WO2016159639A1

WO2016159639A1 - Method for manufacturing transparent electrode and apparatus for manufacturing transparent electrode

Info

Publication number: WO2016159639A1
Application number: PCT/KR2016/003218
Authority: WO
Inventors: 윤석구; 안성필
Original assignee: 고려대학교 산학협력단
Priority date: 2015-03-30
Filing date: 2016-03-29
Publication date: 2016-10-06
Also published as: KR20160117660A; KR101715224B1

Abstract

Provided is a method for manufacturing a transparent electrode, including: an electrospinning step for forming a nanofiber web fiberized by discharging a polymer spinning solution through an electrospinning nozzle of an electrospinning module by means of a high voltage; and an electroplating step for electroplating the nanofiber web by a predetermined metal in an electroplating module.

Description

Transparent electrode manufacturing method and transparent electrode manufacturing apparatus

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent electrode manufacturing apparatus and a method for manufacturing the same, and includes a thin film display such as an OLED and an LCD, an electrochromic window, a transparent thin film transistor, a touch screen panel, The present invention relates to a method and apparatus for manufacturing a transparent electrode using nanofibers that can improve the performance of a transparent electrode used in advanced electronic products such as a solar cell.

There is an increasing demand for durability for long life and stable use of electrical and electronic products, but the same problem is also raised for electrodes used in various electrical and electronic products.

In other words, ITO, which is a widely used transparent electrode, has the performance of sheet resistance of 1 ~ 10 ³ Ω / sq and transmittance of about 85%, but has reached the limit to realize higher performance. Due to the nature of the materials used, flexible ITO transparent electrodes are difficult to manufacture due to bending, and durability due to oxidation of materials is weak.

The present invention utilizes nanofiber line patterning technology and sputtering technology to enable the use of metals with excellent electrical conductivity and at the same time to realize high performance in a small amount, thereby providing a great advantage in efficiency and cost. It is an object to provide a manufacturing apparatus and a manufacturing method.

In addition, in the case of the transparent electrode obtained by the nanofiber line patterning of the present invention, it is possible to secure high permeability to improve the quality satisfaction, and also to increase the adhesion of the metal nanofibers and prevent the oxidation of the metal nanofibers in the sputtering process. The purpose of the present invention is to provide a method and apparatus for manufacturing a transparent electrode which can be applied to a flexible electronic product, which can be applied to a substrate having various finishes and sizes, which can greatly improve the durability of the product and can be applied to a flexible electronic product. do.

The present invention provides an electrospinning step of forming a nanofiber web in which a polymer spinning liquid is discharged through high voltage through an electrospinning nozzle of an electrospinning module to form a fiber, and electroplating the nanofiber web with a predetermined metal in an electroplating module. It provides a method for manufacturing a transparent electrode having an electroplating step.

In the method of manufacturing the transparent electrode, in the electrospinning step, a nanofiber web frame is applied to the electrospinning nozzle through the high voltage unit 200 of the electrospinning module and grounded at a corresponding position of the electrospinning nozzle. In this arrangement, the nanofiber web may be formed in the nanofiber web frame.

In the transparent electrode manufacturing method, in the electroplating step, the electroplating anode formed of a predetermined plating metal in the electroplating module tank of the electroplating module and a plating solution in which the nanofiber web frame can be immersed An immersion step of immersing the electroplating anode and the nanofiber web frame; And applying a voltage to the nanofiber web frame and the electroplating anode as an electroplating power supply unit of the electroplating module.

In the method of manufacturing the transparent electrode, further comprising a plating enhancement film forming step of forming a plating enhancement film on the nanofiber web formed on the nanofiber web frame in the nanofiber web frame between the electrospinning step and the electroplating step with a plating enhancement metal. It can be provided.

In the method for manufacturing a transparent electrode, the predetermined plating enhancing metal includes at least one of gold and platinum, and the forming of the plating enhancing film is performed by sputtering deposition of the predetermined plating promoting metal on the nanofiber web sputtering module. It may be a step.

In the method of manufacturing the transparent electrode, after the electrospinning step and before the electroplating step, the polymer spinning liquid is discharged through the high voltage through the electrospinning nozzle of the electrospinning module to the nanofiber web to support the nanofiber web A web reinforcing step of forming a reinforcing web may be further provided.

