WO2011030950A1

WO2011030950A1 - Organic-inorganic hybrid photonic crystal, and preparation method thereof

Info

Publication number: WO2011030950A1
Application number: PCT/KR2009/005786
Authority: WO
Inventors: 강영종; 강창준; 김은주; 구준모; 양정윤
Original assignee: 한양대학교 산학협력단
Priority date: 2009-09-14
Filing date: 2009-10-09
Publication date: 2011-03-17
Also published as: KR101192941B1; KR20110029066A; WO2011030950A9

Abstract

Provided are an organic-inorganic hybrid photonic crystal, and a preparation method thereof. The photonic crystal comprises a hydrophobic-hydrophilic block copolymer film having an alternate structure of a hydrophobic polymer domain and a hydrophilic polymer domain, and a metal oxide introduced into the hydrophobic polymer domain of the film. The photonic crystal can be formed by forming a hydrophobic-hydrophilic block copolymer film having an alternate structure of a hydrophobic polymer domain and a hydrophilic polymer domain by the self-assembly of a block copolymer having a hydrophobic polymer block and a hydrophilic polymer block, dipping the block copolymer film in a hydrophilic solvent to swell the hydrophilic polymer domain, and introducing a metal oxide into the swollen hydrophilic polymer domain. The photonic crystal having a photonic band gap in a desired band among a wide wavelength band can be prepared by selectively introducing a metal oxide into the hydrophilic polymer domain inside one block copolymer film formed by self-assembly. In addition, the synthesis and control of a copolymer are advantageous since a block copolymer having a relatively low molecular weight can be used.

Description

Organic-Inorganic Hybrid Photonic Crystals and Manufacturing Method Thereof

The present invention relates to a photonic crystal and a method of manufacturing the same, and more particularly, to an organic-inorganic hybrid photonic crystal using a block copolymer and a metal oxide and a method of manufacturing the same.

There is an increasing need for the development of photoelectronic devices with improved efficiency and integration in order to realize a high-speed information society, and interest in the use of photonic crystals that can control photons in micro spaces. It is concentrated. Photonic crystals have a photonic band gap in which the refractive index of the material is changed periodically so that electromagnetic waves in a specific wavelength band are not transmitted. Applicability to various optoelectronic devices.

Photo-crystal manufacturing method is largely a top-down method based on nano-micron processing technology such as lithography, ion beam etching, and physical or colloidal particles or polymers It can be divided into bottom-up methods using chemical self-assembly.

However, the micro-machining technique has the disadvantage that the process is complicated, expensive optical equipment is required, and the cost is high. On the other hand, colloidal particle self-assembly does not require expensive auxiliary equipment, so there is an advantage in that it is possible to make photonic crystals at low cost. However, it is difficult to control fine colloidal particles, and since one material exhibits only one stop-band, photonic crystals must be grown each time in a different colloidal solution to form a photonic crystal structure having various optical band gaps. There was an inconvenience.

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a photonic crystal manufacturing method capable of obtaining photonic crystals having different optical bandgaps from a block copolymer film, and a photonic crystal prepared therefrom.

One aspect of the present invention to achieve the above technical problem provides an organic-inorganic hybrid photonic crystal. The photonic crystal includes a hydrophobic-hydrophilic block copolymer film having a structure in which a hydrophobic polymer domain and a hydrophilic polymer domain are alternately repeated, and a metal oxide introduced into the hydrophilic polymer domain of the film.

The block copolymer film may be made of polystyrene-poly (vinylpyridine) copolymer, polystyrene-polymethylmethacrylate (poly (methylmethacrylate)) copolymer, polystyrene-poly (t-butylacrylate) ( poly (tert-butylacrylate) copolymer, polyisoprene-poly (ethyleneoxide) copolymer, polystyrene-polylactide copolymer, polycyclohexylethylene -Polylactide copolymer, or polymethylstyrene-polyhydroxystyrene copolymer, Preferably, the block copolymer film may be a polystyrene-polyvinylpyridine copolymer film. .

The structure in which the hydrophobic polymer domain and the hydrophilic polymer domain are alternately repeated may be a lamellar structure.

The metal oxide may be any one selected from the group consisting of SiO ₂ , TiO ₂ , ZnO, Al ₂ O _3, and ZrO ₂ .

