KR101272483B1 - Manufacturing Method of Transparent Conducting Plate using Carbon Nanotubes-Conducting Polymer Hybrid Multilayer - Google Patents
Manufacturing Method of Transparent Conducting Plate using Carbon Nanotubes-Conducting Polymer Hybrid Multilayer Download PDFInfo
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- KR101272483B1 KR101272483B1 KR1020100125701A KR20100125701A KR101272483B1 KR 101272483 B1 KR101272483 B1 KR 101272483B1 KR 1020100125701 A KR1020100125701 A KR 1020100125701A KR 20100125701 A KR20100125701 A KR 20100125701A KR 101272483 B1 KR101272483 B1 KR 101272483B1
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Abstract
The present invention relates to a method for manufacturing a transparent conductive plate and a transparent conductive plate produced by the present invention, the present invention comprises the steps of cleaning the surface of the transparent substrate 100 to remove foreign matters; Forming a positive charge layer using aminopropyl dioxide silane (APTES) on the surface of the cleaned substrate 100; Carbon nanotubes (CNT) and polysodium 4-styrene sulfonate (PSS) are mixed in water and subjected to high frequency to produce CNT aqueous solution in which CNTs and PSS mixed in water are evenly dispersed in water. Impregnating the substrate 100 having a charge layer into the CNT aqueous solution to form a CNT layer having a negative charge on the surface of the substrate 100; And impregnating the substrate 100 coated with the CNT layer in a conductive polymer solution made of a conductive polymer having a positive charge, thereby forming a transparent conductive polymer layer on the CNT layer of the substrate 100. Provided is a method of manufacturing a transparent conductive plate material, comprising the step, and a transparent conductive plate material produced thereby.
Description
The present invention relates to a method for manufacturing a transparent conductive plate using carbon nanotubes and a conductive polymer, and a transparent conductive plate produced by the same, specifically, glass, acrylic plate, polyethylene terephthalate film (hereinafter referred to as "PET film Repeating the coating of carbon nanotubes (hereinafter abbreviated as "CNT") and conductive polymers on a transparent substrate such as "" by dipping, repeating the electrically conductive layer of the thin film The present invention relates to a method of manufacturing a transparent conductive plate material of a new way to have a high light transmittance while having excellent electrical conductivity, and a transparent conductive plate material produced thereby.
The transparent conductive plate material has a thickness or a thin film like a glass plate, and is a core product used in many fields such as a flat panel display panel, a solar cell, a transparent electrode, a touch panel, and an electromagnetic shielding material. In manufacturing such a transparent conductive plate, the conventional metal oxide-based materials are widely used in various fields due to high electrical conductivity and high light transmittance, but it is impossible to manufacture flexible plate that is continuously bent and the price of materials is rising. Disadvantages have limited utility, and there is a need for developing alternative materials. In particular, there is an urgent need for a technology for producing a plate that has excellent electrical conductivity and light transmittance, but also has a large area, is capable of producing a flexible plate that is bent, and is chemically and physically stable. .
The present invention has been developed to meet the needs of the technical field as described above, specifically, by coating a thin alternating coating of CNTs and conductive polymers having a high electrical conductivity in nanometer units to have a high level of electrical conductivity and high light transmittance. An object of the present invention is to provide a technology capable of manufacturing flexible and flexible sheet metal.
In order to achieve the above object, in the present invention, the step of cleaning the surface of the transparent substrate to remove the foreign matter; Forming a positive charge layer using aminopropyl dioxide silane (APTES) on the surface of the cleaned substrate; Carbon nanotubes (CNT) and polysodium 4-styrene sulfonate (PSS) are mixed in water and subjected to high frequency to produce CNT aqueous solution in which CNTs and PSS mixed in water are evenly dispersed in water. Impregnating the substrate (100) having a charge layer into the CNT aqueous solution to form a CNT layer having a negative charge on the surface of the substrate; And impregnating the substrate coated with the CNT layer in a conductive polymer solution made using a conductive polymer having a positive charge, thereby forming a transparent conductive polymer layer on the CNT layer of the
According to the present invention, since the CNTs are individually separated into strands, and then dispersed and mixed with water to form an aqueous solution, the contact resistance between the CNTs is greatly reduced, and the surface of the substrate is coated to form a CNT layer. In addition, the electrical conductivity of the CNT layer is not only greatly improved, but also the light transmittance is greatly improved while the void space between the CNT networks is greatly increased, thus providing a transparent conductive plate having excellent light transmittance while ensuring high electrical conductivity on the substrate. It has an effect.