In the method of manufacturing the transparent electrode, after the electroplating step, the nanofiber web transfer step of transferring the nanofiber web frame on a nanofiber substrate may be provided.

In the method of manufacturing the transparent electrode, the nanofiber substrate may be at least one of glass, polyimide (Polyimide), polyethylene terephthalate (PET), and polydimethylsiloxane (PDMS).

In the method of manufacturing the transparent electrode, after the nanofiber web transfer step, the cleaning step of cleaning the nanofiber web transferred to the substrate may be further provided.

In the method of manufacturing the transparent electrode, after the nanofiber web transfer step, the protective film forming step of forming a protective film of the nanofiber web transferred to the substrate with a predetermined oxide may be further provided.

In the transparent electrode manufacturing method, the preset oxide may be at least one of ITO, ZnO, IZO, AZO.

In the method of manufacturing the transparent electrode, in the electrospinning step, the ground electrode formed on the stage on which the nanofiber web frame is disposed is disposed so that two or more of a pair facing each other with the nanofiber web frame interposed therebetween. The ground electrode pairs may be sequentially charged alternately.

According to another aspect of the present invention, the present invention provides an electrospinning module for forming a nanofiber web in which a polymer spinning solution is discharged through a high voltage through an electrospinning nozzle to form a fiber, and the nanofiber web is electroplated with a predetermined metal. And an electroplating module for electroplating in the electrospinning module, wherein the electrospinning module includes a stage on which the nanofiber web frame is disposed to face the electrospinning nozzle to form the nanofiber web, and applies a high voltage to the electrospinning nozzle. A high voltage generator; And a grounding power source that forms an electric field in a space between the electrospinning nozzle and the fiber discharged from the electrospinning nozzle so as to be induced by an electrostatic force, wherein the grounding power sources are: facing each other with the nanofiber web frame therebetween. Provided is a transparent electrode manufacturing apparatus comprising a ground electrode pair disposed so that two or more of the pairs intersect with each other, and a movable terminal capable of intermittent connection with the ground electrode pair.

The present invention provides a method and apparatus for manufacturing a transparent electrode having a nanofiber web and a nanofiber substrate using electrospinning and electroplating, by varying the type of metal used in various electroplating to suit the purpose, Applicable to the application.

First, the transparent electrode manufacturing method and apparatus of the present invention, by using a nanofiber line patterning technology and sputtering technology, it is possible to use a metal with excellent electrical conductivity and at the same time to realize a high performance in a small amount, It can provide a great effect in terms of cost.

Second, the transparent electrode manufacturing method and apparatus of the present invention, in the case of the transparent electrode obtained by nanofiber line patterning can ensure a high permeability to improve the quality satisfaction, and also increase the adhesion of the metal nanofibers in the sputtering process And it is possible to obtain the anti-oxidation effect of the metal nanofibers, greatly improve the durability of the product and can be applied to a substrate having a variety of finishes and sizes can be applied to the flexible electronic products strong in bending characteristics.

1 and 2 are schematic and detailed configuration diagrams conceptually showing the configuration of a method for manufacturing a transparent electrode according to an embodiment of the present invention.

Figure 3 (a), (b) is a photograph of the transparent electrode calculated by the method and apparatus for manufacturing a transparent electrode according to an embodiment of the present invention, the copper-coated nano-attached in a non-planar position, such as a human hand It is a photographic diagram showing a state of being energized by connecting a photo of a transparent electrode implemented with a nanofiber web having fibers and connecting a battery and an LED to the transparent electrode.

Figure 4 (a), (b) is a photograph of the transparent electrode calculated by the method and apparatus for manufacturing a transparent electrode according to an embodiment of the present invention, the copper-coated nanofibers attached to a non-planar position, such as leaves It is a photographic diagram showing a state of being energized by connecting a battery and an LED to a transparent electrode and a transparent electrode formed of a nanofiber web provided thereon.

Figure 5 (a) is a sheet resistance diagram, (b) to (d) is a photograph of the transparent electrode calculated by the method and apparatus for manufacturing a transparent electrode according to an embodiment of the present invention, the nanofiber substrate is implemented in PDMS Is a photograph showing a transmission state of the transparent electrode according to the present invention, and (e) is a transmittance-wavelength diagram of the transparent electrode calculated by the method and apparatus for manufacturing a transparent electrode according to an embodiment of the present invention.

