KR20200121417A - The manufacturing method of functionalized-patterned films using interface reaction, functionalized-patterned films by thereof and uses thereof - Google Patents

Abstract

The present invention relates to a method for manufacturing a patterned film, which is capable of patterning a surface of a film in a honeycomb pattern or a moth-eye pattern through an in-situ chemical reaction, and also, can functionalize the surface thereof at the same time; a patterned film manufactured thereby; and a use thereof. According to the present invention, the method for manufacturing a patterned film in which a surface is functionalized with a functional material, in particular, a conductive material has a process advantage since the surface of a film is patterned and can be coated with the functional material to be functionalized at the same time, can manufacture the film uniformly coated with the functional material and having flexibility, and can use the film for a solar cell as a conductive film when the functional material has conductivity.

Description

Manufacturing method of a pattern film coated with a functional material by an interfacial reaction, patterned film manufactured thereby, and uses thereof {THE MANUFACTURING METHOD OF FUNCTIONALIZED-PATTERNED FILMS USING INTERFACE REACTION, FUNCTIONALIZED-PATTERNED FILMS BY THEREOF AND USES THEREOF}

The present invention relates to a method of manufacturing a patterned film coated with a functional material by an interfacial reaction, a patterned film prepared thereby, and a use of the patterned film, and more specifically, to a film through an in-situ chemical reaction. A method of manufacturing a patterned film that can functionalize the surface by patterning the surface in a honeycomb pattern or a moth-eye pattern and coating the surface of the pattern or the entire film surface with a conductive material, one of the functional materials , To the patterned film produced thereby and the use of the patterned film.

The Breath figure (BF) method is a method for manufacturing a honeycomb-patterned (Honeycomb-Patterned; HCP) film, and is a bottom-up surface patterning technique. HCP films have potential for application in fields such as separation membranes, catalytic reactions, optoelectronics, and cell culture. The BF method uses condensed water droplets as a template after evaporation to engrave a water droplet shape on the film surface. The BF method is simple and convenient when compared to other mold patterning techniques, which generally involve the addition and removal of mold material.

Selective functionalized HCP films, especially pore-selective functionalized films, are available for use in light emitting devices, optical bandgap materials, selective antibacterial and functionalized protein materials, and thus are used in various fields. Is paying attention to. Because it can be applied to various fields, the development of a new method for pore-selective functionalization of HCP films using a method that combines the BF process at the interface of condensed water droplets and polymer solutions, and self-assembly of organic molecules or nanoparticles. It is being done. As an example, an HCP film functionalized with carboxyl-, hydroxyl- or amine- using a polymer having a polar end group or block was prepared through self-assembly, and PS-bP (GalEMA-co-S) Through self-assembly of a diblock copolymer, an HCP film functionalized with β-galactose was prepared and used as an active substrate for patterning the peanut coagulant protein. In addition, similarly to the functionalization of the organic molecules, pore-selective functionalization of inorganic nanoparticles in HCP films has also been reported. For example, Boker et al. Has studied the selective functionalization of CdSe nanoparticles in the pores of the PS HCP film through self-assembly during the BF process. In addition, Sun et al. The SiO ₂ nanoparticle suspension was directly added to the PS solution containing silver-soluble ethanol, and it was confirmed that the pores of the PS HCP film were functionalized with SiO ₂ nanoparticles. However, the pore-selective functionalization as described above has a disadvantage in that it is difficult to uniformly form a coating layer inside the pores, and it is difficult and complicated because the modification of the inorganic nanoparticles has to go through several steps. Therefore, there is a need to develop a new BF method capable of producing an HCP film having a uniform coating layer formed through a simple process.

On the other hand, as fossil fuels are depleted and adversely affect the environment, efforts are being made to find eco-friendly and renewable energy sources, and solar energy is drawing attention as a renewable energy source. However, the efficiency of solar cells does not reach the theoretical maximum. Because photons are lost due to reflection, absorption and energy conversion are difficult. Therefore, in order to maximize absorption efficiency, a method of morphologically controlling the surface layer of a solar cell is being studied, and for this purpose, a moth's snow pattern that mimics the eye of a moth is one of the surface layers of a solar cell to maximize absorption efficiency. Is considered as The moth's eyes feature nano-sized conical protrusions and regular arrangements to enhance night vision.

Moth-Eye Patterns (MEP) are used in antireflective coatings, microlens arrays, light emitting diodes and photonic applications. MEP is known to have self-cleaning, anti-reflective and remarkable light absorption capabilities over a wide spectrum. In some studies, it is known to use the moth shape to improve the efficiency of solar cell systems. However, the method of manufacturing the MEP used in this report is not economically desirable in terms of the process because it requires expensive measurement and highly skilled manpower. In addition, the material used in the above study is a rigid material that is not flexible, which is not desirable for the flexibility of solar cells. Therefore, there is a need for a new economical method for manufacturing a film of MEP using a flexible material.

The honeycomb-patterned (HCP) film can be easily fabricated by fabricating the BF (breath figure) method. However, due to the difficulty in functionalization of the pore selectivity of the honeycomb pattern (HCP) film and the transferability of the functional material, a honeycomb pattern (HCP) film was formed by selective coating of a functional material on the film surface using a honeycomb pattern (HCP) film as a template. It is not easy to manufacture.

Accordingly, as a result of the present inventors making diligent research efforts to overcome the problems of the prior art, when using a modified BF method that occurs through an in situ chemical reaction, while forming pores on the honeycomb pattern (HCP) film, pore-selective Pore-selectively functionalized HCP film can be prepared by coating a conductive material uniformly and thinly, and when a honeycomb pattern (HCP) film manufactured through the above manufacturing method is used to prepare a moth pattern (MEP) film , Confirming that the microdome-selectively functionalized moth-eye pattern (MEP) film can be manufactured by selectively coating a conductive material uniformly and thinly on the microdome of the MEP film, and to complete the present invention. Became.

KR 10-2009-0089041 A

The main object of the present invention is to pattern the surface of the film in a honeycomb shape and at the same time selectively coat the patterned honeycomb pores with a conductive material as a functional material when using a modified BF method that occurs in situ chemical reaction. A method of manufacturing a functionalized patterned film with a functional material capable of manufacturing a pore-selectively functionalized patterned film through a simple process, and a honeycomb with pore-selective coating of a conductive material manufactured through the manufacturing method. ) To provide a porous film having a pattern.

Another object of the present invention is a method for producing a porous film having a microdome-selectively coated conductive material-moth-eye pattern using the porous film having the honeycomb pattern as a template, and its preparation It is to provide a porous film having a moth-eye pattern in which a microdome manufactured through the method is selectively coated with a conductive material.

Another object of the present invention is a method for producing a porous film in which the entire surface of a porous film having a honeycomb pattern or a porous film having a moth-eye pattern is functionalized with a functional material, and a porous film manufactured thereby To provide.

Another object of the present invention is to provide a porous film for solar cells using a patterned film functionalized with the functional material.

According to one aspect of the present invention, the present invention provides a method of manufacturing a porous film having a honeycomb pattern in which a conductive material is pore-selectively coated, including the following steps.