In particular, in the present invention, rather than forming a thick layer of CNT at once, by forming a very thin layer of nanometer level repeatedly with a conductive polymer layer in a multi-layer, it is possible to form a very even and uniform coating layer on the substrate surface By controlling the number of laminations of the CNT layer and the conductive polymer layer, the thickness of the entire transparent conductive plate including the substrate and the amount of CNT and the conductive polymer contained can be controlled very finely, thereby controlling the electrical and optical properties of the transparent conductive plate. There is an advantage that can be adjusted as desired by the user.
Furthermore, in the present invention, in stacking the CNT layer into a plurality of layers, the conductive polymer having a surface charge opposite to that of the dispersed CNTs is alternately stacked, thereby making the layer stable and stable due to the strong electrical attraction between the two layers. Bonding can be achieved. This has the advantage of being able to form a rigid and highly durable electrically conductive layer on the substrate.
As such, in the present invention, the CNT and the conductive polymer having excellent electrical conductivity form a complex multilayer network structure, and thus, the transparent conductive plate material according to the present invention has more excellent electrical and optical properties than the conventional transparent conductive plate material.
The transparent conductive plate material of the present invention may be used as a material such as a flat panel display panel, a solar cell, a transparent electrode, a touch panel, or may be used as an electromagnetic shielding material.
1 is a schematic cross-sectional view illustrating a state in which a positive charge layer is formed on a surface of a substrate by treating the surface of the substrate with APTES.
2 is a conceptual diagram illustrating a state in which a PSS having a negative charge is wound on a surface of a SWNT.
FIG. 3 is a schematic conceptual view illustrating a state in which a negatively charged CNT is attached to a surface of a substrate by impregnating a substrate having a positively charged layer in an aqueous CNT solution.
4 is a schematic conceptual view illustrating a state in which a conductive polymer having a positive charge is adsorbed on an outer surface of a CNT layer of a substrate formed by attaching CNTs.
5 and 6 are schematic conceptual views illustrating a state in which the CNTs and the conductive polymer layers are repeatedly formed by additionally coating the CNTs and the conductive polymers onto the substrate on which the CNTs and the conductive polymers are adsorbed.
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. Although the present invention has been described with reference to the embodiments illustrated in the drawings, it is described as one embodiment, whereby the technical spirit of the present invention and its core configuration and operation are not limited.
In the present invention, the surface of the
Looking at the method of manufacturing a transparent electromagnetic shielding material in accordance with the present invention in detail with reference to the drawings, first prepare a
Specifically, after cleaning the surface of the
As such, when the OH group attachment solution is prepared and the
The surface of the
To this end, first, a solution containing APTES is prepared. For example, the APTES solution is prepared by adding 1% volume of APTES to toluene. The prepared APTES solution is heated, preferably at a heating temperature of about 60 ° C. At this time, it is preferable to use a water bath method when heating the APTES solution. The
As such, when the
As such, the CNT, which is a highly conductive material, is subsequently coated on the
As a coating material, CNTs are not hydrophobic due to their hydrophobic surface and are present as a bundle, rather than as individual strands, due to the strong van der Waals attraction between CNTs and CNTs. The properties of CNTs not only make it difficult to make CNT aqueous solution, but also impede the development of electrical properties even after coating the
In order to solve this problem, in the present invention, when preparing a CNT aqueous solution, by performing a powerful ultrasonic grinding process for the CNTs that are bundled in a bundle, to separate the CNTs in the individual strands, and with hydrophilicity And encapsulating polysodium 4-styrene sulfonate (hereinafter, abbreviated as "PSS"), a polymer having negative charge characteristics, on the surface of the CNT, thereby improving the dispersibility of the CNT. A modification of the CNTs is performed, which changes the surface of the CNTs to hydrophilicity. That is, in the present invention, by mixing the CNT and PSS in water and dispersing the particles mixed in the water by using a high frequency disperser (Ultra Sonicator) or the like, the CNT is evenly dispersed in the water while wrapped in the PSS It will make a CNT aqueous solution.