6 and 7 are diagrams showing another modified example of the method and apparatus for manufacturing a transparent electrode according to an embodiment of the present invention.

8 is a result diagram for the durability test of the film-type transparent electrode calculated by the manufacturing method of the present invention.

9 is an enlarged diagram of nanofibers of a nanofiber web formed on a nanofiber substrate of a transparent electrode produced by the manufacturing method of the present invention.

The present invention has excellent thermal conductivity. It provides a device for producing a nano-textured film as a fiber film having a high specific surface area covered with a metal that generates high heat, through the nano-textured film of the ecological imitation devil visible structure produced through the present invention, With its heat dissipation capability, it can be easily removed from the heat generated from various electrical, electronic and mechanical products.

1 and 2 are schematic and detailed configuration diagrams conceptually showing the configuration of a method for manufacturing a transparent electrode according to an embodiment of the present invention. The transparent electrode manufacturing method according to an embodiment of the present invention includes an electrospinning step (S10) and an electroplating step (S40).

The transparent electrode manufacturing apparatus 1 of the present invention may include a control unit 20 and a storage unit 30. The control unit 20 controls the operation of the electrospinning module 10 and the electroplating module 11a. In some cases, it is possible to control the operation of the transfer unit for transporting the nanofiber web frame or the substrate to be used in some cases, and simultaneously control the operation of a roll-to-roll module (not shown) as a continuous process. The storage unit 30 is connected to the control unit 20 and controls the data according to the operation mode, including preset data such as the radiation amount of the polymer spinning solution, the interruption order of the ground power cutoff unit, and the reference power value of the electroplating power supply unit. ) To enable a certain smooth operation.

In the electrospinning step S10, the polymer spinning liquid is discharged through a high voltage through the electrospinning nozzle 100 of the electrospinning module 10 to form a nanofiber web.

The electrospinning module 10 in which the electrospinning step S10 is performed includes an electrospinning nozzle 100, a high voltage generator 200, and a ground power source 300 connected to the ground plate 310.

The electrospinning nozzle 100 is configured to discharge the polymer spinning liquid through a high voltage and to form a fiber, and supply the polymer spinning liquid from the polymer spinning liquid supply unit 110 connected to the electrospinning nozzle 100 as shown in FIG. 1. It is configured in such a way that it receives and discharges. For example, a syringe pump for supplying a fixed amount of the polymer spinning solution to the polymer spinning solution is used.

In the present embodiment, the polymer spinning solution is prepared by preparing 8 wt% of polyacrylonitrile in dimethylformamide and using a syringe pump (not shown) at a temperature of 24 ° C. and a humidity of 60%. The electrospinning was performed by supplying a flow rate of / hr and applying a voltage of 7 kV in the high voltage generator 200 described below. Polymer spinning solution and conditions are not limited to this, the polymer spinning solution may be a solution of a mixture of polyvinyl alcohol (PVA) and water other than polyacrylonitrile (polyacrylonitrile), using a polymer having excellent mechanical properties such as nylon In this case, a variety of polymer materials may be used in a range that takes a structure capable of discharging through an electrospinning nozzle, such as a strong acid solution such as formic acid. The electrospinning nozzle 100 may be a nozzle in the form of a cone jet to receive and discharge the polymer spinning liquid from a syringe pump (not shown).

The high voltage generator 200 applies a high voltage to the electrospinning nozzle 100, and correspondingly, a separate ground power source 300 is provided at a position spaced apart from the electrospinning nozzle 100. The ground power supply 300 may be grounded to the nanofiber web frame 301 as shown in FIG. 1. In some cases, although not shown in FIG. 1, a separate stage may be provided, a ground electrode connected to the ground power source may be disposed on the stage, and the nanofiber web frame 300 may be connected to the ground electrode.

The nanofiber web frame 301 is formed in the rectangular frame of the conductive material in the present embodiment, which is not limited to this as an example for explaining the present invention. When the nanofiber web frame 301 is connected to the ground power source 300, a high voltage is applied from the high voltage generator 200, and the polymer spinning liquid is discharged from the electrospinning nozzle at the same time, the electrospinning nozzle 100 and the nanofiber web frame ( The polymer spinning liquid charged by the electric field formed between the 301 is fiberized and attached to the nanofiber web frame 301 so that the polymer spinning liquid forms the nanofiber web 3a, which is formed on the nanofiber web frame 301. The nanofiber webs 3a are randomly formed. That is, the nanofiber web 3a formed on the nanofiber web frame 301 is not biased to either side of the nanofiber web frame 301 due to random formation when a predetermined time spinning of the polymer spinning solution is achieved. Attached to the nanofiber web frame 301 is formed.