(a) preparing a polymer solution by mixing a polymer and a first reactant in a volatile organic solvent;

(b) applying the polymer solution to the substrate surface;

(c) introducing and contacting moisture air containing a second reactant on the surface of the substrate on which the polymer solution is applied; And

(d) drying the surface of the substrate in contact with the moisture air to form a honeycomb pattern and coating the pores of the honeycomb pattern with a conductive material that is a reaction product of the first and second reactants.

Conventionally, in order to manufacture a porous film having a honeycomb pattern, it is manufactured using a breath figure (BF) method, but in order to coat a functional material on a patterned film manufactured using the BP method, Since an additional process has to be performed, it is not efficient in the process. Accordingly, the present inventors have invented a new method of coating a functional material on the surface while patterning the film through the BF method.

The method of manufacturing a porous film having a honeycomb pattern in which a conductive material is pore-selectively coated using a novel BF method according to the present invention comprises a first reactant and a second reactant capable of forming a conductive material, respectively. It is based on coating a conductive material by reacting it with a polymer solution and moisture air. Specifically, a polymer solution containing a first reactant causes an interfacial reaction with moisture air containing a second reactant. By patterning the surface of the film through an interfacial reaction and coating a conductive material as a functional material selectively on the pores of the pattern, it is possible to manufacture a pore-selectively functionalized HCP film.

The term conductive material of the present invention refers to a material having high electrical conductivity, and refers to a conductive polymer material or a semiconductor material.

In the method for manufacturing a porous film having a honeycomb pattern in which the conductive material of the present invention is pore-selectively coated, the substrate in step (b) may be any substrate on which a polymer solution can be applied. Hagi is characterized by a glass Petri dish.

In the method for manufacturing a porous film having a honeycomb pattern in which the conductive material of the present invention is pore-selectively coated, the volatile organic solvent in the step (a) is any volatile that can dissolve the polymer or the first reactant. An organic solvent may also be included, and preferably, one or more solvents selected from the group consisting of chloroform, carbon disulfide, and tetrahydrofuran.

In the method for producing a porous film having a honeycomb pattern in which the conductive material of the present invention is pore-selectively coated, the polymer of step (a) is any polymer that is soluble in an organic solvent used to prepare a film. It may also be included, preferably one or more selected from the group consisting of polystyrene (PS), polycaprolactone (PCL), polymethylmethacrylate (PMMA), and polyimide (PI). It is characterized by being a polymer.

In the method of manufacturing a porous film having a honeycomb pattern in which the conductive material of the present invention is pore-selectively coated, the first reactant in step (a) is tin chloride II (SnCl ₂ ), tin chloride IV ( SnCl ₄ ) or cadmium chloride (CdCl ₂ ), and the second reactant in step (b) is hydrogen sulfide (H ₂ S).

In the method for producing a porous film having a honeycomb pattern in which the conductive material of the present invention is pore-selectively coated, the first reactant in step (a) is BPO (benzoyl peroxide), and in step (b) The second reactant of is characterized in that it is aniline hydrochloride.

In the method for manufacturing a porous film having a honeycomb pattern in which the conductive material of the present invention is pore-selectively coated, the conductive material is tin sulfide (SnS), cadmium sulfide (CdS), and polyaniline. To do.

The conductive material according to the present invention is a functional material generated by a chemical reaction between a first reactant and a second reactant, and the first reactant and the second reactant may vary depending on the functional material to be imparted to the film. For example, according to an embodiment of the present invention, when tin chloride (SnCl ₂ ) is included as a first reactant and hydrogen sulfide (H ₂ S) is included as a second reactant to impart a conductive function to the film, a semiconductor By selectively coating the pores of the patterned film with tin sulfide (SnS) as a material, a functional porous film coated with a functional material may be prepared (see Example 1). In addition, when SnCl ₄ or CdCl ₂ is included as the first reactant and Na ₂ S is included as the second reactant, a porous film coated with SnS or CdS may be prepared. In addition, when benzoyl peroxide is included as a first reactant and aniline hydrochloride as a second reactant is included, a functional porous film coated with polyaniline can be prepared, and the first reactive material When PS-CHO is included as a second reactant and oxone is included as a second reactant, a functional porous film coated with PS-CHO can be prepared, including PI as a first reactant, and a second reactant. When KOH is included as, a porous film coated with PICOOK can be prepared, and when ferrocene is included as a first reactive material and AgNO ₃ is included as a second reactive material, functional porosity coated with Ag A film may be prepared, and when GO is included as a first reactive material and NaBH ₄ is included as a second reactive material, a porous film coated with RGO may be prepared.

In the method for producing a porous film having a honeycomb pattern in which the conductive material of the present invention is pore-selectively coated, the step (a),

(a-1) preparing a first mixture by mixing a polymer in a volatile organic solvent;

(a-2) preparing a second mixture by mixing the first reactant in a volatile organic solvent; And

and (a-3) preparing a polymer solution by mixing the first mixture and the second mixture. In the step of preparing the polymer solution, the polymer and the first reactant may be simultaneously mixed with the volatile organic solvent, but the polymer and the first reactant are added to each volatile organic solvent and dissolved, and then mixed to form a polymer solution. It is desirable to manufacture.

In the method for producing a porous film having a honeycomb pattern in which the conductive material of the present invention is pore-selectively coated, the first reactant is mixed at a concentration of 0.04 to 0.06 M. When the concentration of the first reactant is less than 0.04 M, the formation of a functional material, which is a conductive material, is insufficient, and when the concentration of the first reactant is more than 0.06 M, the conductive material, which is a functional material, is selectively coated on the pores, but the coating layer is not formed uniformly or a coating layer formed There is a problem that this cracking phenomenon appears.

According to an experimental example of the present invention, as a result of confirming the formation of the HCP film coating layer according to the concentration of SnCl _{2 as} the first reactant, when the concentration of SnCl ₂ was less than 0.01 M, the layer of SnS could not be identified, and 0.075 and 0.01 When M was exceeded, non-uniformity or cracking of the SnS thin film appeared, whereas when the concentration of SnCl ₂ was 0.05 M, it was confirmed that the SnS layer was uniformly coated (see Experimental Example 4 and FIG. 5). From these results, it can be seen that the concentration of the first reactant is an important component in order to selectively coat the pores with the conductive material, which is a functional material.

According to another aspect of the present invention, the present invention is prepared according to a method of manufacturing a porous film having a pore-selectively coated honeycomb pattern, and the conductive material is pore-selectively coated honeycomb ( Honeycomb) provides a porous film having a pattern.

In the porous film having a honeycomb pattern in which the conductive material of the present invention is pore-selectively coated, the conductive material is coated with 150 to 250 nm.

In the porous film having a honeycomb pattern in which the conductive material of the present invention is pore-selectively coated, the pore size of the porous film having a honeycomb pattern is 20 to 18 μm.

According to an experimental example of the present invention, as a result of confirming the coating layer of a porous film having a honeycomb pattern in which the conductive material according to the present invention is pore-selectively coated with an SEM image, selectively on the surface of the honeycomb pores It was confirmed that the formed conductive material was uniformly coated with SnS to a thickness of 200 nm (see Experimental Example 4 and FIG. 5c-1). In addition, as a result of confirming through elemental mapping and XPS spectrum to confirm whether the porous film having the honeycomb pattern was functionalized as a conductive material, it was confirmed that Sn and S exist in the pores of the film (Experimental Example 3 and See Fig. 4). These results suggest that the porous film having a honeycomb pattern according to the present invention is functionalized by pore-selective coating of a conductive material.

