KR20110070530A - Patterning method for nano-structure - Google Patents

Abstract

PURPOSE: A nanostructure patterning method is provided to give hybrid functions of collecting and dehumidifying water to a surface of a substrate by combining a colloidal lithography and a printing technique or a tape masking technique and by arraying nanostructures to a specific location. CONSTITUTION: The nanostructure patterning method includes following steps.(a) The colloidal particle single-layer film is coated in the surface of the substrate.(b) Except a pattern section of the substrate, the rest of surface is masked.(c) The masked substrate is etched and the nanostructures are formed in the pattern part. And(d) the masking formed on the substrate is eliminated. The step(a) is operated by more than one method selected among a spin-coating, a dip-coating, a lifting up, an electrophoretic deposition, a chemical or electrochemical deposition and an electrospray.

Description

Patterning Method for Nano-Structure

The present invention relates to a method for patterning nanostructures, and more particularly, to a technique for partially patterning nanostructures using colloidal lithography, which can be applied to produce superficial or superhydrophilic functional surfaces. It is about how it can be.

In general, colloidal lithography is an easy and economical lithography method of bottom-up, top-down, or a combination thereof that can produce various nanostructures, and is a method of making nanostructures by etching a substrate using colloidal particles as a mask. However, examples of selectively coating colloidal particles or selectively etching a substrate have not been published, and thus, it is difficult to selectively pattern nanostructures on the surface of the substrate and is still limited in widespread application.

Therefore, if nanopatterning is performed by inexpensive colloidal lithography, and the nanostructure can be patterned only on the desired area, it can be used in various applications. Particularly, the application of nanostructures partially superhydrophilic or superhydrophobic By regulating the water trapping function of the desert beetle shell, it captures water vapor in the air to solve the water shortage problem, improve the function when printing or function printing using printing technology, or improve the flow of fluid in the biochip. It can be useful to adjust.

There are several ways to pattern nanostructures, including nanoimprint lithography, soft lithography, e-beam lithography, and focused ion beams (FIB). Nanoimprint lithography (NIL) technology is an economical and effective technique for producing nanostructures. Spin-coating or dispensing a stamp on which a nanostructure is imprinted is applied onto a substrate. It is a technique for transferring nanostructures by pressing them on the surface of a dispensed resist. Soft lithography technology is similar to nanoimprint lithography technology, except that the stamp used in nanoimprint lithography is made of a hard material, whereas in soft lithography technology, a soft mold is used. E-beam lithography is a technique of forming a nanostructure through plasma etching after partially curing a resist coated with an e-beam having an energy of several tens of keV on a substrate. Focused ion beam (FIB) is a technology that forms nanostructures by directly cutting substrates with high-energy ion beams.

However, in the case of nanoimprint lithography, there is a disadvantage in that it is easy to manufacture a nanoscale pattern, but it is expensive to manufacture a stamp in which a pattern is formed, whereas in the case of soft lithography, there is a problem in that a nanoscale pattern cannot be produced. In addition, the e-beam lithography technology and the FIB technology require expensive equipment and have a long time in forming the structure.

First of all, in the past, when forming a nanostructure on a substrate in general, there was little use of the technology to the extent that it gives only simple functions such as water repellent treatment or hydrophilic treatment. Accordingly, there is an urgent need for research on surface modification techniques that can perform new functions such as water collection, which are more advanced than simple functions such as water repellency or hydrophilicity.

Accordingly, the present invention has been made to solve the problems of the prior art as described above, the object of the present invention is to combine the economic colloidal lithography and printing techniques or tape masking techniques to align the nanostructures in a specific location water repellency Another object of the present invention is to provide a simple nanostructure patterning method for treating a surface of a substrate to perform a complex function such as moisture capture and dehumidification, rather than a simple function such as hydrophilicity.

Nanostructure patterning method according to the present invention for achieving the object as described above, the colloidal particle monolayer coating step of coating a colloidal particle monolayer film on the surface of the substrate (1); A masking step of masking (3) the surface of the portion except for the pattern (2) region of the substrate (1); Forming a nanostructure on the pattern (2) by etching the masked substrate (1); A masking removing step of removing the masking (3) formed on the substrate (1); Characterized in that comprises a.

