KR101263194B1 - Transparent electroconductive thin layer comprising a plurality of conjugated conductive layers consisting of metal nano-structure and conductive polymer, and it's fabrication method - Google Patents

Abstract

PURPOSE: A transparent electroconductive thin layer comprising a plurality of conjugated conductive layers consisting of metal nanostructure and conductive polymer, and a fabrication method thereof are provided to improve the stability and reliability of a thin film by preventing the penetration of moisture and oxygen. CONSTITUTION: A transparent substrate(100) is prepared. A metal nanostructure solution is coated on the transparent substrate to form a metal nanowire conduction layer. A metal nanowire thin film is formed on the metal nanowire conduction layer. A conductive polymer composition is coated on the metal nanowire thin film. The conductive polymeric composition is annealed to form a first conductor layer(200) consisting of conductive films(201,20n), and a second conductor layer(300) made of conductive polymer(500).

Description

Transparent electroconductive thin layer comprising a plurality of conjugated conductive layers consisting of metal nano-structure and conductive polymer, and it's fabrication method .}

Due to the nature of the product to be transmitted through the light, the upper plate of the display element is a transparent and conductive thin film is required to be connected to the wiring and ground. To this end, indium tin oxide (ITO) has been applied for a long time, but indium tin oxide (ITO) is inflexible, weak to physical impact, difficult to bond with flexible substrates, and vacuum It has been pointed out that the use of the deposition process is uneconomical.

The present invention is to provide a transparent conductive thin film having a multi-layer structure including a metal nanostructure and a method for manufacturing the same as an alternative to solve the shortcomings of the indium tin oxide (ITO). The present invention maintains high light transmittance, has a low sheet resistance value, has a small variation in sheet resistance throughout the thin film, and prevents deterioration of physical properties due to oxygen or moisture in the air, thereby increasing the stability and reliability of the thin film at the same time. It relates to a transparent conductive thin film and a method for manufacturing the same.

Generally, the transparent conductive thin film means a thin conductive film coated on an insulating surface or a substrate having high light transmittance, and the conductive thin film is required to have high light transmittance and high surface conductivity. If the conductivity is low, smooth driving is difficult, and if the transmittance is lowered, the display performance is degraded. However, when the thickness of the conductive thin film is formed to improve the conductivity of the conductive thin film, the transmittance is reduced while the surface reflectance and the absorption rate of the conductive thin film are increased. Therefore, it is recognized that it is very difficult to improve both the conductivity and the transmittance. have.

Currently, vacuum deposited metal oxide, such as indium tin oxide (ITO), is widely used as a transparent conductive thin film, but the metal oxide film has a weak mechanical strength and is not flexible to use a flexible substrate. The application of flexible displays is limited, and the modification of organic functional films employed in substrates or devices is necessary because annealing at high deposition temperatures or high temperatures is required to achieve high conductivity levels. Can also generate

Korean Patent No. 10-2011-0129612 relates to a method for manufacturing a transparent conductive material. After manufacturing and purifying nanoseeds from a compound, silver nanowires are grown using a polyol process and coated on a substrate to form a transparent conductive coating film. Forming and annealing is characterized in that it comprises. However, the thin metal nanowire thin film is susceptible to moisture, and the electrical property change is severe, and when silver nanowires are coated on a substrate, when the coating film is a certain thickness or more, agglomeration between metal nanostructures occurs in the annealing process. There is a disadvantage that the sheet resistance variation is severe according to the position of the thin film.

Therefore, in the present invention, by forming a conductive polymer film on the conductive film including the metal nanostructure, to increase the moisture resistance of the metal nanostructure thin film, to reduce the electrical property change to increase the reliability, and in combination with the conductive polymer By increasing the contact of the metal nanostructure to obtain a high light transmittance and high electrical conductivity. In addition, the conductive layer including the nanostructures is composed of a plurality of nanostructure conductive films formed by repeating the coating and annealing processes several times, so that each conductive film layer is less than or equal to the thickness of the aggregation phenomenon between the metal nanostructures in the annealing process. By adjusting to, it is to reduce the sheet resistance variation according to the position of the thin film.