According to another aspect of the present invention, the present invention is prepared according to a method of manufacturing a porous film having a pore-selectively coated honeycomb pattern, and the conductive material is pore-selectively coated honeycomb ( Honeycomb) provides a porous film for solar cells having a pattern.

According to an experimental example of the present invention, it was confirmed that the porous film having a honeycomb pattern in which SnS, which is a conductive material, is pore-selectively coated, exhibits excellent photocurrent characteristics (see Experimental Example 5 and FIG. 6). From these results, it is suggested that the porous film according to the present invention can be used as a conductive film for solar cells in the future, since it has excellent current response to light.

According to another aspect of the present invention, the present invention provides a method of manufacturing a porous film having a honeycomb pattern coated with a conductive material including the following steps.

(a) preparing a polymer solution by mixing a polymer and a first reactant in a volatile organic solvent;

(b) applying the polymer solution to the surface of the substrate and introducing it into the breath figure chamber, and then maintaining the relative humidity inside the chamber;

(c) evaporating water droplets generated on the surface of the substrate in a breath figure chamber at room temperature to prepare a porous film having a honeycomb pattern; And

(d) a conductive material that is a reaction product of the first reactant and the second reactant over the entire film surface including the porous inner surface by immersing the porous film prepared in step (c) in a solution containing a second reactant Coating.

The method of manufacturing a porous film having a honeycomb pattern in which a conductive material is coated on the entire film according to the present invention includes a film having a honeycomb pattern made of a polymer solution containing a first reactant capable of forming a conductive material. It is based on coating a conductive material by immersing in an aqueous solution containing a second reactant and interfacially reacting the first reactant and the second reactant. Through this interfacial reaction, the surface of the film is patterned, and at the same time, not only the pores of the pattern, but also the entire surface of the film are coated with a conductive material, which is a functional material, thereby manufacturing an HCP film coated with a conductive material.

In the method for manufacturing a porous film having a honeycomb pattern in which the entire film is coated with a conductive material, the polymer, the first reactant, the second reactant, and the conductive material are pore-selectively coated honeycomb patterns. It can be used in the same manner as used in the method of manufacturing a porous film having.

According to another aspect of the present invention, it is prepared by a method of manufacturing a porous film having a honeycomb pattern coated with the conductive material, and provides a porous film having a honeycomb pattern coated with the conductive material over the entire film. do.

According to another aspect of the present invention, a porous film for solar cells having a honeycomb pattern in which a conductive material is coated on the entire film is prepared by a method of manufacturing a porous film having a honeycomb pattern coated with a conductive material. to provide.

According to one aspect of the present invention, the present invention provides a method for manufacturing a porous film having a microdome-selectively coated moth-eye pattern including the following steps.

(a) preparing a polymer solution by mixing a polymer and a first reactant in a volatile organic solvent;

(b) applying the polymer solution to the substrate surface;

(c) introducing and contacting moisture air containing a second reactant on the surface of the substrate on which the polymer solution is applied;

(d) drying the surface of the substrate in contact with the moisture air to form a honeycomb pattern and coating the pores of the honeycomb pattern with a conductive material that is a reaction product of the first and second reactants to prepare a template film;

(e) preparing a conductive polymer solution;

(f) pouring the conductive polymer solution into the mold film of step (d) and drying it; And

(g) removing the dried template film to selectively coat the microdome of the porous film having a moth-eye pattern with a conductive material.

Moth-eye patterns are being used in anti-reflective coatings, microlens arrays, light-emitting diodes and photon applications, and in recent years, attention has been paid to moth-eye patterns to improve the efficiency of solar cell systems. Are doing. However, a method of manufacturing a film having a moth-eye pattern is economically unfavorable in the process, and there is a problem that the material is not flexible, which is not desirable for the flexibility of a solar cell. Accordingly, the present inventors use a porous film having a honeycomb pattern in which the conductive material manufactured through the modified BF method of the present invention is pore-selectively coated as a template to form a moth-eye pattern film. In the case of manufacturing, it was confirmed that the conductive material can easily produce a microdome-selectively functionalized porous pattern film, and the present invention was completed.

In the method of manufacturing a porous film having a microdome-selectively coated moth-eye pattern of the conductive material of the present invention, the volatile organic solvent in step (a) dissolves a polymer or a first reactant. Any volatile organic solvent that may be included may be included, and preferably, it is characterized in that it is one or more solvents selected from the group consisting of chloroform, carbon disulfide, and tetrahydrofuran.

In the method for producing a porous film having a microdome-selectively coated moth-eye pattern of the present invention, the polymer of step (a) is an organic material that has been conventionally used to prepare a film. Any polymer soluble in a solvent may be included, preferably one or more polymers selected from the group consisting of polystyrene, polycaprolactone, polymethylmethacrylate, and polyimide. It is characterized.

In the method for manufacturing a porous film having a microdome-selectively coated moth-eye pattern of the conductive material of the present invention, the first reactant in step (a) is tin chloride II (SnCl ₂ ), Tin IV (SnCl ₄ ), or cadmium chloride (CdCl ₂ ), and the second reactant in step (d) is hydrogen sulfide (H ₂ S).

In the method for manufacturing a porous film having a microdome-selectively coated moth-eye pattern of the conductive material of the present invention, the first reactant in step (a) is BPO (benzoyl peroxide), and the The second reactant in step (d) is characterized in that it is aniline hydrochloride.

In the method for manufacturing a porous film having a microdome-selectively coated moth-eye pattern of the conductive material of the present invention, the conductive material is tin sulfide (SnS), cadmium sulfide (CdS), and polyaniline ( polyaniline).

In the method of manufacturing a porous film having a microdome-selectively coated moth-eye pattern of the conductive material of the present invention, the conductive polymer solution may be a hydrophilic polymer solution, preferably PEDOT: It is characterized in that it is a PSS solution.

In the method for manufacturing a porous film having a microdome-selectively coated moth-eye pattern of the conductive material of the present invention, the (f) step is a conductive material produced in the template film of step (d) It is characterized in that it selectively moves to the microdome.

According to an experimental example of the present invention, as a result of confirming whether the microdome of a porous film having a moth-eye pattern manufactured according to the manufacturing method of the present invention is selectively coated with a conductive material as a functional material to be functionalized , It was confirmed that the height and diameter of the microdome in the MEP (Moth-Eye Pattern) film prepared according to Example 3 was about 16 μm x 16 μm, and these results were the size of the pores of the film of Example 1 used as a template. It was consistent with (see Experimental Example 9 and Figs. 11a-c). In addition, it was confirmed that the SnS coating layer was present on the microdome surface of the Example 　3 film, whereas the SnS coating layer was not present on the surface of the pores of the film of Example 1 used as a template (see Experimental Example 9 and FIGS. ). From these results, it is possible to prepare a porous film having a microdome-selectively coated moth-eye pattern with a conductive material by moving the SnS coating layer on the surface of the film pores of Example 1 to the microdome. Suggests.

