KR101283665B1

KR101283665B1 - Forming Method Of Nano Structure For High Light-Transmissive And Super-Water-Repellent Surface

Info

Publication number: KR101283665B1
Application number: KR1020100095523A
Authority: KR
Inventors: 김윤택; 양순석; 조상무; 김병찬
Original assignee: 바코스 주식회사
Priority date: 2010-09-30
Filing date: 2010-09-30
Publication date: 2013-07-08
Also published as: WO2012044054A3; KR20120033805A; WO2012044054A2

Abstract

The present invention relates to a method for forming nanostructures for implementing a highly translucent and super water-repellent surface, and more particularly, to form island fine metal particles on the surface of the substrate and to form the island fine metal particles as a protective mask. After etching, by removing the metal particles remaining on the surface of the etched substrate, to a method for producing a highly translucent, super water-repellent nanostructure surface.
According to the nanostructure forming method of the present invention, it is possible to easily form a random fine concavo-convex surface on the surface of the substrate without using expensive low-efficiency method such as lithography method, forming a nanostructure showing high permeability and super water repellency The surface can be produced at low cost and high efficiency.

Description

Forming Method Of Nano Structure For High Light-Transmissive And Super-Water-Repellent Surface}

The present invention relates to a method for forming nanostructures for implementing a highly translucent and super water-repellent surface, and more particularly, to form island fine metal particles on the surface of the substrate and to form the island fine metal particles as a protective mask. After etching, by removing the metal particles remaining on the surface of the etched substrate, to a method for producing a highly translucent, super water-repellent nanostructure surface.

The antireflective coating refers to a coating capable of eliminating the reflection of light generated by the sharp refractive index change in the cross section of the optical device and increasing the amount of transmitted light. In general, when minimizing the reflection of light incident vertically at a single wavelength, a material having a refractive index corresponding to the square root of the refractive index of the substrate is applied to the substrate at a quarter thickness of a single wavelength by using electron beam deposition or ion assisted deposition. If you want to have minimal reflectance at different wavelengths, you need to deposit different layers of different materials. However, this method has a problem that the antireflection effect is insufficient in a wide angle of incidence and the wavelength region and it is expensive to implement.

On the other hand, as another method of reducing surface reflection in optical elements such as glass, a method of forming a fine concavo-convex structure on the surface of the optical element is known. A typical example of this method is moth eyes, which are made of aligned nanostructures that have very low light reflections to protect themselves from predators like birds and to secure visibility at night with less light. Your activities are easy.

In the case of forming periodic irregularities on the surface of the optical element, the light is diffracted when passing through the surface of the optical element, and the linear component of the transmitted light is greatly reduced. However, the pitch of the irregularities formed on the optical element surface is shorter than the wavelength of the transmitted light. Since the diffraction does not occur in the shape, light having a single wavelength corresponding to the pitch and depth of the unevenness may have an antireflection effect.

At this time, it is known that the antireflection effect is obtained for light having a wide wavelength if it is a so-called vertebral shape in which the volume ratios of the peaks and valleys, that is, the optical element material side and the atmospheric side, are continuously changed without forming the uneven shape. (Japanese Patent Publication No. 2001-272505, Japanese Patent Publication No. 2006-243633)

Electron beam lithography is generally used to produce such a fine structure because fine patterns below the wavelength of light are required to obtain the anti-reflection effect for such a wide wavelength.

This method is a method in which an electron beam resist is applied, patterned using an electron beam, and then processed using reactive etching. Since the electron beam is scanned and patterned, there is a problem that production speed is very slow and manufacturing cost is high. Thus, there is a need for the development of a technology that can easily manufacture fine patterns, while low manufacturing costs by using expensive equipment.

On the other hand, the water repellency refers to a property that is difficult to wet the water, the water repellency is evaluated by the contact angle θ of the water droplets placed on the surface, in general, if θ exceeds 90 degrees, water repellency, 120 degrees <θ <150 degrees is high water repellency, θ is 150 degrees Above is defined as superhydrophobic.

Super water-repellent surface technology is a field of surface modification technology to control the surface wetting phenomenon, which makes the surface of the solid physically or chemically modify the surface so that the contact angle is 150 ° or more when the liquid contacts the surface of the solid. Say

As a representative model of the super water-repellent surface, there is a lotus leaf. In the case of the lotus leaf, there are numerous micro to nano-sized ciliary protrusions on the surface and the wax component is coated at the same time. The surface is super water-repellent and exhibits a feature that does not get wet.

