KR101701603B1 - Electro-spinning apparatus and method of manufacturing a transparent electrode using the same - Google Patents

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

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KR101701603B1
KR101701603B1 KR1020150050248A KR20150050248A KR101701603B1 KR 101701603 B1 KR101701603 B1 KR 101701603B1 KR 1020150050248 A KR1020150050248 A KR 1020150050248A KR 20150050248 A KR20150050248 A KR 20150050248A KR 101701603 B1 KR101701603 B1 KR 101701603B1
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South Korea
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nanofibers
integrated substrate
nanomaterial
spinning
layer
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KR1020150050248A
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Korean (ko)
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KR20160121655A (en
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박장웅
현병관
지상윤
안병완
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희성전자 주식회사
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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

Abstract

The present invention can arrange the nanofibers because the integrated substrate can be disposed within a straight radiation distance range in which the nanofibers are radiated in a linear form, and the nanofibers can be radiated in a linear form. Further, since the nanofibers can be aligned in a certain direction, a transparent electrode made of nanofibers having a directionality can be produced. 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 apparatus and a method of manufacturing a transparent electrode using the electrospinning apparatus,

The present invention relates to an electrospinning apparatus and a method of manufacturing a transparent electrode using the electrospinning apparatus, and more particularly, to an electrospinning apparatus for manufacturing nanofibers having an orientation and a coaxial double layer structure aligned in a predetermined direction as electrodes, And a method of manufacturing an electrode.

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

An object of the present invention is to provide an electrospinning device capable of manufacturing a transparent electrode having a grid pattern with flexibility and stretchability in a simple and economical process and a method of manufacturing a transparent electrode using the electrospinning device.

An electrospinning device according to the present invention is an electrospinning device including: an inner nozzle to which a voltage is applied and which radiates at least one of a nano material and a polymer material; and an inner nozzle that surrounds the inner nozzle and emits the other of the nano material and the polymer material A spinning nozzle for spinning a nanofiber comprising a nanomaterial layer formed of the nanomaterial and a polymer material layer formed of the polymer material, the nanofiber including an outer nozzle being a coaxial double layer; and a spinning nozzle for spinning the nanofiber from the spinning nozzle in a linear form An integrated substrate on which the nanofibers are integrated, and at least one of the spinning nozzle and the integrated substrate is moved in a direction perpendicular to the spinning direction of the nanofibers, A moving mechanism for aligning the radiated nanofibers in a predetermined alignment direction .

A method of manufacturing a transparent electrode using an electrospinning device according to the present invention is characterized in that at least one of the spinneret and the integrated substrate is disposed so that the distance between the spinneret and the integrated substrate is within a range of a straight- Applying a voltage to the spinneret to spin the nanofiber layer formed of the nanoparticle material and the polymer material layer formed of the polymer material into a linear form of a nanofiber composed of a coaxial bilayer layer; Moving at least one of the spinning nozzle and the integrated substrate in an aligned direction of the predetermined nanofibers so that nanofibers radiating in a linear form from the spinning nozzle are formed on the integrated substrate in alignment with the alignment direction; The nanofibers are arranged on the substrate in the alignment direction, To remove, and forming a transparent electrode composed of the nano material.

According to another aspect of the present invention, an electrospinning device of the present invention includes: an inner nozzle to which a voltage is applied and radiates at least one of a nano material and a polymer material; A spinneret for spinning nanofibers composed of a nanomaterial layer formed of the nanomaterial and a polymer material layer formed of the polymer material, the nanofibers being formed of a double-tube structure; And at least one of the spinning nozzle and the integrated substrate is moved in a direction perpendicular to the spinning direction of the nanofibers so that the nanofibers are stacked in a direction perpendicular to the spinning direction of the nanofibers, The nanofibers radiating in a linear form from the spinneret are aligned in a predetermined alignment direction And a moving mechanism for alignment.

