KR101641537B1 - Surface Modification Method for Superamphiphilic Surface - Google Patents

Abstract

More particularly, the present invention relates to a method for modifying a surface to exhibit amphiphilic properties, the method comprising: (A) coating a nanosilica-polymer composite on a substrate; And (B) subjecting the substrate coated by step (A) to plasma treatment.

Description

{Surface Modification Method for Superamphiphilic Surface}

The present invention relates to a surface modification method for causing a surface to exhibit amphiphilic properties.

Wetting of solid surfaces by liquids plays an important role in various applications such as self-cleaning, water repellency, smart fibers, super-hydrophobic coatings, and infection of medical polymers, so surface modification The method is receiving much attention. When a droplet comes into contact with a solid surface, the liquid retains the shape of the droplet in the extreme, or spreads on the surface of the solid to form a thin film, usually a part of which has an intermediate form of droplet and thin film. The wetting property of the droplet in contact with the surface of the solid is measured by the contact angle (CA). The larger the affinity between the surface and the liquid, the smaller the contact angle. The contact angle of 0 ° indicates that the thin film is completely diffused on the surface. If the contact angle of water (or oil) on the solid surface is greater than 150 °, the surface is said to have superhydrophobic (or superfine) properties, respectively. Conversely, if the contact angle with water (or oil) is less than 5 °, the surface is said to have superhydrophilic (or superficial) properties.

The wettability of solid surfaces is mainly determined by the chemical composition or structural roughness affecting the surface energy or geometry (Rhiz A. et al.). Decreasing the free energy of the surface increases the hydrophobicity of the surface, and increasing the surface free energy is known to increase the hydrophilicity. It is also effective to increase the hydrophobicity and hydrophilicity by increasing the surface roughness by introducing micro / nano pattern on the surface. Therefore, by using these properties, the surface properties can be appropriately adjusted to suit the application without greatly influencing the overall properties of the material.

Many surface modification methods such as chemical treatment, introduction of micro / nano patterns by vapor deposition or etching, plasma treatment, UV or laser treatment have been developed to control the wettability of the surface without significantly affecting the overall properties of the polymer . Much research has been done to increase the hydrophilicity of the polymer surface, since most polymers are not suitable for biomedical or industrial applications due to their hydrophobicity. Patent No. 601308 discloses that by treating a polyimide surface with a plasma, a polar functional group containing oxygen is introduced into the surface, the roughness is improved by the surface etching, and the hydrophilic property is greatly increased by the increase of the surface free energy Respectively. J. Kong et al. Have found that when a fine pattern is formed by a hot embossing process using a silicon template in polystyrene, the contact angle with water increases greatly from 76 DEG to 130 DEG to increase hydrophobicity, The contact angle is reduced to 5 deg. Or less and the superhydrophilic property is exhibited. In the above patents and papers, there is no significant change or no mention of lipophilic properties.

In general, a substance exhibiting hydrophilicity is regarded as possessing lipophilicity, while a substance exhibiting hydrophobicity is regarded as having lipophilicity. However, in terms of wettability, hydrophilicity and lipophilicity or hydrophobicity and lipophobicity can be simultaneously obtained. Both hydrophilic and lipophilic are referred to as amphiphilic. Since Wang et al. Reported that light irradiation converts the surface of TiO ₂ to super amphiphilic with super wettability to both water and oil, the amphipathic material has been used for functional fibers, transparent displays in refrigeration cabinets, Goggles, and spectacle lenses, but it has not been reported yet. TiO ₂ reported by Wang et al. Shows super-amphipathic effect by irradiation of ultraviolet rays. However, since the hydrophobicity is restored by turning off the ultraviolet rays, the use of TiO ₂ is restricted in a place where it is not exposed to the dark or ultraviolet rays. There is a limitation in the materials that can be used because of problems such as the thin film being easily cracked.

Xuyan Liu et al., Including the present inventors, found that silver nanoparticles (Ag-NPs) attached to carbon nanotubes (CNTs) exhibit (A) Ag-NPs and CNTs in the form of ethylcellulose (B) a thin film is formed using a silicon wafer by a casting process using the paste, (C) a thin film is subjected to heat treatment at 250 ° C to remove organic substances, and (D) CNT films having amphipathic properties can be prepared by subjecting the thin film from which the material has been removed to atmospheric plasma treatment. However, this method is based on the properties of CNTs and Ag. Therefore, this method can not be applied widely to modify the surface of materials of other materials.