Or, the nanostructure patterning method according to the present invention, the colloidal particle monolayer coating step of coating a colloidal particle monolayer film on the surface of the substrate (1); A masking step of masking (3) the surface of the portion except for the pattern (2) region of the substrate (1); Forming a nanostructure on the pattern (2) by etching the masked substrate (1); A surface treatment step of performing a surface treatment of the pattern (2) region in which a nanostructure is formed; A masking removing step of removing the masking (3) formed on the substrate (1); Characterized in that comprises a.

Or, the nanostructure patterning method according to the present invention, the colloidal particle monolayer coating step of coating a colloidal particle monolayer film on the surface of the substrate (1); Forming a nanostructure by etching the substrate (1); A masking step of masking (3) the surface of the portion except for the pattern (2) region of the substrate (1); A surface treatment step of performing a surface treatment of the pattern (2) region in which a nanostructure is formed and masking is performed; A masking removing step of removing the masking (3) formed on the substrate (1); Characterized in that comprises a.

In this case, the colloidal particle monolayer coating step is spin-coating, dip-coating, lifting up, electrophoretic deposition, chemical or electrochemical coating ( coating the surface of the substrate by at least one method selected from chemical or electrochemical deposition and electrospray; It is preferable that it consists of.

In this case, the masking step may include attaching a masking tape to a surface of a portion excluding the region of the pattern 2 of the substrate 1; Or printing with masking ink on the surface of the portion except for the pattern 2 region of the substrate 1; It is preferable that it consists of at least one selected from among.

In this case, the nanostructure forming step, CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₆ , C ₃ F ₈ , C ₄ F ₁₀ , HF, HBr, SF ₆ , NF ₃ , SiCl ₄ , Performing dry etching using at least one etching gas selected from SiF ₄ , BCl ₃ , CCl ₄ , CClF ₃ , CCl ₂ F ₂ , C ₂ ClF ₅ , and O ₂ ; It is preferable that it consists of.

In this case, the masking removing step, ethanol, methanol, isopropyl alcohol ((CH ₃ ) ₂ CHOH), acetone, hexane, dimethyl fluoride (DMF), trichloroethane (C ₂ HCl ₃ ), trichloro Selecting and soaking one or more of methane to perform washing or ultrasonic cleaning; O ₂ plasma treatment step; Or a Piranha solution (H ₂ SO ₄ : H ₂ O ₂ ) treatment step; Dilute HF solution steam treatment step; It is preferable that it consists of at least one selected from among.

At this time, the surface treatment step, the step of performing a water repellent treatment on the substrate (1); Or performing a hydrophilic treatment on the substrate (1); It is preferable that it consists of at least one selected from among.

At this time, the surface treatment step is to perform the water-repellent treatment to the substrate (1), dip coating, spin coating, self-assembled monolayer treatment method of the fluorine silane compound, atom transfer of fluorinated monomer Surface polymerization method using Atom transfer radical polymerization method, grafting-from surface polymerization method of fluorine monomer, grafting-to surface polymerization method of fluorine compound, plasma Using at least one method selected from a surface polymerization method of a fluorine compound and a surface modification method of a fluorine compound using plasma; It is preferable to comprise a.

Alternatively, the surface treatment step is to perform a hydrophilic treatment to the substrate 1, O ₂ plasma treatment or ultraviolet ozone (Ultra-visible Ozone) treatment, or in order to give a photocatalytic effect TiO ₂ or ZnO and other hydrophilic materials Using at least one selected from a sol-gel method, a sputtering method, an electron beam deposition method, and a thermal depostion method; It is preferable to comprise a.

According to the present invention, the treatment of the surface of the substrate to impart a certain function, unlike the conventionally only providing a simple function such as water repellency or hydrophilicity, it is possible to give a complex function such as water collection There is. Specifically, according to the present invention, the water-repellent or hydrophilic region is formed on a part of the substrate rather than the entire surface of the substrate in a pattern form, and thus various functions can be provided according to the pattern form, pattern range, pattern material, and the like. Accordingly, according to the present invention, since the nanostructure can be formed as desired, there is also an effect that the improvement or conversion of the function to be given is much easier.

Hereinafter, a nanostructure patterning method according to the present invention having the configuration as described above will be described in detail with reference to the accompanying drawings.

