KR101676760B1 - Electro-spinning apparatus using electric field and method of manufacturing a transparent electrode using the same - Google Patents

Electro-spinning apparatus using electric field and method of manufacturing a transparent electrode using the same Download PDF

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KR101676760B1
KR101676760B1 KR1020150050246A KR20150050246A KR101676760B1 KR 101676760 B1 KR101676760 B1 KR 101676760B1 KR 1020150050246 A KR1020150050246 A KR 1020150050246A KR 20150050246 A KR20150050246 A KR 20150050246A KR 101676760 B1 KR101676760 B1 KR 101676760B1
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South Korea
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nanofibers
voltage
electrode
alignment direction
nanomaterial
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KR1020150050246A
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Korean (ko)
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KR20160120966A (en
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박장웅
현병관
지상윤
안병완
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울산과학기술원
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Priority to KR1020150050246A priority Critical patent/KR101676760B1/en
Priority to PCT/KR2016/002446 priority patent/WO2016163650A1/en
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like

Abstract

The electrospinning apparatus according to the present invention can concentrate the nanofibers emitted from the spinning nozzle to the central portion of the concentrated auxiliary electrode by disposing the concentrated auxiliary electrode between the integrated substrate and the spinning nozzle, . The control auxiliary electrode is disposed between the integrated substrate and the spinning nozzle, and the voltage is periodically changed and applied so that a voltage difference is generated between the opposing electrodes, thereby aligning and moving the nanofibers radiated from the spinning nozzle in a predetermined alignment direction It is possible to produce a transparent electrode made of nanofibers having a directionality. Further, since the transparent electrode using the nanofibers of the grid pattern can be produced, the surface roughness and density of the transparent electrode can be precisely controlled. In addition, it is possible to provide a transparent electrode having a grid pattern having flexibility and stretchability by a simple and economical process, and the flexible display device or the flexible display device can be easily realized using the transparent electrode. Further, since the co-axial double-layer fiber is formed by spinning the nanomaterial and the polymer material together, and the polymer material is removed to provide the transparent electrode, the process is very simple and economical.

Description

TECHNICAL FIELD The present invention relates to an electrospinning device using an electric field and a method of manufacturing a transparent electrode using the electrospinning device.

The present invention relates to an electrospinning device using an electric field and a method of manufacturing a transparent electrode using the electrospinning device. More particularly, the present invention relates to an electrospinning device using an electric field, To an electrospinning device using an electric field capable of producing nanofibers of a bilayer structure and a method of manufacturing a transparent electrode using the electrospinning device.

Due to the recent development of smart electronic devices, studies are being made on a flexible display device or a stretchable display device that replaces a conventional solid display device. A transparent electrode having transparency is required for a display device, and indium tin oxide (ITO) has been conventionally used. However, such indium tin oxide is low in flexibility and stretchability, and thus is hardly applicable to a flexible display device.

In order to overcome the limitations of such indium main line oxides, transparent electrodes using other materials, for example, graphene or silver nanowires, have been developed. However, research results to date show that transparent electrodes using graphene or silver nanowire have complicated processes, low reliability of the products, and high cost.

Korean Patent No. 10-1197986

It is an object of the present invention to provide an electrospinning device using an electric field capable of producing coaxial double layered nanofibers having flexibility and stretchability in a simple and economical process and a method for manufacturing the transparent electrode using the same .

An electrospinning device using an electric field according to the present invention includes an inner nozzle to which a voltage is applied and which emits at least one of a nano material and a polymer material, A spinneret for spinning nanofibers made of the nanomaterial and a polymeric material layer made of the polymer material, the nanofibers being made of a coaxial double layer; An integrated substrate on which nanofibers emitted from the spinning nozzle and nanofibers including the polymer material are integrated; The nanofibers are disposed between the spinning nozzle and the integrated substrate to generate an electric field to prevent dispersion of the nanofibers so that the nanofibers radiated from the spinning nozzle are concentratedly radiated in a linear shape, And an electric field generating module for aligning the electric field.