On the other hand, the electrospinning module of the transparent electrode manufacturing apparatus 1 of the present invention is not limited to the above configuration, various configurations are possible. That is, as shown in FIGS. 6 and 7, the electrospinning module 10a includes an electrospinning nozzle 100, a stage 3, a high voltage generator 200, and a ground power supply 300. 100, the high voltage generator 200, and the ground power source 300 are the same as described above. The stage 3 is disposed opposite to the electrospinning nozzle 100, and a nanofiber web frame 301 in which the nanofiber web 2 is formed may be seated on one surface of the stage 3. On one surface of the stage 3 is provided with a stage mounting portion (not shown) in which the nanofiber web frame 301 is seated and held, and the nanofiber web frame 301 may be held in place. The stage 3 is provided with

ground electrode portions

3a, 3b, 3c, and 3d, and the nanofiber web frame 301 is connected to the ground power supply 300 through the

ground electrode portions

3a, 3b, 3c, and 3d. Can be. The

ground electrode portions

3a, 3b, 3c, and 3d include ground electrode pairs 3b and 3c and a ground movable terminal 3d, and the ground controller 3a applies a ground control signal to the ground movable terminal 3d. To implement a predetermined ground movable terminal function.

The ground electrode pairs 3b and 3c are formed on one surface of the stage 3, and two or more pairs of mutually facing each other with the nanofiber web frame 301 interposed therebetween are disposed so that two or more pairs cross each other, that is, The virtual line segments formed by the ground electrode pairs facing each other are arranged such that the virtual line segments formed by the other ground electrode pairs cross each other. That is, as shown in FIGS. 6 and 7, the ground electrode 3b is a pair of ground electrodes facing each other, and the other ground electrode 3c is another pair of ground electrodes facing each other, and these pairs Take the structure of 90 degrees cross each other. At this time, the ground movable terminal 3d is connected to a predetermined actuator, for example, an electric motor, and operated according to the ground control signal of the ground control unit 3a, so that the ground movable terminal 3d achieves a predetermined rotation operation. The ground movable terminal 3d forms an always-connected state with the ground power supply 300. The contact state with the ground electrode may be changed by the rotation of the ground movable terminal 3d. As shown in FIGS. 6A and 6B, the ground movable terminal is rotated by the rotation of the ground movable terminal 3d. 3d is a polymer which is in contact with the ground electrode pair 3c indicated by the reference 3c or in contact with the ground electrode pair 3b indicated by the reference 3b and is alternately ground charged and ultimately discharged from the electrospinning nozzle 100 The nanofiber webs 2 formed in the nanofiber web frame 301 continuously formed in the direction in which the spinning solution is perpendicular to each other may have a structure that is substantially orthogonally arranged.

After the electrospinning step S10 made in the predetermined electrospinning module 1 is completed, the electroplating step S40 is executed. The nanofiber web 2 formed in the electrospinning step S10 is electroplated in the electroplating module 11 with a predetermined metal. The electroplating module 11 may generate a control signal for controlling the power supply of the electroplating power supply 11b of the electroplating module 11 from the control unit 20.

The electroplating module 11 includes an electroplating module water tank 11a, an electroplating anode 11c, and an electroplating power supply portion 11b. The electroplating module bath 11a accommodates the plating liquid 11e in which the nanofiber web frame 301 formed by collecting and attaching the nanofiber web 2 is immersed, and the electroplating anode 11c is a plating solution in the electroplating module bath ( 11e) and is immersed and formed of a predetermined plating metal, and the electroplating power supply 11b applies a voltage to the film base 500 and the electroplating anode 11c from which the fibers 600 are collected. Although the electroplating power supply portion 11b is a DC power supply in the drawing, it is apparent from the present invention to form a structure applicable to an AC power supply at an actual manufacturing site.

The plating solution 11e includes a metal to be electroplated as an electrolyte solution, which is determined according to a predetermined plating metal of the electroplating anode 11c. For example, when the electroplating anode is formed of copper, the plating liquid may include a Cu plating liquid, and various selections are possible within a range of forming a predetermined electroplating. The time during which the nanofiber web frame 301 is immersed in the plating solution 11e may be variously changed according to design specifications.