The present invention can arrange the nanofibers because the integrated substrate can be disposed within a straight radiation distance range in which the nanofibers are radiated in a linear form, and the nanofibers can be radiated in a linear form. Further, since the nanofibers can be aligned in a certain direction, a transparent electrode made of nanofibers having a directionality can be produced.

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 schematically showing a state in which a spinning solution is radiated from the spinning nozzle shown in FIG. 1; FIG.
3 is an enlarged cross-sectional view of the spinning nozzle and the integrated substrate shown in Fig.
4 is an enlarged perspective view of nanofibers made up 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.
Figure 6 is a schematic diagram illustrating the nanofiber crossing method shown in Figure 5;
7 is a photograph showing a nanofiber grid fabricated by the method shown in FIG.
8 is a view showing another example of the substrate in the electrospinning apparatus shown in Fig.

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 schematically showing a state in which a spinning solution is radiated from the spinning nozzle shown in FIG. 1; FIG. 3 is an enlarged cross-sectional view of the spinning nozzle and the integrated substrate shown in Fig. 4 is an enlarged perspective view of nanofibers made up of a coaxial double layer by the electrospinning apparatus shown in FIG.

1, an electrospinning device 1 according to an embodiment of the present invention includes a spinning nozzle 10, an integrated substrate 20, a distance adjusting mechanism (not shown), a moving mechanism (not shown) (46).

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 the tip of the spinning nozzle 10a 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. However, the present invention is not limited to this, and the nanomaterial layer 51 and the polymer material layer 52 may have a double-tube structure and may not have a coaxial 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 nanofibers 50 radiated from the spinning nozzle 10 are integrated. 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 positioned below the spinning nozzle 10.

The distance adjusting mechanism (not shown) moves at least one of the spinning nozzle 10 and the integrated substrate 20 in the radial direction (-Z) or the opposite direction (Z) Thereby adjusting the distance between the spinneret 10 and the integrated substrate 20. The distance adjusting mechanism (not shown) adjusts the distance between the spinning nozzle 10 and the integrated substrate 20 to within a range of a linear irradiation distance d in which the nanofibers are linearly radiated. In the present embodiment, the distance adjustment mechanism (not shown) moves the integrated substrate 20 by way of example, but it is also possible to move the spinning nozzle 10, of course. The distance adjustment mechanism (not shown) may have a variety of structures such as a rack, a pinion structure, and a sliding rail structure. The distance adjustment mechanism may be configured to move the integrated substrate 20 in the radial direction (-Z) Any device capable of linearly moving the workpiece W to the workpiece Z can be used.

2, the liquid jet 30 emitted from the spinning nozzle 10 is influenced by various external forces until it reaches the integrated substrate 20. Particularly, in the process of forming the nanofibers 50 in the liquid jet 30, the shape varies depending on the ratio of the surface tension of the spinning solution to the electrostatic repulsive force. That is, the liquid jet 30 is composed of a portion A forming a Taylor cone T, a portion B radiating in a linear shape, and a portion C where whipping occurs. Here, the straight line emitting distance d is a length including a portion forming the tail cone T and a portion irradiating the straight line. Therefore, when the integrated substrate 20 is disposed so as to be located at a portion forming the Taylor cone T and a portion irradiated with the linear shape, the nanofibers radiated from the spinning nozzle 10 are linearly obtained . That is, the integrated substrate 20 can be disposed within the range of the linear irradiation distance d from the spinning nozzle 10, so that the nanofibers radiated from the spinning nozzle 10 can be obtained in a linear form. The nanofibers 50 are oriented in a direction (-Z) perpendicular to the integrated substrate 20 and the nanofibers 50 are oriented in the radial direction (-Z) perpendicular to the integrated substrate 20 It can be radiated in a linear form.

The linear irradiation distance d may vary depending on the diameter of the spinning nozzle 10, the voltage applied to the spinning nozzle 10, the moving speed of the integrated substrate 20, and the like.

