KR20220140245A - Method for manufacturing inorganic photonic crystal pattern, and inorganic photonic crystal pattern manufactured by using the same - Google Patents

Abstract

Provided is a method for manufacturing an inorganic photonic crystal pattern, which comprises: a first step of coating flexible particles on a substrate in a form of a close-packed colloidal monolayer; and a second step of applying a solution containing an inorganic precursor to the monolayer to form an inorganic photonic crystal pattern.

Description

Method for manufacturing an inorganic photonic crystal pattern and an inorganic photonic crystal pattern prepared thereby

The present invention relates to a method for manufacturing an inorganic photonic crystal pattern and to an inorganic photonic crystal pattern prepared thereby.

Micro-patterns or nano-patterns have been applied to various industries such as semiconductor industry, electronics industry, medical care, automobiles, solar energy, etc. has been used in various ways.

The most widely applied pattern manufacturing method so far is a lithography method, in which a substrate is etched using a mask having a predetermined pattern and various light sources. The soft lithography method is mainly used when various types of organic and polymer patterns are manufactured using a soft material having a predetermined pattern formed thereon. In the colloid lithography method, various colloids are prepared in the form of close-packed photonic crystals and then produced in a colloidal pattern through etching or the substrate is further etched to form a cone or wire on the substrate. It is used when manufacturing a pattern or structure in the form of a wire.

In the case of polymers and organic patterns, several other alternatives have been proposed in addition to etching and lithography methods so far, but the method for manufacturing inorganic patterns is photolithography using a mask, colloidal, soft pattern, or block copolymer pattern on top. It relied on a so-called top-down method of manufacturing an inorganic pattern by back-etching.

On the other hand, an effective bottom-up method capable of manufacturing an inorganic pattern through a wet process using a solution has not been invented. One of the reasons is a solution containing an inorganic precursor for forming a regular pattern. Alternatively, it is because it is difficult to form a thermodynamic condition in which a solution containing an inorganic material can form a pattern on the substrate.

Since one embodiment proceeds without a lithography process, it does not use equipment that forms a mask and uses an expensive light source, it can form a pattern on a substrate that is easily damaged due to a process such as etching, and the thermodynamics of the solution without special manufacturing equipment A regular photonic crystal pattern can be easily controlled by controlling only the phosphorus properties, and the formed photonic crystal pattern can describe excellent light transmittance due to an anti-reflective effect, and the optical properties of inorganic materials, optical properties by photonic crystals, Provided is a method for manufacturing an inorganic photonic crystal pattern capable of variously changing the surface structure and surface properties.

Another embodiment provides an inorganic photonic crystal pattern prepared by a method for manufacturing an inorganic photonic crystal pattern.

According to one embodiment, the first step of coating the soft particles in the form of a close-packed colloidal monolayer on the substrate, and the first step of forming an inorganic photonic crystal pattern by adding a solution containing an inorganic precursor to the monolayer It provides a method for producing an inorganic photonic crystal pattern, comprising two steps.

The inorganic photonic crystal pattern may be one in which a plurality of inorganic photonic crystal particles are regularly arranged at intervals.

The first step may be accomplished by dispersing the soft particles in a dispersion medium and then self-assembling the soft particles in a regular hexagonal lattice shape.

Soft particles are poly(N-isopropylacrylamide)[poly(N-isopropylacrylamide), pNIPAM], poly(N-isopropyl acrylamide-co-allylamine)[poly(N-isopropyl acrylamide-co-allylamine) , poly(NIPAM-co-AA)], poly(N-isopropylacrylamide-co-2-(dimethylamino)ethyl methacrylate)[poly(N-isopropylacrylamide-co-2-(dimethylamino)ethyl methacrylate) , poly(NIPAM-co-DMAEMA)], poly(N-isopropyl acrylamide-co-2-(dimethylamino)ethyl acrylate)[poly(N-isopropyl acrylamide-co-2-(dimethylamino)ethyl acrylate) , poly(NIPAM-co-DMAEA)], poly(N-isopropyl acrylamide-co-acrylic acid) [poly(N-isopropyl acrylamide-co-acrylic acid), poly(NIPAM-co-AAc)], poly( N-isopropyl acrylamide-co-methacrylic acid) [poly(N-isopropyl acrylamide-co-methacrylic acid), poly(NIPAM-co-MAAc)], poly(N,N-diethylacrylamide) [poly( N,N-diethylacrylamide)], poly(N-vinylcaprolactam)[poly(N-vinlycaprolactam)], poly(ethylene glycol)[poly(ethylene glycol)], poly(ethylene glycol-b-propylene glycol-b -ethylene glycol) [poly(ethylene glycol-b-propylene glycol-b-ethylene glycol)], or a combination thereof.