In order to solve the above problems, first, by forming a conductive film made of a conductive polymer on the upper portion of the conductive film containing a metal nano-body, to prevent the reaction of the conductive film containing a metal nano-material with moisture in the air, moisture resistance and chemical resistance In this way, the electrical properties such as electrical conductivity can be prevented. In addition, since the conductive polymer is positioned inside a matrix made of the metal nanostructure, the conductive polymer serves to electrically connect the metal nanostructures, thereby maintaining high transmittance while maintaining high electrical conductivity.

Secondly, in particular, the conductive layer formed of the metal nanostructure is formed into a multilayer structure composed of a thin mixed conductive film containing a plurality of metal nanostructures and a conductive polymer. At this time, the annealing process is performed every time the coating for forming each thin layer is finished, thereby preventing the aggregation of the metal nanostructures. Therefore, the sheet resistance variation according to the position of the thin film was reduced. In addition, by uniformly distributing the nanostructure over the entire conductive layer, it is possible to prevent the local concentration of current to prevent changes in the structure and physical properties of the metal nanostructure. In addition, the lengths of the conductive polymers connecting the metal nanostructures are relatively evenly distributed, and thus, finally, a series of uniform resistance values can be seen, resulting in low resistance values of the entire conductive film.

First, the conductive polymer layer prevents the reaction of the conductive film including the metal nano-body with moisture in the air, thereby improving moisture resistance and chemical resistance, and thereby preventing deterioration of electrical properties such as electrical conductivity.

Second, since the conductive polymer is positioned inside a matrix made of the metal nanostructure, the conductive polymer serves to electrically connect the metal nanostructures, thereby maintaining high transmittance while maintaining high electrical conductivity.

Third, the metal nanostructure conductive layer may be formed in a multilayer structure including a plurality of thin mixed conductive films including the metal nanostructure and the conductive polymer, thereby preventing aggregation of the metal nanostructure.

Fourth and fifth, it is possible to reduce the sheet resistance variation according to the position of the thin film by preventing the cohesion of the metal nanostructures, and by uniformly distributing the nanostructures over the entire conductive layer, thereby preventing the concentration of local currents. It is possible to prevent changes in the structure and physical properties.

1 relates to a manufacturing process of a transparent conductive thin film having a multilayer structure.
FIG. 1 (a) shows a first metal nanostructure thin film formed by coating, annealing, and coating a metal nanostructure solution on a transparent substrate and a transparent substrate.
FIG. 1 (b) shows a state immediately after coating the first layer and the conductive polymer formed on the first layer by repeating the coating and annealing of the metal nanostructure solution n times on the transparent substrate and the transparent substrate.
FIG. 1 (c) shows a state after annealing the conductive polymer on the first conductive layer and shows a transparent conductive thin film composed of a transparent substrate, a first conductive layer, and a second conductive layer.
2 is an enlarged view of structures of various transparent conductive thin films.
2 (a) is a structure of a transparent conductive thin film made of a transparent substrate and a metal nanostructure thin film thereon.
2 (b) is a structure of a transparent conductive thin film composed of a mixed conductive thin film made of a transparent substrate, a metal nanostructure and a conductive polymer, and a conductive polymer layer.
Figure 2 (c) is a structure of a transparent conductive thin film of the present invention consisting of a plurality of mixed conductive thin film made of a metal nanostructure and a conductive polymer, and a conductive polymer layer on a transparent substrate.
3 (a) is a sheet resistance modeling of a transparent conductive thin film made of a transparent substrate and a metal nanostructure thin film thereon.
3 (b) is a sheet resistance modeling of a transparent conductive thin film composed of a transparent substrate, a mixed conductive thin film made of a metal nanostructure and a conductive polymer, and a conductive polymer layer.
3 (c) is a sheet resistance modeling of the transparent conductive thin film of the present invention comprising a plurality of mixed conductive thin films made of a metal nanostructure and a conductive polymer, and a conductive polymer layer on a transparent substrate.
4 (a) is experimental data on the transmittance and sheet resistance of the transparent conductive thin film composed of the transparent substrate and the metal nanostructure thin film thereon.
FIG. 4 (b) is experimental data of transmittance, sheet resistance, and sheet resistance of the transparent conductive thin film composed of the transparent substrate, the metal nanostructure, the conductive polymer, and the transparent conductive thin film.
4 (c) shows experimental data of transmittance, sheet resistance, and sheet resistance variation of the transparent conductive thin film of the present invention comprising a plurality of mixed conductive thin films made of a metal nanostructure and a conductive polymer, and a conductive polymer layer on a transparent substrate.
FIG. 5 (a) is an experimental result of the sheet resistance change with time of the transparent conductive thin film made of a transparent substrate and a metal nanostructure thin film thereon.
FIG. 5 (b) is an experimental result of the sheet resistance change with time of the transparent conductive film, the mixed conductive thin film made of the metal nanostructure and the conductive polymer, and the transparent conductive thin film made of the conductive polymer layer.
5 (c) is an experimental result of the sheet resistance change with time of the transparent conductive thin film of the present invention composed of a plurality of mixed conductive thin films made of a metal nanostructure and a conductive polymer, and a conductive polymer layer on a transparent substrate.