In addition, as a result of confirming the coating layer of a porous film having a microdome-selectively coated moth-eye pattern according to the present invention by SEM image, SnS, a conductive material selectively formed on the surface of the microdome It was confirmed that was uniformly coated with a thickness of 170 nm (see Experimental Example 9 and FIG. 11D). In addition, as a result of checking through elemental mapping and XPS spectrum to confirm whether the porous film having the moth-eye pattern was functionalized as a conductive material, it was confirmed that Sn and S exist in the pores of the film ( See Experimental Example 10 and Fig. 12). These results suggest that the porous film having a moth-eye pattern according to the present invention is functionalized by pore-selective coating of a conductive material.

According to another aspect of the present invention, the present invention is manufactured according to a method of manufacturing a porous film having a microdome-selectively coated moth-eye pattern, and the conductive material is microdome- It provides a porous film having an optionally coated moth-eye pattern.

The conductive material of the present invention is a microdome-selectively coated porous film having a moth-eye pattern, wherein the conductive material is coated with 150 to 200 nm.

The porous film in which the conductive material of the present invention has a microdome-selectively coated moth-eye pattern is characterized in that the height of the microdome is 10 to 20 μm and the diameter is 15 to 25 μm.

According to another aspect of the present invention, the present invention is manufactured according to a method of manufacturing a porous film having a microdome-selectively coated moth-eye pattern, and the conductive material is microdome- It provides a porous film for solar cells having a selectively coated moth-eye pattern.

According to an experimental example of the present invention, it was confirmed that the porous film having a pore-selectively coated moth-eye pattern of SnS as a conductive material exhibits excellent photocurrent characteristics (see Experimental Example 13 and FIG. 15). ). From these results, it is suggested that the porous film according to the present invention can be used as a conductive film for solar cells in the future, since it has excellent current response to light.

According to another aspect of the present invention, the present invention provides a method of manufacturing a porous film having a moth-eye pattern coated with a conductive material including the following steps.

(a) preparing a polymer solution by mixing a polymer and a first reactant in a volatile organic solvent;

(b) pouring the polymer solution into a film having a honeycomb pattern and drying to obtain a porous film having a moth-eye pattern;

(c) immersing the obtained porous film having a moth-eye pattern in a solution containing a second reactant to coat the entire surface of the film with a conductive material that is a reaction product of the first reactant and the second reactant.

According to another aspect of the present invention, the moth-eye (moth-eye) is manufactured by a method of manufacturing a porous film having a moth-eye pattern coated with the conductive material, and the conductive material is coated on the entire film. ) It provides a porous film having a pattern.

According to another aspect of the present invention, a moth-eye coated with a conductive material is produced by a method of manufacturing a porous film having a moth-eye pattern, and the conductive material is coated on the entire film. It provides a porous film for solar cells having a pattern.

In the method of manufacturing a porous film having a moth-eye pattern in which the entire film is coated with a conductive material, the polymer, the first reactant, the second reactant and the conductive material are microdome-selectively coated moth -It can be used in the same manner as used in the method of manufacturing a porous film having a moth-eye pattern.

As described above, the pattern film in which the surface is functionalized with the functional material according to the present invention can be functionalized by coating the film with a functional material while patterning the surface of the film, thereby providing a process advantage.

In addition, it is possible to uniformly coat a functional material, and to manufacture a film having flexibility, and when the functional material has conductivity, it can be used for a solar cell as a conductive film.

1 is a schematic diagram of a method of manufacturing a porous film according to Example 1 of the present invention.
2 is a diagram showing the results according to Experimental Example 1 of the present invention ((a) moisture air, (b) moisture air containing H ₂ S)
3 is a diagram showing the results according to Experimental Example 2 of the present invention (the concentration of SnCl ₂ is (a) 0.01, (b) 0.025, (c) 0.05, (d) 0.075, (e) 0.1).
4 is a diagram showing a result according to Experimental Example 3 of the present invention ((a) elemental mapping image, (b) XPS spectrum).
5 is a diagram showing the results according to Experimental Example 4 of the present invention (the concentration of SnCl ₂ is (a) 0.01, (b) 0.025, (c) 0.05, (d) 0.075, (e) 0.1).
6 is a diagram showing the results according to Experimental Example 5 of the present invention.
7 is a diagram showing the results according to Experimental Example 6 of the present invention ((a) SEM image, (b) XPS spectrum, (c) flexibility measurement image).
8 is a schematic diagram of a mechanism in which inorganic nanomaterials are coated in a method of manufacturing a porous film according to Example 1 of the present invention.
9 is a schematic diagram of a method of manufacturing a porous film according to Example 3 of the present invention.
10 is a diagram showing the results according to Experimental Example 8 of the present invention ((a, b) SEM images of microdome, (c, d) SEM images of honeycomb).
11 is a view showing the results according to Experimental Example 9 of the present invention ((ad) SEM images of the conductive material coated on the surface of the microdome, (e, f) SEM images of honeycomb pores).
12 is a view showing the results according to Experimental Example 10 of the present invention ((a) all elements, (b) tin, (c) S element).
13 is a diagram showing the results according to Experimental Example 11 of the present invention ((a, b) coating layer before sonication, (c, d) coating layer after sonication).
14 is a diagram showing the results according to Experimental Example 12 of the present invention ((a) an internal SEM-EDX spectrum. (b) an external SEM-EDX spectrum).
15 is a diagram showing a result according to Experimental Example 13 of the present invention ((a) a voltage graph, (b) a reactivity graph, (c) a graph of change of current over time).

Hereinafter, the present invention will be described in more detail through examples. Since these examples are for illustrative purposes only, the scope of the present invention is not to be construed as being limited by these examples.

Example 　 1: Preparation of pore-selectively functionalized HCP (Honeycomb-Pattern) film

Pore-selectively functionalized HCP films were prepared by a modified BF process involving an in-situ chemical reaction. The overall manufacturing method is to prepare a polystyrene (PS) solution containing SnCl ₂ as the first reactant, and then supply moisture air (Na ₂ S aqueous solution) containing H ₂ S as the second reactant at room temperature. -Optionally functionalized HCP film was prepared. Specifically, 250 mg of PS was dissolved in 4.5 mL of THF and sonicated for 1 hour to prepare a homogeneous PS solution, and 48.4 mg of SnCl ₂ was dissolved in 0.5 mL of THF with stirring for 5 minutes with 0.5 mL of SnCl. ₂ solutions were obtained. Thereafter, the SnCl ₂ solution was mixed with 4.5 mL of PS solution to obtain 5 mL of PS solution containing 0.05 mL of SnCl ₂ . The final solution was poured into a glass Petri dish and placed in a closed chamber. A Na ₂ S aqueous solution containing H ₂ S was supplied onto the surface of the SnCl ₂ -PS solution during the BF process. Moisture air containing H ₂ S was prepared by using an air pump with a flow rate of 0.4 L/min in an aqueous Na ₂ S solution of 1 m of ambient air. A SnS-functionalized HCP film selectively only for pores was obtained after completely drying for about 3 hours. The experimental process for the in-situ interfacial reaction between SnCl ₂ and H ₂ S during the BF process is shown in Scheme 1.