1 is a flow chart of a nanostructure patterning method according to the present invention, Figure 2 is a schematic diagram of the substrate and masking patterned nanostructures according to the present invention, Figure 3 is a schematic diagram of the patterning step. As shown in Figure 1 (A), the nanostructure patterning method of the present invention comprises a colloidal particle monolayer coating step; Masking step; Forming a nanostructure; And a masking removal step. At this time, as shown in Figure 1 (B) it can be made by further comprising a surface treatment step before the masking removal step. Each step will be described in more detail below.

In the colloidal particle monolayer coating step, the colloidal particles are spin-coated, dip-coated, lifting up, electrophoretic deposition, chemical or electrochemical coating ( It is preferably arranged on the surface of the substrate by any one or more methods selected from chemical or electrochemical deposition and electrospray.

In the masking step, masking 3 is performed on the surface of the portion except for the pattern region 2 in which the nanostructure of the substrate 1 is to be formed. In this case, the masking step may include attaching a masking tape to a surface of a portion excluding the region of the pattern 2 of the substrate 1; Or printing with masking ink on the surface of the portion except for the pattern 2 region of the substrate 1; It may be made by a combination of the above-described methods (masking tape attached / masking ink printing). For smooth printing of the masking ink, the energy of the surface of the substrate 1 coated with the colloidal monolayer film can be controlled by treatment with plasma or a self-assembled monolayer film. As described above, by masking an area excluding the pattern 2 on the surface of the substrate 1, a subsequent nanostructure formation or surface treatment is performed at the portion of the pattern 2.

The material used for the masking 3 may use any kind of tape that can be easily obtained, and can be implemented by cutting and pasting the tape to a desired size. In addition, masking can be performed by printing at a desired line width using one or more methods selected from office inkjet printers and commercial printing methods such as inkjet printing, gravure offset printing, gravure printing, flexo offset printing, flexo printing, and silk screen. have.

In addition, the function provided to the substrate 1 may vary depending on the shape of the pattern 2. The pattern 2 may have various shapes such as lines, circles, squares, polygons, or letters according to a designer's intention, and the minimum size of the pattern is determined by the size of the printing nozzle in the case of inkjet printing. For example, when the substrate 1 exhibits a water collection function, the hydrophilic pattern should collect water and the hydrophobic pattern should flow to the collected area. In this case, therefore, it is advantageous to ensure that the hydrophilic pattern is in the shape of circles and polygons so that the hydrophilic pattern is isolated by the hydrophobic pattern, and that the hydrophobic pattern is present in a linear form around it.

Next, in the nanostructure forming step, a nanostructure is formed on the masked substrate 1 by using colloidal lithography. When the surface is etched using the colloidal monolayer as a mask to form a nanostructure, the etching method may use dry etching using an etching gas. In addition, the substrate is preferably any one of glass, quartz plate, silicon, and plastic. Etching gases that can be used for the dry etching are CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₆ , C ₃ F ₈ , C ₄ F ₁₀ , HF, HBr, SF ₆ , NF ₃ , SiCl ₄ , SiF ₄ , BCl ₃ , CCl ₄ , CClF ₃ , CCl ₂ F ₂ , C ₂ ClF _{5 It} may be any one or more selected from Ar, O ₂ , it is preferable to mix H ₂ gas.

As shown in FIG. 1 (A), after the colloidal particle monolayer coating step, the masking step, and the nanostructure forming step are performed, a portion of the substrate 1 covered by the masking 3 is disposed on the surface of the substrate 1. While the original material of the surface remains, an array of nanostructures is formed in the pattern 2 region.

Subsequently, when the masking 3 formed on the substrate 1 on which the pattern 2 region is surface-treated is removed in the masking removing step, the substrate 1 having the nanostructure patterned at a desired position can be obtained. In the masking removing step, one or more of ethanol, methanol, isopropyl alcohol ((CH ₃ ) ₂ CHOH), acetone, hexane, dimethyl fluoride (DMF), trichloroethane (C ₂ HCl ₃ ), trichloromethane It is preferable to select and soak to perform washing or ultrasonic cleaning. If necessary, the surface may be cleaned by performing O ₂ plasma treatment, immersing Piranha solution (H ₂ SO ₄ : H ₂ O ₂ ), or applying a vapor of a moderately diluted HF solution.

