KR101069587B1 - Manufacturing method and omnidirectional writing method of a 3D conducting polymer ultrafine wire, and 3D conducting polymer ultrafine wire and writing obtained by the same - Google Patents
Manufacturing method and omnidirectional writing method of a 3D conducting polymer ultrafine wire, and 3D conducting polymer ultrafine wire and writing obtained by the same Download PDFInfo
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- KR101069587B1 KR101069587B1 KR1020100005880A KR20100005880A KR101069587B1 KR 101069587 B1 KR101069587 B1 KR 101069587B1 KR 1020100005880 A KR1020100005880 A KR 1020100005880A KR 20100005880 A KR20100005880 A KR 20100005880A KR 101069587 B1 KR101069587 B1 KR 101069587B1
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Abstract
The present invention relates to a method for producing a high aspect ratio three-dimensional conductive polymer ultra fine wire using a micro pipette local chemical polymerization method, the manufacturing method, (a) the lower end of the micro pipette filled with a monomer (monomer) aqueous solution of the conductive polymer Locating near the alignment position of the conductive polymer microwire on the surface of the substrate; (b) contacting a lower end of the micro pipette to an alignment position of the conductive polymer on the surface of the substrate; (c) forming a meniscus of the aqueous solution between the surface of the substrate and the lower end of the pipette by separating the pipette a predetermined distance from the surface of the substrate; And (d) moving the pipette in the direction of growth of the conductive polymer microwire at a constant rate such that the meniscus reacts with oxygen in the air to cause polymerization and grow into an aspect ratio conductive polymer microwire. do.
Description
The present invention relates to the production of a three-dimensional conductive polymer ultra fine wire and a omnidirectional wiring method, and to a conductive polymer ultra fine wire and wiring produced thereby. More specifically, the present invention provides a method for producing a three-dimensional conductive polymer ultra fine wire (particularly a microwire or a nanowire) and omnidirectional wiring through local chemical polymerization using a micro pipette, and a conductive polymer ultra fine prepared thereby. Relates to wires and wiring.
Because conducting polymers (also called π-conjugated polymers) have a low density, their specific conductivity is higher than that of metal, and the conductivity can be changed according to doping. It has strengths as a material. In addition, mechanical and chemical aspects are superior to metals in terms of workability, flexibility, strength, light weight, and chemical inertness. Such conductive polymers have excellent properties such as microelectronics, optics, communication, sensors, displays, life sciences, and drug delivery systems. It can be used in various applications.
For the effective approach of such applications, the fabrication and patterning of three-dimensional structures of conductive polymers is essential. In particular, three-dimensional structure in the form of wire becomes a basic unit in the production of complex structures, the application range is wide. Among them, the importance of “micro wires”, which are extremely fine wires having a diameter of about 1 to 1000 microns, and “nano wires,” which are about 1 to 1000 nanometers in diameter, are of interest. It is increasing day by day. The requirements for the application of these "microwires" or "nanowires" are: First, a structure having a high aspect ratio is required, the structure must be able to be manufactured individually at a desired position, and property modification of the fabricated structure should be easy. Finally, the process must be simple and inexpensive.
Currently used conductive polymer micro or nanowire fabrication techniques can be broadly classified into lithography, template synthesis, and electrospinning. Lithography in this context includes soft lithography and "Dip-pen" lithography, as well as the common techniques used in silicon processing. Lithography in this comprehensive sense allows precise alignment of the microstructures and nanostructures to be fabricated, but has a disadvantage in that it is difficult to manufacture a wire having a high three-dimensional aspect ratio. Therefore, template technology and electro-pinning technology are widely used for 3D wire fabrication. Template technology has the advantage of being able to fabricate large quantities of wire at one time. At this time, the size and the number of wires is determined according to the size and number of pores (pore) of the template. Another representative method, electrospinning technology, has the advantage that wires can be made long without limiting the aspect ratio. Both of these methods, however, have difficulty in aligning the fabricated wire exactly in the desired position, which requires an additional process, which involves many technical difficulties in micro and nanometer units.