A method of manufacturing a transparent electrode using an electrospinning device according to the present invention includes the steps of disposing a plurality of auxiliary electrodes between an integrated substrate and a spinneret so as to surround nanofibers radiated from the spinneret; Applying a voltage to the spinneret to spin nanofibers formed of a nanomaterial layer formed of a nanomaterial and a polymer material layer formed of a polymer material from the spinneret on the integrated substrate; Applying a predetermined voltage to the plurality of auxiliary electrodes to concentrate the nanofibers emitted from the spinning nozzle in a linear form by an electric field generated between the plurality of auxiliary electrodes; Wherein a voltage is applied to the auxiliary electrodes opposite to each other among the plurality of auxiliary electrodes so that a voltage opposite to the auxiliary voltage is applied or a voltage of a different magnitude is applied, Wherein the nanofibers concentrated in a linear form are aligned in a predetermined alignment direction; And removing the polymer material from the nanofibers to form a transparent electrode composed of the nanomaterial.

The electrospinning apparatus according to the present invention can concentrate the nanofibers emitted from the spinning nozzle to the central portion of the concentrated auxiliary electrode by disposing the concentrated auxiliary electrode between the integrated substrate and the spinning nozzle, .

The control auxiliary electrode is disposed between the integrated substrate and the spinning nozzle, and the voltage is periodically changed and applied so that a voltage difference is generated between the opposing electrodes, thereby aligning and moving the nanofibers radiated from the spinning nozzle in a predetermined alignment direction It is possible to produce a transparent electrode made of nanofibers having a directionality.

Further, since the transparent electrode using the nanofibers of the grid pattern can be produced, the surface roughness and density of the transparent electrode can be precisely controlled.

In addition, it is possible to provide a transparent electrode having a grid pattern having flexibility and stretchability by a simple and economical process, and the flexible display device or the flexible display device can be easily realized using the transparent electrode.

Further, since the co-axial double-layer fiber is formed by spinning the nanomaterial and the polymer material together, and the polymer material is removed to provide the transparent electrode, the process is very simple and economical.

1 is a view showing an electrospinning apparatus according to an embodiment of the present invention.
FIG. 2 is a view showing a method of aligning nanofibers using the electrospinning apparatus shown in FIG. 1. FIG.
3 is an enlarged cross-sectional view of the spinneret shown in Fig.
4 is a perspective view showing nanofibers made of a coaxial double layer by the electrospinning apparatus shown in FIG.
5 is a flowchart illustrating a method of manufacturing a transparent electrode using an electrospinning device according to an embodiment of the present invention.
6 is a view showing an electrospinning device according to another embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.

1 is a view showing an electrospinning apparatus according to an embodiment of the present invention. FIG. 2 is a view showing a method of aligning nanofibers using the electrospinning apparatus shown in FIG. 1. FIG. 3 is an enlarged cross-sectional view of the spinneret shown in Fig. 4 is a perspective view showing nanofibers made of a coaxial double layer by the electrospinning apparatus shown in FIG.

Referring to FIG. 1, an electrospinning device according to an embodiment of the present invention includes a spinning nozzle 10, an integrated substrate 20, an electric field generating module, and a power supply unit 70.

Referring to FIG. 3, the spinning nozzle 10 is connected to a spinning solution tank 40 and a syringe pump (not shown).

The spinning solution tank 40 stores a spinning solution for spinning. The spinning solution comprises a nanomaterial and a polymeric material. The spinning solution tank 40 includes a nanomaterial tank 41 including the nanomaterial having conductivity and a polymer material tank 42 including the polymer material.

The nanomaterial layer 51 formed from the nanomaterial and the nanomaterial may be composed of various nanoparticles and may include nanoparticles, nanowires, nanotubes, nano- And may include at least one selected from the group consisting of a nanorod, a nanowall, a nanobelt, and a nanorring.

The nanomaterial and nanomaterial layer 51 may include nanoparticles such as copper, silver, gold, copper oxide, cobalt, and the like. The nanomaterial and nanomaterial layer 51 may include nanowires such as copper nanowires, silver nanowires, gold nanowires, and cobalt nanowires.

Also, the nanomaterial and the nanomaterial layer 51 may be composed of a nanomaterial solution in which the nanomaterial is dissolved in a soluble solvent such as methanol, acetone, tetrahydrofuran, toluene, or dimethylformamide. For example, the soluble solvent may be selected from the group consisting of Alkanes such as hexane, Aromatics such as toluene, ethers such as diethyl ether, chloroform, Such as alkyl halides, such as Alkyl halides, Esters, Aldehydes, Ketones, Amines, Alcohols, Amides, Carboxylic acids, Carboxylic acids, and water. In addition, for example, the nanomaterial solution can be formed using the organic solvent described below. However, the nanomaterials are illustrative, and the technical idea of the present invention is not limited thereto.