On the surface of the fiber of the nanofiber web 2 formed on the nanofiber web frame 301 immersed in the plating solution, the metal forming the electroplating anode expands the surface area, that is, the outer surface of the fiber is uniformly uniformed in one layer thickness. It is possible to maximize the surface area of the metal plated coated fiber on the film base by forming a continuous continuous growth structure from the plated surface coated with metal to the outer surface as the tree branches rather than coating. The process in the electroplating module is, for example, when the electroplating anode 11c in which the predetermined electroplating metal is made of copper (Cu) is provided, the plating solution 11e is also an electrolyte solution containing a copper (Cu) component. Is formed.

More specifically, the electroplating step S40 of the present invention includes an immersion step S41 and a power applying step S43. In the immersion step S41, the electroplating module tank 11a of the electroplating module 11 is provided. The nano-electrode (11c) and the nanofiber web frame (301) formed of a predetermined plating metal in the accommodating plating solution that can be immersed and connected to the cathode of the electroplating anode (11c) and the electroplating power supply (11b) The fiber web frame 301 is immersed, and in the power application step S43, the control unit 20 is an electroplating power supply 11b of the electroplating module 11, and the nanofiber web frame 301 and the electroplating anode 11c. Apply voltage to it. In this embodiment, the electroplating anode 11c is formed of a copper metal plate, and the plating solution is formed by mixing sulfuric acid, hydrochloric acid, copper sulfate, formaldehyde, and distilled water, 10 g of sulfuric acid, 1 g of hydrochloric acid, and copper sulfate. 32 g of copper sulfate and 20 g of formaldehyde are mixed with 200 mL of deionized water. Electroplating was performed for about 3 seconds at a current density of 100 mA / cm ² , which is one example. The present invention is capable of various modifications within the range of the electroplating structure.

In addition, a separate cleaning step and / or strengthening step may be further provided after the electroplating step. That is, a strengthening step of supporting the formaldehyde solution for a predetermined time after the electroplating step and a cleaning step of cleaning the foreign matter after the strengthening step may be further provided. In this embodiment, a 10 minute formaldehyde solution was immersed in a 10% formaldehyde solution for 5 minutes and then rinsed with distilled water for 1 minute to perform a cleaning process to take a structure for strengthening the bond between the copper metal, which is an electroplating material, and nanofibers covered with gold / platinum. As one example, various modifications are possible.

On the other hand, the method of manufacturing a transparent electrode of the present invention may further include a plating enhancement film forming step (S20) between the electrospinning step and the electroplating step. Plating enhancement film forming step (S20) is to form a plating enhancement film with a predetermined plating enhancement metal on the nanofiber web 2 formed on the nanofiber web frame. In the present embodiment, the plating enhancement film forming step S20 is performed in the nanofiber web sputtering module 9, but the plating enhancement film forming step of the present invention may be performed by another deposition method in addition to sputtering. The nanofiber web sputtering module 9 corresponds to a conventional sputtering device. An electric field is applied to the nanofiber web frame 301 in which the nanofiber web is formed in the vacuum sputtering chamber (not shown) and the plating enhancing metal, a plasma is formed in the sputtering chamber, and an inert gas, argon, is accelerated to the plating promoting metal 9a. It is possible to take a structure in which the plating enhancement metal particles generated by the collision is formed to the nanofiber web frame side. In this embodiment the preset plating enhancing metal comprises one or more of gold (Au) and platinum (Pt).

In this way, in the plating enhancement film forming step (S20), a thin coating of gold or platinum on the surface of the nanofibers formed by the nanofiber web is performed, followed by the electroplating step (S40). The particles may be plated on the surface of the nanofibers constituting the nanofiber web more quickly and easily. In the present embodiment, sputtering deposition in the plating enhancement film forming step was performed for 200 seconds in gold (Au) under a 0.08 Pa atmosphere.

As described above, the transparent electrode manufacturing apparatus and the manufacturing method of the present invention are not limited to opposing sputtering modules, and various methods are possible in a range of forming a plating enhancement film on a nanofiber web.