Because water droplets easily roll on super water-repellent surfaces, they are waterproof, anti-fogging, anti-skid, snow-preventing, anti-corrosion by tides, and anti-fingerprints, making them attractive for a wide range of applications including building materials, cosmetics, textile processing, and electronic components. I am getting it.

The water-repellent film prepared by coating various conventional fluorine-based materials is an example in which a coating film is formed using a material having a low surface energy. Since a contact angle of 150 ° or more cannot be obtained only by low surface energy, a super water-repellent material of 150 ° or more is required. It is necessary to fabricate nanostructures on the surface.

As described above, the highly transparent and super water-repellent surface using the nanostructure, when applied to optical devices such as computers or notebooks, reduces the glare of the reflection of external light, and increases the amount of light from the inside It is expected to have a ripple effect in related industries if it is possible to form a large amount of nanostructures at low cost in an optical device because it can provide bright and bright image quality.

In addition, in the case of a mobile phone with a touch panel, which is increasing in demand in recent years, if the antireflection and super water repellency is given to tempered glass and plastic, which are window windows, the screen may be clearer and contamination by fingerprints may be reduced. Conventionally, a method of adhering a film having nanostructures formed on a window sight glass is used, but there are problems such as defects in lamination, durability after lamination, and scratch resistance of the film.

The present invention was devised to solve the above problems, and by forming fine unevenness on the surface of the substrate and coating it with a fluorine compound, not only shows excellent super water repellency but also reduces the reflectance of the surface of the substrate to show high transparency It is an object of the present invention to provide a manufacturing method that can easily produce the surface at a low manufacturing cost.

In order to achieve the above object, the present invention provides a method of forming an island-shaped metal particles on a surface of a substrate, etching the substrate surface using the island-shaped metal particles as a protective mask, and etching the substrate surface. It provides a method for forming a nanostructure comprising the step of removing the remaining metal particles.

In addition, in order to achieve the above object, the present invention comprises the steps of forming an intermediate layer on the surface of the substrate, the step of forming the metal particles of the island form on the surface of the substrate on which the intermediate layer is formed, the metal particles of the island form as a protective mask Etching the intermediate surface, etching the substrate surface using the metal particles in the intermediate and island form remaining after the etching as a protective mask, removing the metal particles remaining on the etched substrate surface, and the etched It provides a method of forming a nanostructure comprising the step of removing the intermediate remaining on the substrate surface.

Here, the island-like metal fine particles are discontinuous thin films formed on the surface of the substrate by physical vapor deposition (PVD), and the intermediate is preferably made of silicon or polymer.

The method may further include oxidizing, nitriding, or oxynitrating the island-shaped metal particles after forming the island-like metal particles on the surface of the substrate, wherein the island-shaped islands of the oxidized, nitrided, or oxynitride are formed. Using the metal fine particles as a protective mask, the substrate surface or the intermediate layer is etched and the oxidized, nitrided or oxynitride metal particles remaining on the etched substrate surface are removed.

In addition, the method may further include coating a fluorine compound on the surface of the substrate from which the metal fine particles are removed, wherein the chemical formulas of the fluorine compound are (CF _3- ), (-(CF ₂ -CF ₂ ) n-,- (O (CF ₂ ) m) n-,-((CF ₂ ) mO) n-,-(OC (CF ₃ ) FCF ₂ ) n- and-(C (CF ₃ ) FCF ₂ O) n- At least one (m = 1-25, n = 1-100), the fluorine compound may be coated by any one or more of dip coating, spin coating, surface polymerization method using plasma and surface modification method using plasma. have.

The metal fine particles may be formed of any one of low melting point metals such as indium, tin, lead, zinc, and aluminum, and the average particle diameter of the metal fine particles may be in the range of 10 to 1000 nm. It is preferable that the average particle diameter is 10-400 nm.

The average spacing between the metal fine particles is 20 to 2000 nm, and the shape of the metal fine particles formed on the surface of the base material is a weight in which the surface-area-to-volume ratio of the base side and the atmospheric side continuously changes. Preferably, the nanostructures are formed on both surfaces of the substrate.