The polymer material layer 52 formed from the polymer material and the polymer material is a polymer solution including various polymer materials. The polymeric material may be selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polydimethylsiloxane (PDMS), polyurethane, polyether urethane, cellulose acetate, cellulose acetate butyl (PMA), polyvinyl acetate (PVAc), polyacrylonitrile (PAN), polyperfuryl alcohol (PPFA), polystyrene, polyethylene oxide (PEO), polypropylene oxide (PPO), polycarbonate (PC), polyvinyl chloride (PVC), polycaprolactone, polyvinyl fluoride, and polyamide.

In addition, the polymer material and the polymer material layer 52 may include a copolymer of the above-described materials, and examples thereof include a polyurethane copolymer, a polyacrylic copolymer, a polyvinyl acetate copolymer, a polystyrene copolymer, Polyethylene oxide copolymer, polypropylene oxide copolymer, and polyvinylidene fluoride copolymer. [0033] The term " copolymer "

The polymer material and the polymer material layer 52 may be composed of a polymer solution in which the above polymer material is dissolved in a soluble solvent such as methanol, acetone, tetrahydrofuran, toluene, or dimethylformamide. For example, the soluble solvent may be selected from the group consisting of Alkanes such as hexane, Aromatics such as toluene, ethers such as diethyl ether, chloroform, Such as alkyl halides, such as Alkyl halides, Esters, Aldehydes, Ketones, Amines, Alcohols, Amides, Carboxylic acids, Carboxylic acids, and water. However, such a polymer solution is illustrative, and the technical idea of the present invention is not limited thereto.

The spinning nozzle 10 receives the nanomaterial and the polymer material from the spinning solution tank 10 and radiates through a tip of the spinneret located at the end. The spinning nozzle 10 includes an inner nozzle 11 for radiating at least one of the nanomaterial and the polymer material and a spinneret 11 surrounding the inner nozzle 11, And an outer nozzle 12 that emits radiation. In this embodiment, the inner nozzle 11 is connected to the nanomaterial tank 41 to emit the nanomaterial supplied from the nanomaterial tank 41, and the outer nozzle 12 is connected to the polymer material The polymer material tank 42 is connected to the polymer material tank 42 and the polymer material supplied from the polymer material tank 42 is radiated. That is, since the spinning nozzle 10 has a coaxial double cylinder structure, the nanomaterial and the polymer material can be radiated together without being mixed. Accordingly, the spinning nozzle 10 can spin the nanomaterial layer 51 formed of the nanomaterial and the polymer material layer 52 formed of the polymer material to form a coaxial double layer structure.

The syringe pump (not shown) pumps the spinning solution filled in the spinning nozzle 10. In the present embodiment, the spinning nozzle 10 is shaped like a syringe, and the syringe pump (not shown) presses the piston of the syringe. A pump (not shown) is built in the spinning solution tank 40 so as to press the spinning solution in the spinning solution tank 40 from the spinning solution tank 40 to the spinning nozzle 10 It is also possible to provide a spinning solution.

The integrated substrate 20 is a substrate on which the nano material layer 51 and the polymer material layer 52 radiated from the spinning nozzle 10 are integrated with the nanofibers 50 having a coaxial double layer structure. The integrated substrate 20 has a flat plate shape, but the present invention is not limited thereto. For example, the integrated substrate 20 may have a plate shape, a drum shape, a parallel rod shape, an intersecting rod shape, or a grid shape. The integrated substrate 20 is located on the lower side of the spinning nozzle 10 and is a nonconductive substrate. In the present embodiment, the integrated substrate 20 is a plate-shaped substrate. However, the present invention is not limited thereto, and a free standing substrate which does not support the lower side of the object to be integrated may be used. It may be a frame shape having a central portion penetrating therethrough, or a horseshoe shape having a central portion opened and an outer frame not connected. It may also have a polygonal shape with a central portion open and an outer rim connected, or a polygonal shape with a central portion open and an outer rim connected. The method further comprises a step of separating the nanofibers irradiated and aligned on the integrated substrate when the free standing substrate is used, from the integrated substrate and transferring the separated nanofibers to a separate substrate.

Integrated electrodes (21) are provided under the integrated substrate (20). The integrated electrode 21 has a voltage opposite to that of the spinning nozzle 10 or is grounded so as to generate an electric field by generating a voltage difference between the spinning nozzle 10 and the spinning nozzle 10.