As mentioned above, conductive polymer microwires and even nanowires are the core materials of nanotechnology, but the precise alignment and fabrication of three-dimensional wires, and the control of individual wire characteristics, still pose significant challenges.
The first object of the present invention is to use a chemical polymerization of a locally produced monomer solution through a micro pipette to align the wires produced simultaneously with the fabrication of a three-dimensional conductive polymer ultra fine wire having a high aspect ratio It is to provide a method for producing a three-dimensional conductive polymer ultra fine wire and a three-dimensional conductive polymer ultra fine wire produced thereby.
In addition, a second object of the present invention is a method for manufacturing a three-dimensional conductive polymer ultra-fine wire wiring and simultaneously manufactured by wiring a three-dimensional conductive polymer ultra-fine wire produced through a micro pipette in a desired position and direction and 3 To provide a three-dimensional conductive polymer ultra fine wire wiring.
In addition, a third object of the present invention is to provide a method for individually controlling the physical or chemical properties of the three-dimensional conductive polymer ultra-fine wire to the wiring and the conductive polymer ultra-fine wire or wiring produced thereby.
Method for producing a high aspect ratio three-dimensional conductive polymer ultra fine wire using a micro pipette local chemical polymerization method according to an aspect of the present invention,
(a) placing the lower end of the micropipette filled with an aqueous monomer solution of the conductive polymer near the alignment position of the conductive polymer microwire in the surface of the substrate;
(b) contacting a lower end of the micro pipette to an alignment position of the conductive polymer on the surface of the substrate;
(c) separating the pipette from the surface of the substrate by a predetermined distance to form a meniscus of the aqueous solution between the surface of the substrate and the lower end of the pipette; And
(d) moving the pipette in the growth direction of the conductive polymer microwire at a constant rate such that the meniscus reacts with oxygen in the air to cause polymerization and grow into an aspect ratio conductive polymer microwire. .
Preferably, the aqueous solution of the conductive polymer monomer of step (a) is a mixed solution of pyrrole monomer and H 2 SO 4 .
Preferably, the mixed solution comprises 50 g / L pyrrole monomer and 25 g / L H 2 SO 4 .
Preferably, the predetermined distance of step (c) is determined in the range of 1 μm to 10 μm.
Preferably, the moving speed of the micro pipette in step (d) is determined in the range of 1 μm / sec to 3000 μm / sec.
Preferably, the faster the moving speed of the micropipette, the diameter of the ultra fine wire is reduced.
Preferably, the ultrafine wire is a microwire or a nanowire.
Preferably, in the above steps (a), (b), (c) and (e), the micropipettes are each adjusted in microns by a stepping motor.
Preferably, 2-Naphtalenesulfonic acid (2-NSA) is added to the aqueous monomer solution of the conductive polymer to control the electrical conductivity.
In addition, the high aspect ratio three-dimensional conductive polymer ultrafine wire of the present invention is characterized in that the production and alignment is made at the same time by the manufacturing method.
Method for producing a three-dimensional conductive polymer ultra fine wire wiring from the first point to the second point using a micro pipette local chemical polymerization method according to another aspect of the present invention,
(a) placing a lower end of the micropipette filled with an aqueous monomer solution of the conductive polymer near a first point on the surface of the substrate;
(b) contacting a lower end of the micro pipette with a first point on the surface of the substrate;
(c) forming a meniscus of the aqueous solution between the first point of the surface of the substrate and the lower end of the pipette by separating the pipette a predetermined distance from the first point of the surface of the substrate;
(d) conducting the pipette at a constant rate so that the meniscus reacts with oxygen in the air to cause polymerization to grow into a conductive polymer ultra fine wire having a length corresponding to the distance between the first point and the second point. Moving in the growth direction of the ultra fine wire; And
(e) contacting the lower end of the pipette to a second point on the substrate.