1 relates to a method for manufacturing a transparent conductive thin film 1 having a multilayer structure of the present application. First, a metal nanostructure solution including a metal nanostructure, a binder resin, and a solvent is prepared, and the metal nanostructure solution is coated and coated on the prepared transparent substrate 100 as shown in FIG. 1 metal nanostructure thin film 211 is formed. As shown in FIG. 1 (b), the coating and annealing are repeated a plurality of times with the same metal nanostructure solution on the first metal nanostructure thin film 211 to form a first layer 210 made of a plurality of metal nanowire conductive thin films. Form. At this time, if the coating and annealing process is repeated n times, the top film will be represented by the n-th metal nanostructure thin film 21n.

After the formation of the first layer 210, as shown in FIG. 1 (c), the conductive polymer composition including the conductive polymer, the dopant, and the organic solvent is coated on the first layer 210 to form a second layer 310 thereon. 1 and finally annealed as shown in FIG. 1 (d) to form a second conductive layer 300. During the coating and annealing process of the conductive polymer composition, the metal nanostructure thin films 211 and 21n of the first layer 210 are mixed conductive materials such that the conductive polymer 500 is disposed in the substrate made of the metal nanostructure 400. The thin films 201 and 20n are changed, and the plurality of mixed conductive thin films 201 and 20n form one layer of the first conductive 200. Finally, a transparent conductive thin film 1 having a multilayer structure having the structure of FIG. 1 (d) can be obtained. At this time, the thickness of the first conductive layer 200 can be selected according to the purpose, but it is suitable to form a thickness of 20 ~ 250 nm, a plurality of mixed conductive thin films 201 forming the first conductive layer 200, The thickness of 20n) may vary depending on the number and purpose of the metal nanostructure conductive thin films. The thickness of 20n) is suitable for the transparent electrode.

In addition, before coating the metal nanostructure solution on the transparent substrate 100, a pretreatment step of modifying the surface of the transparent substrate using at least one of plasma, ultraviolet light, or ozone may be included. Before the coating of the conductive polymer composition, impurities of the conductive polymer composition are removed by an ultra filtration process using at least one of a hollow fiber membrane, dialysis, or a serum replacement. It is also possible to carry out the steps.

In addition, the metal nanostructure solution is a wet coating method including at least one of spin coating, spray coating, roll to roll, or bar coating. Method for producing a transparent conductive thin film, characterized in that consisting of.

The metal nanostructure 400 and the conductive polymer 500 are not limited to a specific material, and the metal constituting the metal nanostructure 400 may be gold, silver, copper, iron, nickel, zinc, indium, tin, It may be made of any one or a combination of two or more selected from antimony, magnesium, cobalt, lead, platinum, titanium, tungsten, germanium, aluminum, the shape is nanoribbon (nanoribbon), nanorod (nanorod), nanowire (nanowire) It may be configured to include at least one of, or nanoparticles (nanosphere). In addition, the solvent contained in the metal nanostructure solution is also not limited to a specific material, isopropanol (isopropanol), methanol (methanol), ethanol (ethanol), water, diethylene glycol monobutyl ether (diethylene glycol monobutyl ether) or a combination of two or more.