The power supply unit (70) applies a voltage to the spinning nozzle (10). When a voltage is applied to the spinning nozzle 10 by the power supply unit 70, The integrated electrode 21 is grounded to generate a voltage difference with the spinning nozzle 10. In this embodiment, about 11.8 kV is applied to the spinning nozzle 10, and the integrated electrode 21 has a ground voltage, for example, a voltage of 0 V, for example. In the present embodiment, the voltage is DC (DC), but it is of course possible to use alternating current (AC). When the alternating current is used, the spinning nozzle 10 and the ground electrode 21 are controlled to have voltages opposite to each other. When the alternating current is used, the thickness of the nanofibers to be integrated in the integrated substrate 20 can be increased to manufacture a thicker transparent electrode.

The electric field generation module includes a plurality of auxiliary electrodes 60 disposed between the spinneret 10 and the integrated substrate 20 to generate an electric field and a plurality of auxiliary electrodes 60 And an auxiliary electrode power supply unit.

The plurality of auxiliary electrodes 60 are formed to have a ring shape. In the present embodiment, the plurality of auxiliary electrodes 60 are composed of four auxiliary electrodes, for example. However, the present invention is not limited to this, and the number of the plurality of auxiliary electrodes 60 may be set to be proportional to the alignment direction of the nanofibers. The four auxiliary electrodes 60 are formed in a ring shape and spaced apart from each other by a predetermined distance so that different voltages may be applied to the four auxiliary electrodes 60.

When the predetermined voltage is applied from the auxiliary electrode power supply unit, the plurality of electrodes 60 are used as a central electrode that concentrates the nanofibers in a linear shape. When the voltage is periodically changed and applied from the auxiliary electrode power supply unit And may be used as a steering electrode for aligning the nanofibers in a predetermined alignment direction. The voltage applied to the plurality of electrodes 60 may be applied to the spinneret 10 in a voltage similar to the voltage applied to the spinneret 10. In the present embodiment, for example, when a voltage of about 11.8 kV is applied to the spinning nozzle 10, about 11 kV is applied to the plurality of electrodes 60 when used as the concentrated electrode . On the other hand, when used as the steering electrode, at least a part of the plurality of electrodes 60 is applied or grounded in a voltage opposite to the voltage applied to the spinning nozzle 10. In this embodiment, a ground voltage, for example, a voltage of 0 V, is applied to at least a portion of the plurality of electrodes 60 when used as the steering electrode, for example.

As described above, in the present embodiment, the plurality of electrodes 60 serve as both the central electrode and the steering electrode. However, the present invention is not limited to this, The central electrode and the steering electrode may be included, or the central electrode and the steering electrode may be separately provided. When the plurality of electrodes 60 serve only as the central electrode, a moving mechanism for moving the integrated substrate 20 in the alignment direction may be provided.

The plurality of electrodes 60 includes a pair of first and second control assistant electrodes 61 and 62 spaced apart from each other by a predetermined first alignment direction X of the nanofibers 50, And a pair of third and fourth control auxiliary electrodes 63 and 64 arranged at a predetermined distance from each other in the second alignment direction Z intersecting the first alignment direction X with a predetermined angle . The first, second, third, and fourth steering assist electrodes 61, 62, 63, and 64 are spaced from each other by a predetermined distance from each other to form a single ring. In the present embodiment, the setting angle is 90 degrees, for example.

The auxiliary electrode power supply unit includes four first, second, third, and fourth power supply units for applying voltages to the first, second, third, and fourth steering assist electrodes 61, 62, 63, 71) (72) 73 (74). A first power supply unit 71 for applying a voltage to the first control assistant electrode 61, a second power supply unit 72 for applying a voltage to the second control assistant electrode 62, A third power supply part 73 for applying a voltage to the third control auxiliary electrode 63 and a fourth power supply part 74 for applying a voltage to the fourth control auxiliary electrode 64. The voltage applied from the auxiliary electrode power supply unit is an alternating current (AC), for example.

5 is a flowchart illustrating a method of manufacturing a transparent electrode using an electrospinning device according to an embodiment of the present invention.

Referring to FIG. 5, a method of manufacturing a transparent electrode using an electrospinning device according to an embodiment of the present invention will now be described.