Preferably, the aqueous monomer solution of the conductive polymer of step (a) is a mixed solution of pyrrole monomer and H 2 SO 4 .
Preferably, the mixed solution comprises 50 g / L pyrrole monomer and 25 g / L H 2 SO 4 .
Preferably, the predetermined distance of step (c) is determined in the range of 1 μm to 10 μm.
Preferably, the moving speed of the micro pipette in step (d) is determined in the range of 1 μm / sec to 3000 μm / sec.
Preferably, the faster the moving speed of the micropipette, the diameter of the ultra fine wire is reduced.
Preferably, the ultrafine wire is a microwire or a nanowire.
Preferably, in the steps (a), (b), (c), (d) and (e) the micropipettes are each adjusted in microns by a stepping motor.
Preferably, 2-Naphtalenesulfonic acid (2-NSA) is added to the aqueous monomer solution of the conductive polymer to control the electrical conductivity.
In addition, the three-dimensional conductive polymer ultra-fine wire wiring of the present invention is characterized in that the production and the wiring is made at the same time by the manufacturing method of the conductive polymer ultra-fine wire wiring.
According to the present invention, a method for producing a three-dimensional conductive polymer micro wire, which can not only be precisely aligned in a desired position but also requires no additional process for the preparation of the three-dimensional conductive polymer micro wire of a desired diameter and length through a micropipette, and It is possible to obtain a three-dimensional conductive polymer ultra fine wire produced by the.
In addition, according to the present invention, a method for manufacturing a three-dimensional conductive polymer ultra-fine wire wiring for manufacturing the wiring of the three-dimensional conductive polymer ultra-fine wire produced through a micro pipette in a desired position and direction, and the three-dimensional conductive polymer pole manufactured thereby Fine wire wiring can be obtained.
In addition, according to the present invention, it is possible to obtain a method for individually controlling the physical or chemical properties of the three-dimensional conductive polymer ultra-fine wire to the wiring and the conductive polymer ultra-fine wire or wiring produced thereby.
In other words, the present invention relates to the development of local chemical polymerization via micropipettes based on the use of oxygen in the air as an oxidant in the polymerization of conductive polymer monomers. The aqueous solution meniscus has a high effective oxygen concentration around the polymerization occurs faster than in the case of the existing aqueous film and the conductive polymer structure is formed in a quick time. In the present invention, the diameter of the meniscus is controlled by controlling the pulling speed of the pipette, thereby effectively controlling the diameter of the conductive polymer ultrafine wire from micrometer to nanometer. In addition, the physical and chemical properties of the conductive polymer ultra fine wire were individually realized by adding a specific substance to the monomer. Compared with other approaches, such as lithography, the present invention has been developed to develop a method that can produce three-dimensional conductive polymer micro, nanowires in a fast and inexpensive manner and can be aligned in any position and direction at the same time and can be manipulated their properties. It suggests the possibility of industrialization.
1 is a schematic diagram of a technique for fabricating high aspect ratio three-dimensional conductive polymer ultrafine wires (particularly micro or nanowires) by using a micropipette local chemical polymerization method according to the present invention and simultaneously aligning them.
FIG. 2A is a schematic diagram based on a real-time X-ray image of a polypyrrole wire generated when a micropipette having a 5 μm radius containing a pyrrole aqueous solution is spaced at a interval of 0.7 seconds at 2.5 μm intervals. Here, the radius of the wire is 3.5 μm smaller than the radius of the micro pipette.
FIG. 2B is a schematic diagram based on a real-time X-ray image of a polypyrrole wire generated when a 5 μm radius micro pipette containing an aqueous solution of pyrrole is spaced at 2.5 second intervals at 1.0 second intervals. Here, the radius of the wire is 5.0 μm, which is equal to the radius of the micro pipette.