In addition, the transparent electrode manufacturing method of the present invention after the electroplating step before the electroplating step, if the plating enhancement film forming step (S20) is optionally further provided, after the plating enhancement film forming step web strengthening step (S30) It may be further provided. In the web reinforcing step (S30), the reinforcing web 4 supporting the nanofiber web 2 by discharging the polymer spinning liquid through the high voltage through the electrospinning nozzle 100 of the electrospinning module 10 to the nanofiber web. The polymer spinning liquid for forming the reinforcing web may be formed of the same material as the material forming the nanofiber web, and in some cases, may form the reinforcing web with different polymer spinning liquid, The thickness is also adjustable. In the case of the reinforcing web as described above, it may be formed in a random manner, or various configurations are possible, such as taking an orthogonal form using an electrospinning module arranged orthogonally.

The nanofibers constituting such a reinforcing web serves as a supporting structure that allows the nanofibers coated with gold or platinum to maintain their shape without breaking in a subsequent electroplating step (S40). That is, when the nanofibers of the reinforcing web do not form a support structure, the nanofibers formed in the step S10 are immersed in the plating solution of the electroplating module and drawn out in the process of capillary action. A fine attraction occurs between the solvent and the nanofibers in the nanofiber web, so that the nanofibers of the nanofiber web are broken. This structure can be prevented by forming a structure supported by the reinforcing web.

As described above, the transparent electrode manufacturing method of the present invention performs the nanofiber web transfer step (S50) after the electroplating step is completed. In the nanofiber web transfer step S50, the nanofiber web 2 of the nanofiber web frame 301 is transferred onto the nanofiber substrate 2a. The nanofiber substrate 2a transfers the nanofiber web 2 to the nanofiber substrate 2a when the nanofiber substrate 2a includes at least one of glass, polyimide, polyethylene terephthalate (PET), and polydimethylsiloxane (PDMS). . The transfer process may be performed through a conventional transfer process. In this embodiment, a small amount of methanol is applied to the nanofiber substrate 2a on which the nanofiber web 2 is to be transferred, and then a transfer process is performed to produce the nanofiber substrate 2a. It is also possible to enhance the transfer adhesion of the nanofiber web 2 attached to it. After applying a small amount of methanol to the nanofiber substrate 2a, the nanofiber web frame 301 is placed on the nanofiber substrate 2a to bring the nanofiber web 2 into close contact with the nanofiber substrate 2a. Thereafter, the halogel lamp is operated to transfer the nanofiber web 2 to the nanofiber substrate 2a. In this embodiment, the halogen lamp forms an irradiation state for about 5 hours with a 50W halogen lamp. The copper metal component coated on the surface of the nanofibers of the nanofiber web 2, which receives heat from the halogen lamp, forms a plasmonic effect to form heat at a localized site, and the formed heat is copper-plated metal. May be melted by a predetermined portion to enhance adhesion to the surface of the nanofiber substrate 2a.

In addition, in the above embodiment, the nanofiber substrate 2a may be formed on an amorphous material such as glass, and may be formed of a polymer compound such as polyimide, polyethylene terephthalate (PET), and polydimethylsiloxane (PDMS). It may be implemented as a substrate, the thickness of the substrate can be various configurations depending on the design specifications. For example, when a predetermined rigidity is required, the nanofiber substrate 2a may be implemented as a substrate having a predetermined thickness, or may be formed as a film-based film base and attached to other components. ) Can be variously modified according to the design purpose.

The method for manufacturing a transparent electrode of the present invention may further include a cleaning step S60 as a subsequent process executed after the nanofiber web transfer step S50 is completed. In the cleaning step S60, foreign matter attached to the nanofiber web 2 transferred and attached to the nanofiber substrate 2a may be removed, and the transparent electrode formed by the nanofiber web is implemented by performing the cleaning step. Transparency can be further improved.

In particular, in the method for manufacturing a transparent electrode of the present invention, when the web reinforcing step (S30) is further provided, the fibers constituting the reinforcing web formed to support the nanofiber web in the electroplating step are disposed outside the nanofiber web. The gap between the space where the nanofiber web forming the electrode is formed and the space other than the space may be filled to impede the permeability in terms of the overall configuration, which is unnecessary by cleaning the nanofiber web 2 as the final product performed in the cleaning step S60. It is also possible to exclude the reinforced web. In the cleaning step (S60) according to the present embodiment, a dimethylformamide solution is sprayed onto the nanofiber web 2 in which foreign substances or reinforcing webs remain, thereby forming a random-type reinforcing web formed in the foreign substance to web reinforcing step. It is also possible to remove the nanofibers, thereby improving the transmittance of the final transparent electrode.