According to the nanostructure forming method of the present invention, it is possible to easily form a random fine concavo-convex surface on the surface of the substrate without using expensive low-efficiency method such as lithography method, forming a nanostructure showing high permeability and super water repellency The surface can be produced at low cost and high efficiency.

1-a flow chart showing a method of manufacturing a non-reflective surface and super water-repellent surface according to a preferred embodiment of the present invention
Figure 2-Flow chart showing a method of manufacturing a non-reflective surface and super water-repellent surface in accordance with a preferred embodiment of the present invention
3-a flow chart showing a method of manufacturing the anti-reflective surface and super water-repellent surface in accordance with a preferred embodiment of the present invention
Figure 4-Flow chart showing a method of manufacturing a non-reflective surface and super water-repellent surface according to a preferred embodiment of the present invention
Figure 5-Electron micrograph of the surface of the substrate coated with fine particles in the form of islands on one side of the glass substrate
6 to 4 are cross-sectional views illustrating a state in which oxidized, nitrided, and oxynitride particles are formed on an intermediate layer according to the flowchart of FIG. 4.
7 to 6 are cross-sectional views illustrating a state in which an intermediate layer is etched.
8 to 7 are cross-sectional views illustrating a state in which the substrate is etched.
9-A graph showing the transmittance of the glass with the nanostructure formed according to the present invention compared with the transmittance of the common glass

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately The present invention should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention.

The present invention does not use conventional low-productivity and costly electron beam lithography to form nanostructures on the surface of the substrate, and immediately forms the island-like metal fine particles on the surface of the substrate, which is then etched as a protective mask. It is made into the summary to form a nanostructure by the following.

As shown in FIG. 1, the method of forming a nanostructure for realizing a highly permeable and super water-repellent surface according to an embodiment of the present invention includes forming metal fine particles in island form on the surface of the substrate (P100), and in the island shape. Etching the substrate surface using the metal fine particles of the protective mask (P200), and removing the metal fine particles remaining on the etched substrate surface (P300), wherein the metal particles have been removed from the fluorine on the surface of the substrate. The method may further include coating the compound (P400).

As shown in FIG. 2, in the method of forming a nanostructure according to another embodiment of the present invention, forming an intermediate layer on a surface of a substrate (P50) and forming fine metal particles in island form on the surface of the substrate on which the intermediate layer is formed. (P100), etching the intermediate surface using the island-shaped metal particles as a protective mask (P150), etching the substrate surface using the intermediate and island-type metal particles remaining after the etching as a protective mask ( P200), removing metal particles remaining on the etched substrate surface (P300), removing intermediates remaining on the etched substrate surface (P350), and removing the metal particles on the substrate surface from which the metal particles are removed. The method may further include coating a fluorine compound (P400).

As shown in FIG. 3, in the nanostructure forming method according to another embodiment of the present invention, after forming the island fine metal particles on the surface of the substrate in FIG. 1, the island fine metal particles are oxidized, Further comprising nitriding or oxynitriding, wherein the surface of the substrate is etched using the metal particles in the form of the oxidized, nitrided or oxynitrided island as a protective mask, and the oxidation, nitriding or acid remaining on the surface of the etched substrate Nitrided metal particles are removed.

That is, the embodiment is a step (P100) of forming the island-like metal fine particles on the surface of the substrate, the step of oxidizing, nitrating or oxynitrating the island-shaped metal particles (P110), the oxidized, nitrided or oxynitride island form Etching the substrate surface using the metal fine particles of the protective mask (P200), and removing the metal oxide particles oxidized, nitrided or oxynitized remaining on the surface of the etched substrate (P300). The method may further include coating a fluorine compound on the removed substrate surface (P400).

As shown in Figure 4, another method of forming a nanostructure according to another embodiment of the present invention, after the step of forming the island-like metal fine particles on the surface of the substrate formed with the intermediate layer in Figure 2, And oxidizing, nitriding or oxynitrating the metal fine particles, wherein the substrate surface and the intermediate layer are etched using the metal fine particles in the oxidized, nitrided or oxynitrated island form as a protective mask, and the etched substrate surface is etched. It will remove the remaining oxidized, nitrided or oxynitride metal particles.

