity illumination 10 seconds~5 minutes of 1kw~25kw.
On the one hand, the stage for carrying out ultraviolet light (UV) processing to the macromolecular fibre of the heat treatment can be while implement
Ozone (O3) processing.
On the one hand, the stage for forming macromolecular fibre on the substrate can bear (-) voltage to apply to the substrate
And it implements.
On the one hand, described negative (-) voltage can be the DC voltage or alternating voltage of -1KV~-10KV range.
On the one hand, the transparent electrode can be 80% or more for light transmittance, and film resistor is 100 Ω/sq or less.
On the one hand, the diameter of the macromolecular fibre can be 100nm~1 μm.
On the one hand, the polymer substance may include selected from following at least one: polyvinylpyrrolidone (PVP),
Polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), dimethyl silicone polymer (PDMS), polypropylene, polyurethane
Ester, polyether urethane, cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, polymethacrylates
(PMA), polyvinyl acetate (PVAc), polyacrylonitrile (PAN), poly- furfuryl alcohol (PPFA), polystyrene, polyethylene oxide
(PEO), polypropylene oxide (PPO), polycarbonate (PC), polyvinyl chloride (PVC), polycaprolactone, polyvinyl fluoride and polyamide.
On the one hand, the substrate can be no support (free standing) substrate.
On the one hand, the metal layer may include selected from following at least one: silver-colored (Ag), copper (Cu), platinum (Pt), gold
(Au), cobalt (Co), scandium (Sc), titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium
(Zr), aluminium (Al), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten
(W), rhenium (Re), osmium (Os) and iridium (Ir).
On the one hand, the thickness of the metal layer can be 50nm~1 μm.
The transparent electrode with high-transmittance and low resistance characteristic is provided in other embodiments, by according to an embodiment
The transparent electrode with high-transmittance and low resistance characteristic manufacturing method manufacture, the nanofiber of hollow structure is arranged as having
There are net (mesh) shape or net (web) shape.
On the one hand, the transparent electrode can be 80% or more for light transmittance.
On the one hand, the transparent electrode can be 100 Ω/sq or less for film resistor.
[The effect of invention]
The manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic of an embodiment according to the present invention can
There is low resistance (high conductance while manufacture by heat treatment and UV treatment with high-transmittance (bloom light transmittance)
Rate) transparent electrode.
The transparent electrode with high-transmittance and low resistance characteristic of an embodiment according to the present invention can have 80% with
On high-transmittance and 100 Ω/sq low resistance below (high conductivity) characteristic.
[simple illustration of figure]
Fig. 1 is the system for showing the transparent electrode with high-transmittance and low resistance characteristic of an embodiment according to the present invention
Make the flow chart of method.
Fig. 2 is a diagram embodiment according to the present invention in stage of the quadrangle without formation macromolecular fibre on supporting substrate
Skeleton diagram.
Fig. 3 is the polymer substance of an embodiment according to the present invention, the metal layer formed on polymer substance and in
The ideograph of the nanofiber of hollow structure.
Fig. 4 a is the photo for showing the manufacturing process of transparent electrode of embodiment according to the present invention.
Fig. 4 b is the photo for showing the manufacturing process of transparent electrode of embodiment according to the present invention.
Fig. 4 c is the photo for showing the manufacturing process of transparent electrode of embodiment according to the present invention.
Fig. 5 a is scanning electron microscope (SEM) low power of the nonheat-treated nanofiber of comparative example according to the present invention
Rate image.
Fig. 5 b is scanning electron microscope (SEM) high power of the nonheat-treated nanofiber of comparative example according to the present invention
Rate image.
Fig. 6 a is scanning electron microscope (SEM) low range of the nanofiber of the heat treatment of embodiment according to the present invention
Image.
Fig. 6 b is scanning electron microscope (SEM) high magnification of the nanofiber of the heat treatment of embodiment according to the present invention
Image.
Fig. 7 a is carved before the nanofiber to embodiment according to the present invention carries out metal evaporation, before UV treatment
Scanning electron microscope (SEM) image.