The coating of the conductive polymer composition may include wet coating including at least one of spin coating, spray coating, roll to roll, or bar coating. The conductive polymer composition may be prepared by a coating method, and the conductive polymer composition may include an aqueous solution including a conductive polymer or a derivative of the conductive polymer and at least one organic solvent. The conductive polymer may be polythiophene or polypyrrole. (polypyrrole), poly (3,4-ethylenedioxythiophene), polyaniline, poly p-phenylene, poly p-phenylene It comprises at least one of poly (p-phenylenevinylene), polyacetylene, polydiacetylene, polydiacetylene, poly (thiophenevinylene), polyfluorene (polyfluorene) , An aqueous solution containing the derivative of the conductive polymer or conductive polymer may be added to a variety of dopants in accordance with the object, in particular polystyrene sulfonate; can be configured by adding a (polystyrene sulfonate PSS) as a dopant.

The organic solvent included in the conductive polymer composition may be aliphatic ketone including water, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, ethylene glycol, dimethyl sulfoxide, N-methylpyrrolidone, N, Any one of N-dimethylformamide may be selected or two or more selected and mixed, but is not limited thereto. In addition, it can be selected and used according to the purpose and application field, the conductive polymer composition is preferably pH 1 ~ 10, the content of the solid content is preferably 0.1 to 50% by weight.

2 shows the structure of the transparent conductive thin film using the metal nanostructure 400. In particular, the metal nanostructure 400 and the conductive polymer 500 inside the thin film are actually incomplete mesh structures on a three-dimensional micro scale, but the metal nanostructures 400 are two-dimensional in order to easily understand the effects of the present invention. ) Is an enlarged view of only the weak link.

2 (a) shows a structure of a transparent conductive thin film in which a metal nanostructure thin film is formed on a transparent substrate, and the metal nanostructure 410 aggregated by agglomeration of the nanostructure on a portion of the metal nanostructure thin film during an annealing process. Will be formed. Accordingly, the distance between the metal nanostructures 400 is relatively large, and the electrical coupling between the metal nanostructures 400 is relatively incomplete.

2B is a structure of a transparent conductive thin film in which a mixed conductive thin film and a conductive polymer layer are sequentially formed on a transparent substrate. As shown in FIG. 2A, in the annealing process, agglomeration of the metal nanostructures is formed on a portion of the metal nanostructure thin film to form agglomerated metal nanostructures 410, but the upper conductive polymer 500 is formed of the metal nanostructures ( Filled between 400, it has a structure that electrically connects between the metal nanostructures (400).

2 (c) is a structure of the transparent conductive thin film 1 of the present invention consisting of a plurality of mixed conductive thin films, a conductive polymer layer on the transparent substrate 100, which is coated with a plurality of thin layers, annealing the thin film Therefore, since the aggregation of the metal nanostructure 400 occurs less, the metal nanostructure 400 is relatively evenly distributed, and the distance between the metal nanostructures 400 is relatively short, so that the length of the conductive polymer 500 connecting the metal nanostructure 400 is also short. It has a relatively short structure.

In addition, since the electrical resistance is proportional to the length of the conductor and inversely proportional to the cross-sectional area, the conductive polymer connecting the metal nanostructure 400 in the case of the first conductive layer of the multilayer structure of FIG. The shorter the length of the 500 and the greater the length of the conductive polymer 500 that connects the metal nanostructure 400, the more difficult the contact between the conductive polymers 500 is, and the greater the possibility of electrical loss occurring, FIG. 2 (c). In the case of the first conductive layer 200 having the multilayer structure of FIG. 2, the sheet resistance value is smaller than that of FIGS. 2A and 2B. In addition, since the metal nanostructure 400 is evenly distributed, the length distribution of the conductive polymer 500 is also uniform, and the sheet resistance variation is greatly lowered.