That is, the embodiment of the present invention comprises the steps of forming an intermediate layer on the surface of the substrate (P50), forming the fine metal particles of the island form on the surface of the substrate on which the intermediate layer is formed (P100), oxidizing, nitriding or oxidizing the island-shaped metal particles Oxidizing (P110), etching the surface of the intermediate with the metal particles in the form of the oxidized, nitrided or oxynitride as a protective mask (P150), oxidizing, nitriding or the oxynitride in the form of oxidized, nitrided or oxynitride islands. Etching the substrate surface with the metal fine particles as a protective mask (P200), removing the oxidized, nitrided or oxynitride metal particles remaining on the etched substrate surface (P300), remaining on the etched substrate surface And removing the intermediate (P350), and may further include coating (P400) a fluorine compound on the surface of the substrate from which the metal fine particles have been removed.

In general, when the thin film is manufactured by physical vapor deposition such as thermal evaporation, electron beam evaporation, sputtering, etc., nuclei are generated in the initial stage of thin film formation, and island-shaped fine particles, which are discontinuous thin films, are formed through the growth thereof. Channeling is achieved by the growth of island-like fine particles, and finally, it grows into a continuous thin film by increasing the channeling.

When manufacturing the thin film, it is possible to control the size and spacing of the fine particles in the form of islands by adjusting pressure, film formation speed, temperature, applied power, and the like, and the non-conductive coating applied to mobile phones in recent years uses materials such as indium or tin. It is made of fine particles in the form of a protective coating on it, but the metal thin film on the naked eye, but in fact, island-like fine particles are not connected to each other, so that they are not electrically connected to pass radio frequency waves in the communication band.

Thus, by using the island-like fine particles used in non-conductive coating or the like as a mask without using electron beam lithography technology, nano-size masks can be randomly manufactured on the surface of the substrate easily and inexpensively.

Various metals may be used to prepare the island-like fine particles, but it is preferable to coat a low melting point metal. In general, when a high melting point metal such as silver or gold is used, even though the thin film is as thin as 10 nm, it grows into a continuous thin film. Therefore, nanoparticles are usually produced by annealing, but the temperature is high. Even after the annealing, it is difficult to process.

Therefore, it is preferable to fabricate island-like fine particles using low melting point metals such as indium, tin, lead, zinc, and aluminum, and aluminum is the highest melting point metal, but is easily formed when formed at an appropriate temperature. Particulates can be formed.

FIG. 5 is a SEM photograph of a thin film state in which film formation is stopped in an island-like fine particle state, and shows a state in which fine particles of several hundred nanometers are formed on the glass surface at intervals of several hundred nanometers. These sizes can be controlled by pressure, film formation speed, temperature, and applied power as described above.

On the other hand, as described above, in one embodiment of the present invention, the substrate may be formed of glass. Even if the substrate is a transparent material, the substrate becomes opaque when the size of the unevenness formed on the surface of the substrate is 400 nm or more.

In this case, the average particle diameter of the metal particles for high permeability and super water repellency is preferably 10 to 1000 nm, but since the wavelength of visible light that can be detected by the human eye is 400 nm to 800 nm, the substrate is a transparent material. In the case of, the average particle diameter of the metal fine particles is preferably 10 to 400 nm, more preferably 200 nm or less.

In addition, in order to achieve high permeability and super water repellency, the average spacing between the metal fine particles is preferably 20 to 2000 nm, and the shape of the metal fine particles formed on the surface of the substrate has a volume ratio between the substrate side and the atmosphere side (Surface-area-to). It is preferable that it is a weight shape which -volume ratio) changes continuously.

After forming the island-like fine particles, the substrate is used to etch (etch) the mask, wherein the etching may use a reactive etching method using an etching gas. Since the island-type fine particles used as a mask can be removed by a reactive etching process using a suitable gas or a wet process using an etching solution, depending on the material.

In this case, as shown in the photograph of FIG. 5, the nanoparticles are randomly mixed with small ones and large ones, and too small nanoparticles may be etched together when the substrate is etched in a subsequent etching process. It may not be possible to serve as a protective film until it is.

Accordingly, even small particles may be used as a protective film by separately forming an intermediate layer (FIGS. 2 and 4) or by using one or more methods of oxidizing, nitriding and oxynitrating the particles (FIGS. 3 and 4). .

In the method of forming the intermediate layer, when the silicon or polymer having a large difference in the etching ratio from the base glass or plastic according to the type of etching gas is used as the intermediate layer, the island-like fine particles form the protective mask until the intermediate layer is etched. After that, the intermediate layer becomes a new mask and can later etch the substrate to a desired depth, so that even small sized particles can act as a protective mask.