Fig. 7 b is carved before the nanofiber to embodiment according to the present invention carries out metal evaporation, after UV treatment
Scanning electron microscope (SEM) image.
Fig. 8 is the photo of the transparent electrode of embodiment according to the present invention manufacture.
Fig. 9 is the figure for showing the light transmittance according to wavelength band of transparent electrode of embodiment according to the present invention manufacture.
Figure 10 is the figure for showing the film resistor of transparent electrode of comparative example according to the present invention and embodiment manufacture.
Figure 11 is the figure for showing the light transmittance of the metal layer thickness according to transparent electrode of embodiment according to the present invention.
[specific embodiment]
Next, referring to attached drawing and the embodiment that the present invention will be described in detail.In the course of describing the present invention, when
When being judged as will cause spirit of the invention to the specific description of associated known function or composition and not knowing unnecessarily,
Detail explanation should be omitted.In addition, the term used in the present specification is to suitably indicate of the invention preferred
Embodiment and the term used, with user, can transport user intention or convention of the art etc. and it is different.
To which the definition to these terms should be provided based on the content of this specification.The identical reference prompted in each figure
Symbol indicates identical component.
In specification entirety, when mentioning certain component at another component "upper", this not only indicates certain component and another portion
The case where part contacts, include thes case where that there is also other components between two components.
In specification entirety, when mentioning certain part "comprising" constituent element, if being recorded without especially opposite, indicate not
Other constituent elements are excluded, also can further include other constituent elements.
Next, for the manufacturing method and utilization of the transparent electrode with high-transmittance and low resistance characteristic of the invention
The transparent electrode with high-transmittance and low resistance characteristic of this method manufacture, is specifically illustrated referring to embodiment and figure.
But the present invention is not limited to such an embodiment and figure.
The manufacturing method for having the transparent electrode of high-transmittance and low resistance characteristic is provided in one embodiment comprising:
Polymer substance is sprayed on substrate using electrojet method and forms the stage of macromolecular fibre on the substrate；To the height
The stage that molecular fiber is heat-treated；The stage of ultraviolet light (UV) processing is carried out to the macromolecular fibre of the heat treatment；?
The stage of metal layer is formed on the macromolecular fibre of the UV treatment；And it removes the macromolecular fibre and is formed comprising receiving
The stage of the transparent electrode of rice fiber.
Fig. 1 is the system for showing the transparent electrode with high-transmittance and low resistance characteristic of an embodiment according to the present invention
Make the flow chart of method.Referring to Fig.1, the manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic includes: high score
Subbundle formation stages (110)；Macromolecular fibre heat treatment stages (120)；The macromolecular fibre UV treatment stage (130)；
The stage (140) of metal layer is formed on macromolecular fibre；It removes macromolecular fibre and forms the transparent electricity comprising nanofiber
The stage (150) of pole.
On the one hand, macromolecular fibre formation stages (110) can be for using spraying polymer on electrojet normal direction substrate
Matter and macromolecular fibre is formed on substrate.
Fig. 2 is a diagram embodiment according to the present invention in stage of the quadrangle without formation macromolecular fibre on supporting substrate
Skeleton diagram.Referring to Fig. 2, polymer substance (220) are sprayed on substrate (210) using electrojet method and form macromolecule
Fiber (230).
On the one hand, an embodiment according to the present invention, the transparent electrode with high-transmittance and low resistance characteristic can
Using comprising spraying liquor box, injection nozzle, injection nozzle tip, the electrical spraying device of external power supply and collector substrate is (not
Diagram) manufacture.Collector substrate can be identical as the substrate in the present invention.Injection liquor box can store injection solution.Spray solution
The substance of (Spinning) can be sprayed according to expectation and change.