The dispersion medium may include water, methanol, ethanol, butanol, isopropyl alcohol, tetrahydra furan, dimethylsulfoxide, dimethylformaide, ethylene glycol, glycerol, or a combination thereof.

In the second step, the solution containing the inorganic precursor may contract the soft particles to form a photonic crystal pattern, and the inorganic precursor may be adsorbed on the surface of the photonic crystal particle or penetrated into the photonic crystal particle.

The inorganic precursor is mercaptopropyltrimethoxysilane (MPTMS), mercaptopropyltriethoxysilane (3-mercaptopropyltriethoxysilane), methyltrimethoxysilane (MTMS), triethoxymethylsilane, triethoxymethylsilane Methoxy(1H,1H,2H,2H-heptadecafluorodecyl)silane (1H,1H,2H,2H-heptadecafluorodecyl)silane, vinyltrimethoxysilane, tetraethylorthosilicate ), titanium isopropoxide, aluminum nitrate, or a combination thereof.

The solution containing the inorganic precursor may include different types of inorganic precursors.

The solution containing the inorganic precursor may include a mixed solvent of water and alcohol.

The solution containing the inorganic precursor may include alcohol and water in a molar ratio of 15:85 to 50:50.

The solution including the inorganic precursor may include a catalyst including sodium hydroxide, ammonium hydroxide, or a mixture thereof.

The second step may be made at a temperature of 10° C. or higher and lower than the boiling point of the mixed solvent.

The method of manufacturing the inorganic photonic crystal pattern may further include annealing the inorganic photonic crystal pattern at 120° C. to 150° C. for 1 hour to 2 hours.

According to another embodiment, a substrate and an inorganic photonic crystal pattern on the substrate in which a plurality of inorganic photonic crystal particles are regularly arranged at intervals, wherein the inorganic photonic crystal particles are located on the soft particle and on the surface of the flexible particle or inside the soft particle. It provides an inorganic photonic crystal pattern comprising an inorganic material.

The inorganic material may include silica, organosilica, aluminum oxide, titanium dioxide, or a combination thereof.

The surface of the inorganic photonic crystal particle may include a plurality of protrusions having a size of 1 nm to 50 nm.

The inorganic photonic crystal particles may include a first inorganic material positioned on the surface of the soft particle and a second inorganic material positioned on the surface of the first inorganic material.

The inorganic photonic crystal particles may have a particle diameter of 50 nm to 1000 nm.

The method for manufacturing an inorganic photonic crystal pattern according to an embodiment does not use equipment that forms a mask and uses an expensive light source because it proceeds without a lithography process, and a pattern can be formed even on a substrate that is easily damaged due to a process such as etching. In addition, a regular photonic crystal pattern can be easily controlled by adjusting only the thermodynamic properties of the solution without special manufacturing equipment, and the formed photonic crystal pattern can describe excellent light transmittance due to an anti-reflective effect, and inorganic materials The optical properties, the surface structure and the surface properties can be variously changed by the optical properties and photonic crystals.

1 is a diagram schematically illustrating a method of manufacturing an inorganic photonic crystal pattern according to an embodiment.
FIG. 2 is an electron micrograph showing a process of forming an inorganic photonic crystal pattern in Example 1. FIG.
3(A) is an electron micrograph of the inorganic photonic crystal pattern prepared in Example 2(A), and FIG. 3(B) is an electron micrograph of the inorganic photonic crystal pattern prepared in Example 2(B).
4 is a graph showing the light transmittance (Transmittance) of the inorganic photonic crystal pattern prepared in Example 2 (B).
5 (A) and 5 (B) are electron micrographs of the inorganic photonic crystal pattern prepared in Example 3.
6 is an electron micrograph of the inorganic photonic crystal pattern prepared in Example 4 (A).
7 is an electron micrograph of the inorganic photonic crystal pattern prepared in Example 4 (B).
8 is a graph showing the light transmittance of the inorganic photonic crystal pattern prepared in Example 4 (A).