In order to confirm the effect of the concentration of SnCl ₂ on the production of the film, by changing the manufacturing method of Example 1, the concentration of SnCl ₂ in an amount of 0.01, 0.025, 0.05, 0.075 and 0.1M were prepared HCP film, PS, The concentration of H ₂ S proceeded in the same manner. Conditions according to the concentration of SnCl ₂ are shown in Table 1 below.

Concentration of SnCl ₂ ( _M ) Same condition Example 1 0.05 PS (dissolve 250mg PS in 5mL THF)
H ₂ S (1 _M Na ₂ S) Comparative Example 1 0.01 Comparative Example 2 0.025 Comparative Example 3 0.075 Comparative Example 4 0.1

Experimental Example 1: Comparison of HCP film form according to moisture air

In order to compare the film form according to the moisture air, an HCP film was prepared by supplying pure moisture air and moisture air containing H ₂ S, which is the second reactant according to the present invention, to a PS solution not containing SnCl ₂ . The results are shown in Fig. 2(a, b). The shape of the HCP film was confirmed through image capture using SEM (CX-100, COXEM, Daejeon, Korea).

As a result, as can be seen in Figures 2a and 2b, both films show good HCP form, but as the average pore size of the PS HCP film changes from pure water air to water air containing H ₂ S, 21 μm Slightly decreased to 19 μm. The decrease in pore size may be due to H ₂ S in the moisture air, and as a result, the surface tension between the condensed vapor and the polymer solution decreases, and thus smaller pores appear to be formed in the process of forming the pores.

Experimental Example 2: SnCl ₂ Comparison of HCP film form according to concentration

As in Example 1 and Comparative Examples 1 to 4, the form of the HCP film prepared by SnCl ₂ concentration was confirmed through image capture using SEM (CX-100, COXEM, Daejeon, Korea), and the results are shown in FIG. 3 It is shown in (a to e).

As a result, as a result of checking FIGS. 3a to 3e, it was confirmed that the average pore size was 16, 15, 13, 12 and 10 μm, respectively, when the SnCl ₂ concentration was 0.01, 0.025, 0.05, 0.075 and 0.1M. The decrease in pore diameter is due to the increase in the hydrophilicity of the polymer solution as the SnCl ₂ concentration increases, and this action is attributed to the effect of stabilizing the air/water interface at the surface of the polymer solution.

Experimental Example 3: Confirmation of Functionalization of SnS in HCP Film

In order to check and compare whether the pores of the HCP film prepared according to Example 1 were functionalized with SnS, as a comparative example, pure water vapor was supplied to a PS solution containing 0.05 m SnCl ₂ to prepare an HCP film and compared.

Specifically, the elemental composition distribution of the HCP film prepared according to Example 1 was confirmed by using a SEM (FEI Inspect F50, Hillsboro, USA) equipped with electron backscattering diffraction (Pikasus with Hikari) to confirm the elemental mapping image, and monochromatic The XPS spectrum was confirmed using a spectrometer with an Al Kα of 1486.6 eV and an output of 72 kW (12 kV), and the results are shown in FIGS. 4(a, b).

As a result, as can be seen in Figure 4a, it can be confirmed that Sn and S exist in the pores of the HCP film by the interfacial reaction of SnCl ₂ and H ₂ S. These results show that the pores are selectively functionalized with SnS by a modified BF process involving an in situ chemical reaction according to the present invention.

In addition, as can be seen in Figure 4b, the XPS spectrum shows that the sample is mainly composed of Sn, S, O, Cl and C. Here, C is derived from PS and Cl is derived from SnCl ₂ . The spectrum showed 4 peaks after fitting. The two strong peaks at about 486.8 and 495.2 eV are due to the Sn3d _5/2 and 3d _3/2 binding energies of SnS, respectively, and are characteristic peaks of Sn ²⁺ of SnS. The split Sn3d peaks (3d _5/2 and 3d _3/2 ) have a binding energy difference of 8.4 eV and are exactly the same as the Sn3d value of SnS. The two small peaks at 487.8 and 495.6 eV are related to SnO bonding, which may be attributed to small amounts of by-products from the hydrolysis of SnCl ₂ in water. The binding energy of S2p _3/2 (161.8eV) and S2p _1/2 (163.0eV) is consistent with that of SnS. The atomic ratio of S2p and Sn3d was about 1.10:1, and the formation of SnS can be confirmed through these results.

Experimental Example 4: Confirmation of the formation of the SnS coating layer in the pore-selectively SnS functionalized HCP film

Whether SnS was uniformly coated inside the pores of the HCP film, the SnS thin film of the HCP film (Example 1 and Comparative Examples 1 to 4) prepared according to the concentration of SnCl ₂ was confirmed through SEM image capture, and the result It is shown in Figure 5 (a to e).

As a result, as shown in FIG. 5A, when the concentration of SnCl ₂ was 0.01 μm (Comparative Example 1), the layer of SnS could not be identified. These results suggest that the concentration of the SnCl ₂ insufficient concentration to form a uniform thin layer of SnS by the interface reaction between SnCl ₂ and H ₂ S. In addition, as can be seen in FIGS. 5b to 5e, it was confirmed that the thickness of the SnS layer increased from about 100 nm to 230 nm as the SnCl ₂ concentration was increased. In particular, Figure 5c clearly shows the coating layer of SnS. That is, these results suggest that in order to form a uniform and thin layer of SnS, when the concentration of SnCl ₂ is 0.05 _M , it is most preferable. On the other hand, as can be seen in FIGS. 5D and 5E, when the concentration of SnCl ₂ is 0.075 _M and 0.1 _M (Comparative Examples 3 and 4), the non-uniformity or cracking phenomenon of the SnS thin film increases as the SnCl ₂ concentration further increases. It was confirmed that it appeared along.

In order to more clearly confirm the uniform thin layer of SnS on the walls of the pores, a thin cross section of the thin film was confirmed with a TEM image, and the results are shown in FIG. 5C. As a result, a uniform SnS thin film coated with a thickness of about 200 nm on the pore walls of the film can be clearly confirmed through the TEM image of FIG. 5C-1. It can be seen that these results are consistent with the results of elemental mapping and SEM images showing selectively uniform SnS thin film formation in the pores of the thin film.

Experimental Example 5: Pore-selectively check the photocurrent characteristics of the SnS functionalized HCP film

For the future application of the PS-SnS HCP film for flexible devices, the photocurrent characteristics of the PS-SnS HCP film prepared in Example 1 were confirmed through a current-voltage graph in dark room and indoor lighting (0.04 lm cm ^-2 ) lighting. , The results are shown in FIG. 6.

As a result, as can be seen in Fig. 6, the current significantly increased when the PS-SnS HCP film was irradiated with light at the same bias voltage. This result can be attributed to the generation of electron-hole pairs by illumination with energy higher than the energy band gap of SnS.