FIG. 3 is modeled as a resistor, and FIG. 3 (a) is a sheet resistance modeling of the transparent conductive thin film on which the metal nanostructure thin film 220 is formed on the transparent substrate. R1 represents the resistance formed by the void space between the metal nanostructures 400, which will have a relatively large value. 3 (b) is a sheet resistance modeling of the transparent conductive thin film on which the conductive polymer layer is formed on the mixed conductive thin film 230 on the transparent substrate 100, and R 2 is formed by the conductive polymer 500 between the metal nanostructures 400. Resistance will be less than R1.

3 (c) shows the transparent conductive thin film 1 of the present invention in which the second conductive layer 300 is formed on the first conductive layer 200 including the plurality of mixed conductive thin films 201 and 20n on the transparent substrate. In the sheet resistance modeling, r3 is mainly dominated by the resistance of the conductive polymer 500 between the metal nanostructures, and the length of the conductive polymer 500 is shorter than that of FIG. 3 (b), which is the length of the conductive polymer 500. As the number of r3 increases as the contact loss between the conductive polymer 500 and the electrical loss may occur, the number of r3 increases based on the same distance in the metal nanostructure conductive thin films 201 and 20n. Has a smaller value than one R2 value. In addition, in FIG. 2 (c), the resistance component r3 is evenly distributed, whereas in FIG. 2 (b), the dense and small portions of the structure appear irregularly due to the aggregation of the metal nanostructure 400. The length of the conductive polymer 500 that connects the nanostructure 400 body varies depending on the location, so that the resistance component R2 also varies greatly depending on the location. Therefore, the structure of FIG. 2 (c) exhibits a smaller sheet resistance deviation than that of FIG. 2 (b).

In FIG. 4, (a) shows a single metal nanostructure thin film, (b) shows a single mixed conductive thin film and a conductive polymer film, and (c) shows a transmittance and sheet resistance of a transparent conductive film composed of a plurality of mixed conductive thin films and a conductive polymer film. As shown, it is an experimental result for the transparent conductive thin film prepared according to Examples 1, 2, 3 to be described later. In fact, it is shown that FIG. 4 (b) has a smaller sheet resistance at the same transmittance than that of FIG. 4 (a), and that of FIG. 4 (c) is the same as that of FIG. It can be seen that the smaller the sheet resistance value and the sheet resistance deviation are. At the same 99% transmittance, Fig. 4 (a) has an average sheet resistance of about 500 Ω / □, whereas Fig. 4 (b) has a smaller average sheet resistance of about 300 Ω / □, and Fig. 4 (c) It can be seen that the sheet resistance value of about 150 Ω / square smaller than FIGS. 4 (a) and 4 (b) can be obtained. On the other hand, the sheet resistance deviation is ± 350 Ω / □ sheet resistance variation in case of 4 (a), and the sheet resistance variation of ± 135 Ω / □ case in case of 4 (b). On the other hand, in the case of 4 (c), only the sheet resistance variation of about ± 25 Ω / □ was found. The sheet resistance value or sheet resistance variation may vary depending on the thickness and other process variables selected according to the purpose of use, and lower sheet resistance and sheet resistance when a plurality of metal nanostructure conductive thin films of the present invention are formed, rather than the exact values or ranges thereof. It is important to show a tendency to have a deviation, and even if it has a value different from the sheet resistance value or the deviation of Fig. 4, it is apparent that different values can be obtained by adjusting thickness and the like in the same structure. Particularly, when the thickness of the first conductive layer is 20 to 250 nm, a sheet resistance value of 0.01 to 10K Ω / □ can be obtained at a transmittance of 99%.

5 is a sheet resistance with time of a transparent conductive film composed of (a) a single metal nanostructure thin film, (b) a single mixed conductive thin film and a conductive polymer layer, (c) a plurality of mixed conductive thin films and a conductive polymer layer. Experimental results for the change of, which are the experimental results for the transparent conductive thin film prepared according to Examples 1, 2 and 3 to be described later. In order to observe the change in sheet resistance over time, the thicknesses of the samples (a), (b), and (c) were selected to have a sheet resistance of about 65 Ω / □. In fact, the case of FIG. 5 (b) shows a smaller sheet resistance change than that of FIG. 5 (a), and the case of FIG. 5 (c) is smaller than that of FIG. 5 (a) and FIG. 5 (b) when left in the air. It can be seen that the sheet resistance changes. After the same 96 hours, Fig. 5 (a) shows a change in sheet resistance of about 30 Ω / □, while Fig. 5 (b) shows a smaller sheet resistance change of about 10 Ω / □, and Fig. 5 (c) shows the change in sheet resistance. There is little change, and it can be seen that the thin film is much more stable than FIGS. 5 (a) and 5 (b).