Patent No. 601308

Rhiz A. et al., Langmuir, 23, 12984-12989 (2007). Wang et al., Adv. Mater. 10, 135 (1998) Xuyan Liu et al., Current Applied Physics 13 S122-S126 (2013)

It is an object of the present invention to provide a method for modifying a surface of a substrate having various amphipathic properties by a simple method in order to solve the problems of the related art as described above.

It is another object of the present invention to provide a surface modification method capable of exhibiting amphipathicity regardless of the material and environment of use of the substrate.

According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: (A) coating a nanosilica-polymer composite on a substrate; And (B) subjecting the substrate coated by step (A) to plasma treatment.

In the present specification, 'amphipathic' means both hydrophilic and lipophilic, and 'hydrophilic' and 'lipophilic' means that the contact angle of water and oil to the material is less than 20 °. In particular, when the contact angles of water and oil to the material are 0 ° to 5 °, they are defined as 'super hydrophilic' and 'super-hydrophobic oil,' respectively. If they have both superhydrophilic and super- do.

In the present invention, when the substrate is coated with the nano-silica-polymer composite layer and then the plasma is treated, the surface roughness is increased due to the fact that the low molecular weight material and the amorphous organic material are more easily etched than the nano silica particles by plasma The layer formed by protruding the nanosilica particles together and the layer formed by the substrate or the partially etched coating layer have a microstructure constituting two layers and the oxygen bonds to the surface due to the plasma and the hydrophilic And the lipophilicity are both increased to have amphiphilic properties. Therefore, the present invention can be used to modify the surface to be amphipathic regardless of the material of the substrate. That is, any material may be used without being limited to polymer resin or glass.

The coating of the nanosilica-polymer composite can be performed by mixing the nanosilica particles with the polymer and mixing the nanosilica particles with the molten polymer itself or by coating the nanosilica particles and the polymer after dissolving the nanosilica particles and the polymer in the solvent, and drying the solvent . Or nano silica particles and a polymer monomer (including a solvent if necessary) are mixed and coated on a substrate, followed by polymerization to form a nano-silica-polymer composite layer. In this case, the mixed solution of the nanosilica particles and the polymeric monomer may contain an initiator or a catalyst for polymerization. When the solvent is contained in the mixture of the nanosilica particles and the polymeric monomer, it is of course possible to remove the solvent before or after the polymerization. Polymerization methods, catalysts, initiators, and the like of polymers are well-known and those skilled in the art can appropriately select and use them from the prior art, so that detailed description thereof will be omitted. In addition, the coating method may be appropriately applied, such as spin coating, dip coating, spray coating, etc., depending on the properties of the nanosilica-polymer composite or the precursor thereof, and the present invention is not limited by the coating method.

The thickness of the nanosilica-composite layer is preferably in the range where the nanosilica forms a single layer. The thickness of the nano silica-polymer composite layer may vary depending on the particle diameter of the nanosilica composing the composite, but it is preferable that the particle size of the nanosilica is about the same. The nanosilica particles have an average particle diameter of 1 μm or less, . That is, the nanosilica used in the present invention preferably has an average particle diameter of 5 to 1,000 nm. When the thickness of the coating layer of the nanosilica-polymer composite is too thick to form a multi-layer structure, adhesion stability between the particles and the surface may be deteriorated, and bubbles may be formed inside.

In the present invention, the polar functional group including oxygen is introduced into the surface of the nanosilica-polymer composite layer coated on the surface by the plasma treatment to increase the surface energy, while the nanosilica particles are not etched while only the polymer layer is etched, This is due to the change in structure. Therefore, the surface covering ratio by the nano silica particles is an important factor for showing the amphipathic property, and the surface covering ratio is preferably 5 to 78.5%. When the surface coverage is less than 5%, the surface free energy is increased but the surface roughness is not increased by microstructure formation. Therefore, the (hydrophobicity) increases, but the effect on the lipophilic property is small and the amphiphilic property is hardly exhibited. Even if the amphiphilic property is exhibited, the high voltage is required for the plasma treatment or the treatment time becomes too long. When the surface coverage is 78.5% or more, a multi-layered structure is formed, which makes it difficult to modify the surface to an amphipathic surface.

Since the surface coverage of the nanosilica is affected by the size and concentration of the nanosilica particles, the content of the nanosilica in the nanosilica-polymer composite, which can realize the surface coverage, But it is preferably 3 to 20 wt%. When the content of the nanosilica is too large, the viscosity of the nanosilica-polymer composite increases in addition to the factor due to the surface coverage, and it is difficult to realize a uniform coating layer.