In addition, the photocurrent increases according to the applied bias voltage due to an increase in the carrier drift rate that is directly proportional to the applied bias voltage. I _light / I _dark ratio values were confirmed to be 27, 24, 20 and 19 at bias voltages of 3, 5, 7 and 10 V, respectively. The values obtained are consistent with the I _light /I _dark values obtained by SnS nanoflakes corresponding to 5 to 31 under applied bias voltages of 3 and 5 V in visible light with a wavelength of 380 nm to 850 nm.

Experimental Example 6: Confirmation and comparison of the shape of a film manufactured through a conventional BF process

The modified BF process involving the interfacial chemical reaction between the first reactant of the polymer solution and the second reactant contained in the moisture air was first discovered by the present inventors, so it was referred to as rBF (response breath figure). .

In the present invention, in order to compare with the previous technology similar to the manufacturing method of the present invention, a PS HCP film (Comparative Example 5) was prepared by introducing moisture air without H ₂ S into a PS solution containing 0.05 m SnCl ₂ . The results of confirming the SEM image and XPS spectrum of are shown in Fig. 7(a, b).

As a result, as can be seen in Fig. 7A, the film of Comparative Example 5 exhibited an ordered honeycomb shape, but exhibited a semi-thin film shape. In addition, as shown in Fig. 7b, as a result of examining the composition of the half-moon-shaped particles of the film by XPS analysis, it is shown that the film is mainly composed of Sn, O, Cl, and C. Here, Cl is from the SnCl ₂ precursor and C is from PS. These results show that the film prepared in Comparative Example 5 exhibits a honeycomb shape similar to that of the film prepared according to the example of the present invention, but the SnS coating layer is not thin and uniformly coated, so the second reaction to moisture air It suggests that it is preferable to include the substance H ₂ S.

In addition, the flexibility of the film was compared, and the results are shown in Fig. 7c. As a result, it was confirmed that the film according to Example 1 was almost the same as the flexibility of the conventional PS film, whereas the film of Comparative Example 5 had little flexibility and was easily broken. These results suggest that the HCP film produced according to the present invention is very useful in applications for flexible devices.

Example 2: Preparation of a pore-selectively functionalized HCP (Honeycomb-Patterne) film according to the reactant

A film was prepared in the same manner as in Example 1, but the HCP film was prepared by changing the first and second reactants and the solvent. The first reactant and the second reactant are shown in Table 2 below.

First reactant Second reactant menstruum Final product CdCl ₂ H ₂ S Na ₂ S in H ₂ O CdS BPO Aniline hydrochloride H ₂ O polyaniline

Experimental Example 7: Confirmation of CdS and polyaniline coating layer formation in pore-selectively functionalized HCP film

The color change of the coating layer film surface on the surface of the HCP film prepared in Example 2, elemental mapping analysis, UV-Visible spectrophotometry, and conductivity were confirmed through, and the results are shown in Table 3 below.

Test Items Polystyrene Polystyrene coated with polyaniline color White or
Weak color green Elemental
mapping Carbon: PS Carbon: PS and aniline
Nitrogen: aniline
Chlorine: HCl
Oxygen: Benzoyl peroxide (unreacted) and Benzoic acid (after reaction of benzoyl peroxide) UV-Visible
spectrum No peak in visible region (400-800 nm) Broad peaks appear in the visible area
(400-800 nm) Conductivity No conductivity There is conductivity

Example 3: Preparation of microdome-selectively SnS-functionalized MEP (Moth-Eye Pattern) film

In order to prepare an MEP film selectively coated with an SnS thin film on the surface of the microdome, the pore-selectively functionalized HCP film with SnS prepared in Example 1 was prepared as a template.

The MEP film, optionally coated with a thin SnS layer on the surface of the microdome, poured 0.5 mL PEDOT:PSS solution into the HCP film prepared in Example 1, and then dried at room temperature. After complete drying, the HCP film was carefully separated to obtain a microdome-selectively functionalized HCP (Moth-Eye Pattern) film. The manufacturing process is schematically illustrated in FIG. 9.

Experimental Example 8: Confirmation of the shape of the MEP film

After manufacturing the MEP film using a generally used porous PS film, the shape of the MEP film was confirmed, and the result was confirmed through SEM images as shown in FIGS. 10 (a to d).

As a result, as can be seen in Figure 10a, it can be seen that the MEP (Moth-Eye Pattern) film prepared according to Example 3 exhibits an average dome size having a height and diameter of about 18 μm x 15 μm. In addition, FIG. 10B is an upper SEM image of the MEP film prepared according to Example 3, and it can be seen that it has a hexagonal pattern.

10(c, d) are SEM images of the surface and cross-section of a PS film having porosity used as a template for manufacturing an MEP film. As can be seen in FIGS. 10C and 10D, it can be seen that the MCP film according to Example 1 has honeycomb holes and oval pores. In addition, it can be seen that the height and diameter of the pores are about 15 μm and 18 μm, respectively, and these sizes correspond to the size of the microdome of the MEP film.

Experimental Example 9: Confirmation of the shape of the microdome-selectively SnS-functionalized MEP film

The pores prepared according to Example 1-the microdome of Example 3 prepared with a SnS-functionalized MCP film as a template-the shape of the selectively SnS-functionalized MEP film was confirmed through SEM images, and the result It is shown in Figure 11 (a to f).

As a result, as can be seen in FIGS. 11A and 11B, it can be seen that the MEP film according to Example 3 has a typical moth eye pattern. The average size of the moth's eye microdome is 15 to 16 μm in height and 16 μm in diameter.

11C is a high magnification SEM image, and it can be seen that an SnS thin film is coated on the surface of the microdome. The microdome size of the MEP film according to Example 3 was consistent with the pore size of the HCP film according to Example 1.

11D is an image confirming the thickness of the SnS coated on the microdome, and the thickness of the SnS thin film in the microdome was confirmed to be 170 nm, and this thickness is the SnS thin film coated on the pores of the HCP film prepared according to Example 1. It is almost the same as its thickness.

11E and 11F show SEM images of the HCP film of Example 1 used as a template after separating the MEP film prepared in Example 3. As a result, it can be seen that both the low magnification SEM image (FIG. 11E) and the high magnification SEM image (FIG. 11F) form pores without debris. These results suggest that the SnS layer formed in the pores of the HCP film of Example 1 completely migrated to the microdome of Example 3.

Experimental Example 10: Checking whether the microdome-selectively SnS-functionalized MEP film was functionalized with SnS

In order to confirm the SnS distribution in the MEP film prepared in Example 3, elemental mapping analysis was performed on the film surface, and the results are shown in FIGS. 12 (a to c).

As a result, as can be seen in Figure 12a, C, Sn, S and O can be confirmed on the surface of the MEP film, the presence of C and O is due to PEDOT:PSS, S is from PEDOT:PSS and SnS , Sn is caused by SnS coated on the surface of the microdome.

In addition, it can be seen from Figs. 12b and 12c that Sn and S are selectively coated on the surface of the microdome.

Experimental Example 11: Checking the stability of the SnS layer selectively coated on the surface of the microdome in the MEP film

The stability of the SnS layer selectively coated on the surface of the microdome of the MEP film prepared in Example 3 was confirmed. Specifically, the MEP film prepared in Example 3 was sonicated in CHCl ₃ for 1 hour using a bathtub sonicator. The SEM images before sonication are shown in FIGS. 13A and 13B, and the SEM images after sonication are shown in FIGS. 13C and 13D.