The linear irradiation distance d is in a range larger than the diameter of the outer nozzle 12 of the spinning nozzle 10 and smaller than about 45 mm.

The outer nozzle 12 may have a diameter of 0.2 mm to 0.4 mm, and the inner nozzle 11 may have a diameter of 0.08 mm to 0.1 mm. In the present embodiment, the outer nozzle 12 has a diameter of 0.3 mm and the inner nozzle 11 has a diameter of 0.089 mm. Here, the diameter of the outer nozzle 12 means the diameter of the inner surface of the polymer material, and the diameter of the inner nozzle 11 means the diameter of the inner surface of the nanomaterial. Therefore, in the present embodiment, the linear emission distance d is 7 mm, which is larger than the diameter of the external nozzle 12, for example.

An electrode is provided under the integrated substrate 20, and the electrode has a ground voltage, for example, a voltage of 0V. However, the present invention is not limited thereto, and the integrated substrate 20 may be grounded or the integrated substrate 20 may have a voltage opposite to the spinning nozzle 10.

The power supply unit 46 represents an external power source for applying a voltage to the spinning nozzle 10. A voltage is applied to the spinning nozzle 10 by the external power source 46, and the electrode is grounded to generate a voltage difference with the spinning nozzle 10. 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 electrode are controlled to have voltages opposite to each other. A voltage is applied to the spinning nozzle 10 by the external power source 46, and a voltage difference is generated between the spinning nozzle 10 and the electrode. The voltage applied to the spinning nozzle 10 ranges from 100V to 2500V. In this embodiment, the voltage applied to the spinning nozzle 10 is about 2200 V, for example. When the distance between the spinneret 10 and the integrated substrate 20 is about 7 mm, if the voltage applied to the spinneret 10 is about 2500 V or more, the nanofibers are spun in a spiral rather than a straight line If the voltage is about 3000V or more, a corona discharge phenomenon may occur.

The moving mechanism (not shown) is configured to move at least one of the spinning nozzle 10 and the integrated substrate 20 in a radial direction (-Z) of the nanofibers and in a direction perpendicular to the radial direction (-Z) (-X or -Y). The moving mechanism (not shown) moves at least one of the spinning nozzle 10 and the integrated substrate 20 so that the nanofibers radiated in a straight line from the spinning nozzle 10 are aligned Direction (Y). In the present embodiment, the moving mechanism (not shown) moves the integrated substrate 20 by way of example, but it is also possible to move the spinning nozzle 10. When the integrated substrate 20 is moved in the alignment direction Y by the moving mechanism (not shown), the nanofibers 50 radiated from the spinning nozzle 10 are aligned in the alignment direction Y . The plurality of nanofibers 50 are moved in the direction X perpendicular to the alignment direction Y by the moving mechanism (not shown) And may be formed in a plurality of rows spaced apart from each other by a predetermined distance. The moving mechanism (not shown) may have various structures such as a rack, a pinion structure, and a sliding rail structure, and any device capable of linearly moving the integrated substrate 20 in the horizontal direction is possible.

The moving speed and the moving time of the moving mechanism (not shown) may be set in advance according to the intervals of the rows of the nanofibers 50 and the like. The moving speed of the moving mechanism (not shown) is equal to the moving speed of the integrated substrate 20, and may be set to be proportional to the diameter of the outer nozzle 12 of the spinning nozzle 10. That is, if the diameter of the outer nozzle 12 is small, the nanofibers can be aligned even if the moving speed is low. However, as the diameter of the outer nozzle 12 is increased, .

Further, when the diameter of the outer nozzle 12 is increased, the diameter of the nanofibers to be radiated is increased. However, if the moving speed of the moving mechanism is increased even though the diameter of the outer nozzle 12 is relatively large, the nanofibers radiated from the spinning nozzle 10 are stretched at a higher speed, The diameter of the nanofibers to be integrated into the nanofiber may be smaller. Therefore, when the diameter of the nanofibers to be integrated in the integrated substrate 20 is set, the moving speed of the moving mechanism and the diameter of the external nozzle 12 are set together.