In the method of oxidizing, nitriding, and oxynitriding particles, oxidizing, nitriding, and oxynitriding the island-like fine particles through plasma treatment increases resistance to etch, so that even small-sized particles can sufficiently serve as a protective mask until the etching completion stage. It becomes possible.

6, 7, and 8 are cross-sectional views illustrating a process of forming nanostructures according to the flowchart of FIG. 4, and FIG. 6 is a step of dry etching the intermediate layer using the fine particles of islands of oxidized, nitrided, and oxynitride as a protective mask. P150) is shown. Here, in the dry etching process applied, etching is preferably performed using an etching gas having a high etching selectivity for the protective mask and the intermediate layer.

In the intermediate layer etching step (P150), when the intermediate layer is silicon, the etching ratio of silicon is higher than that of glass as the etching gas CCl ₄ / Ar, SiF ₄ / Ar, CF ₄ / O ₂ , C ₂ ClF ₃ , C ₂ F ₄ / CF ₃ One of Cl, C ₂ F ₄ / Cl ₂ , CF ₃ Cl can be used.

Figure 7 shows the step of etching the substrate after the intermediate layer etching, the remaining fine particles and the intermediate layer acts as a protective mask, the etching ratio of the glass etch ratio higher than the silicon of the intermediate layer C ₂ F ₄ , CF ₄ / H ₂ , CHF ₃ / CO ₂ , C ₂ F ₄ / CHF ₃ / He can be used. In addition, when the substrate is plastic, the substrate etching step uses Ar / CF ₄ / Ar mixed gas or H ₂ The gas mixed with the gas may be used to etch the plastic substrate.

If the substrate is glass, the polymer may be formed using PECVD as an intermediate layer. The polymer may be etched using an Ar / CF ₄ / O ₂ mixed gas as a protective film using island-shaped fine particles formed on the polymer by removing the polymer as an intermediate layer. Thereafter, to etch the glass, one of C ₂ F ₄ , CF ₄ / H ₂ , CHF ₃ / CO ₂ , and C ₂ F ₄ / CHF ₃ / He may be used as an etching gas.

Then, as shown in FIG. 8, in order to remove the island-like fine particles or the intermediate layer remaining after the substrate etching step, an appropriate gas or a solution may be used to dissolve the metal fine particles or to remove the intermediate layer silicon or polymer.

If the fine particles in the form of islands are not completely removed, the fine particles are pure low melting point metals or their oxidized, nitrided, or oxynitrided materials.The dry etching process, for example, CCl ₄ He, CCl ₄ , BCl ₃ can be removed using a gas or the like.

When the gas is removed, if the intermediate layer is silicon, the remaining silicon may be removed using the etching gas used in the intermediate layer etching step, and even the polymer may be removed by an O ₂ plasma ashing process.

In the case of removing the residue with a solution, for example, when indium or aluminum is used as the island-like particulate material, indium is a solution of HNO ₃ : HCl 2: 1 and aluminum is H ₃ PO ₄ : NHO ₃ : HC ₂ H ₃ O ₂ : H ₂ O can be removed using a solution with 80: 5: 5: 10. Alternatively, when fine particles of indium or aluminum are oxidized, the fine particles can be removed using an ITO etching solution or a H ₃ PO ₄ solution.

When silicon is used as the intermediate layer, KOH or NHO ₃ : HC ₂ H ₃ O ₂ : HF can be removed with a 20: 20: 1 to 20: 80: 1 solution. In the case where the intermediate layer is a polymer, it can be easily removed with a piranha solution or an organic solvent.

On the other hand, when the base material is formed of a glass material, even if fine irregularities are formed on the surface due to the inherent properties of the glass material, it will exhibit hydrophilicity that is easily combined with water molecules. Therefore, in the present invention, by coating the surface of the substrate formed of a glass material with a fluorine compound, it is possible to implement a super water-repellent surface. Even when the substrate is plastic, when the substrate is free of fluorine, it is preferable to coat the fluorine compound to impart super water repellency.

Here, the fluorine compound has a property to be coated on an object to lower the surface energy to exhibit water repellency, and the surface of the substrate coated with the fluorine compound is (CF3-), (-(CF2-CF2) n-,- (O (CF2) m) n-,-((CF2) mO) n-,-(OC (CF3) FCF2) n- and-(C (CF3) FCF2O) n-, preferably at least one of M is 1 or more and 25 or less and n is 1 or more and 100 or less.