As a result, when comparing the images before and after the ultrasonic treatment of FIG. 13, it can be confirmed that they are similar, and this result means that the SnS layer is stably adhered to the microdome surface of the film.

Experimental Example 12: Check the distribution of SnS selectively coated on the surface of the microdome in the MEP film

In order to further confirm the distribution of SnS in the MEP film prepared according to Example 3, SEM-EDX spectra of the inside and the surface of the coated microdome were confirmed, and the results are shown in FIGS. 14(a, b).

As a result, the presence of C, O, S and Au elements can be confirmed inside the film (Fig. 14a), and the presence of C, O, Sn, S and Au elements on the coated microdome surface can be confirmed (Fig. 14b ). The presence of C, O, and S elements inside the microdome is due to PEDOT:PSS, while the presence of Sn and S elements on the coated microdome surface is due to SnS, showing that Sn and S are coated. The presence of Au appears to be due to gold sputtering during SEM sample preparation.

Experimental Example 13: Microdome-Selectively SnS Functionalized MEP Film Photoreaction Characteristics Confirmation

Considering the application as a film for a flexible device, the photoreaction characteristics of the MEP film prepared in Example 3 were confirmed, and the results are shown in FIGS. 15 (a to c).

15A shows the current and voltage characteristics of the MEP film prepared in Example 3 under dark and simulated solar irradiation. In order to investigate the photocurrent behavior of the MEP film prepared in Example 3, light simulated in a wider range of UV to near-infrared wavelengths was used using a xenon short arc lamp (1 solar, 150W) as a light source. As a result, under the same bias voltage, the current significantly increased when the MEP film prepared in Example 3 was illuminated more brightly than in dark conditions. Further, the photocurrent increases with the applied bias voltage due to an increase in the carrier drift speed proportional to the applied bias voltage.

Fig. 15b shows the response behavior of the film at a 1V bias voltage identified as 4V. FIG. 15C shows the change of current with time at a 1V bias voltage while alternating dark and lighting conditions with an ON/OFF switch cycle of 25 seconds. As a result, it is shown that the maximum value of the photocurrent obtained by illumination does not change over several cycles and is relatively stable, and this result means that the light response of the MEP film prepared according to Example 3 is reproducible and stable.

Example 4: Preparation of HCP film in which the entire film was functionalized with SnS

A polystyrene (PS) solution containing SnCl ₂ as a first reactant was prepared, and then immersed in a solution containing H ₂ S as a second reactant at room temperature. The specific method is as follows.

First, 250 mg of PS was dissolved in 4.5 mL of THF and sonicated for 1 hour to prepare a homogeneous PS solution, and 48.4 mg of SnCl ₂ was dissolved in 0.5 mL of THF with stirring for 5 minutes to obtain 0.5 mL of SnCl ₂ solution. Was obtained. Thereafter, the SnCl ₂ solution was mixed with 4.5 mL of PS solution to obtain 5 mL of PS solution containing 0.05 mL of SnCl ₂ . The final solution was poured into a glass Petri dish as a substrate and placed in a closed chamber. The Petri dish is maintained inside a BF chamber with a relative humidity of about 90%. The polymer solution is evaporated until completely dry inside a BF chamber at room temperature to form HCP pores in the polymer film.

The polymer film, which is completely dried and HCP pores are formed, is immersed in an aqueous solution containing Na ₂ S for 1 hour. After 1 hour, the film was taken out and washed with water to remove and dry unreacted precursors present on the film.

Example 5: Preparation of MEP film in which the entire film was functionalized with SnS

In order to manufacture the MEP film in which the SnS thin film is entirely coated on the microdome surface, first, a hydrophilic honeycomb structured polymer film is made and used as a mold. The reason why a hydrophilic porous polymer film should be used as a template is that the PS solution poured into the template film is a hydrophobic solution, and thus dissolves when hydrophobic molding is used. Thereafter, 250 mg of PS was dissolved in 4.5 mL of THF and sonicated for 1 hour to prepare a homogeneous PS solution, and 48.4 mg of SnCl ₂ was dissolved in 0.5 mL of THF with stirring for 5 minutes to obtain 0.5 mL of SnCl ₂ solution. Obtained. Thereafter, the SnCl ₂ solution was mixed with 4.5 mL of PS solution to prepare 5 mL of PS solution containing 0.05 mL of SnCl ₂ . This solution is poured into a hydrophilic honeycomb polymer film having a porous structure. After drying the film, it was removed and immersed in an aqueous Na ₂ S solution to obtain a SnS-coated MEP (Moth-Eye Pattern) film by interfacial reaction.

Claims (46)