In addition, in the method for manufacturing a transparent electrode of the present invention, after the nanofiber web transfer step S50 is completed, a protective film forming step S70 may be further provided to protect the nanofiber web. In the present embodiment, the protective film forming step S70 is performed after the cleaning step S60 is performed, and the configuration of the step may be variously modified according to manufacturing design specifications. In the protective film forming step (S70), a protective film is formed by using a predetermined oxide on the nanofiber web 2 transferred to the nanofiber substrate 2a. In this embodiment, the protective film forming step (S70) is executed in the sputtering module 9b. The sputtering module 9b used in this embodiment is a magnetron sputtering device, unlike a physical deposition method using an impact amount in which particles of argon inert gas collide with a metal target charged in a plasma atmosphere. HIPIMS (High Power Impulse Magnetron Sputtering) is used to perform coating with a strong physical force at a locally high density on a desired deposition area, but this is an embodiment of the present invention. Configuration is possible.

The preset oxide used in this embodiment is implemented with IZO, but the present invention is not limited thereto. That is, the preset oxide used in the protective film forming step S70 may be one or more of ITO, ZnO, IZO, and AZO. The protective film formed on the sputtering module 9b is applied on one surface of the nanofiber web 2 formed on one surface of the nanofiber substrate 2a, thereby forming a predetermined protective film or protective layer. In this embodiment, the high power impulse magnetron sputtering (HIPIMS) device described above was selected to enhance the selection and concentration of the deposition region. The IZO is 150 W power, 4 sccm of argon (Ar) gas flow rate, and vacuum pressure. Sputtering under 0.5 mTorr conditions, the metal fiber is more strongly adhered to the substrate so that the nanofiber web (2), the surface of the fiber is copper plated to be more closely adhered to the nanofiber substrate (2a), and at the same time IZO By forming a very thin oxide film of 10 nm or less as a protective film implemented as a coating layer, the nanofibers in the fine copper-coated nanofiber web (2) is not oxidized, it is possible to significantly increase the durability to maintain performance for a long time.

Figure 2 shows an enlarged diagram of the copper-coated nanofibers of the nanofiber web formed by the transparent electrode manufacturing method of the transparent electrode manufacturing apparatus of the present invention. SEM pictures ((a), (b), (c)) of fine copper nanofibers are shown, with perfect bonding between the copper plated coated nanofibers of the fine nanofiber webs. 3 (a), 3 (b) and 4 (a), (b) each show a nanofiber web having copper coated nanofibers attached to non-planar positions, such as a human hand or a leaf. A picture of a transparent electrode and a picture of a state capable of conducting electricity by connecting a battery and an LED to the transparent electrode are shown.

5 (a) to (e) shows a diagram of a transparent electrode implemented as a nanofiber substrate with a nanofiber web formed in accordance with an embodiment of the present invention, (a) a sheet resistance-transmittance of the transparent electrode The diagram shows that the transparent electrode of the present invention is represented by a red dot so that the sheet resistance is significantly reduced compared to other electrodes, and thus the conductivity is significantly improved. In addition, (b) to (d) of FIG. 5 is a photograph showing the transmission state of the transparent electrode according to the present invention when the nanofiber substrate is implemented by PDMS, the transmittance of the transparent electrode is shown in (e) of FIG. The wavelength diagram is shown, whereby the transmittance is kept flat over a wide range of wavelengths, thereby making it possible to confirm the versatility of the wavelength band of the transparent electrode according to the present invention. You can see the widening.

Figure 8 shows the results of the durability test of the film-type transparent electrode calculated by the manufacturing method of the present invention, (a) is a bending curvature test, (b) is a bending durability test, (c) As a diagram of the stretch test results, it can be seen that the bending curvature has an excellent value, the number of bending repetitions is excellent, the elongation with respect to elongation is excellent, and the durability of the fracture is reduced.

9 is an enlarged diagram for nanofibers of a nanofiber web formed on a nanofiber substrate of a transparent electrode produced by the manufacturing method of the present invention, as shown in (a) / (b), (c) / (d) As described above, the nanofibers can have excellent electrical properties by forming a fully bonded state by copper metal to facilitate the movement of electrons and rapidly reduce the sheet resistance.