Advantages and features of the techniques described hereinafter, and methods of achieving them, will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the implemented form may not be limited to the embodiments disclosed below. Unless otherwise defined, all terms (including technical and scientific terms) used herein may be used with meanings commonly understood by those of ordinary skill in the art. In addition, terms defined in a commonly used dictionary are not to be interpreted ideally or excessively unless clearly defined in particular. In the entire specification, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

The singular also includes the plural, unless the phrase specifically dictates otherwise.

The method of manufacturing an inorganic photonic crystal pattern according to an embodiment includes a first step of coating soft particles in the form of a close-packed colloidal monolayer on a substrate, and adding a solution containing an inorganic precursor to the monolayer, and a second step of forming an inorganic photonic crystal pattern.

1 is a diagram schematically illustrating a method of manufacturing an inorganic photonic crystal pattern according to an embodiment. Referring to FIG. 1 , a method of manufacturing an inorganic photonic crystal pattern will be described in detail.

In a first step, the soft particles 121 are coated on the substrate 110 in the form of a dense monolayer 120 (close-packed colloidal monolayer).

The substrate 110 is not particularly limited in the present invention, and for example, a silicon wafer, silicon/silicon oxide material glass, quartz cover glass, indium tin oxide, ZnO, or a metal oxide layer such as TiO ₂ . , poly (dimethylsiloxane) (poly (dimethylsiloxane)), polyethylene (polyethylene), polypropylene (polypropylene), poly (methyl methacrylate) (poly (methylmethacrylate)), polystyrene (polystyrene), poly (ethylene terephthalate) ( Poly(ethylene terephtalate)), polycarbonate, or a polymer substrate such as a copolymer thereof may be used.

Specifically, the first step may be accomplished by dispersing the soft particles 121 in a dispersion medium and then self-assembling the soft particles 121 in a regular hexagonal lattice shape.

The soft particles 121 may be polymer particles including hydrogel particles that can be dispersed by swelling in water or alcohol. For example, the soft particles 121 may include poly(N-isopropylacrylamide) [poly(N-isopropylacrylamide), pNIPAM], poly(N-isopropyl acrylamide-co-allylamine) [poly(N-isopropyl) acrylamide-co-allylamine), poly(NIPAM-co-AA)], poly(N-isopropylacrylamide-co-2-(dimethylamino)ethyl methacrylate)[poly(N-isopropylacrylamide-co-2- (dimethylamino)ethyl methacrylate), poly(NIPAM-co-DMAEMA)], poly(N-isopropyl acrylamide-co-2-(dimethylamino)ethyl acrylate)[poly(N-isopropyl acrylamide-co-2- (dimethylamino)ethyl acrylate), poly(NIPAM-co-DMAEA)], poly(N-isopropyl acrylamide-co-acrylic acid) [poly(N-isopropyl acrylamide-co-acrylic acid), poly(NIPAM-co-) AAc)], poly(N-isopropyl acrylamide-co-methacrylic acid) [poly(N-isopropyl acrylamide-co-methacrylic acid), poly(NIPAM-co-MAAc)], poly(N,N-diethyl acrylamide)[poly(N,N-diethylacrylamide)], poly(N-vinylcaprolactam)[poly(N-vinlycaprolactam)], poly(ethylene glycol)[poly(ethylene glycol)], poly(ethylene glycol- b-propylene glycol-b-ethylene glycol) [poly(ethylene glycol-b-propylene glycol-b-ethylene glycol)], or a combination thereof.

Any dispersion medium may be used as long as it can swell or stably disperse the soft particles 121 including the hydrogel particles without agglomeration and does not dissolve them. For example, the dispersion medium may include water, methanol, ethanol, butanol, isopropyl alcohol, tetrahydra furan, dimethylsulfoxide, dimethylformaide, ethylene glycol, glycerol, or a combination thereof.