On the one hand, the substrate (210) can be no support (free standing) substrate.The no supporting substrate can
The shape penetrated through for center portion, being made of shell rim, the unsupported substrate in downside.Concrete ground, substrate (210) may include
The substrate of all categories of the subject of unbraced structure can be formed.The substrate (210) can have center as shown in Fig. 2
The quadrangle form of part perforation, shell rim connection.In addition, substrate is not only quadrangle, can have such as triangle, pentagon
Polygonal shape, the polygonal shape that can have center portion perforation, shell rim not connected.In addition, substrate (210) can have
There is the annular shape of center portion perforation, shell rim connection.In addition, substrate can have center portion perforation, shell rim not
Horseshoe (horseshoe) shape of connection.In addition, can also have with the perforation of trellis center portion, shell rim connection
Polygonal shape.
On the one hand, the injection liquor box of injection apparatus can using built-in pump and to injection solution pressurizeed and to spray
It penetrates nozzle and injection solution is provided.Injection nozzle can pass through the injection nozzle positioned at one end from injection liquor box receiving injection solution
Tip and spray injection solution.Injection nozzle tip can by pump pressurizeed to injection solution and after filling internal blast tube,
Injection solution is sprayed by the voltage of external power supply application.
On the one hand, the injection solution may include the polymer substance and solvent of energy electrojet.
On the one hand, the polymer substance may include selected from following at least one: polyvinylpyrrolidone (PVP),
Polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), dimethyl silicone polymer (PDMS), polypropylene, polyurethane
Ester, polyether urethane, cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, polymethacrylates
(PMA), polyvinyl acetate (PVAc), polyacrylonitrile (PAN), poly- furfuryl alcohol (PPFA), polystyrene, polyethylene oxide
(PEO), polypropylene oxide (PPO), polycarbonate (PC), polyvinyl chloride (PVC), polycaprolactone, polyvinyl fluoride and polyamide.
On the one hand, the solvent may include selected from following at least one: water, methanol, ethyl alcohol, propyl alcohol, butanol, third
Ketone, trifluoro ethylidene (TFE), trifluoroacetic acid (TFA), dimethylformamide (DMF), dimethyl acetamide (DMA), dimethyl are sub-
Sulfone, hexafluoroisopropanol (HFIP), hexane, benzene, acetic acid, formic acid, chloroform, tetrahydrofuran (THF) and methylene chloride (DCM).
On the one hand, the concentration of macromolecular fibre form can be maintained when the concentration of the injection solution is suitably electrojet,
The appropriate range relative to solvent and with polymer substance benchmark to be 5 weight of weight %~90 %.In the ratio of polymer substance
In the case where rate is less than 5 weight %, in electrojet, formed macromolecular fibre, due to decline caused by forming low concentration
The case where macromolecular fibre can not be formed, is more, and in the case where more than 90 weight %, the content of polymer substance is more and can occur
The case where macromolecular fibre can not be formed.To, it is necessary to macromolecular fibre can formed according to the polymer substance used
Concentration range appropriate manufacture injection solution.Especially, the case where the polymer substance mixing by more than one is sprayed
In, macromolecule and solvent need to have compatibility, implement under conditions ofs not occurring mutually to separate etc..In addition, solvent can be for a kind or by 2
Kind mixing preferably also considers the volatilization of solvent and manufactures injection solution.
On the one hand, the stage (110) for forming macromolecular fibre on the substrate can apply negative (-) electricity to the substrate
It presses and implements.
On the one hand, described negative (-) voltage can be the DC voltage or alternating voltage of -1KV~-10KV range.It is described
Voltage can change with the type and the amount of injection of injection solution.
On the one hand, the discharge speed that can spray solution is 0.1ml/h~10ml/h, and spray distance is 3cm~30cm
And the electrojet condition of relative humidity 1%~50% sprays polymer substance 3 minutes~10 minutes on substrate.With the model
In the case where the macromolecular fibre for the electrojet condition harvest enclosed, the engineering properties of tensile strength, elongation at break etc. is outstanding, soft
Soft increase, specific surface area are high.