In addition, the method of coating the fluorine compound on the surface of the substrate is a dip coating for dipping the substrate in a solution in which the fluorine compound is dissolved and taking it out at a speed of 10 mm / min, or after dropping the solution on the substrate, the substrate is subjected to 3000 rpm. A method such as spin coating that rotates for 1 minute at a rotational speed may be used.

Alternatively, the fluorine compound may be vaporized into a plasma state in the plasma chamber, and free radicals formed on the surface of the fluorine compound may be coated by graft polymerization on a substrate exposed to the plasma, or may be coated by surface modification of the fluorine compound using plasma. .

On the other hand, the manufacturing method of the surface of the nanostructure according to the embodiment of the present invention can achieve the object of the present invention by one side treatment, but more preferably by treating the other side of the substrate when the substrate is an optical element It is possible to maximize the transmittance of the substrate.

Hereinafter, look at an embodiment of the nanostructure forming method of the present invention. However, the scope of the present invention is not limited to the following preferred embodiments, and a person skilled in the art can carry out various modifications of the contents described in the present invention within the scope of the present invention.

Example 1

The glass was used as a substrate and 10 nm sputter-coated silicon as an intermediate layer on one side, and indium was coated on the silicon. Indium oxide was oxidized by an oxygen plasma treatment in a reactive etching process, and silicon interlayer was etched using CF ₄ / O ₂ as a silicon etching gas.

In order to etch the glass, the etching gas was etched using CF ₄ / Ar for 1 minute, indium oxide was removed using a commercially available ITO etching solution, and rinsed to remove silicon using a KOH 30% solution. By vaporizing evaporation in an electron beam device, a fluorine compound was coated on the surface of the nanostructure to form a nanostructure on one side of the glass.

As can be seen in Figure 9, the produced glass has a conventional reflectance is reduced and the optical transmittance was increased from 91.0% to 94.0% at 550nm wavelength optically improved and the contact angle of water droplets was also increased to 160 degrees from the conventional 35 degrees to show super water repellency.

[Example 2]

As a substrate, a plastic (a transparent acrylic sheet or an injection molded product coated with UV curable resin on the surface), which is generally used for a mobile phone sight glass, was used, and nanostructures were formed on one side of the substrate by the same process as in Example 1. The plastic surface on which the nanostructures were formed showed super water repellency and the transmittance was increased by the reflection reduction effect.

[Example 3]

As the substrate, a plastic (a polycarbonate opaque injection molded surface coated with a UV curable resin or a thermosetting resin) commonly used in a cell phone case was used and coated with indium. In the reactive etching treatment process, indium was oxidized by oxygen plasma treatment, and the plastic substrate was etched by the Ar / CF ₄ / O ₂ mixed gas, and changed to BCl ₃ gas to remove the remaining indium oxide.

By vaporizing evaporation in the electron beam equipment by coating a fluorine compound on the surface of the nanostructures to form a nanostructure on one side of the substrate. The plastic surface on which the nanostructures were formed showed super water repellency and the transmittance was increased by the reflection reduction effect.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It is to be understood that various modifications and changes may be made without departing from the scope of the appended claims.

Claims

i) forming fine metal particles in island form on the surface of the substrate;
Ii) etching the substrate surface using the island-like metal particles as a protective mask; And
Iii) removing metal particulates remaining on the etched substrate surface;
Including but not limited to:
The metal structure is a nanostructure forming method for implementing a high translucent, super water-repellent surface, characterized in that made of any one of the low melting point metal, indium, tin, lead, zinc and aluminum.

The method of claim 1,
And forming the island-like metal particles on the surface of the substrate, and then oxidizing, nitriding or oxynitrating the island-shaped metal particles.

The method of claim 1,
The method of claim 1, wherein the island-like metal particles are discontinuous thin films formed on the surface of the substrate by physical vapor deposition (PVD).

The method of claim 1,
The method of claim 1, further comprising coating a fluorine compound on the surface of the substrate from which the metal fine particles have been removed.