As a method of self-assembling the soft particles 121 in a regular hexagonal lattice form, a Petri dish is filled with water, and a dispersion medium containing the soft particles 121 is dropped on the surface of the water to fill the entire surface of the water to fill the dispersion medium. Self-assembly of the dispersed soft particles 121, or a dispersion medium containing the soft particles 121 is dropped on the substrate 110 and then the dispersion medium is evaporated to self-assemble the flexible particles 121 on the surface of the substrate 110 can do it Evaporation of the dispersion medium is generally required to be performed below the boiling point of the dispersion medium, and as the evaporation rate of the dispersion medium increases, the time for self-assembly of the photonic crystal on the surface of the substrate 110 is shortened, whereas if the evaporation rate is too fast, the photonic crystal is defective If the evaporation rate is too slow, regular photonic crystals cannot be obtained.

In the case of densely self-assembled particles at the water-air interface, the single-layer film 120 may be formed by moving the self-assembled soft particles 121 onto the substrate 110 . For example, when the washed substrate 110 is immersed in water in which the flexible particles 121 are self-assembled to remove the single layer film 120 floating on the surface of the water and dried, the particles dispersed in the water become magnetic as the water evaporates. Photonic crystals may be formed in the process of association.

In a second step, an inorganic photonic crystal pattern 130 is formed by adding a solution containing an inorganic precursor to the monolayer film 120 .

The solution containing the inorganic precursor contracts the soft particles 121 to form a photonic crystal pattern, and at the same time adsorbs the inorganic precursor on the surface of the particles constituting the photonic crystal or penetrates into the particle to form the inorganic photonic crystal pattern 130 . Accordingly, in the inorganic photonic crystal pattern 130 , a plurality of inorganic photonic crystal particles 131 are regularly arranged at intervals.

That is, the inorganic photonic crystal pattern 130 is formed through a solution wet process. Specifically, when a solution containing an inorganic precursor is added to the dense monolayer film 120 of the soft particles 121, the inorganic precursor is converted into a photonic crystal pattern structure due to the thermodynamic properties of the particles with respect to the solution and at the same time, the inorganic precursor is converted into the soft particles 121. The inorganic photonic crystal pattern 130 is formed through the process of being adsorbed on the surface or penetrating into the particle to be converted into an inorganic material.

For example, the soft particles 121 have a property of being very well swollen and dispersed in an organic solvent such as water, methanol, ethanol, or tetrahydrofuran. On the other hand, in a solvent condition that is not thermodynamically mixed with the particles, it is converted from a swollen state to a contracted state. Therefore, when a solvent capable of swelling the particles is added to the dense monolayer film 120 of the soft particles 121, the monolayer film 120 swells, but at this time, a solvent that cannot be thermodynamically mixed with the polymer constituting the particles When added, the monolayer film 120 is contracted. If conditions are formed so that the size of the particles can be contracted into particles much smaller than that in the dry state during shrinkage, the monolayer film 120 is converted into a photonic crystal pattern.

Therefore, the solution containing the inorganic precursor must include a solution characteristic in which a monolayer film having a dense structure can form a pattern having a non-dense structure, and may include, for example, a mixed solvent of water and alcohol. The alcohol may be, for example, methanol, ethanol, or propanol.

For example, when the solution containing the inorganic precursor includes a mixed solvent of water and alcohol, alcohol and water may be included in a molar ratio of 15:85 to 50:50. When the molar ratio of alcohol is less than 15 or exceeds 50, the soft particles 121 may maintain a swollen state to maintain a dense monolayer structure.

In addition, the second step, when using a mixed solvent of water and alcohol, may be made at a temperature above room temperature and lower than the boiling point of the mixed solvent. Here, the room temperature may be 10 °C or higher, for example, 20 °C or higher, or 25 °C or higher.

In the second step, when the temperature is less than 10° C., the soft particles 121 may maintain a swollen state depending on the type and composition of the mixed solvent, thereby maintaining a dense monolayer structure. At a temperature near or above the boiling point of the mixed solvent, the composition of the solvent is changed, so that it may not be possible to effectively prepare a pattern.