A glass substrate having a thickness of 500 μm was prepared as a transparent substrate, and impurities were removed from the surface using acetone and isopropanol, and then the surface of the glass substrate was modified to be hydrophilic through plasma treatment.

The metal of the metal nanostructure was selected from silver (Ag), and the silver nanowire solution (nanopixis, length 25 μm, width 45 nm) in which silver nanowires and a binder resin were dispersed in isopropanol at 0.1% by weight was glass. After coating on top of the substrate, after spin coating at 5000 rpm for 10 seconds, the silver nanowire thin film was annealed at 150 ° C. for 1 minute. The finally annealed silver nanowire thin film was 50 nm.

The light transmittance was measured using a UV-Visible spectrophotometer (UV-1601PC manufactured by SHIMADZU Co., Ltd.) for light having a wavelength of 550 nm. At this time, the transmittance of the transparent substrate was set to 100% and the transmittance after coating was expressed as a ratio. The sheet resistance was measured using a 4-point prove method conductivity meter (NAPSON RT-70), and the stability of the membrane was adjusted by the transmittance, so that the sheet resistance ranged from 60 to 65 Ω / □ at ambient temperature. The change in sheet resistance was measured every 12 hours while being in contact.

Experimental results on the transmittance and sheet resistance of the transparent conductive film made of such a single silver nanostructure film are shown in FIG. 4 (a), and the change in sheet resistance with time is shown in FIG. 5 (a).

The conductive polymer composition was prepared by PEDOT: PSS [Poly (3,4-ethylenedioxythiophene); poly (styrenesulfonate)] to the aqueous solution, based on the weight of the aqueous solution, 5% by weight of ethylene glycol (ethylene glycol) and 300% by weight of N-methylpyrrolidone are sequentially added, and then uniformly mixed for about 5 hours to conduct conductivity A polymer composition was prepared.

The conductive polymer composition thus prepared was spin coated at 5000 rpm for 10 seconds on top of the thin film including silver nanowires prepared in Example 1, and then the conductive polymer was formed at 150 ° C. for 10 minutes. The thin film was annealed.

Thus, finally, a transparent conductive film having a structure of FIG. 2 (b) consisting of a single mixed conductive thin film and a conductive polymer layer was obtained.

Under the same measurement conditions as those of <Example 1>, the light transmittance was measured using a UV-Visible spectrophotometer (UV-1601PC manufactured by SHIMADZU Co., Ltd.) for light having a wavelength of 550 nm. At this time, the transmittance of the transparent substrate was set to 100% and the transmittance after coating was expressed as a ratio. The sheet resistance was measured using a 4-point prove method conductivity meter (NAPSON RT-70), and the stability of the membrane was measured by changing the sheet resistance every 12 hours in contact with the air at room temperature.

Experimental results of the transmittance and sheet resistance of the transparent conductive film composed of the single mixed conductive thin film and the conductive polymer layer are shown in FIG. 4 (b), and the change in sheet resistance with time is shown in FIG. 5 (b).

After the thin film containing the silver nanowires obtained as a result of <Example 1> was prepared, the manufacturing process of the silver nanowire thin film of <Example 1> was repeated once more to obtain a conductive thin film containing silver nanowires. Laminated in layers.

Conductive polymer composition is the same as in <Example 2> PEDOT: PSS [Poly (3,4-ethylenedioxythiophene); poly (styrenesulfonate)] 5 wt% ethylene glycol and 300 wt% N-methylpyrrolidone were sequentially added to the aqueous solution based on the weight of the aqueous solution, followed by uniform mixing for about 5 hours to prepare the conductive polymer composition. Prepared.