The transparent electrode obtained through the transparent electrode manufacturing method and the transparent electrode manufacturing apparatus of the present invention can be used in various fields such as electronic products, mechanical devices, etc. in fields requiring heat dissipation, heat transfer, heat reception, and the like, such as heat dissipation or heat transfer.

The above description is merely illustrative of the technical idea of the present invention, and those skilled in the art to which the present invention pertains may make various modifications and changes without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

The present invention provides an apparatus and method for manufacturing a transparent electrode using nanofiber line patterning technology and sputtering technology, but in addition to the transparent electrode, it is possible to use a metal having excellent electrical conductivity and at the same time to realize high performance in a small amount. Therefore, the present invention may be applied to various fields such as an electric device to have a great advantage in efficiency and cost.

Claims

An electrospinning step of forming a nanofiber web into which the polymer spinning solution is discharged through high voltage through an electrospinning nozzle of the electrospinning module to form a fiber;

And electroplating the nanofiber web with a predetermined metal in an electroplating module.
The method of claim 1,

In the electrospinning step,

The electrospinning nozzle is provided with a nanofiber web frame which is applied with a voltage through the high voltage unit 200 of the electrospinning module and grounded at a corresponding position of the electrospinning nozzle, and the nanofiber web is the nanofiber web frame. It is formed in the transparent electrode manufacturing method characterized in that.
The method of claim 2,

In the electroplating step,

Immersion step of receiving an electroplating anode formed of a predetermined plating metal and a plating solution in which the nanofiber web frame can be immersed in the electroplating module tank of the electroplating module and immersing the electroplating anode and the nanofiber web frame. ;

And applying a power to the nanofiber web frame and the electroplating anode to an electroplating power source of the electroplating module.
The method of claim 3, wherein

And a plating enhancement film forming step of forming a plating enhancement film with a plating enhancement metal on the nanofiber web formed on the nanofiber web frame between the electrospinning step and the electroplating step. Manufacturing method.
The method of claim 4, wherein

The preset plating enhancing metal comprises at least one of gold and platinum,

And the plating enhancing film forming step is a deposition step of sputtering deposition of the predetermined plating enhancement metal on the nanofiber web sputtering module.
The method of claim 2,

A web reinforcing step of forming a reinforcing web supporting the nanofiber web by discharging a polymer spinning liquid through a high voltage through an electrospinning nozzle of an electrospinning module to the nanofiber web after the electrospinning step and before the electroplating step. Transparent electrode manufacturing method characterized in that it further comprises.
The method of claim 2,

And a nanofiber web transfer step of transferring the nanofiber web frame onto a nanofiber substrate after the electroplating step.
The method of claim 7, wherein

The nanofiber substrate is a transparent electrode manufacturing method, characterized in that at least one of glass, polyimide (Polyimide), PET (Polyethylen Terephthalate), and PDMS (Polydimethylsiloxane).
The method of claim 7, wherein

After the nanofiber web transfer step, the transparent electrode manufacturing method characterized in that it further comprises a cleaning step for cleaning the nanofiber web transferred to the substrate.
The method of claim 7, wherein

And a protective film forming step of forming a protective film using a predetermined oxide on the nanofiber web transferred to the substrate after the nanofiber web transferring step.
The method of claim 10,

And said preset oxide is at least one of ITO, ZnO, IZO, and AZO.
The method of claim 1,

In the electrospinning step,

The ground electrode formed on the stage where the nanofiber web frame is disposed is disposed so that two or more pairs facing each other with the nanofiber web frame interposed therebetween, and the pair of ground electrodes are alternately charged. Transparent electrode manufacturing method.
An electrospinning module for forming a nanofiber web into which a polymer spinning liquid is discharged through high voltage through an electrospinning nozzle to form a fiber;

An electroplating module for electroplating the nanofiber web in a electroplating module with a predetermined metal,

The electrospinning module,

A stage on which the nanofiber web frame is disposed to face the electrospinning nozzle to form the nanofiber web;

A high voltage generator for applying a high voltage to the electrospinning nozzle;

And a ground power source for forming an electric field in a space between the electrospinning nozzle and the fiber discharged from the electrospinning nozzle so as to be induced by an electrostatic force.

The ground power source is:

A pair of ground electrodes disposed to intersect two or more of the pair facing each other with the nanofiber web frame interposed therebetween,

And a movable terminal capable of intermittent connection with the ground electrode pair.