Since the time in the second step varies depending on the type of the inorganic precursor used, it is preferable to set an appropriate time according to the type of the precursor used. If the time is short, the amount of inorganic material contained in the soft particles 121 is not sufficient, so that the properties of the soft particles 121 are maintained, so that the swelling/contraction properties of the particles are continuously affected by the composition and temperature of the solvent. In particular, when the substrate 110 is removed from the solution in this state, a change in the composition of the solvent occurs due to evaporation of the mixed solvent included in the mixed solution, which causes the soft particles 121 to be converted into a dense structure. It may or may not be formed into a perfect pattern. On the other hand, if the time is long, the amount of the inorganic layer may increase and a thick film layer may be formed. For example, when the inorganic precursor is mercaptopropyltrimethoxysilane, the second step may be performed for 24 hours to 48 hours.

Meanwhile, when the inorganic photonic crystal pattern 130 is formed, when the solvent includes the inorganic precursor, the inorganic precursor penetrates into the inside of the soft particle 121 or is adsorbed on the surface. When the solidification process sufficiently occurs, inorganic materials are generated from the particles constituting the pattern, and thus the inorganic photonic crystal pattern 130 may be formed. The optical properties, surface structure and surface properties of photonic crystals can be variously changed by the optical properties of inorganic materials.

For example, the inorganic precursor is mercaptopropyltrimethoxysilane (MPTMS), mercaptopropyltriethoxysilane (3-mercaptopropyltriethoxysilane), methyltrimethoxysilane (MTMS), triethoxymethylsilane ), trimethoxy(1H,1H,2H,2H-heptadecafluorodecyl)silane, vinyltrimethoxysilane, tetraethylortho It may include silicate (tetraethylorthosilicate), titanium isopropoxide (titanium isopropoxide), aluminum nitrate (aluminium nitrate), and combinations thereof.

The solution containing the inorganic precursor may include different types of inorganic precursors. In this case, the surface properties of the inorganic photonic crystal particles 131 may be changed or a hierarchical structure may be formed. In this case, the inorganic photonic crystal particles 131 may include a first inorganic material positioned on the surface of the soft particle 121 and a second inorganic material positioned on the surface of the first inorganic material.

Meanwhile, the solution including the inorganic precursor may include a catalyst including sodium hydroxide, ammonium hydroxide, or a mixture thereof. The catalyst serves to speed up the condensation reaction of the inorganic precursor. The catalyst may be included in an amount of 0.01 wt% to 5 wt% based on the total weight of the solution including the inorganic precursor. The content of the catalyst may be appropriately adjusted according to the content of the inorganic precursor.

The method of manufacturing the inorganic photonic crystal pattern 130 may further include annealing the inorganic photonic crystal pattern 130 at 120° C. to 150° C. for 1 hour to 2 hours. Annealing can help the inorganic layer to cure more effectively.

An inorganic photonic crystal pattern according to another embodiment includes a substrate and an inorganic photonic crystal pattern in which a plurality of inorganic photonic crystal particles are regularly arranged at intervals on the substrate.

The inorganic photonic crystal particles may be disposed at regular or different distances from each other, and accordingly, the lattice parameter indicating the distance between the particles is almost constant, thereby exhibiting photonic crystal properties. For example, the lattice constant is correlated with the diameter of the soft particles used, and the inorganic photonic crystal particles may have a particle diameter of 50 nm to 1000 nm, or 200 nm to 600 nm.

At this time, when the solvent includes an inorganic precursor when forming the inorganic photonic crystal pattern, as the inorganic precursor penetrates into or adsorbs to the surface of the soft particle, the inorganic photonic crystal particle is located on the surface of the soft particle or inside the soft particle. Contains minerals.

The inorganic material is derived from an inorganic precursor, and may include silica, organosilica, aluminum oxide, titanium dioxide, or a combination thereof.

In addition, as the inorganic precursor is adsorbed on the surface of the soft particle, the surface of the inorganic photonic crystal particle may have a roughness including a plurality of protrusions having a size of 1 nm to 50 nm.

In addition, when the solution containing the inorganic precursor includes different types of inorganic precursors, the inorganic photonic crystal particles may include a first inorganic material positioned on the surface of the soft particle and a second inorganic material positioned on the surface of the first inorganic material.

Hereinafter, specific embodiments of the invention are presented. However, the examples described below are only for specifically illustrating or explaining the invention, and the scope of the invention is not limited thereto.