On the one hand, the diameter of the macromolecular fibre can be 100nm~1 μm.The macromolecular fibre diameter not
In the case where sufficient 100nm, after removing macromolecular fibre later, there is the transparent of the manufactured nanofiber comprising hollow structure
The worry that the light light transmittance of electrode reduces, in the case where 1 μm, the resistance of transparent electrode can increase.
The diameter range of the macromolecular fibre obtained when in this way, can be sprayed according to initial stage and the Nanowire for adjusting hollow structure
The internal diameter of dimension and the size of outer diameter.
On the one hand, the macromolecular fibre heat treatment stages (120) can be in Glass Transition (glass
Transition) temperature is implemented 30 minutes~3 hours.The heat treatment can increase the binding force between macromolecular fibre.It is described
Heat treatment can be implemented under air atmosphere, the inert atmosphere comprising argon gas or nitrogen or reproducibility atmosphere comprising hydrogen.
On the one hand, macromolecular fibre ultraviolet light (UV) processing stage (130) can form gold on macromolecular fibre
Execution is carved before belonging to layer.It is handled by the ultraviolet light (UV) and is made the surface active of macromolecular fibre and improve macromolecular fibre and gold
Belong to the engaging force between layer.
On the one hand, the stage for carrying out ultraviolet light (UV) processing to the macromolecular fibre of the heat treatment can will have
The ultraviolet light of the wavelength of 150nm~370nm was with intensity illumination 10 seconds~5 minutes of 1kw~25kw.It is being lower than the ultraviolet light
Wave-length coverage wavelength in the case where, the engaging force that can not occur between macromolecular fibre and metal layer is increased of the invention
Effect crosses UV wavelength band and is unable to get effect of the invention in the case where being higher than the wavelength of the range.Described ultraviolet
Line exposure intensity less than 1kw or irradiation time less than 10 seconds in the case where, be unable to get between macromolecular fibre and metal layer
The increased effect of the invention of engaging force, be more than 25kw or when more than 5 minutes in exposure intensity, effect of the invention is small.
On the one hand, the stage for carrying out ultraviolet light (UV) processing to the macromolecular fibre of the heat treatment can be for example, heat
Ultraviolet light (UV) processing is implemented after processing 1 hour.
On the one hand, the stage for carrying out ultraviolet light (UV) processing to the macromolecular fibre of the heat treatment can be while implement
Ozone (O3) processing.
On the one hand, heat treatment according to the present invention and ultraviolet light (UV) processing stage, it is fine to improve macromolecule with low expense
The engaging force of peacekeeping metal layer.
On the one hand, the stage (140) for metal layer being formed on the pretreated macromolecular fibre is at the pre- place
Form metal layer on the macromolecular fibre of reason, can for around the outside of macromolecular fibre at least part and form metal layer.
On the one hand, the formation of the metal layer can be used comprising selected from sputtering, vapour deposition method, ion plating, chemical plating and electricity
At least one method of plating.
On the one hand, the metal layer may include selected from following at least one: silver-colored (Ag), copper (Cu), platinum (Pt), gold
(Au), cobalt (Co), scandium (Sc), titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium
(Zr), aluminium (Al), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten
(W), rhenium (Re), osmium (Os) and iridium (Ir).
On the one hand, the thickness of the metal layer can be 50nm~1 μm.Preferably, the thickness of the metal layer can be
50nm~500nm.In the case where the thickness of the metal layer is less than 50nm, it is difficult to which uniform thickness is formed, as electrode
Conductivity is too low, and resistance can become larger, more than 1μIn the case where m, the macromolecular fibre used as template fracture can occur
Phenomenon.
On the one hand, the stage (150) for removing the macromolecular fibre and forming transparent electrode is to remove the macromolecule
Fiber and form the transparent electrode comprising nanofiber, can for the macromolecular fibre carry out heat treatment or at organic solvent
It manages and removes macromolecular fibre.