A plurality of auxiliary electrodes 60 are disposed between the integrated substrate 20 and the spinneret 10. (S11)

In this embodiment, the four first, second, third, and fourth steering assist electrodes 61, 62, 63, and 64 are disposed, for example. The first, second, third, and fourth steering assist electrodes 61, 62, 63, and 64 are spaced from each other by a predetermined distance to form a single ring. If the first, second, third, and fourth steering assist electrodes 61, 62, 63, and 64 have a circular or oval ring shape, the first, 61, 62, 63, 64, the nanofibers can be concentrated to the center of the ring shape. However, the shape formed by the first, second, third, and fourth steering assist electrodes 61, 62, 63, and 64 is not limited to the ring shape and the nanofibers emitted from the spinning nozzle 10 may be surrounded A polygonal shape or the like is of course possible. In addition, the number of the auxiliary electrodes 60 is not limited to four, but may be set to be proportional to the alignment direction of the nanofibers 50.

 When a voltage is applied to the spinning nozzle 10, the nanomaterial and the polymer material are emitted together from the spinning nozzle 10. The voltage may vary depending on the type of the spinning solution, the type of the integrated substrate 20, the process environment, and the like, and may range from about 100 V to 30000 V. In this embodiment, a description will be given of an example in which a voltage of about 11.8 kV is applied to the spinning nozzle 10. The nanomaterial and the polymeric material may be simultaneously emitted and may have the same emission length. The polymer material in the outer nozzle 12 of the spinning nozzle 10 is radiated into a hollow cylinder shape and the nanomaterial in the inner nozzle 11 is discharged while being filled in the polymer material, And solidified into the nanofibers 50 having a bilayer structure. That is, referring to FIG. 4A, the nanofibers 50 emitted from the spinning nozzle 10 have a coaxial double layer structure composed of the polymer material layer 52 and the nanomaterial layer 51. At this time, the nanomaterial and the polymer material are not mixed with each other. It is preferable that the spinning speed of the polymer material is equal to or larger than the spinning speed of the nanomaterial. The polymer material and the nanomaterial should have the same or similar vapor pressure. Also, the viscosity of the polymer material should be equal to or greater than the viscosity of the nanomaterial. (S12)

When a voltage is applied to the spinning nozzle 10, a preset voltage is also applied to the first, second, third, and fourth steering assist electrodes 61, 62, 63, The set voltage is a voltage having a magnitude similar to that applied to the spinning nozzle 10 and is applied to the first, second, third, and fourth steering assist electrodes 61, 62, 63, Are set to be equal in size to each other. When the set voltage of a predetermined magnitude is applied to the first, second, third, and fourth steering assist electrodes 61, 62, 63 and 64, the nanofibers 50 radiated from the spinning nozzle 10, The first, second, third, and fourth steering assist electrodes 61, 62, 63, and 64, respectively. The nanofibers 50 are concentrated at the central portions of the first, second, third and fourth steering assist electrodes 61, 62, 63 and 64 so that the nanofibers 50 are not whipped or dispersed, (S13). ≪ RTI ID = 0.0 >

When the nanofibers 50 are concentrated in a linear shape, the voltages applied to the first, second, third and fourth steering assist electrodes 61, 62, 63 and 64 are periodically changed, (50) in the alignment direction. The change period of the voltage may be set in consideration of an alignment direction or a length of the nanofibers 50. (S14) The larger the difference in voltage applied to the first, second, third and fourth steering assist electrodes 61, 62, 63 and 64 is, the more the nanofibers 50 can move in the alignment direction have. Also, as the distance between the first, second, third, and fourth steering assist electrodes 61, 62, 63, and 64 is closer, the nanofibers 50 can move more easily in the alignment direction.

2A and 2B, when the nanofibers 50 are aligned in the first alignment direction X, the first and second steering assist electrodes 61, The voltage of the capacitor C is periodically changed. That is, when voltages opposite to each other or voltages having different magnitudes are applied to generate the voltage difference between the first control auxiliary electrode 61 and the second control auxiliary electrode 62 disposed opposite to each other, The nanofibers 50 can be moved in the first alignment direction X and aligned. In this embodiment, a voltage having a magnitude similar to that of the spinning nozzle 10 is applied to either the first control assist electrode 61 or the second control assist electrode 62, A voltage of 0 V is applied to the nanofibers 50 to move the nanofibers 50 toward the ground voltage.

2A, if a ground voltage is applied to the first steering assist electrode 61, the positively charged nanofibers 50 move in the direction toward the first steering assist electrode 61 do. Therefore, the nanofibers 50 are aligned while moving in the direction (-X) toward the first control assist electrode 61. At this time, if the difference in voltage between the third control auxiliary electrode 63 and the fourth control auxiliary electrode 64 is controlled, the nanofibers aligned in the first alignment direction X are aligned in the second alignment direction And may be formed in a plurality of rows in the second alignment direction Z while being moved in the Z direction. Referring to FIG. 2B, when the ground voltage is applied to the second control assist electrode 62, the nanofibers 50 that are positively charged move in the direction toward the second control assist electrode 62 do. Accordingly, the nanofibers 50 are aligned while moving in the direction X toward the second control assist electrode 62. At this time, it is possible to control the difference in voltage between the third control auxiliary electrode 63 and the fourth control auxiliary electrode 64 so as to move to the second alignment direction Z as well.