A surface treatment step of treating the surface of the substrate 1 before the masking removing step to impart a function to the patterned nanostructure as shown in FIG. It can be performed including more. The surface treatment method performed in the surface treatment step depends on the function to be imparted to the substrate 1, for example, the surface treatment method may be a water repellent treatment, or may be a hydrophilic treatment. In order to smoothly perform the surface treatment, it is preferable to perform O ₂ plasma or ultraviolet ozone treatment.

When the surface treatment method is water repellent, the surface treatment step, it is preferable to coat a fluorine compound. The surface of the pattern coated with the fluorine compound is (CF _3- ), (-(CF ₂ -CF ₂ ) _n -,-(O (CF ₂ ) _m ) _n -,-((CF ₂ ) _m O) _n -,-(OC (CF ₃ ) FCF ₂ ) _n -and-(C (CF ₃ ) FCF ₂ O) _n- ( _where 1≤m≤25, 1≤n≤100). Here, m is 1 or more and 25 or less, and n is 1 or more and 100 or less.

In addition, the fluorine compound coating step, dip coating, spin coating, self-assembled monolayer treatment method of the fluorine silane compound, Atom transfer radical polymerization method of the fluorine monomer Surface polymerization method, grafting-from surface polymerization method of fluorinated monomer, grafting-to surface polymerization method of fluorine compound, surface polymerization method of fluorine compound using plasma and plasma It is preferable to use any one or more of the surface modification of the fluorine compound used.

If the surface treatment is a hydrophilic surface treatment step, O ₂ plasma treatment or UV ozone (Ozone Ultra-visible), or the treatment, the TiO ₂ or ZnO, and other hydrophilic materials in order to impart a photocatalytic effect the sol-gel (Sol- It is preferable to use any one or more methods of vapor deposition using any one of a gel method, a sputtering method, an electron beam deposition method, and a thermal depostion method. The masking removal step after the surface treatment step is ethanol, methanol, isopropyl alcohol ((CH ₃ ) ₂ CHOH), acetone, hexane, dimethyl fluoride (DMF), trichloroethane (C ₂ HCl ₃ ), trichloromethane It is preferable to soak one or more of them, or to perform ultrasonic cleaning. Alternatively, it may be immersed in a Piranha solution or steamed with dilute HF solution, if necessary.

In addition, as shown in FIG. 1C, the nanostructures are first formed to form nanostructures in all areas of the substrate 1, and then the masking step is followed by the surface treatment step. The pattern 2 of nanostructures having different chemical functions and properties on the surface may be formed in different sizes and shapes according to the designer's intention. This method eliminates the difference in the optical properties of the pattern (2) and the masked part (3) of the substrate caused by the presence of nanostructures in only a few parts, thereby making the optical application of the substrate 1 more versatile. There is this.

In the method shown in FIG. 1C, after the nanostructure forming step, the surface treatment is performed, the masking step is performed, and the surface treatment material of the pattern (2) portion is subjected to O ₂ plasma treatment or ultraviolet ozone (Ultraviolet Ozone) treatment. Eliminating, after surface treatment of different properties; It can be modified and executed by. This method also eliminates differences in the optical properties of the patterned (2) and masked (3) portions of the substrate, as well as the nanostructures in both the patterned (2) and masked (3) portions. This presence has the advantage of further maximizing the difference in surface properties of the two parts.

As described above, according to the present invention, the properties of the (substrate / pattern) may be variously formed such as (flat / water repellent), (flat / hydrophilic), (water repellent / hydrophilic), (hydrophilic / water repellent), and the masking. According to (3), the shape, size, arrangement and the like of the pattern 2 can be easily formed as the designer intends. Accordingly, according to the nanostructure patterning method of the present invention, it is possible to easily give the substrate 1 a complex function desired by the designer.

The present invention is not limited to the above-described embodiments, and the scope of application of the present invention is not limited to those of ordinary skill in the art to which the present invention pertains without departing from the gist of the present invention as claimed in the claims. Of course, various modifications can be made.

1 is a step flowchart of a patterning method according to the present invention;

2 is a schematic diagram of a substrate and masking patterned nanostructures according to the present invention.

3 is a schematic diagram of a patterning step.

4 is an electron micrograph in which nanostructures are patterned.