CNTs can be broadly divided into single-walled carbon nanotubes (hereinafter referred to as "SWNT") and multi-walled carbon nanotubes (hereinafter referred to as "MWNT"). Although, the electrical properties of the SWNT is much better than the MWNT, it is preferable to use SWNT as the CNT to be used in the CNT aqueous solution. In the specific manufacturing process, SWNT is added to the water together with the PSS polymer at a mass concentration of 0.2%. In the case of the PSS polymer, there are various types depending on the molecular weight, it is preferable to use a molecular weight of 70,000. At this time, the ratio of SWNT and PSS polymer is very important. If the amount of PSS polymer is too high, the amount of PSS polymer which is not bonded with SWNT increases in solution, which lowers the electrical conductivity (PSS itself is a non-conductor, which has very low electrical conductivity. On the contrary, if the amount of PSS is too small, the PSSs may not be sufficiently bonded to the SWNTs, so that the dispersion and surface charge modification of the SWNTs may not be performed properly. Therefore, in the present invention, it is preferable to put SWNT and PSS in water at a ratio of 1: 1 by mass ratio.
As such, when an aqueous solution in which SWNT and PSS are mixed is prepared, dispersion is performed by irradiating high frequency waves. Specifically, by irradiating high frequency to the aqueous solution mixed with the SWNT and PSS by the water tank-type high-frequency disperser to perform a dispersion operation for about 30 minutes, and further irradiated with a high frequency through the tip-type high-frequency disperser to strongly disperse for about 1 hour It is preferable to perform the dispersion operation for 30 minutes using the tank-type high- parking disperser. Through such a high-frequency dispersion process, a number of SWNTs that existed as a bunch of bundles are separated into individual strands, and PSSs are enclosed and adsorbed on the surface of each separated SWNT. 2 conceptually illustrates a state in which the
In order for the CNT layer to have electrical conductivity and to be used as the material of the conductive plate, the CNTs must be intricately intertwined to form a network. However, when the bundled CNTs are used, the contact resistance between the CNTs and the CNTs is increased more than when they are separated separately, resulting in low electrical conductivity and a sharp decrease in optical transparency due to the bundled CNTs. have. In the present invention, as described above, instead of simply mixing the CNTs in water, the CNTs are treated separately to form separate strands, and then mixed in water to form an aqueous solution, thereby greatly reducing the contact resistance between the CNTs. When coated on the surface of the
In addition to forming a CNT layer by impregnating the
Typical polymers can also be used to form multilayer structures by coating between CNT layers if they have a positive charge. However, the general polymer is an electrical insulator and has a very low electrical conductivity, which is not suitable for manufacturing a conductive plate. Therefore, in the present invention, a conductive polymer solution having high electrical conductivity while having a positive charge was prepared and used. A conductive polymer solution having a positive charge and high electrical conductivity is typically polyaniline, and poly 3,4-ethylenedioxythiophene / Hereinafter, a poly 3,4-ethylenedioxythiophene-polyethylene glycol block hybrid polymer (Poly (3,4-ethylenedioxythiophene) -block-poly (ethylene glycol) / perchlorate) made using "PEDOT" Impurity added / hereinafter abbreviated as "PEDOT-PEG") also has good properties for this purpose. The dual PEDOT-PEG is a polymer material having high electrical conductivity, high optical transparency and positive charge, and suitable for use in the purpose of the present invention. However, since it is insoluble in water, in the present invention, a solution in which PEDOT-PEG is dissolved in propylene carbonate (Propylene Carbonate) (hereinafter, abbreviated as "PEDOT-PEG solution") is used and used as a conductive polymer solution. At this time, the PEDOT-PEG concentration in the conductive polymer solution is preferably about 0.0005% by mass concentration. If the concentration of PEDOT-PEG is higher than 0.0005%, it is not preferable because the optical characteristics of the PEDOT itself are rapidly degraded.