2C, when the grid structure is formed by aligning the nanofibers 50 in the second alignment direction Z, the third control auxiliary electrode 63 and the fourth control auxiliary electrode 64 ) Is periodically changed. That is, a voltage opposite to that of the third control auxiliary electrode 63 and the fourth control auxiliary electrode 64, which are arranged to face each other in the second alignment direction Z, The nanofibers 50 can be aligned while moving in the second alignment direction Z by an electric field generated by a voltage difference. In this embodiment, a voltage having a magnitude similar to that of the spinning nozzle 10 is applied to either the third control auxiliary electrode 63 or the fourth control auxiliary electrode 64, and the other is a ground voltage, A voltage of 0 V is applied to the nanofibers 50 to move the nanofibers 50 to the ground voltage side.

2C, when the grounding voltage is applied to the third control auxiliary electrode 63, the nanofibers 50 having a positive charge can move in the direction toward the third control auxiliary electrode 63 have. Therefore, the nanofibers 50 can be aligned while moving in the direction (-Z) toward the third control assist electrode 63. At this time, if the difference in voltage between the first and second control assist electrodes 61 and 62 is controlled, the nanofibers 50 aligned in the second alignment direction (Z) And may be formed in a plurality of rows in the first alignment direction X while being shifted by a predetermined distance in the first alignment direction X as well. 2 (d), when the ground voltage is applied to the fourth control auxiliary electrode 64, the nanofibers 50 that are positively charged are directed in the direction toward the fourth control auxiliary electrode 64 Move. Therefore, the nanofibers 50 can be aligned while moving in the direction Z toward the fourth control assist electrode 64. At this time, if the difference in voltage between the first and second control assist electrodes 61 and 62 is controlled, the nanofibers 50 aligned in the second alignment direction (Z) And may be formed in a plurality of rows in the first alignment direction X while being shifted by a predetermined distance in the first alignment direction X as well.

When the nanofibers of the grid structure are formed as described above, annealing is performed. The annealing may increase the bonding force between the nanomaterials in the nanomaterial layer 51. The annealing may be performed in a temperature range in which the integrated substrate 20 is not damaged. The anneal may be performed at a temperature in the range of, for example, about 20 캜 to about 500 캜, and may be performed at a temperature in the range of, for example, about 20 캜 to about 300 캜. The annealing may be performed in an air atmosphere, an inert atmosphere containing argon gas or nitrogen gas, or a reducing atmosphere containing hydrogen gas. The annealing is optional and may be omitted. (S15)

Thereafter, the polymer material layer 52 is removed to form a transparent electrode composed only of the nanomaterial layer 51. (S16) (S17) The polymer material layer 52 is removed by using an organic solvent can do. Referring to FIG. 4, it can be confirmed by comparing before and after the removal of the polymer material layer.

The organic solvent may include all kinds of solvents capable of dissolving the polymer material layer 52. The organic solvent may be selected from the group consisting of Alkanes such as hexane, Aromatics such as toluene, ethers such as diethyl ether, alkyl halides such as chloroform, Alkyl halides, Esters, Aldehydes, Ketones, Amines, Alcohols, Amides, Carboxylic acids, Carboxylic acids, And water. The organic solvent may be, for example, acetone, fluoroalkanes, pentanes, hexane, 2,2,4-trimethylpentane, decane Decene, cyclohexane, cyclopentane, diisobutylene, 1-pentene, carbon disulfide, carbon tetrachloride, 1- Examples of the solvent include chlorobutane, 1-chloropentane, xylene, diisopropyl ether, 1-chloropropane, 2-chloropropane, ), Toluene (Toluene), Chlorobenzene, Benzene, Bromoethane, Diethyl ether, Diethyl sulfide, Chloroform, Dichloromethane Dichloromethane, 4-Methyl-2-propanone, Tetrahydrofuran, 1,2-Dichloroethane, 2- But are not limited to, 2-butanone, 1-nitropropane, 1,4-dioxane, ethyl acetate, methyl acetate, 1-pentanol, dimethyl sulfoxide, aniline, diethylamine, nitromethane, acetonitrile, pyridine, 2-butoxyethanol (2- Butoxyethanol, 1-propanol and 2-propanol), ethanol, methanol, ethylene glycol, and acetic acid. And may include at least any one of them.