On the one hand, the organic solvent may include the solvent that can dissolve all categories of macromolecular fibre.The solvent
It may include the alkanes (Alkanes) such as hexane (hexane), such as the aromatics (Aromatics) of toluene (toluene), such as diethyl
The ethers (Ethers) of ether (diethyl ether), such as the alkyl halide base class (Alkyl of chloroform (chloroform)
Halides), esters (Esters), aldehydes (Aldehydes), ketone (Ketones), amine (Amines), alcohols
(Alcohols), amides (Amide), the substance of the multiplicity such as carboxylic acids (Carboxylic acids) and water.In addition, can wrap
Containing selected from following at least one: acetone (Acetone), fluothane (Fluoroalkanes), pentane (Pentanes), hexane
(Hexane), 2,2,4- trimethylpentanes (2,2,4-Trimethylpentane), decane (Decane), hexamethylene
(Cyclohexane), pentamethylene (Cyclopentane), diisobutylene (Diisobutylene), 1- amylene (1-Pentene),
Carbon disulfide (Carbon dissulfide), carbon tetrachloride (Carbontetrachloride), 1-chlorobutane (1-
Chlorobutane), 1-chloropentane (1-Chloropentane), dimethylbenzene (Xylene), Di Iso Propyl Ether
(Diisopropylether), n-propyl chloride (1-Chloropropane), 2 cbloropropane isopropyl chloride (2-Chloropropane), toluene
(Toluene), chlorobenzene (Chlorobenzene), benzene (Benzene), bromoethane (Bromoethane), Anaesthetie Ether
(Diethyl ether), diethyl sulfide (Diethylsulfide), chloroform (Chloroform), methylene chloride
(Dichloromethane), 4- methyl -2- acetone (4-Methyl-2-propanone), tetrahydrofuran
(Tetrahydrofuran), 1,2- dichloroethanes (1,2-Dichloroethane), 2- butanone (2-Butanone), 1- nitro
Propane (1-Nitropropane), Isosorbide-5-Nitrae-dioxanes (Isosorbide-5-Nitrae-Dioxane), ethyl acetate (Ethylactate), methyl acetate
(Methyl acetate), 1- amylalcohol (1-Pentanol), dimethyl sulfoxide (Dimethyl sulfoxide), aniline
(Aniline), diethylamide (Diethylamine), nitromethane (Nitromethane), acetonitrile (Acetonitrile), pyrrole
Pyridine (Pyridine), butoxy ethanol (2-Butoxyethanol), 1- propyl alcohol (1-Propanol), 2- propyl alcohol 2-
Propanol), ethyl alcohol (Ethanol), methanol (Methanol), ethylidene glycol (Ethylene glycol) and acetic acid
(Acetic Acid)。
Fig. 3 is the polymer substance of an embodiment according to the present invention, the metal layer formed on polymer substance and in
The ideograph of the nanofiber of hollow structure.As shown in Fig. 3, due at least one of the outside around macromolecular fibre (230)
Metal layer (240) partially are formed, if removing macromolecular fibre (230), metal layer (240) there can be the hollow of internal sky
(hollow) structure forms the nanofiber (250) of hollow structure as a result,.Nanofiber (250) can be by having the nanometer of multiplicity
The substance of shape is constituted, for example, may include selected from following at least one: nano wire (nanowire), nanotube
(nanotube) and nanometer rods (nanorod).
On the one hand, the transparent electrode with high-transmittance and low resistance characteristic of an embodiment according to the present invention can arrange
1 for being classified as the overlapped connection of nanofiber (250) for constituting hollow structure and being formed is tieed up, 2 dimensions or 3 dimension conductive network structures
Body.Because of such network structure, the transparent electrode with high-transmittance and low resistance characteristic can ensure that the biography of certain level or more
Conductance.In addition, the transparent electrode with high-transmittance and low resistance characteristic can be arranged as the shape with specified pattern, example
Such as, it can be arranged as with net (mesh) shape or there is net (web) shape.