Another aspect of the present invention to achieve the above technical problem provides a method for producing an organic-inorganic hybrid photonic crystal. First, a block copolymer having a hydrophobic polymer block and a hydrophilic polymer block is self-assembled to form a hydrophobic-hydrophilic block copolymer film having a structure in which the hydrophobic polymer domain and the hydrophilic polymer domain are alternately repeated. The block copolymer film is immersed in a hydrophilic solvent to swell the hydrophilic polymer domain. Metal oxides are introduced into the swollen hydrophilic polymer domain.

The block copolymer may be polystyrene-polyvinylpyridine copolymer, polystyrene-polymethylmethacrylate copolymer, polystyrene-poly (t-butylacrylate) copolymer, polyisoprene-poly (ethylene oxide) copolymer, polystyrene-poly Lactide copolymers, polycyclohexylethylene-polylactide copolymers, or polymethylstyrene-polyhydroxystyrene copolymers. Preferably the block copolymer may be a polystyrene-polyvinylpyridine copolymer.

The block copolymer film may be prepared by preparing a solution containing the block copolymer, applying the solution onto a substrate to form a film, and then annealing the film.

Haloalkanes can be added to the hydrophilic solvent. The haloalkane may be methyl iodide.

The glass transition temperature of the hydrophobic polymer domain may be higher than the temperature at which the swelling step is performed.

Introduction of the metal oxide into the swollen hydrophilic polymer domain is performed by adding a metal oxide precursor into a hydrophilic solvent in which the block copolymer film is immersed, and then adding the metal oxide precursor to a sol-gel reaction. can do.

As described above, according to the present invention, there is an advantage in that a photonic crystal having an optical band gap in a desired band of all wavelength bands of ultraviolet-visible-infrared rays can be manufactured from one block copolymer film formed by self-assembly. In addition, since a relatively low molecular weight block copolymer may be used, it may have advantages in synthesis and copolymer control of the copolymer as compared with the case of using a high molecular weight block copolymer.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a flowchart illustrating a method of manufacturing an organic-inorganic hybrid photonic crystal according to an embodiment of the present invention.

2 is a schematic view showing a method of manufacturing an organic-inorganic hybrid photonic crystal according to an embodiment of the present invention.

3 is a cross-sectional view showing a cross section of an organic-inorganic hybrid photonic crystal according to an embodiment of the present invention.

4 is a transmission spectrum of organic-inorganic hybrid photonic crystals prepared according to Preparation Examples 1 to 6, respectively.

5 is a graph showing the maximum reflection wavelength (λ max) versus the aging time (τa) of the organic-inorganic hybrid photonic crystals prepared according to Preparation Examples 1 to 6, respectively.

6 is a photograph of the organic-inorganic hybrid photonic crystals prepared according to Preparation Examples 1 to 6 under white light, respectively.

7 is an SEM image of a block copolymer film before introducing a metal oxide.

8, 9 and 10 are SEM images of organic-inorganic hybrid photonic crystals prepared according to Preparation Example 1, Preparation Example 3 and Preparation Example 6, respectively.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosure may be made thorough and complete, and to fully convey the spirit of the present invention to those skilled in the art. In the drawings, the thicknesses of layers and bands are exaggerated for clarity.

1 and 2 are a flow chart and a schematic diagram showing a method for manufacturing an organic-inorganic hybrid photonic crystal according to an embodiment of the present invention, respectively.

1 and 2, a block copolymer having a hydrophobic polymer block and a hydrophilic polymer block is self-assembled to alternately repeat _a hydrophobic polymer domain (P _a ) and a hydrophilic polymer domain (P _b ). A copolymer film (BF) is formed (S10). The hydrophobic polymer domain (P _a ) and the hydrophilic polymer domain (P _b ) mean regions that are predominantly occupied by hydrophobic polymers and hydrophilic polymers, respectively.

The block copolymer may be, for example, a polystyrene-poly (vinylpyridine) copolymer, a polystyrene-polymethyl methacrylate copolymer, a polystyrene-poly (t-butylacryl) (Poly (tert-butylacrylate) copolymer, polyisoprene-poly (ethyleneoxide) copolymer, polystyrene-polylactide copolymer, polycyclohexylethylene (poly ( cyclohexylethylene))-polylactide copolymer, or polymethylstyrene-polyhydroxystyrene copolymer, but is not limited to polystyrene, polyisoprene, polycyclohexylethylene, And polymethylstyrene corresponds to a hydrophobic polymer, and polyvinylpyridine, polymethylmethacrylate, poly (t-butylacrylate), poly (ethylene Oxide), polylactide, polyhydroxystyrene may correspond to a hydrophilic polymer.