Figure 2c is a graph showing the correlation between the time interval and the radius of the wire when the micropipette of 5μm radius containing pyrrole aqueous solution separated by 2.5μm. As the time interval increases, the radius of the wire increases and after 1.0 seconds the radius of the micropipette is reached and remains constant. Define the minimum time that the wire radius / pipette radius = 1 is "polymerization point".
2D is a graph showing the correlation between the micropipette radius and the polymerization point. It can be seen that the polymerization point decreases as the pipette radius decreases.
Figure 3a is a schematic diagram based on the X-ray image showing the phenomenon that the radius of the wire decreases as the separation speed of the micro pipette increases.
Figure 3b is a graph showing the correlation between the separation speed of the micro pipette and the radius of the wire. It can be seen that as the separation speed of the pipette increases, the radius of the wire decreases to obtain a nanometer scale radius.
4 is a three-dimensional polypyrrole wire array image produced through the omnidirectional space of the micro pipette. Field emission scanning electrons of high aspect ratio wire array (60: 1) (FIG. 4A), nanowire bridge (FIG. 4B), junction structure of two nanowires, and three-dimensional arch wire array (FIG. 4D) Microscope (FE-SEM) image.
FIG. 5 is an IV graph of conductive polymer nanowires prepared by local chemical polymerization of a micropipette. FIG. As the current increases linearly with the applied voltage, it can be seen that the conductive polymer ultra fine wire (radius 500 nm) connecting the two gold (Au) electrodes is in ohmic contact. Figure 5b is a graph showing that the electrical conductivity increases as the doping concentration of 2-naphtalenesulfonic acid added to the pyrrole aqueous solution.
6 is a process diagram of a technique for fabricating a high aspect ratio three dimensional conductive polymer ultra fine wire (preferably microwire or nanowire) wiring from a first point to a second point using a micropipette local chemical polymerization method.
Preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings.
1 is a process diagram of a technique for producing a high aspect ratio three-dimensional conductive polymer ultra fine wire (preferably microwire or nanowire) using a micro pipette local chemical polymerization method. In the present invention, a key idea for simultaneously aligning the conductive polymer ultrafine wire with a desired position is to locally supply an aqueous monomer solution.
To this end, a
In the preferred embodiment of the present invention, the following experimental conditions were used.
Preferably, the glass
In the present invention, it is important to secure a constant diameter during the manufacturing process of the conductive polymer (polypyrrole)
To understand this, the cross-sectional area reduction of the meniscus was measured while the micropipette was spaced at regular time intervals of 2.5 μm. Here, the terminal radius of the
The relationship between the cross-sectional area of the aqueous meniscus, the diffusion time of oxygen, and the viscosity determines the polypyrrole wire of constant diameter. This allows the production of polypyrrole wire of the desired diameter by controlling the separation speed of the micro pipette. 3A shows that the polypyrrole wire radius decreases from 5 to 1.75 μm as the separation rate of the micropipette increases from 2.5 to 25 μm / s. Furthermore, in Figure 3b to increase the separation speed to 2100μm / s to produce a wire of 110nm radius.
Figure 4 shows the alignment direction and the position of the polypyrrole micro, nanowires are precisely adjusted through the omnidirectional separation of the micro pipette. 4A is a high aspect ratio (60: 1) polypyrrole wire array. 4B is a polypyrrole nano bridge (separation rate: 500 μm / sec, radius 450 nm). Such a structure is an essential form for connecting three-dimensional leads between boards of a three-dimensional electronic circuit. 4C is a junction structure made by crossing two nanowires (separation rate: 1200 μm / sec, radius 200 nm). Finally, Figure 4d is a three-dimensional arched wire structure (radius 2.5μm).