On the one hand, the transparent electrode with high-transmittance and low resistance characteristic of an embodiment according to the present invention can be
The 2nd substrate (not shown) is configured on the downside of no supporting substrate, is lifted the 2nd substrate, is placed nanometer on the 2nd substrate from no supporting substrate
Fiber is used with the transparent electrode with high-transmittance and low resistance characteristic of net (mesh) or net (web) shaped formation.2nd
Substrate may include the transparent substance passed light through or the light for it is expected wavelength made to select the substance qualitatively passed through.2nd substrate, example
Such as, may include selected from following at least one: glass, quartz, Si oxide, aluminum oxide or polymer, for example, may include gathering
Acid imide (polyimide), polyethylene naphthalate (polyethylenenaphthalate, PEN), poly terephthalic acid
Second diester (polyethyleneterephthalate, PET), polymethyl methacrylate (PMMA) and dimethyl silicone polymer
(PDMS).2nd substrate may include substance flexible, as a result, the manufactured transparent electricity with high-transmittance and low resistance characteristic
Pole can have characteristic flexible.
The manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic of an embodiment according to the present invention can
There is low resistance (high conductance while manufacture by heat treatment and UV treatment with high-transmittance (bloom light transmittance)
Rate) transparent electrode.
The transparent electrode with high-transmittance and low resistance characteristic is provided in other embodiments, by according to an embodiment
The transparent electrode with high-transmittance and low resistance characteristic manufacturing method manufacture, the nanofiber of hollow structure is arranged as having
There are net (mesh) shape or net (web) shape.
On the one hand, the transparent electrode can be 25cm2Above large area.With high-transmittance and low resistance characteristic
The area of transparent electrode is not particularly limited, can be according to equipment arbitrarily control.The feelings of execution are equipped used in through the invention
In condition, the area of graphene transparent electrode is 25cm2, such area is without limitation.
On the one hand, the light transmittance of the transparent electrode can be 80% or more, preferably 85% or more.
On the one hand, the film resistor of the transparent electrode can be 100 Ω/sq or less.
On the one hand, the light transmittance and film resistor can be random and adjusting the content of metal layer in manufacturing process
Control, can be produced in a manner of conforming to applicable range of product size.For example, as the transparent electrode that touch tablet uses, it can
Smart phone etc. use instead it is according to the present invention be made of the nanofiber of hollow structure have high-transmittance and low resistance special
The transparent electrode of property.
Next, explaining the present invention in detail referring to Examples and Comparative Examples shown below.But technical idea of the invention
It is not limited except as or limits.
[embodiment]
Polyvinylpyrrolidone (PVP) 1.6g and ethyl alcohol 20ml are mixed, in 40 DEG C, with 750ppm mixing 10 minutes~15
Minute and manufacture injection solution.Injection solution is put into injection apparatus, the environment in relative humidity 50%, the jet length with 20cm
Jet velocity from, 1.0ml/h, the voltage of 9.0kV, electrojet 3 minutes~10 minutes on metal form.Fig. 4 a~Fig. 4 c is
Show the photo of the manufacturing process of the transparent electrode of embodiment according to the present invention.As shown in fig.4, electrojet and manufacture
The macromolecular fibre of net (web) form of overlapped connection.By the macromolecular fibre of net (web) form of manufacture in 150 DEG C
Heat treatment 1.5 hours.It is carved before metal evaporation after heat treatment, to macromolecular fibre irradiation ultraviolet light (UV) 60 seconds of heat treatment
Clock.Then, as the metal material for being used as electrode, the silver (Ag) of 100nm thickness is deposited on macromolecular fibre.Fig. 4 b is in height
The photo after silver-colored (Ag) is deposited on molecular fiber.Then, it as shown in Fig. 4 c, is removed using acetone solution PVP works,
Thus the nanofiber for manufacturing hollow structure is in the transparent electrode of net (web) form.
[comparative example]
In addition to not being heat-treated, transparent electrode is manufactured in method identical with embodiment.