Forming the block copolymer film (BF) is specifically, preparing a block copolymer solution containing a hydrophobic-hydrophilic block copolymer and a solvent, and applying the block copolymer solution on a substrate to form a block copolymer film After forming, the film may be annealed.

Herein, the solvent in the block copolymer solution may be appropriately selected in consideration of the viscosity of the block copolymer solution and the mobility during the self-assembly process. In one example, the solvent is butyrolactone, cyclopentanone, cyclohexanone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl pyrrolidone, tetrahydroperfural alcohol, propylene glycol monomethyl ether (PGME ), Propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate or mixtures thereof.

The block copolymer solution is coated on a substrate by spin coating, dip coating, ink-jet printing, spray coating, or screen printing. It may be a screen printing method, a drop casting method or a doctor blade method.

Annealing the film may be carried out using thermal annealing or solvent annealing. In the annealing process, the degree of repeat alignment of the hydrophobic polymer domain and the hydrophilic polymer domain in the block copolymer film may be greatly improved.

Meanwhile, the repeating alignment structure of the hydrophobic polymer domain (P _a ) and the hydrophilic polymer domain (P _b ) in the block copolymer film (BF) is _a lamellar according to the volume fraction of the hydrophobic polymer block and the hydrophilic polymer block contained in the block copolymer. It may have a structure, a cylinder structure or a spherical structure. Although the lamellar structure is illustrated as a repeating alignment structure in the drawings, the present invention is not limited thereto. However, when the hydrophobic polymer block and the hydrophilic polymer block have similar volume fractions, the hydrophobic polymer domain (P _a ) and the hydrophilic polymer domain (P _b ) in the block copolymer film (BF) may be repeatedly aligned in a lamellar structure. Can be.

Thereafter, the block copolymer film (BF) is immersed in an optional solvent to selectively swell any one of the polymer domains, and the hydrophilic polymer domain (P _b ) is selective when the selective solvent is a hydrophilic solvent. Swelling (S12).

The hydrophilic solvent may be water or a hydrophilic organic solvent, and the hydrophilic organic solvent may be an alcohol.

In addition, suitable additives may be added in the hydrophilic solvent to facilitate the selective penetration of the hydrophilic solvent into the hydrophilic polymer domain (P _b ). For example, when the hydrophilic polymer block in the hydrophilic polymer domain (P _b ) is poly (2-vinylpyridine), haloalkanes (haloalkane) and the like are used as additives, so that the It is possible to facilitate the penetration of the hydrophilic solvent by quaternization of pyridine to pyridinium through a nuclear substitution reaction. In this case, the hydrophilic solvent may be water. In addition, the haloalkaine may be methyl iodide (CH ₃ I).

As the hydrophilic polymer domain P _b is swollen by the hydrophilic solvent, formation of a substantial volume of regions in the hydrophilic polymer domain P _b is not occupied by the hydrophilic polymer.

The hydrophilic polymer domain (P _b ) may be selectively swollen in the normal direction, that is, Z-axis direction with respect to the block copolymer film (BF). To this end, the glass transition temperature of the hydrophobic polymer domain (P _a ) is higher than the temperature of the environment in which the swelling process is carried out, so that the hydrophobic polymer domain (P _a ) has little elasticity during the swelling process ( glass state).

Thereafter, a metal oxide (MO) is introduced into the swollen hydrophilic polymer domain (P _b ) (S14) to form an organic-inorganic hybrid photonic crystal (PC). Specifically, the metal oxide (MO) may be introduced into a region that is not occupied by the hydrophilic polymer block in the swollen hydrophilic polymer domain (P _b ). The metal oxide (MO) may be any one selected from the group consisting of SiO ₂ , TiO ₂ , ZnO, Al ₂ O _3, and ZrO ₂ .