However, the present invention is not limited to this, and the polymer material layer 52 may be removed by reactive ion etching.

Referring to FIG. 4A, the nanofibers 50 surround the polymeric material layer 52. Referring to FIG. 4B, when the polymer material layer 52 is removed, only the nanomaterial layer 51 is left, and the transparent electrode is composed of the nanomaterial layer 51 only. The nanomaterial layer 51 is rod-shaped.

The transparent electrode may further include a transparent conductive layer (not shown) formed on the nanomaterial layer 51. The transparent conductive layer may include a transparent material and may include a conductive material. The transparent conductive layer can reduce the electrical resistance of the transparent electrode and realize an electrode that applies more current more uniformly. The transparent conductive layer may cover the transparent electrode, and the nanomaterial layer 51 may be shielded from external air to prevent oxidation. The transparent conductive layer may include a conductive two-dimensional nanomaterial layer. The two-dimensional nanomaterial layer may be composed of two-dimensional nanomaterials and may include carbon nanomaterials such as graphene, graphite, or carbon nanotubes. The meaning of the two-dimensional nanomaterial means that the nanomaterial has a planar shape, for example, a shape such as a sheet.

Alternatively, the nanofibers 50 may be radiated so that the nanomaterial layer formed from the nanomaterial is surrounded by the polymer material layer. When the polymer material layer is removed, It is also possible that a transparent electrode made of a layer is formed.

6 is a view showing an electrospinning device according to another embodiment of the present invention.

6, a plurality of auxiliary electrodes of the electrospinning device according to another embodiment of the present invention is different from the above embodiment in that the concentration assist electrode 65 and the steering assist electrode 60 are separately provided, The different points will be described in detail.

The concentrated auxiliary electrode 65 is disposed so as to surround the nanofibers 50 radiated from the spinning nozzle 10 and a predetermined voltage is applied from the concentrated auxiliary electrode power supply unit 75. The concentration-assisting electrode 65 is composed of a single ring-shaped electrode. The concentrated auxiliary electrode 65 is applied with the same voltage as that of the spinning nozzle 10 to concentrate the nanofibers 50 at the center of the ring.

The steering assist electrode 60 is disposed at a position spaced apart from the concentration-assisting electrode 65 in the radial direction -Y of the nanofibers 50. The steering assist electrode 60 is exemplified by four first, second, third and fourth steering assist electrodes 61, 62, 63 and 64, and the four first, 3 and 4 control assistant electrodes 61, 62, 63 and 64 are spaced apart from each other by a predetermined distance to form one ring. When a voltage is applied to the first, second, third, and fourth steering assist electrodes 61, 62, 63, and 64 so that a pair of electrodes facing each other generate a voltage difference, 50) in the first alignment direction (X) or the second alignment direction (Z).

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

10: Spinning nozzle 20: Integrated substrate
50: nanofiber 51: nanomaterial layer
52: Polymer material layer 60: Steering assist electrode
65: Concentrating auxiliary electrode

Claims (15)