The present invention utilizes that the polymer region is relatively easily etched by the plasma in the nano-silica-polymer composite layer compared with the nano silica, so that the present invention is not limited by the kind of the polymer constituting the nano-silica-polymer composite. Although only examples of polyurethane and polyacrylate were described in the following examples, the polyethylene, polyether, polyester, polyimide, and polycarbonate also differed in plasma treatment time, but all of them were used as polymers of nano silica- And thus can be effectively used in a surface modifying method that exhibits a high melting point. Here, the kind of the polymer means a polymer series, and does not mean simply a per se. For example, polyethylene is collectively referred to as a polymer of an ethylene derivative, and is collectively referred to as polyethylene, polystyrene, polyethylene terephthalate (PET), polyvinyl chloride (PVC), polypropylene and polyvinyl alcohol (PVA). Particularly, even when the same polyimide as that described in Japanese Patent No. 601308 is used, if the plasma is treated after coating in the form of a nanosilica-polyimide composite, the surface is modified so as to exhibit amphipathicity, There was a difference between the results.

Since the treatment conditions of the plasma in the present invention can be appropriately adjusted depending on the type, composition and thickness of the nanosilica-polymer composite, it is not meaningful to limit the specific conditions, but considering that the power of a conventional plasma reactor is 50 to 500 W , For 10 seconds to 30 minutes. As the power of the plasma reactor increases, the time required to treat the surface is reduced so that the same effect can be obtained. The increase in hydrophilicity and lipophilicity is proportional to the plasma processing time and the processing power. Therefore, it was possible to modify the surface to have a desired range of hydrophilicity and lipophilicity by controlling the electric power of the plasma and the treatment time. In particular, if the content of silica is within the above specified range and the treatment time or intensity of the plasma is sufficient, the surface of the substrate can be polished by the surface modification method of the present invention in such a manner that the contact angle with respect to the polar water and the nonpolar diiodomethane is 5 Deg.], Indicating a second amphipathic state.

At this time, the treatment of the plasma is preferably performed in an oxygen atmosphere. In the present invention, 'oxygen atmosphere' means that oxygen is present in the plasma reactor. It is sufficient not only to inject oxygen as an injection gas but also to oxygen in the atmosphere existing in the reactor even if oxygen is not separately injected. In the oxygen atmosphere, hydrophilic oxygen including ketone, carboxy and peroxide groups is introduced on the surface of the material to exhibit hydrophilicity.

The plasma apparatus used in the present invention may be any commercially available apparatus, but it is preferably an atmospheric pressure plasma apparatus in view of economical efficiency, convenience, and process stability. It should be understood, however, that the same effect can be obtained by plasma apparatuses of all pressure ranges operating at 10 ^-8 to 1000 torr in addition to atmospheric pressure.

The present invention also relates to an amphipathic material surface-modified by the method. The amphipathic material is excellent in absorption of sweat and secretions, so it can be used as a functional fiber, and can be applied to swimming goggles, eyeglass lenses, and side mirrors of automobiles. In addition, it has high coating strength and adhesive force of materials, so it is highly applicable to electronic devices such as solar cells and transparent displays. Polymer films having transparency and flexibility properties are widely used as substrates for transparent electrodes such as OLED touch screens, but have a problem of low adhesion and coating ability to the conductive coating layer. In addition, when the conductive coating layer is not uniformly formed, it is important that the conductive coating layer can be uniformly coated because the reliability and efficiency are greatly reduced. It was confirmed that the surface modified material by the method of the present invention is useful for a transparent electrode of a flexible material because the surface resistance is low as well as transparency when the transparent electrode is manufactured. The amphipathic material may be particularly useful when it has an ultra-wettability with a contact angle of 5 DEG or less for both polar and non-polar materials.

As described above, according to the present invention, by increasing the surface free energy by a simple method and by forming a fine structure on the surface to increase the surface roughness, the surface of the substrate can be modified to have amphiphilic property, And can be efficiently used for manufacturing materials.

Further, by using the atmospheric pressure plasma apparatus, the surface of the workpiece can be modified more economically and conveniently so that the surface of the workpiece has amphiphilic property.

In particular, unlike conventional TiO ₂ , the surface-modified material according to the present invention does not require light in order to exhibit amphipathic properties, and the surface can be modified irrespective of the material of the substrate, .