The conductive polymer composition prepared as described above was spincoated at 5000 rpm for 10 seconds on the silver nanowire thin film layer formed of the two layers, and then the conductive polymer thin film was annealed at 150 ° C. for 10 minutes. .

Therefore, finally, a transparent conductive film having the structure of FIG. 2 (c) having a first conductive layer composed of a plurality of mixed conductive thin films and a second conductive layer composed of a conductive polymer layer was obtained.

Under the same measurement conditions as those of <Example 1> and <Example 2>, the light transmittance was measured using a UV-Visible spectrophotometer (UV-1601PC manufactured by SHIMADZU Co., Ltd.) for light having a wavelength of 550 nm. At this time, the transmittance of the transparent substrate was set to 100% and the transmittance after coating was expressed as a ratio. The sheet resistance was measured using a 4-point prove method conductivity meter (NAPSON RT-70), and the stability of the membrane was measured by changing the sheet resistance every 12 hours in contact with the air at room temperature.

Experimental results of the transmittance, sheet resistance, and sheet resistance of the transparent conductive film including the first conductive layer including the plurality of mixed conductive thin films and the second conductive layer including the conductive polymer layer are shown in FIG. The change in sheet resistance is shown in FIG. 5 (c).

Although the present invention has been described with reference to the accompanying drawings, it is merely one example of various embodiments including the gist of the present invention, which can be easily implemented by those skilled in the art. It is clear that the present invention is not limited to the above-described embodiment only. Accordingly, the scope of protection of the present invention should be construed according to the following claims, and all technical ideas which fall within the scope of equivalence by alteration, substitution, substitution, Range. In addition, it should be clarified that some configurations of the drawings are intended to explain the configuration more clearly and are provided in an exaggerated or reduced size than the actual configuration.

1: Transparent conductive thin film of multi-layer structure 100: Transparent substrate
200: first conductive layer
201: first mixed conductive thin film
20n: nth mixed conductive thin film
210: first layer
211: first metal nanostructure thin film
21n: nth metal nanostructure thin film
220: metal nanostructure thin film without conductive polymer
230: single mixed conductive thin film filled with conductive polymer
300: second conductive layer
310: second layer
400: metal nanostructure
410: Aggregated metal nanostructure
500: conductive polymer
R1: resistance formed by empty space between metal nanostructures
R2: resistance formed by a conductive polymer between metal nanostructures when a single metal nanostructure thin film is employed
r3: resistance formed by a conductive polymer between metal nanostructures when a plurality of metal nanostructure thin films are employed

Claims (20)