5. The method of claim 4,
Chemical formulas of the fluorine compounds are (CF _3- ), (-(CF ₂ -CF ₂ ) n-,-(O (CF ₂ ) m) n-,-((CF ₂ ) mO) n-,-(OC (CF ₃ ) FCF ₂ ) n- and-(C (CF ₃ ) FCF ₂ O) n- comprising one or more of the method for forming nanostructures for realizing a highly translucent, super water-repellent surface.
(Said m is 1-25, and said n is 1-100.)

delete

The method of claim 1,
Method for forming a nanostructure for implementing a high translucent, super water-repellent surface, characterized in that the average particle diameter of the metal fine particles 10 ~ 1000nm.

The method of claim 1,
When the substrate is a transparent material, the nanostructure formation method for implementing a high translucent, super water-repellent surface, characterized in that the average particle diameter of the metal fine particles 10 ~ 400nm.

The method of claim 1,
The nanostructure forming method for implementing a high translucent, super water-repellent surface, characterized in that the average spacing between the metal particles 20 ~ 2000nm.

The method of claim 1,
Nano-structure for forming a highly translucent, super water-repellent surface, characterized in that the shape of the metal particles formed on the surface of the substrate is a weight that continuously changes the surface-area-to-volume ratio between the substrate side and the atmosphere side Method of forming the structure.

The method of claim 1,
The nanostructure forming method for implementing a high translucent, super water-repellent surface, characterized in that both nanostructures are formed on both surfaces of the substrate.

i) forming an intermediate layer on the surface of the substrate;
Ii) forming metal fine particles in island form on the surface of the substrate on which the intermediate layer is formed;
Iii) etching the intermediate surface using the island-like metal fine particles as a protective mask;
Iii) etching the surface of the substrate using the intermediate and island-shaped metal particles remaining after the etching as a protective mask;
Iii) removing metal particulates remaining on the etched substrate surface; And
Iii) removing intermediates remaining on the etched substrate surface;
Including but not limited to:
The metal structure is a nanostructure forming method for implementing a high translucent, super water-repellent surface, characterized in that made of any one of the low melting point metal, indium, tin, lead, zinc and aluminum.

The method of claim 12,
After forming the island-shaped metal particles on the surface of the intermediate layer is formed, and further comprising the step of oxidizing, nitriding or oxynitizing the island-shaped metal particles nanostructures for implementing a high translucent, super water-repellent surface Forming method.

The method of claim 12,
The island-shaped metal microparticles forming method is characterized in that the discontinuous thin film formed on the surface of the substrate by physical vapor deposition (PVD) nanostructure formation method for implementing a high translucent, super water-repellent surface.

The method of claim 12,
Method for forming a nanostructure for implementing a high translucent, super water-repellent surface, characterized in that the intermediate is made of silicon or polymer.

The method of claim 12,
The method of claim 1, further comprising coating a fluorine compound on the substrate surface from which the metal fine particles and intermediates are removed.

17. The method of claim 16,
Chemical formulas of the fluorine compounds are (CF _3- ), (-(CF ₂ -CF ₂ ) n-,-(O (CF ₂ ) m) n-,-((CF ₂ ) mO) n-,-(OC (CF ₃ ) FCF ₂ ) n- and-(C (CF ₃ ) FCF ₂ O) n- comprising one or more of the method for forming nanostructures for realizing a highly translucent, super water-repellent surface.
(Said m is 1-25, and said n is 1-100.)

delete

The method of claim 12,
Method for forming a nanostructure for implementing a high translucent, super water-repellent surface, characterized in that the average particle diameter of the metal fine particles 10 ~ 1000nm.

The method of claim 12,
When the substrate is a transparent material, the nanostructure formation method for implementing a high translucent, super water-repellent surface, characterized in that the average particle diameter of the metal fine particles 10 ~ 400nm.

The method of claim 12,
The nanostructure forming method for implementing a high translucent, super water-repellent surface, characterized in that the average spacing between the metal particles 20 ~ 2000nm.

The method of claim 12,
Forming nanostructures for implementing a highly translucent, super water-repellent surface, characterized in that the weight ratio of the surface-area-to-volume ratio of the substrate side and the atmosphere side of the metal particles formed on the substrate surface continuously change Way.

The method of claim 12,
The nanostructure forming method for implementing a high translucent, super water-repellent surface, characterized in that both nanostructures are formed on both surfaces of the substrate.

A highly translucent, super water-repellent surface having a nanostructure formed by the method of any one of claims 1 to 5, 7 to 17 and 19 to 23.