5 shows that the electrical conductivity of the nanowires can be individually controlled through doping. This is an essential form of multifunctional circuit. For this purpose, gold (Au) was fabricated on the glass plate of the insulator and the electrodes were connected with polypyrrole nanowires. FIG. 5A is a graph of current-voltage measurement results in which 2-naphtalenesulfonic acid of polypyrrole nanowires with 500 nm radius was added up to 0 M-0.15 M, and the inserted image shows an electric field showing polypyrrole nanowires connecting two gold electrodes. Emission scanning electron microscopy image. This result shows that the electrical conductivity of individual nanowires is regulated between 10 −2 and 10 −1 S / cm (FIG. 5B).
The high aspect ratio three-dimensional conductive polymer ultra
FIG. 6 shows a high aspect ratio three dimensional conductive polymer ultra fine wire 40 (preferably microwire or nanowire) wiring from a first point X to a second point Y using a micropipette local chemical polymerization method. This is a process chart of the technology to produce.
First, a conductive polymer monomer solution 3 containing a monomer of a conductive polymer is filled in a
Next, the
Next, the
Then, the meniscus (M) reacts with oxygen in the air to cause a polymerization action and grow the
Finally, the
The three-dimensional conductive polymer ultra
※ Definition of Terms
1. Conducting polymer: It refers to a plastic through electricity while maintaining the advantages of light and easy processing. Examples thereof include polypyrrole, polyaniline, and PEDOT.
2. Ultrafine wire: A wire whose diameter of cross section is about 1000㎛ or less.
3. microwire: A micro wire having a diameter of about 1 탆 to 1000 탆 in cross section.
4. Nanowire: A nanowire having a diameter of about 1 nm to 1000 nm in cross section.
Although the invention has been described with reference to specific exemplary embodiments, the invention is not limited by the embodiments but only by the appended claims. Those skilled in the art should recognize that the embodiments can be changed or modified without departing from the scope and spirit of the present invention.
Claims (20)
(a) placing the lower end of the micropipette filled with the aqueous monomer solution of the conductive polymer near the alignment position of the conductive polymer microwire in the surface of the substrate;
(b) contacting a lower end of the micro pipette to an alignment position of the conductive polymer on the surface of the substrate;
(c) forming a meniscus of the aqueous solution between the surface of the substrate and the lower end of the pipette by separating the pipette a predetermined distance from the surface of the substrate; And
(d) moving the pipette in the growth direction of the conductive polymer microwire at a constant rate such that the meniscus reacts with oxygen in the air to cause polymerization and grow into an aspect ratio conductive polymer microwire. Method for producing a high aspect ratio three-dimensional conductive polymer ultra fine wire, characterized in that.
(a) aligning a lower end of the micropipette filled with an aqueous monomer solution of the conductive polymer near a first point on the surface of the substrate;
(b) contacting a lower end of the micro pipette with a first point on the surface of the substrate;
(c) forming a meniscus of the aqueous solution between the first point of the surface of the substrate and the lower end of the pipette by separating the pipette a predetermined distance from the first point of the surface of the substrate;
(d) conducting the pipette at a constant rate so that the meniscus reacts with oxygen in the air to cause polymerization to grow into a conductive polymer ultra fine wire having a length corresponding to the distance between the first point and the second point. Moving in the growth direction of the ultra fine wire; And
and (e) contacting the lower end of the pipette with a second point of the substrate.
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| KR1020100005880A KR101069587B1 (en) | 2010-01-22 | 2010-01-22 | Manufacturing method and omnidirectional writing method of a 3D conducting polymer ultrafine wire, and 3D conducting polymer ultrafine wire and writing obtained by the same |
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| KR101969844B1 (en) * | 2017-03-24 | 2019-04-18 | 주식회사 레신저스 | Manupacturing method of nanowire connected optical fiber |
| US11911983B2 (en) * | 2021-02-01 | 2024-02-27 | POSTECH Research and Business Development Foundation | Method of forming micro- or nanowires at predetermined positions of an object using a micro- or nanopipette |
| US20220242726A1 (en) * | 2021-02-01 | 2022-08-04 | POSTECH Research and Business Development Foundation | Method for fabricating micro- or nanowire at predetermined position of object using micro- or nanopipette |
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