The amphiphilic material surface-modified by the present invention can be applied to various industrial fields such as functional fibers, transparent electrodes, glasses, and the like.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing changes in contact angle and surface energy according to an FESEM image of a surface material treated by an embodiment of the present invention and a material of a comparative example, and a plasma treatment time.
FIG. 2 is a spectrum and a graph showing XPS analysis results of a surface-treated material according to an embodiment of the present invention. FIG.
Fig. 3 is an FESEM image and AFM image showing the surface characteristics of the material before and after the plasma surface treatment.
FIG. 4 is a graph and FESEM image showing the change of the contact angle and surface free energy according to the plasma treatment time of the surface-treated material according to one embodiment of the present invention. FIG.
5 is a graph and FESEM image showing the change of contact angle and surface free energy according to the content of nano silica in the composite layer in one embodiment of the present invention.
6 is an image conversion example for calculation of the surface coverage of nano silica particles.
FIG. 7 is an image showing a coating force of a conductive paste and an electrode characteristic of a transparent electrode according to an embodiment of the present invention. FIG.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these embodiments are merely examples for explaining the content and scope of the technical idea of the present invention, and thus the technical scope of the present invention is not limited or changed. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea of the present invention based on these examples.

Example

Example 1: Preparation of nanosilica-polymer composite coated material

Nano silica (Aerosil R972, Degussa Huls) was added to an acryl-based polyurethane solution (PU340, Worldtex Specialty Chemical) containing 30% solids so that the weight ratio to polyurethane was 0 to 20 wt% Followed by stirring to prepare a nanosilica-polyurethane composite solution. The solvent in the polyurethane solution is composed of toluene / isopropanol / ethyl acetate in a volume ratio of 6: 3: 1. The average diameter of the nanosilica used was about 16 nm.

1 g of the nanosilica-polymer composite dispersion prepared by the above method was coated on a PET film with a film thickness of 6.86 쨉 m using a rod-will rod (bar # 3) technology and dried at 25 캜 for 24 hours To form a nano-silica-polymer composite layer.

Example 2: Plasma treatment of material

Manufacturing Example: Plasma treatment of materials with nano-silica-polymer composite coating layer

The material prepared in Example 1 was cut into a size of 3 cm x 3 cm and then treated with atmospheric plasma. AC plasma (ATMOS, creative engineering) generated at a frequency of 13.56 MHz was used as the atmospheric plasma treatment, and the plasma power was fixed to 100 W, the moving speed of the sample holder was 20 mm / min, and the gap between the electrode and the sample holder was 3 mm. Ar was mixed at a flow rate of ₅ lpm and O ₂ at a flow rate of 6 sccm, and mixed to be used as an injection gas.

Comparative Example: Plasma treatment of a material formed only with a polymer coating layer

Plasma was treated in the same manner for the material coated with the polymer layer by the same method as in Example 1, except that the content of the nano-silica was 0%.

Example 3: Measurement of contact angle of material

The contact angle of the plasma-treated material in Example 2 was measured using a drop shape analyzer (Krans DSA 100, Germany). Distilled water (DW) and diiodomethane (DI) were used as polar and nonpolar probes. Each experiment was repeated 5 times and the average value was used as the contact angle of the sample.

1 (a) and 1 (b) are images of FESEM (JSM-7000F, JEOL) of the production example (nanosilica (5 wt%) -Polyurethane composite coating formed PET layer) , and c is a graph showing changes in the contact angle and surface energy of the production example according to the plasma treatment time.

The contact angles of DW and DI before the plasma treatment were 90 ° and 52.2 °, respectively. However, after the plasma treatment, the contact angle gradually decreased with the elapse of the plasma treatment time, and after 720 seconds, 0 < / RTI > to exhibit ultra wettability for both polar and non-polar materials (see Fig. 1c).

On the contrary, in the comparative PET film, when the plasma was treated for 900 seconds, the contact angle for DW decreased from 68 ° to 0 °, and the contact angle of DI was 27 °, which was 34.1 ° before the plasma treatment But it did not show the superficial meteors.

Example 4: Chemical characterization of the surface

Changes in the chemical composition of the material surface by plasma treatment were observed with XPS (VG Micro Tech Co.). The pressure in the chamber was maintained at 10 ^-9 Torr, the surface area of analysis was 1 mm x 1 mm, and the takeoff angle of the photoelectron was 45 °. Data analysis and quantification were performed using XPSPEAK 4.1 software.