Fig. 5 a is scanning electron microscope (SEM) low power of the nonheat-treated nanofiber of comparative example according to the present invention
Rate image, Fig. 5 b are scanning electron microscope (SEM) high powers of the nonheat-treated nanofiber of comparative example according to the present invention
Rate image, Fig. 6 a are scanning electron microscope (SEM) low ranges of the nanofiber of the heat treatment of embodiment according to the present invention
Image, Fig. 6 b are scanning electron microscope (SEM) high magnification figures of the nanofiber of the heat treatment of embodiment according to the present invention
Picture.
Referring to Fig. 5 a~Fig. 6 b, can confirm embodiment according to the present invention manufacture nanofiber be between nanofiber not
It separates and is attached to each other.
Fig. 7 a is carved before the nanofiber to embodiment according to the present invention carries out metal evaporation, before UV treatment
Scanning electron microscope (SEM) image, Fig. 7 b be to embodiment according to the present invention nanofiber carry out metal evaporation
Preceding quarter, scanning electron microscope (SEM) image after UV treatment.Referring to Fig. 7 a and Fig. 7 b, carved before metal evaporation into
Row UV treatment, then can confirm whether metal is equably vaporized on nanofiber.
Fig. 8 is the photo of the transparent electrode of embodiment according to the present invention manufacture, and Fig. 9 is display implementation according to the present invention
The figure of the light transmittance according to wavelength band of the transparent electrode of example manufacture.Referring to Fig. 8 and Fig. 9, implementation according to the present invention can be confirmed
The transparent electrode of example manufacture equably sees the transparency close to 90% in all wavelength bands.
Figure 10 is the figure for showing the film resistor of transparent electrode of comparative example according to the present invention and embodiment manufacture, Figure 11
It is the figure for showing the light transmittance of the metal layer thickness according to transparent electrode of embodiment according to the present invention.0 and Figure 11 referring to Fig.1
It is found that although the thickness of the metal layer of vapor deposition increases, film resistor is reduced, and light transmittance is but without big difference.
As described above, the present invention is not limited to institutes although the present invention is described by limited embodiment and figure
The embodiment stated, those skilled in the art can carry out the amendment and deformation of multiplicity according to such record.
So the scope of the present invention is not limited by embodiment described, but by aftermentioned patent claims and patent right
The equivalent technical solutions of claim define.
[explanation of symbol]
210: substrate
220: polymer substance
230: macromolecular fibre
240: metal layer
250: nanofiber
Claims (15)
1. the manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic comprising:
Polymer substance is sprayed on substrate using electrojet method and forms the stage of macromolecular fibre on the substrate；
The stage that the macromolecular fibre is heat-treated；
The stage of ultraviolet light (UV) processing is carried out to the macromolecular fibre of the heat treatment；
The stage of metal layer is formed on the macromolecular fibre of the UV treatment；And
It removes the macromolecular fibre and forms the stage of the transparent electrode comprising nanofiber.
2. the manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic of claim 1, wherein to the high score
The stage that subbundle is heat-treated implements 30 minutes~3 hours in Glass Transition (glass transition) temperature.
3. the manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic of claim 1, wherein to the heat
The macromolecular fibre of reason carry out stage of ultraviolet light (UV) processing by the ultraviolet light of the wavelength with 150nm~370nm with 1kw~
The intensity illumination of 25kw 10 seconds~5 minutes.
4. the manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic of claim 1, wherein to the heat
The stage that the macromolecular fibre of reason carries out ultraviolet light (UV) processing implements ozone (O simultaneously3) processing.
5. the manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic of claim 1, wherein in the substrate
The upper stage for forming macromolecular fibre is implemented and applying negative (-) voltage to the substrate.
6. the manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic of claim 5, wherein negative (-) electricity
Pressure is the DC voltage or alternating voltage of -1KV~-10KV range.
7. the manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic of claim 1, wherein the transparent electricity
The light transmittance of pole is 80% or more, and film resistor is 100 Ω/sq or less.
8. the manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic of claim 1, wherein the macromolecule
The diameter of fiber is 100nm~1 μm.