In the method of manufacturing a transparent conductive thin film having a multilayer structure,
(i) preparing a metal nanostructure solution comprising a metal nanostructure, a binder resin, and a solvent,
(ii) preparing a transparent substrate,
(iii) coating the metal nanostructure solution on the transparent substrate to form a metal nanowire conductive thin film,
(iv) annealing the metal nanowire conductive thin film,
(v) forming a plurality of metal nanowire thin films by repeating the annealing of the metal nanostructure solution on the annealed metal nanowire conductive thin film and repeating the annealing step a plurality of times,
(vi) coating a conductive polymer composition on the plurality of metal nanowire thin films,
(vii) annealing the polymer composition to form a first conductive layer made of a plurality of mixed conductive thin films connected by mixing metal nanowires with a conductive polymer and a second conductive layer made of a conductive polymer;
Method for producing a transparent conductive thin film having a multi-layer structure, characterized in that it comprises a. The method of claim 1,
Between the steps (ii) and (iii), a transparent conductive thin film comprising a pretreatment step of modifying the surface of the transparent substrate using at least one of plasma, ultraviolet light, or ozone. Manufacturing method. The method of claim 2,
Between the steps (v) and (vi), the ultrafiltration of the conductive polymer composition using at least one of the hollow fiber membrane, dialysis, or serum replacement (serum replacement) of the conductive polymer composition Method for producing a transparent conductive thin film comprising the step of removing impurities. The method of claim 3,
The process of coating the metal nanostructure solution may include a wet coating including at least one of spin coating, spray coating, roll to roll, or bar coating. Method for producing a transparent conductive thin film, characterized in that the wet coating) method. 5. The method of claim 4,
The metal constituting the metal nanostructure is gold, silver, copper, iron, nickel, zinc, indium, tin, antimony, magnesium, cobalt, lead, platinum, titanium, tungsten, germanium, aluminum or any combination of two or more. Method for producing a transparent conductive thin film, characterized in that consisting of. The method of claim 5,
The metal nanostructure in the first conductive layer may include at least one of a nanoribbon, a nanorod, a nanowire, or a nanosphere. Way. The method according to claim 6,
The solvent included in the metal nanostructure solution may be selected from one or two of isopropanol, methanol, ethanol, water, diethylene glycol monobutyl ether. Method for producing a transparent conductive thin film, characterized in that configured by selecting and combining the above. The method of claim 7, wherein the content of the metal nanostructures included in the metal nanostructure solution is 0.01 to 1.0 wt%. The method of claim 8, wherein the coating of the conductive polymer composition comprises at least one of spin coating, spray coating, roll to roll, or bar coating. Method for producing a transparent conductive thin film, characterized in that consisting of a wet coating (wet coating) comprising. 10. The method of claim 9,
The conductive polymer composition is a method for producing a transparent conductive thin film, characterized in that it comprises a conductive polymer or conductive polymer derivative aqueous solution and at least one organic solvent. The method of claim 10,
The conductive polymer is polythiophene, polypyrrole, poly (3,4-ethylenedioxythiophene) (poly (3,4-ethylenedioxythiophene)), polyaniline, polyp-phenylene (poly (p-phenylene)), poly (p-phenylenevinylene), polyacetylene, polydiacetylene, poly (thiophenevinylene), polyfullerene Method for producing a transparent conductive thin film comprising at least one of (polyfluorene). The method of claim 11,
The organic solvent is water, methanol, ethanol, aliphatic alcohols including isopropanol, acetone, aliphatic ketones including methyl ethyl ketone, ethylene glycol, dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylformamide A method for producing a transparent conductive thin film, characterized in that any one or selected by mixing two or more. The method of claim 12, wherein the conductive polymer composition has an acidity of pH 1 to 10 and a content of the conductive polymer in an amount of 0.1 to 50 wt%. In a transparent conductive thin film having a multilayer structure,
It comprises a first conductive layer formed on the transparent substrate, a second conductive layer formed on the first conductive layer,
The first conductive layer is formed by stacking two or more mixed conductive thin films connected by mixing a metal nanostructure and a conductive polymer, and wherein the second conductive layer is a thin film including a conductive polymer. Transparent conductive thin film. The transparent conductive thin film of claim 14, wherein the metal nanostructure comprises at least one of a nanoribbon, a nanorod, a nanowire, and a nanosphere. The method of claim 15, wherein the metal constituting the metal nanostructure is selected from gold, silver, copper, iron, nickel, zinc, indium, tin, antimony, magnesium, cobalt, lead, platinum, titanium, tungsten, germanium, aluminum Transparent conductive thin film, comprising any one or a combination of two or more. The method of claim 16, wherein the conductive polymer is polythiophene, polypyrrole, poly (3,4-ethylenedioxythiophene), polyaniline, polyaniline, poly p-phenylene (poly (p-phenylene)), poly p-phenylenevinylene (poly (p-phenylenevinylene)), polyacetylene (polyacetylene), polydiacetylene (polydiacetylene), polythiophene vinylene (poly ( thiophenevinylene)), polyfluorene (polyfluorene) or a transparent conductive thin film comprising at least one of the derivatives thereof. 18. The transparent conductive thin film according to claim 17, wherein the transparent conductive thin film has a sheet resistance value of 0.01K or more and 10K Ω / □ or less at a light transmittance of 99%. 19. The transparent conductive thin film according to claim 18, wherein the thickness of the first conductive layer is 20 to 250 nm. The transparent conductive thin film according to claim 19, wherein the sheet resistance is increased by 1 to 10% based on the initial sheet resistance even after 96 hours in the air.

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