Fig. 2 shows the results of XPS analysis of the production example (a PET material in which a coating layer of a nano-silica-polyurethane composite was formed), a shows the XPS spectrum and b shows the XPSPEAK 4.1 software. In FIG. 2, the production examples before plasma treatment show O 1s, C 1s and N 1s peaks derived from polyurethane. As the plasma treatment time elapses, N 1s peaks decrease and Si 2s and Si 2p are newly observed. This is presumably because the polyurethane portion of the coating layer is etched by the plasma treatment and the hard silica nanoparticles remain on the surface.

In the XPS spectrum, the intensity of the O 1s peak for the C 1s peak was greatly increased by the plasma treatment. That is, before the plasma treatment, the ratio of O 1s peak area to C 1s was 36%, but increased to 46.1% after 30 sec plasma treatment and 77% after 900 sec treatment. This indicates that oxygen is introduced on the surface of the film, and it is considered that it plays an important role in increasing the hydrophilicity. The O 1s peak is composed of a CO * peak at 531.7 eV and a peak due to C = O * of a ketone or peroxide group at 533.1 eV. As shown in FIG. 2 b, the ratio of CO * , And the ratio of C = O * increases. It can be interpreted that the plasma treatment of the surface increases hydrophilic oxygen including ketone, carboxy and peroxide groups and decreases the C-O bond of the ester present in the polymer chain.

From this, it can be seen that the treatment of the plasma increases the hydrophilicity of the surface by increasing the hydrophilic functional group.

Example 5: Physical property analysis of the surface

The surface characteristics before and after the plasma treatment were observed by FESEM and AFM (Atomic Force Microscope, Pork Science Instruments), and the results are shown in FIG. 3 (a) and 3 (b) show the FESEM image and AFM image after the plasma treatment, and c and d in FIG. 3 respectively show the FESEM image and the AFM image after the plasma treatment, respectively.

Before the plasma treatment, only a part of the silica nanoparticles protruded on the surface, and the surface roughness measured by AFM was 8.3 nm. As a result of the plasma treatment, low-molecular-weight contaminants and organic (polymer) regions on the amorphous phase are easily removed by plasma, whereas silylated nanoparticles are relatively stable and remain on the surface to a large extent. The surface roughness increased greatly to 16.4 nm. The FESEM image (Fig. 3 (c)) of the sample of the production example plasma treated for 900 seconds shows that the sample surface consists of two layers. One of them is a lower surface layer with a gentle roughness, which corresponds to a PET film substrate, and nanoclusters formed by agglomeration of nanosilica particles form the upper layer. This is a structure contrasted with the FESEM image of the comparative example shown in FIG. 1 (b), and it can be confirmed that the above structure causes the material of the manufacturing example to exhibit ultra wettability for both DW and DI.

Example 6: Observation of effect of super wettability on the spacing of nanosilica particles

And a coating layer of nano-silica-PMMA (poly (methyl methacrylate)) composite was formed on a glass substrate. More specifically, 10 g of PMMA (Aldrich, USA) was dissolved in 100 g of anisole (Aldrich, USA). Nano silica was added to the mixed solution and dispersed uniformly by ultrasonication. The prepared uniform dispersion solution was coated on a glass substrate by spin coating at 1000 rpm for 20 seconds and 2000 rpm for 30 seconds, and the remaining solvent was removed at 50 ° C for 1 hour. The thickness of the formed coating layer was 10 ~ 50 nm according to the spin coating angular velocity.

At this time, the content of the nanosilica in the coating composition was adjusted so that the weight ratio of the nanosilica to the PMMA in the composite was 0.1 to 20 wt%. The prepared material was irradiated with plasma according to the method of Example 2, and the FESEM image and the contact angle were observed, and the results are shown in Figs. 4 and 5. Fig.

FIG. 4 is a graph and FESEM image showing changes in contact angle and surface free energy with plasma treatment time for a composite layer containing 5 wt% nano-silica. 4, the surface free energy and the surface roughness were increased with the elapse of the plasma treatment time, and the contact angle was decreased. When the plasma was treated for 500 seconds, the contact angle with respect to both DW and DI was 0 °, It can be confirmed that it shows an ultra wettability.

FIG. 5 is a graph and FESEM image showing changes in contact angle and surface free energy according to the content of nano-silica in a plasma treated sample for 360 seconds. As the content of nano silica increases, the contact angle decreases rapidly, and the surface structure affects the wettability.