The moving speed of the integrated substrate 20 may be set to 25 cm / s to 40 cm / s. However, in this embodiment, since the diameter of the outer nozzle 12 of the spinning nozzle 10 is about 0.3 mm, the moving speed of the integrated substrate 20 is set to 30 cm / s or more . When the diameter of the outer nozzle 12 of the spinning nozzle 10 is about 0.3 mm and the moving speed of the integrated substrate 20 is less than 30 cm / s, the nanofibers emitted from the spinning nozzle 10 are whipped To form a spiral shape.

The electrospinning device 1 further includes a rotation mechanism (not shown) for rotating the integrated substrate 20. The rotating mechanism (not shown) may be any mechanism that can rotate the integrated substrate 20 in a horizontal direction by a preset angle. The rotation mechanism (not shown) rotates the integrated substrate 20 in the horizontal direction by 90 degrees. However, the present invention is not limited to this, and it is of course possible for the user to directly rotate the integrated substrate 20. The rotation mechanism (not shown) can be used to form the nanofibers aligned in one direction in an alternating structure.

5 is a flowchart illustrating a method of manufacturing a transparent electrode using an electrospinning device according to an embodiment of the present invention. Figure 6 is a schematic diagram illustrating the nanofiber crossing method shown in Figure 5;

5 and 6, a method of manufacturing a transparent electrode using an electrospinning device according to an embodiment of the present invention will be described.

First, the distance between the spinneret 10 and the integrated substrate 20 is adjusted. (S11) The integrated substrate 20 is moved in the direction toward the spinneret 10, and the spinneret 10 ) And the integrated substrate (20) is within the range of the linear irradiation distance (d). The linear irradiation distance d is set to a range larger than the diameter of the outer nozzle 12 of the spinning nozzle 10 and less than about 45 mm. In this embodiment, the diameter of the outer nozzle 12 is about 0.3 mm And the linear emission distance d is about 7 mm, for example. Accordingly, the integrated substrate 20 is positioned such that the distance between the spinneret 10 and the integrated substrate 20 is about 7 mm, so that the spinneret 10 can be irradiated with a near field emission.

A voltage is applied to the spinning nozzle 10 to spin the nanomaterial and the polymer material from the spinning nozzle 10. (S12)

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 100V to 2500V. In this embodiment, the voltage applied to the spinning nozzle 10 is about 2200 V, for example. When the distance between the spinneret 10 and the integrated substrate 20 is about 7 mm, if the voltage applied to the spinneret 10 is about 2500 V or more, the nanofibers are spun in a spiral rather than a straight line If the voltage is about 3000V or more, a corona discharge phenomenon may occur.

The polymer material in the outer nozzle 12 of the spinning nozzle 10 is radiated in a hollow cylinder shape and the nanomaterial in the inner nozzle 11 is filled in the polymer material and discharged in a core shape, And is solidified by the nanofibers (50) having a coaxial 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.

On the other hand, in the case of the proximity radiation in which the distance between the spinneret 10 and the integrated substrate 20 is limited to the range of the linear radiation distance d, the flow rate of the nanomaterial is smaller Should be used. In this embodiment, the flow rate of the polymer material is about 0.2 ml / h, and the flow rate of the nanomaterial is about 0.003 ml / h. When the flow rate of the nanomaterial is about 0.01 ml / h or more, a drop phenomenon of the nanomaterial becomes severe, and current may flow back from the integrated substrate 20 to the spinneret 10. The polymer material and the nanomaterial should have the same or similar vapor pressure. In addition, the viscosity of the polymer material should be equal to or greater than the viscosity of the nanomaterial.