(Example 1)

Poly (N-isopropylacrylamide-co-allyamine) copolymer (Poly (N-isopropylacrylamide-co-allyamine)) Soft particles containing a polymer as a main component are removed by centrifugation to remove the supernatant and then redispersed in isopropanol (IPA). . A silicon wafer (Si wafer) with a size of 1.0 cm Х 1.0 cm is immersed in ethanol and washed for 30 minutes using a bath-type ultrasonic cleaner, then immersed in deionized water, undergoes the same cleaning process, and thoroughly dried.

After that, fill a round-shaped Petri dish (diameter: 3.5 cm) with water, and pour an appropriate amount of isopropanol dispersion containing soft particles on the surface to allow the soft particles to associate and coat the substrate in two dimensions. It is self-assembled in a hexagonal dense structure.

Thereafter, one edge of the cleaned silicon wafer is held with tongs and immersed in water to scoop out the soft particles self-assembled on the water surface to form a dense monolayer of the soft particles on the silicon wafer.

A silicon wafer with a monolayer film is immersed in a methanol/water mixed solution (methanol:water molar ratio = 15:85) in which mercaptopropyltrimethoxysilane (MPTMS) is dissolved at room temperature to form a photonic crystal pattern.

FIG. 2 is an electron micrograph showing a process of forming an inorganic photonic crystal pattern in Example 1. FIG. Referring to FIG. 2 , if the photonic crystal pattern is not converted to the inorganic photonic crystal pattern, it returns to a single-layer film having a dense structure during the drying process (A, B: treatment time of 9 hours and 18 hours). That is, if the inorganic precursor used to make the inorganic photonic crystal pattern is gradually adsorbed to the particle surface, hydrolysis occurs and the pattern can be manufactured. It can be seen that an inorganic photonic crystal pattern is formed as it is immobilized by an inorganic material to such an extent that it cannot be achieved (C), and the pattern is perfectly formed after 40 hours (La to Bar).

It can be seen that the inorganic photonic crystal pattern is very regularly arranged and the lattice parameter indicating the distance between the particles is almost constant, showing photonic crystal characteristics. The surface of the inorganic photonic crystal pattern becomes rough as if protrusions are formed.

(Example 2)

Unlike Example 1, a monolayer film was formed on an organic substrate, and a methanol/water mixed solution (methanol: water molar ratio = 15: 85) in which mercaptopropyltrimethoxysilane (MPTMS) was dissolved was placed at 40 ° C. ( A) and 50 ℃ (B) to form a photonic crystal pattern.

In the case of a glass substrate, it is expected that the adhesion between a single layer and a glass substrate is stronger than that of a silicon wafer, and other thermodynamic conditions for forming an inorganic photonic crystal pattern are required.

3(A) is an electron micrograph of the inorganic photonic crystal pattern prepared in Example 2(A), and FIG. 3(B) is an electron micrograph of the inorganic photonic crystal pattern prepared in Example 2(B).

Referring to FIG. 3 , it can be seen that the photonic crystal pattern is completely formed after 46 hours. Thereafter, an annealing process is performed at 150° C. for 2 hours to cure the sample.

It can be seen that the inorganic photonic crystal pattern is very regularly arranged, and the lattice parameter indicating the distance between the particles is almost constant, indicating that the photonic crystal characteristics are exhibited.

4 is a graph showing the light transmittance (Transmittance) of the inorganic photonic crystal pattern prepared in Example 2 (B).

Light transmittance was measured using a UV-VIS-NIR spectrophotometer (V-670, JASCO, Japan) equipped with an integrating sphere to measure diffuse transmittance.

Referring to FIG. 4 , bare glass and glass (Monolayer) including a dense monolayer of soft particles have similar optical properties, but in the case of the glass having an inorganic photonic crystal pattern prepared in Example 2 (B) After 450 nm, the light transmittance was increased than that of general glass, and it can be seen that the light transmittance of about 92% to 94% was maintained up to 800 nm. This is presumed to be due to the fact that the inorganic photonic crystal pattern formed on the glass substrate minimizes the amount of light reflected on the glass surface due to an anti-reflective effect.