The ratio of the surface cross-sectional area of the nanosilica particles in the total surface cross-sectional area was defined as the surface coverage (? S) of the nanosilica, and the surface coverage of the section showing the amphipathicity was calculated. For the calculation of the surface coverability, first, the time required for PMMA as a polymer to be sufficiently etched was found to be 500 seconds from the contact angle graph according to time in Table 4, and then the poly (methyl methacrylate) composite Were coated with plasma for 500 seconds. A high resolution SEM image of the treated sample was converted to a binary monochrome image using ImageJ software. In order to maintain the high resolution and to minimize the error, a 50,000 times image was selected by repeated test. FIG. 6 is an illustration of a high resolution SEM image and an image transformed therefrom, showing black colored nanosilica particles in the converted image. The surface coverability was calculated by calculating the area occupied by the black color of the entire area. The amphipathic effect was achieved at the surface coverage of 5 ~ 78.5%.

Example 7: Application to high efficiency transparent electrode

Poly (3,4-ethylenedioxythiophene): poly (3,4-ethylenedioxythiophene) conductive polymer PEDOT: PSS was used as a transparent electrode in the production example PET film styrenesulfonate)) conductive paste onto the PET surface with a uniform and strong adhesive force, the work-of-adhesion of the surface modification method of the present invention was ascertained. The bonding work was calculated by the following formula.

In the above equation,? Represents the surface free energy, and the subscript S ₁ represents PET and S ₂ represents a conductive paste. γ ^D and γ ^P mean the dispersion contribution and the polarity contribution of the surface free energy, respectively, and can be calculated from the contact angle with DW and DI by the Owens-Wendt equation.

7 (a) is a graph showing a change in the calculated bonding work in accordance with the plasma treatment time and a FESEM image showing the coating power of the conductive paste. In FIG. 7, it can be seen that the contact time is greatly increased by the plasma treatment. Even when treated for a short period of 30 seconds, it increased by more than 15% from 93.74 mN / m to 107.95 mN / m. The contact days also showed a tendency to increase, but there was no big difference when treated for more than 600 seconds.

PEDOT: PSS conductive paste (Baytron HC grade, solid content: 1.4 wt.% In water) was coated on the PET film of the production example and the sheet resistance and transparency were measured in order to experimentally confirm the applicability of the transparent electrode as the substrate. More specifically, a mixture of 5% by weight of ethylene glycol (EG) and 5% by weight of DMSO and PEDOT: PSS conductive paste was added to each PET film of the production example having different plasma treatment times on a PET film Coated using a bar coating machine (bar No.10) or a doctor blade machine (CKAF-1006D, CK Trading Co.), and dried at 120 ° C for 5 minutes to prepare a transparent electrode. Transparency was measured with an average transmittance using JIS K 7105 method using a UV-VIS spectrometer (Perkin-Elmer Lambda 25 spectrometer), and the sheet resistance was measured with a 4 point probe method (SONICS vibra cell).

In FIG. 7 (b), the transparency of the transparent electrode using the surface-modified PET film by the method of the present invention was remarkably improved to confirm that the conductive paste was uniformly coated, and the sheet resistance was also significantly decreased, Able to know.

Claims (11)

(A) coating a nanosilica-polymer composite on a substrate; And
(B) plasma processing the substrate coated by step (A);
≪ / RTI > The method of claim 1, wherein the surface modification method comprises the steps of:
The method according to claim 1,
Wherein the surface coverage of the nanosilica-polymer composite coating layer is from 5 to 78.5%.
3. The method of claim 2,
Wherein the nanosilica has an average particle size of 5 to 1,000 nm.
The method according to claim 1,
Wherein the content of the nano-silica in the nano-silica-polymer composite is 3 to 20 wt%.
The method according to claim 1,
Wherein the polymer is one or more selected from the group consisting of polyethylene, polyether, polyester, polyimide, polyurethane, polyacrylate, and polycarbonate.
6. The method according to any one of claims 1 to 5,
Wherein said amphipathic is water having polarity and a sec-ampholytic surfactant having a contact angle to non-polar diiodomethane of from 0 to 5 degrees.
6. The method according to any one of claims 1 to 5,
Wherein the plasma treatment is performed in an oxygen atmosphere.
6. The method according to any one of claims 1 to 5,
RTI ID = 0.0 > 1, < / RTI > wherein the plasma is an atmospheric plasma.
Polymer composite coating layer on the substrate, the nanosilica-polymer composite coating layer being treated with a plasma on the substrate.
10. The method of claim 9,
Wherein the amphipathic is a water having a polarity and a contact angle with respect to a non-polar diiodomethane is 0 to 5 degrees.
A transparent electrode produced by forming a conductive layer on a material of claim 10.

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