As described above, when the distance between the spinning nozzle 10 and the integrated substrate 20 is within the range of the linear emission distance d and the voltage is applied at about 2200 V, The nanofibers 50 are radiated in a linear form and integrated on the integrated substrate 20. That is, the nanofibers 50 radiated from the spinning nozzle 10 may be accumulated on the integrated substrate 20 before the whipping phenomenon occurs.

When the nanofibers 50 are irradiated to the integrated substrate 20 in a linear form, the integrated substrate 20 is aligned perpendicular to the alignment direction Y of the predetermined nanofibers or the alignment direction Y of the nanofibers (X) so as to align the nanofibers 50. (S13) (S14)

First, the integrated substrate 20 is moved in the alignment direction Y of the nanofibers 50. When the integrated substrate 20 is moved in the alignment direction Y, the nanofibers radiating linearly from the spinning nozzle 10 can be aligned in the alignment direction Y. [ Since the nanofibers 50 are continuously irradiated from the spinning nozzle 10, the nanofibers 50 aligned in the alignment direction Y may be composed of one strand or multiple strands. At this time, the moving speed of the integrated substrate 20 is set to 30 cm / s or more, for example. When the moving speed of the integrated substrate 20 is less than 30 cm / s, the nanofibers emitted from the spinning nozzle 10 have a spiral shape. In this embodiment, the moving speed of the integrated substrate 20 is set to 30 cm / s, which is the minimum moving speed.

It is also possible to linearly move the integrated substrate 20 by a predetermined distance in a direction X perpendicular to the alignment direction Y when certain strands of the nanofibers 50 are aligned in the alignment direction Y Do. When the integrated substrate 20 is moved in the direction (X) perpendicular to the alignment direction Y, the nanofibers can be arranged in a position spaced apart from the already aligned nanofibers by a predetermined distance. In this way, the plurality of nanofibers 50 are aligned in the alignment direction Y and are spaced apart or overlapped with each other in the direction X perpendicular to the alignment direction Y to be arranged in a plurality of rows .

Referring to FIG. 6, the nanofibers 50 may change the alignment direction to form a desired pattern such as a grid structure. In this embodiment, a grid structure is formed by crossing a plurality of nanofibers. (S15)

6A, when the first nanofiber layer 61 is formed by aligning the plurality of nanofibers 50 in the alignment direction Y, the integrated substrate 20 is rotated 90 degrees as shown in FIG. 6B, Rotate at an angle. The nanofibers of the first nanofiber layer 61 are arranged in a direction X perpendicular to the alignment direction Y when the integrated substrate 20 is rotated by 90 degrees. 6C, when the nanofibers 50 are radiated from the spinning nozzle 10 onto the first nanofiber layer 61, the nanofibers are aligned in the alignment direction Y. As shown in FIG. 6D, a second nanofiber layer 62 is formed on the first nanofiber layer 61 so as to cross the first nanofiber layer 61 at 90 degrees. Thus, a nanofiber layer 60 having a grid structure is formed.

When the nanofiber layer 60 having the grid structure is formed on the integrated substrate 20, 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 (S16)

Thereafter, the polymer material layer 52 is removed to form a transparent electrode composed only of the nanomaterial layer 51. (S17) (S18) The polymer material layer 52 is removed by using an organic solvent can do. 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. 7, it can be confirmed by comparing before and after the removal of the polymer material layer.

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.

Fig. 8 is a view showing another example of the integrated substrate in the electrospinning apparatus shown in Fig. 1. Fig.

Referring to FIG. 8, the integrated substrate 120 may be a free standing substrate that does not support the lower side of the object to be integrated. The integrated substrate 120 may be a ring shape having a central portion penetrating therethrough. For example, the integrated substrate 120 may have a horseshoe shape in which a central portion is opened and an outer frame is 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.

When the integrated substrate 120 is used as the free standing substrate in manufacturing the transparent electrode, the aligned nanofibers irradiated to the integrated substrate 120 are separated from the integrated substrate 120, ).