9. the manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic of claim 1, wherein the macromolecule
Substance includes to be selected from following at least one: polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polymethyl methacrylate
(PMMA), dimethyl silicone polymer (PDMS), polypropylene, polyurethanes, polyether urethane, cellulose acetate, second
Sour cellulose butyrate, cellulose-acetate propionate, polymethacrylates (PMA), polyvinyl acetate (PVAc), polyacrylonitrile
(PAN), poly- furfuryl alcohol (PPFA), polystyrene, polyethylene oxide (PEO), polypropylene oxide (PPO), polycarbonate (PC) gather
Vinyl chloride (PVC), polycaprolactone, polyvinyl fluoride and polyamide.
10. the manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic of claim 1, wherein the substrate is
Without support (free standing) substrate.
11. the manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic of claim 1, wherein the metal layer
Comprising being selected from following at least one: silver-colored (Ag), copper (Cu), platinum (Pt), golden (Au), cobalt (Co), scandium (Sc), titanium (Ti), chromium
(Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), aluminium (Al), niobium (Nb), molybdenum (Mo), technetium
(Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os) and iridium (Ir).
12. the manufacturing method of the transparent electrode with high-transmittance and low resistance characteristic of claim 1, wherein the metal layer
Thickness be 50nm~1 μm.
13. the transparent electrode with high-transmittance and low resistance characteristic has high-transmittance and low resistance by claim 1
The manufacturing method of the transparent electrode of characteristic manufactures,
Wherein the nanofiber of hollow structure is arranged as with net (mesh) shape or net (web) shape.
14. the transparent electrode with high-transmittance and low resistance characteristic of claim 13, wherein the light transmission of the transparent electrode
Degree is 80% or more.
15. the transparent electrode with high-transmittance and low resistance characteristic of claim 13, wherein the film of the transparent electrode
Resistance is 100 Ω/sq or less.
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| KR1020170101562A KR101955104B1 (en) | 2017-08-10 | 2017-08-10 | Method of manufacturing transmittance electrode with high transparent and low resistance and transmittance electrode with high transparent and low resistance manufactured using the method |
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| KR102601396B1 (en) * | 2021-10-01 | 2023-11-13 | 주식회사 레몬 | Method Of Manufacturing Inorganic NanoFiber Web At LowTemperature |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110110643A (en) * | 2010-04-01 | 2011-10-07 | 경희대학교 산학협력단 | Preparation method of electroconductive nanofiber through electrospinning followed by electroless plating |
| KR101514325B1 (en) * | 2013-12-10 | 2015-04-22 | 국립대학법인 울산과학기술대학교 산학협력단 | Method of manufacturing a transparent electrode using electro spinning method |
| CN105283927A (en) * | 2013-02-20 | 2016-01-27 | 国立大学法人东京工业大学 | Electroconductive nanowire network, and electroconductive substrate and transparent electrode using same, and method for manufacturing electroconductive nanowire network, electroconductive substrate, and transparent electrode |
| CN105762291A (en) * | 2015-01-06 | 2016-07-13 | 延世大学校产学协力团 | Transparent electrode and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110110643A (en) * | 2010-04-01 | 2011-10-07 | 경희대학교 산학협력단 | Preparation method of electroconductive nanofiber through electrospinning followed by electroless plating |
| CN105283927A (en) * | 2013-02-20 | 2016-01-27 | 国立大学法人东京工业大学 | Electroconductive nanowire network, and electroconductive substrate and transparent electrode using same, and method for manufacturing electroconductive nanowire network, electroconductive substrate, and transparent electrode |
| KR101514325B1 (en) * | 2013-12-10 | 2015-04-22 | 국립대학법인 울산과학기술대학교 산학협력단 | Method of manufacturing a transparent electrode using electro spinning method |
| CN105762291A (en) * | 2015-01-06 | 2016-07-13 | 延世大学校产学协力团 | Transparent electrode and manufacturing method thereof |
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| KR101955104B1 (en) | 2019-03-06 |
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