When the surface treatment is completed with APTES and the
Specifically, a dip coating operation is performed in which the
After the coating of the CNT layer by the CNT aqueous solution impregnation operation of the
When the CNT aqueous solution impregnation operation of the
After the conductive polymer solution dip coating operation of the
Through this process, an additional transparent conductive polymer layer is formed on the surface of the
In particular, as described above, since the CNTs are uniformly dispersed in forming the CNT layer, even if the CNT layer is formed on the
4 is a schematic conceptual view showing a state in which a conductive polymer having a positive charge (specifically, PEDOT-PEG) 30 is adsorbed on the outer surface of the CNT layer of the
Therefore, when the
As described above, in the present invention, the CNT layer is not formed thick at once, but is formed by stacking in multiple layers, thereby forming an even and uniform coating layer on the surface of the
Furthermore, in the present invention, in stacking the CNT layer into a plurality of layers, the CNT layer is alternately formed with the conductive polymer layer, thereby making it possible to achieve a firm bonding between the CNT layers, thereby providing a firm and durable structure on the
100: substrate, 10 positive charge layer, 20 PSS-SWNT,
21: CNT (SWNT), 22: PSS, 30: PEDOT-PEG
Claims (7)
Dipping the substrate 100 in the OH group attachment solution so that the OH group adheres to the surface of the substrate 100;
Forming a positive charge layer using aminopropyl dioxide silane (APTES) on the surface of the cleaned substrate 100;
Carbon nanotubes (CNT) and polysodium 4-styrene sulfonate (PSS) are mixed in water and subjected to high frequency to produce CNT aqueous solution in which CNTs and PSS mixed in water are evenly dispersed in water. Impregnating the substrate 100 having a charge layer into the CNT aqueous solution to form a CNT layer having a negative charge on the surface of the substrate 100; And
Impregnating the substrate 100 coated with the CNT layer in a conductive polymer solution made of a conductive polymer having a positive charge, thereby forming a transparent conductive polymer layer on the CNT layer of the substrate 100. Method for producing a transparent conductive plate, characterized in that it comprises a.
The method for attaching the OH group is a method of manufacturing a transparent conductive plate, characterized in that the solution consisting of a mixture of H 2 SO 4 and H 2 O 2 of 30% mass concentration in a volume ratio of 3: 1.
CNT mixed in the CNT aqueous solution is a single-walled carbon nanotube (SWNT),
SWNT and PSS are mixed in the CNT aqueous solution in a ratio of 1: 1 by mass ratio.
The conductive polymer solution is produced by dissolving poly3,4-ethylenedioxythiophene-polyethylene glycol in propylene carbonate.
After stacking the positive charge layer, the CNT layer and the conductive polymer layer in sequence on the substrate 100,
Impregnating the substrate 100 with an aqueous CNT solution to form a CNT layer having a negative charge on the surface of the substrate 100, and impregnating the substrate 100 with a conductive polymer solution having a positive charge. Method for producing a transparent conductive plate material, characterized in that to repeat the step of forming a transparent conductive polymer layer on the CNT layer of the substrate (100).
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KR101425283B1 (en) * | 2012-11-30 | 2014-08-01 | 한국세라믹기술원 | Preparing method of cnt-conductive polymer composite using microwave |
CN103928637B (en) * | 2013-01-14 | 2016-05-04 | 北京阿格蕾雅科技发展有限公司 | The preparation method of carbon nano tube transparent combination electrode |
CN105427917A (en) * | 2016-01-06 | 2016-03-23 | 上海交通大学 | Metal nano wire transparent conductive film and preparation method thereof |
CN109980028B (en) * | 2019-04-08 | 2020-07-14 | 西安工业大学 | Method for preparing transparent conductive nanowire grid film by electrically inducing surface of three-dimensional microstructure |
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KR100790216B1 (en) * | 2006-10-17 | 2008-01-02 | 삼성전자주식회사 | A transparent cnt electrode using conductive dispersant and preparation method thereof |
KR20100033097A (en) * | 2008-09-19 | 2010-03-29 | 한국전자통신연구원 | Transparent conductive thin film using carbon nano tube and method for preparation thereof |
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KR20100033097A (en) * | 2008-09-19 | 2010-03-29 | 한국전자통신연구원 | Transparent conductive thin film using carbon nano tube and method for preparation thereof |
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