The method of aligning the nanofibers to the integrated substrate 120 by aligning the nanofibers is the same as that of the above embodiment, and thus a detailed description thereof will be omitted.

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

Claims (17)

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;
And a moving mechanism for moving at least one of the spinning nozzle and the integrated substrate in a direction perpendicular to the spinning direction of the nanofibers so as to align the nanofibers emitted in the spinning nozzle in a predetermined alignment direction,
And removing the polymer material layer from the aligned nanofibers. The method according to claim 1,
Further comprising a distance adjustment mechanism for moving at least one of the spinneret and the integrated substrate in the radial direction to adjust the distance between the spinneret and the integrated substrate to within the range of the linear radial distance. The method according to claim 1,
Wherein the linear radiation distance range is larger than the diameter of the outer nozzle and smaller than 45 mm. The method according to claim 1,
The diameter of the nanofibers to be integrated on the integrated substrate may be,
And is set based on the diameter of the outer nozzle and the moving speed of the integrated substrate. The method according to claim 1,
Further comprising a rotating mechanism for rotating the integrated substrate at a predetermined angle. Moving at least one of the spinneret and the integrated substrate such that a distance between the spinneret and the integrated substrate is within a range of a linear spinning distance in which the nanofibers are linearly radiated;
A voltage is applied to the spinning nozzle to form a nanomaterial mixed with a nanomaterial and a solvent selected from the group consisting of gold, silver, copper, copper oxide and cobalt from the inner nozzle of the spinning nozzle on the integrated substrate A polymer solution containing a polymer material is radiated from an outer nozzle of the spinning nozzle to spin a nanomaterial layer formed of the nanomaterial and a polymer material layer formed of the polymer material to emit nanofibers composed of a coaxial double layer ;
Wherein at least one of the spinneret and the integrated substrate is moved in a predetermined alignment direction of the nanofibers so that the nanofibers emitted in a linear form from the spinneret are aligned on the integrated substrate in the alignment direction;
And removing the polymer material layer from the nanofibers to form an electrode. The method of claim 6,
Prior to forming the electrode,
Rotating the integrated substrate at a predetermined angle when the nanofibers are aligned in the alignment direction to form a first nanofiber layer;
Rotating the integrated substrate and spinning nanofibers comprising the nanomaterial layer and the polymeric material layer comprising a coaxial double layer on the first nanofiber layer;
Wherein at least one of the spinning nozzle and the integrated substrate is moved in an alignment direction of predetermined nanofibers to align the nanofibers emitted from the spinning nozzle in the alignment direction on the first nanofiber layer, And forming a second nanofiber layer crossing at a predetermined angle with respect to the first nanofiber layer. The method of claim 6,
Prior to forming the electrode,
Further comprising the step of separating the nanofibers from the integrated substrate and transferring the nanofibers to a separate substrate. The method of claim 8,
Wherein the integrated substrate is an electrospinning device that is a free standing substrate. The method of claim 6,
Wherein forming the electrode comprises:
Wherein the polymer material is removed using an organic solvent or a reactive ion etching method. The method of claim 6,
Wherein forming the electrode comprises:
And forming a transparent conductive layer on the nanomaterial. ≪ RTI ID = 0.0 > 8. < / RTI > The method of claim 11,
Wherein the transparent conductive layer comprises graphene, graphite, and carbon nanotubes. The method of claim 6,
Wherein the step of spinning the nanofibers in a linear form is performed by applying a voltage in a range of 100 V to 2500 V. The method of claim 6,
Wherein the nanofibers are aligned and formed,
Moving the integrated substrate at a predetermined moving speed,
Wherein the moving speed is set to be proportional to the diameter of the outer nozzle. 15. The method of claim 14,
Wherein the moving speed is set to 25 cm / s to 40 cm / s. delete delete
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