An internal nozzle to which a nanomaterial solution mixed with a nanomaterial selected from the group consisting of gold, silver, copper, copper oxide and cobalt is mixed with a solvent to which a voltage is applied, A spinneret for spinning a nanofiber formed of the nanomaterial and a polymeric material layer formed of the polymer material, the nanofiber comprising a coaxial double layer;
An integrated substrate on which the nanofibers are integrated;
The nanofibers are disposed between the spinning nozzle and the integrated substrate to generate an electric field to prevent dispersion of the nanofibers so that the nanofibers radiated from the spinning nozzle are concentratedly radiated in a linear shape, And an electric field generating module for aligning,
The spinning speed of the polymer material is larger than the spinning speed of the nanomaterial,
And removing the polymer material layer from the aligned nanofibers. The method according to claim 1,
The electric field generation module includes:
A plurality of auxiliary electrodes disposed to surround the nanofibers emitted from the spinning nozzle,
And a power supply for applying a voltage to the plurality of auxiliary electrodes. The method of claim 2,
Wherein the plurality of auxiliary electrodes are spaced apart from each other by a predetermined distance to form one ring. The method of claim 2,
Wherein the plurality of auxiliary electrodes comprise:
Wherein the nanofibers are concentrated in a linear form when a predetermined voltage is applied from the power supply unit,
And wherein when the voltage is periodically changed and applied from the power supply unit, the nanofibers are moved and aligned in the alignment direction. The method of claim 4,
Wherein the plurality of auxiliary electrodes comprise:
When the same voltage is applied to the nanofibers, the nanofibers are concentrated in a linear shape, and when voltages opposite to each other or different voltages are periodically changed and applied A pair of first and second control auxiliary electrodes for moving the nanofibers in the first alignment direction,
And a second alignment direction intersecting the first alignment direction at a predetermined angle. When the same voltage is applied to the nanofibers, the nanofibers are concentrated in a linear shape, and voltages having opposite voltages or different sizes And a pair of third and fourth steering assist electrodes that move the nanofibers in the second alignment direction if they are periodically changed. The method of claim 2,
Wherein the plurality of auxiliary electrodes comprise:
And a concentration auxiliary electrode to which the predetermined voltage is applied from the power supply unit to concentrate the nanofibers in a linear shape. The method of claim 6,
Wherein the plurality of auxiliary electrodes comprise:
Further comprising a steering assist electrode for applying and varying a voltage periodically from the power supply unit to move and align the nanofibers in the alignment direction by the electric field generated according to the change in the voltage. The method of claim 2,
Wherein the plurality of auxiliary electrodes comprise:
A concentrated auxiliary electrode disposed to surround the nanofibers emitted from the spinning nozzle, the concentrated auxiliary electrode being applied with a predetermined voltage from the power supply unit to concentrate the nanofibers in a linear shape;
Wherein the voltage applied from the power supply unit is periodically changed so that the nanofibers are moved in the alignment direction by an electric field generated in accordance with the change of the voltage, And a steering assist electrode for moving and aligning the electrodes. The method according to claim 7 or 8,
The steering assist electrode includes:
The nanofibers are disposed opposite to each other in a predetermined first alignment direction of the nanofibers, and when a voltage or a voltage of a different magnitude is periodically changed, A first and second steering assist electrodes,
And a second alignment direction intersecting the first alignment direction at a predetermined angle. When a voltage having a voltage opposite to the first voltage or a voltage having a different magnitude is periodically applied to the first alignment direction, the nanofibers are aligned in the second alignment direction And a pair of third and fourth steering assist electrodes to be moved. Disposing a plurality of auxiliary electrodes between the integrated substrate and the spinneret so as to surround the nanofibers emitted from the spinneret;
Applying a voltage to the spinneret to form a nano-substance mixed with a solvent and a nanomaterial selected from the group consisting of gold, silver, copper, copper oxide, and cobalt from the inner nozzle of the spinneret, A polymer solution including a polymer material is radiated from an outer nozzle of the spinning nozzle to spin a nanofiber material layer formed of the nanomaterial and a polymer material layer formed of the polymer material, ;
Applying a predetermined voltage to the plurality of auxiliary electrodes to concentrate the nanofibers emitted from the spinning nozzle in a linear form by an electric field generated between the plurality of auxiliary electrodes;
Wherein a voltage is applied to the auxiliary electrodes opposite to each other among the plurality of auxiliary electrodes so that a voltage opposite to the auxiliary voltage is applied or a voltage of a different magnitude is applied, Moving the nanofibers in a predetermined alignment direction to form aligned nanofibers;
And removing the polymer material from the nanofibers to form an electrode composed of the nanomaterial,
Wherein the spinning speed of the polymer material is set to be larger than the spinning speed of the nanomaterial. The method of claim 10,
The method of claim 1, further comprising the step of separating the nanofibers from the integrated substrate and transferring the nanofibers to a separate substrate after the step of forming the nanofibers. The method of claim 11,
Wherein the integrated substrate is an electrospinning device using an electric field that is a free standing substrate. The method of claim 10,
Wherein forming the electrode comprises:
A method of manufacturing a transparent electrode using an electrospinning device using an electric field in which an organic solvent or a reactive ion etching is used to remove the polymeric material. The method of claim 10,
Wherein forming the electrode comprises:
And forming a transparent conductive layer on the nanomaterial. The method of manufacturing a transparent electrode according to claim 1, 15. The method of claim 14,
Wherein the transparent conductive layer is an electrospinning device using an electric field including graphene, graphite, and carbon nanotubes.
KR1020150050246A 2015-04-09 2015-04-09 Electro-spinning apparatus using electric field and method of manufacturing a transparent electrode using the same KR101676760B1 (en)

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