5 is an actual photograph of a substrate patterned nanostructures.

Figure 6 is a photograph of forming a superhydrophilic / ultra-small pattern after patterning the nanostructures using ink.

Claims (10)

A colloidal particle monolayer film coating step of coating a colloidal particle monolayer film on a surface of the substrate 1; A masking step of masking (3) the surface of the portion except for the pattern (2) region of the substrate (1); Forming a nanostructure on the pattern (2) by etching the masked substrate (1); A masking removing step of removing the masking (3) formed on the substrate (1); Nanostructure patterning method comprising a. A colloidal particle monolayer film coating step of coating a colloidal particle monolayer film on a surface of the substrate 1; A masking step of masking (3) the surface of the portion except for the pattern (2) region of the substrate (1); Forming a nanostructure on the pattern (2) by etching the masked substrate (1); A surface treatment step of performing a surface treatment of the pattern (2) region in which a nanostructure is formed; A masking removing step of removing the masking (3) formed on the substrate (1); Nanostructure patterning method comprising a. A colloidal particle monolayer film coating step of coating a colloidal particle monolayer film on a surface of the substrate 1; Forming a nanostructure by etching the substrate (1); A masking step of masking (3) the surface of the portion except for the pattern (2) region of the substrate (1); A surface treatment step of performing a surface treatment of the pattern (2) region in which a nanostructure is formed and masking is performed; A masking removing step of removing the masking (3) formed on the substrate (1); Nanostructure patterning method comprising a. According to any one of claims 1 to 3, wherein the colloidal particle monolayer coating step Selected from spin-coating, dip-coating, lifting up, electrophoretic deposition, chemical or electrochemical deposition, and electrospray Coating the surface of the substrate in any one or more ways; Nanostructure patterning method, characterized in that consisting of. The method according to any one of claims 1 to 3, wherein the masking step Attaching a masking tape to the surface of the portion except for the pattern 2 region of the substrate 1; Or printing with masking ink on the surface of the portion except for the pattern 2 region of the substrate 1; Nanostructure patterning method comprising any one or more selected from. According to any one of claims 1 to 3, wherein forming the nanostructures is CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₆ , C ₃ F ₈ , C ₄ F ₁₀ , HF, HBr, SF ₆ , NF ₃ , SiCl ₄ , SiF ₄ , BCl ₃ , CCl ₄ , CClF ₃ Performing dry etching using at least one etching gas selected from CCl ₂ F ₂ , C ₂ ClF ₅ , and O ₂ ; Nanostructure patterning method, characterized in that consisting of. The method according to any one of claims 1 to 3, wherein the masking removing step Wash by dipping one or more of ethanol, methanol, isopropyl alcohol ((CH ₃ ) ₂ CHOH), acetone, hexane, dimethyl fluoride (DMF), trichloroethane (C ₂ HCl ₃ ), trichloromethane Performing an ultrasonic cleaning; O ₂ plasma treatment step; Or a Piranha solution (H ₂ SO ₄ : H ₂ O ₂ ) treatment step; Dilute HF solution steam treatment step; Nanostructure patterning method comprising any one or more selected from. The method of any one of claims 1 to 3, wherein the surface treatment step Performing a water repellent treatment on the substrate (1); Or performing a hydrophilic treatment on the substrate (1); Nanostructure patterning method comprising any one or more selected from. The method of claim 8, wherein the surface treatment step Performing a water repellent treatment on the substrate (1), Deep coating, spin coating, self-assembled monolayer treatment of fluorine silane compounds, surface polymerization using atom transfer radical polymerization of fluorinated monomers, fluorinated monomers Selected from a grafting-from surface polymerization method, a grafting-to surface polymerization method of a fluorine compound, a surface polymerization method of a fluorine compound using plasma, and a surface modification method of a fluorine compound using plasma. Using any one or more methods; Nanostructure patterning method comprising a. The method of claim 8, wherein the surface treatment step Performing a hydrophilic treatment on the substrate (1), TiO ₂ or ZnO and other hydrophilic materials may be sol-gel method, sputtering method, electron beam deposition method in order to perform O ₂ plasma treatment or ultra-visible ozone treatment or to give a photocatalytic effect. Using at least one method selected from among electron beam deposition and thermal depostion; Nanostructure patterning method comprising a.

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