As a method for producing a porous film having a honeycomb pattern in which a conductive material is pore-selectively coated,
(a) preparing a polymer solution by mixing a polymer and a first reactant in a volatile organic solvent;
(b) applying the polymer solution to the substrate surface;
(c) introducing and contacting moisture air containing a second reactant on the surface of the substrate on which the polymer solution is applied; And
(d) drying the surface of the substrate in contact with the moisture air to form a honeycomb pattern and coating the pores of the honeycomb pattern with a conductive material that is a reaction product of the first and second reactants; Manufacturing method comprising a.
The method of claim 1,
The volatile organic solvent in step (a) is one or more solvents selected from the group consisting of chloroform, carbon disulfide, and tetrahydrofuran.
The method of claim 1,
The polymer of step (a) is a porous film, characterized in that it is at least one polymer selected from the group consisting of polystyrene, polycaprolactone, polymethylmethacrylate, and polyimide Method of manufacturing.
The method of claim 1,
The first reactant in step (a) is tin chloride II (SnCl ₂ ), tin chloride IV (SnCl ₄ ), or cadmium chloride (CdCl ₂ ), and the second reactant in step (b) is hydrogen sulfide (H ₂ S) Method for producing a porous film, characterized in that.
The method of claim 1,
The method of manufacturing a porous film, wherein the first reactant in step (a) is benzoyl peroxide (BPO), and the second reactant in step (b) is aniline hydrochloride.
The method of claim 1,
The conductive material is a method of manufacturing a porous film, characterized in that any one of tin sulfide (SnS), cadmium sulfide (CdS), and polyaniline.
The method of claim 1,
The step (a),
(a-1) preparing a first mixture by mixing a polymer in a volatile organic solvent;
(a-2) preparing a second mixture by mixing the first reactant in a volatile organic solvent; And
(a-3) preparing a polymer solution by mixing the first mixture and the second mixture; Method for producing a porous film comprising a.
The method of claim 1,
The method for producing a porous film, characterized in that the first reactant is mixed at a concentration of 0.04 to 0.06 M.
A porous film having a honeycomb pattern manufactured according to the manufacturing method of claim 1 and having a pore-selectively coated conductive material.
The method of claim 9,
The conductive material is a porous film, characterized in that coated with 150 to 250nm.
The method of claim 9,
The porous film, characterized in that the pore size of the porous film having the honeycomb pattern is 20 to 18um.
A porous film for solar cells manufactured according to the manufacturing method of claim 1 and having a pore-selectively coated honeycomb pattern with a conductive material.
As a method of manufacturing a porous film having a honeycomb pattern coated with a conductive material,
(a) preparing a polymer solution by mixing a polymer and a first reactant in a volatile organic solvent;
(b) applying the polymer solution to the surface of the substrate and introducing it into the breath figure chamber, and then maintaining the relative humidity inside the chamber;
(c) evaporating water droplets generated on the surface of the substrate in a breath figure chamber at room temperature to prepare a porous film having a honeycomb pattern; And
(d) a conductive material that is a reaction product of the first reactant and the second reactant over the entire film surface including the porous inner surface by immersing the porous film prepared in step (c) in a solution containing a second reactant Coating it; Method for producing a porous film comprising a.
The method of claim 13,
The volatile organic solvent in step (a) is one or more solvents selected from the group consisting of chloroform, carbon disulfide, and tetrahydrofuran.
The method of claim 13,
The polymer of step (a) is a porous film, characterized in that it is at least one polymer selected from the group consisting of polystyrene, polycaprolactone, polymethylmethacrylate, and polyimide Method of manufacturing.
The method of claim 13,
The first reactant in step (a) is tin chloride II (SnCl ₂ ), tin chloride IV (SnCl ₄ ), or cadmium chloride (CdCl ₂ ), and the second reactant in step (d) is hydrogen sulfide (H ₂ S) Method for producing a porous film, characterized in that.
The method of claim 13,
The method of manufacturing a porous film, wherein the first reactant in step (a) is benzoyl peroxide (BPO), and the second reactant in step (d) is aniline hydrochloride.
The method of claim 13,
The conductive material is a method of manufacturing a porous film, characterized in that any one of tin sulfide (SnS), cadmium sulfide (CdS), and polyaniline.
The method of claim 13,
The step (a),
(a-1) preparing a first mixture by mixing a polymer in a volatile organic solvent;
(a-2) preparing a second mixture by mixing the first reactant in a volatile organic solvent; And
(a-3) preparing a polymer solution by mixing the first mixture and the second mixture; Method for producing a porous film comprising a.
The method of claim 13,
The method for producing a porous film, characterized in that the first reactant is mixed at a concentration of 0.04 to 0.06 M.
A porous film manufactured according to the manufacturing method of claim 13 and having a honeycomb pattern entirely coated with a conductive material.
The method of claim 21,
The conductive material is a porous film, characterized in that coated with 150 to 250nm.
The method of claim 21,
The porous film, characterized in that the pore size of the porous film having the honeycomb pattern is 20 to 18um.
A porous film for solar cells manufactured according to the manufacturing method of claim 13 and having a honeycomb pattern coated with a conductive material as a whole.
As a method for producing a porous film having a conductive material microdome-selectively coated moth-eye pattern,
(a) preparing a polymer solution by mixing a polymer and a first reactant in a volatile organic solvent;
(b) applying the polymer solution to the substrate surface;
(c) introducing and contacting moisture air containing a second reactant on the surface of the substrate on which the polymer solution is applied;
(d) drying the surface of the substrate in contact with the moisture air to form a honeycomb pattern and coating the pores of the honeycomb pattern with a conductive material that is a reaction product of the first and second reactants to prepare a template film;
(e) preparing a conductive polymer solution;
(f) pouring the conductive polymer solution into the mold film of step (d) and drying it; And
(g) removing the dried mold film to selectively coat a conductive material on the microdome of the porous film having a moth-eye pattern; including, a method for producing a porous film.
The method of claim 25,
The volatile organic solvent in step (a) is at least one solvent selected from the group consisting of chloroform, carbon disulfide, and tetrahydrofuran.
The method of claim 25,
The polymer of step (a) is a porous film, characterized in that it is at least one polymer selected from the group consisting of polystyrene, polycaprolactone, polymethylmethacrylate, and polyimide Method of manufacturing.
The method of claim 25,
The first reactant in step (a) is tin chloride II (SnCl ₂ ), tin chloride IV (SnCl ₄ ), or cadmium chloride (CdCl ₂ ), and the second reactant in step (b) is hydrogen sulfide (H ₂ S) Method for producing a porous film, characterized in that.
The method of claim 25,
The method of manufacturing a porous film, wherein the first reactant in step (a) is benzoyl peroxide (BPO), and the second reactant in step (b) is aniline hydrochloride.
The method of claim 25,
The conductive material is a method of manufacturing a porous film, characterized in that any one of tin sulfide (SnS), cadmium sulfide (CdS), and polyaniline.
The method of claim 25,
The conductive polymer solution is a method of manufacturing a porous film, characterized in that the PEDOT:PSS solution.
The method of claim 25,
The step (f) is a method of manufacturing a porous film, characterized in that the conductive material generated in the template film of step (d) is transferred to the microdome film.
A porous film prepared according to the manufacturing method of claim 25 and having a microdome-selectively coated moth-eye pattern with a conductive material.
The method of claim 33,
The conductive material is a porous film, characterized in that coated with 150 to 200nm.
The method of claim 33,
The height of the microdome is 10 to 20um, the porous film, characterized in that the diameter is 15 to 25um.
A porous film for solar cells manufactured according to the manufacturing method of claim 25 and having a microdome-selectively coated moth-eye pattern with a conductive material.
As a method for producing a porous film having a moth-eye pattern coated with a conductive material,
(a) preparing a polymer solution by mixing a polymer and a first reactant in a volatile organic solvent;
(b) pouring the polymer solution into a film having a honeycomb pattern and drying to obtain a porous film having a moth-eye pattern; And
(c) immersing the obtained porous film having a moth-eye pattern in a solution containing a second reactant to coat the entire surface of the film with a conductive material, which is a reaction product of the first reactant and the second reactant; Method for producing a porous film comprising a.
The method of claim 37,
The volatile organic solvent in step (a) is at least one solvent selected from the group consisting of chloroform, carbon disulfide, and tetrahydrofuran.
The method of claim 37,
The polymer of step (a) is a porous film, characterized in that it is at least one polymer selected from the group consisting of polystyrene, polycaprolactone, polymethylmethacrylate, and polyimide Method of manufacturing.
The method of claim 37,
The first reactant in step (a) is tin chloride II (SnCl ₂ ), tin chloride IV (SnCl ₄ ), or cadmium chloride (CdCl ₂ ), and the second reactant in step (c) is hydrogen sulfide (H ₂ S) Method for producing a porous film, characterized in that.
The method of claim 37,
The method of manufacturing a porous film, wherein the first reactant in step (a) is benzoyl peroxide (BPO), and the second reactant in step (c) is aniline hydrochloride.
The method of claim 37,
The conductive material is a method of manufacturing a porous film, characterized in that any one of tin sulfide (SnS), cadmium sulfide (CdS), and polyaniline.
A porous film having a moth-eye pattern manufactured according to the manufacturing method of claim 37 and coated with a conductive material as a whole.
The method of claim 43,
The conductive material is a porous film, characterized in that coated with 150 to 200nm.
The method of claim 43,
The height of the microdome is 10 to 20um, the porous film, characterized in that the diameter is 15 to 25um.
A porous film for solar cells manufactured according to the manufacturing method of claim 37 and having a moth-eye pattern coated with a conductive material as a whole.

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