(Example 3)

Unlike Example 1, a monolayer film is formed on a polyethylene terephthalate (PET) substrate, and a methanol/water mixture solution in which mercaptopropyltrimethoxysilane (MPTMS) is dissolved Methanol:water molar ratio = 15: 85), respectively, at 40 °C for 48 hours to form photonic crystal patterns. In the case of a PET substrate, in order to prevent damage to the substrate, a drying process is performed at 40° C. for 24 hours instead of a high-temperature annealing process.

5 is an electron micrograph of the inorganic photonic crystal pattern prepared in Example 3. FIG.

Referring to FIG. 5 , it can be seen that the inorganic photonic crystal pattern is very regularly arranged and the lattice constant indicating the distance between the particles is almost constant, showing photonic crystal characteristics.

(Example 4)

As in Example 2, a monolayer film was formed on an organic substrate, and a methanol/water mixed solution (methanol: water molar ratio = 15: 85) in which mercaptopropyltrimethoxysilane (MPTMS) was dissolved was placed at 50 ° C. After the reaction proceeds for 48 hours to form an inorganic photonic crystal pattern, the surface properties and structure of the silica surface are controlled through the following method.

In the case of Example 4 (a), the formed inorganic photonic crystal pattern is reacted with a solution consisting of 2.15 mL of DI-water, 0.85 mL of MeOH, and 50 μl of MTMS (Methyltrimethoxysilane) for 24 hours. The sample is then taken out and annealed at 150° C. for 2 hours.

In the case of Example 4 (b), the formed inorganic photonic crystal pattern was immersed in an ethanol solution containing 1 wt% Trimethoxy (1H,1H,2H,2H-heptadecafluorodecyl) silane (F17), followed by deionized water 0.18 mL and react for 78 hours. The sample is then taken out and annealed at 120° C. for 1 hour.

6 is an electron micrograph of the inorganic photonic crystal pattern prepared in Example 4 (A), and FIG. 7 is an electron micrograph of the inorganic photonic crystal pattern prepared in Example 4 (B).

6 and 7, the surfaces of the inorganic photonic crystal patterns prepared in Examples 4 (A) and 4 (B) have different structures and surface properties depending on the type of silica precursor used. In the case of FIG. 6 , it was observed that particles in which the MTMS precursor was converted to silica were formed on the pattern surface, and more hydrophobic than the MPTMS precursor, resulting in an average water contact angle of 112 degrees. On the other hand, in the case of Figure 7, the hydrophobicity of the pattern further increased, showing an average water contact angle of 136 degrees.

8 is a graph showing the light transmittance of the inorganic photonic crystal pattern prepared in Example 4 (A).

Referring to FIG. 8 , bare glass and glass (Monolayer) including a dense monolayer of soft particles have similar optical properties, but after forming a primary pattern with MPTMS prepared in Example 4(A), MTMS In the case of the glass containing the inorganic photonic crystal pattern further treated with , the light transmittance increased compared to glass after 425 nm, and it showed a maximum light transmittance of 95.5% at 511 nm, and then maintaining about 94% light transmittance until 800 nm. observed.

Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention defined in the following claims are also present. It belongs to the scope of the right of the invention.

110: substrate
120: a dense monolayer of soft particles
121: soft particles
130: inorganic photonic crystal pattern
131: inorganic photonic crystal particles

Claims (18)

A first step of coating the soft particles in the form of a close-packed colloidal monolayer on the substrate, and
A method of manufacturing an inorganic photonic crystal pattern comprising a second step of forming an inorganic photonic crystal pattern by adding a solution containing an inorganic precursor to the monolayer film. In claim 1,
In the inorganic photonic crystal pattern, a plurality of inorganic photonic crystal particles are regularly arranged at intervals. In claim 1,
The first step, after dispersing the soft particles in a dispersion medium, is made by self-assembly (self-assembly) of the soft particles in a regular hexagonal lattice form, the method for producing an inorganic photonic crystal pattern. In claim 3,
The soft particles are, poly (N-isopropyl acrylamide) [poly (N-isopropylacrylamide), pNIPAM], poly (N- isopropyl acrylamide-co-allylamine) [poly (N-isopropyl acrylamide-co-allylamine) ), poly(NIPAM-co-AA)], poly(N-isopropylacrylamide-co-2-(dimethylamino)ethyl methacrylate)[poly(N-isopropylacrylamide-co-2-(dimethylamino)ethyl methacrylate) ), poly(NIPAM-co-DMAEMA)], poly(N-isopropyl acrylamide-co-2-(dimethylamino)ethyl acrylate) ), poly(NIPAM-co-DMAEA)], poly(N-isopropyl acrylamide-co-acrylic acid) [poly(N-isopropyl acrylamide-co-acrylic acid), poly(NIPAM-co-AAc)], poly (N-isopropyl acrylamide-co-methacrylic acid)[poly(N-isopropyl acrylamide-co-methacrylic acid), poly(NIPAM-co-MAAc)], poly(N,N-diethylacrylamide)[poly (N,N-diethylacrylamide)], poly(N-vinylcaprolactam)[poly(N-vinlycaprolactam)], poly(ethylene glycol)[poly(ethylene glycol)], poly(ethylene glycol-b-propylene glycol- b-ethylene glycol) [poly(ethylene glycol-b-propylene glycol-b-ethylene glycol)], or a method for producing an inorganic photonic crystal pattern comprising a combination thereof. In claim 3,
The dispersion medium includes water, methanol, ethanol, butanol, isopropyl alcohol, tetrahydra furan, dimethylsulfoxide, dimethylformaide, ethylene glycol, glycerol, or a combination thereof. manufacturing method. In claim 1,
In the second step,
The solution containing the inorganic precursor contracts the soft particles to form a photonic crystal pattern, and adsorbs the inorganic precursor on the surface of the photonic crystal particle or penetrates into the photonic crystal particle,
A method for manufacturing an inorganic photonic crystal pattern. In claim 1,
The inorganic precursor is mercaptopropyltrimethoxysilane (MPTMS), mercaptopropyltriethoxysilane (3-mercaptopropyltriethoxysilane), methyltrimethoxysilane (MTMS), triethoxymethylsilane, Trimethoxy(1H,1H,2H,2H-heptadecafluorodecyl)silane, vinyltrimethoxysilane, tetraethylorthosilicate ( tetraethylorthosilicate), titanium isopropoxide (titanium isopropoxide), aluminum nitrate (aluminum nitrate), or a combination thereof, including a method for producing an inorganic photonic crystal pattern. In claim 1,
A method for producing an inorganic photonic crystal pattern, wherein the solution containing the inorganic precursor includes different types of inorganic precursors. In claim 1,
The solution containing the inorganic precursor includes a mixed solvent of water and alcohol, the method for producing an inorganic photonic crystal pattern. In claim 9,
The solution containing the inorganic precursor is alcohol and water 15: 85 to 50: a method for producing an inorganic photonic crystal pattern comprising a mixed solvent comprising a molar ratio of 50. In claim 1,
The solution containing the inorganic precursor is sodium hydroxide (sodium hydroxide), ammonium hydroxide (ammonium hydroxide), or a method for producing an inorganic photonic crystal pattern comprising a catalyst comprising a mixture thereof. In claim 9,
The second step, 10 ℃ or more and made at a temperature lower than the boiling point of the mixed solvent, the method for producing an inorganic photonic crystal pattern. In claim 1,
The method of manufacturing the inorganic photonic crystal pattern further comprises annealing the inorganic photonic crystal pattern at 120° C. to 150° C. for 1 hour to 2 hours. board, and
and an inorganic photonic crystal pattern in which a plurality of inorganic photonic crystal particles are regularly arranged at intervals on the substrate;
The inorganic photonic crystal particles,
soft particles, and
An inorganic photonic crystal pattern comprising an inorganic material positioned on the surface of the soft particle or inside the soft particle. 15. In claim 14,
The inorganic material comprises silica, organosilica, aluminum oxide, titanium dioxide, or a combination thereof, inorganic photonic crystal pattern. 15. In claim 14,
The surface of the inorganic photonic crystal particle comprises a plurality of projections having a size of 1 nm to 50 nm, an inorganic photonic crystal pattern. 15. In claim 14,
The inorganic photonic crystal particle includes a first inorganic material positioned on the surface of the soft particle and a second inorganic material positioned on the surface of the first inorganic material, the inorganic photonic crystal pattern. 15. In claim 14,
The inorganic photonic crystal particles have a particle diameter of 50 nm to 1000 nm, an inorganic photonic crystal pattern.

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