In particular, the introduction of the metal oxide may be performed by adding a precursor of the metal oxide to the hydrophilic solvent in a state in which the block copolymer film (BF) is immersed in the hydrophilic solvent. At this time, the added metal oxide precursor is selectively introduced into the swollen hydrophilic polymer domain (P _b ), and then the metal in the hydrophilic polymer domain (P _b ) through a sol-gel reaction. Oxide nanoparticles (MO) may be formed.

The metal oxide nanoparticles (MO) formed during the sol-gel reaction may form a continuous network by growth and aggregation. Accordingly, even after the block copolymer film (BF) is taken out of the solvent and dried, the swollen hydrophilic polymer domain (P _b ) is not completely shrunk and is constant in proportion to the degree of introduction of the metal oxide (MO). It is possible to maintain an increased thickness (meaning an increased thickness than the thickness of the hydrophilic polymer domain before swelling). Accordingly, in the present specification, the process of selective swelling of the hydrophilic polymer domain (P _b ) and fixation to a constant thickness by introduction of a metal oxide (MO) is taken into consideration, which is called a swelling-freezing method. On the other hand, the amount of the metal oxide (MO) is introduced and the degree of increase in the thickness of the hydrophilic polymer domain (P _b ) can be controlled by controlling the sol-gel reaction time.

The pH of the solution in which the sol-gel reaction takes place needs to be appropriately adjusted so that the metal oxide is not overcoated and can be gelated at an appropriate rate. For example, when the metal oxide precursor is tetraethoxysilane (TEOS) and the metal oxide produced therefrom is SiO ₂ , under acidic conditions, a transparent monolith gel is formed and rapid gelation occurs, Under basic conditions a network gel in the form of a powder is produced. Therefore, when the reaction is performed only under the basic conditions, the optical properties of the manufactured photonic crystal may be deteriorated due to the overcoating phenomenon of the powder-type gel, which reduces the sharpness of color due to scattering of reflected wavelengths. On the other hand, when the reaction proceeds only under acidic conditions, a phenomenon in which a sufficient amount of SiO ₂ hardens before being introduced into the hydrophilic polymer domain by rapid gelation occurs. Therefore, it is necessary to initially proceed the reaction under basic conditions to form an appropriate amount of SiO ₂ nanoparticles, and then lower the pH slightly according to the addition of acid so that SiO ₂ is properly aggregated and fixed in the hydrophilic polymer domain. have.

Referring to FIG. 3, as the metal oxide (MO) is introduced, the refractive index (n ₂ ′) of the hydrophilic polymer domain (P _b ) may be different from the refractive index of the pure hydrophilic polymer domain, which is a Lorentz-Lorentz mixing rule (Lorentz). Can be calculated by the Lorenz mixing rule. As an example, the hydrophilic polymer domain (P _b ) is a polyvinylpyridine domain having a refractive index of about 1.62 and the hydrophobic polymer domain (P _a ) is _a polystyrene domain having _a refractive index of about 1.62 and the metal oxide has a refractive index of about 1.25 to 1.34. In the case of phosphorus SiO ₂ , according to the Lorentz-Lorentz mixing rule, the refractive index of the polyvinylpyridine domain in which the SiO ₂ is introduced may exhibit a value between the refractive index of the polyvinylpyridine domain and the refractive index of SiO ₂ . Accordingly, the refractive index n ₂ ′ of the polyvinylpyridine domain in which SiO ₂ is introduced may be smaller than the refractive index n ₁ of the polystyrene domain. As such, the metal oxide (MO) may be introduced to control the refractive index n ₂ ′ of the hydrophilic polymer domain P _b .

Due to the difference in refractive index between the hydrophilic polymer domain (P _b ) and the hydrophobic polymer domain (P _a ), the light L incident on the photonic crystal PC has the two domains P _b , It can be totally reflected on either side between P _a ).

In this case, among the various wavelength bands of the light L incident to the photonic crystal PC, the wavelength λ satisfying the following Equation 1 may be selectively reflected.

[Equation 1]

2dsinθ = nλ

Is the angle between the incident light and the total reflection surface, d is the distance between the total reflection surfaces TR, and n is a positive integer.

Referring to Equation 1, the wavelength λ that is selectively reflected depends on the spacing d between the total reflection surfaces TR, and the spacing d between the total reflection surfaces is a metal as described above. It can be controlled by adjusting the thickness increase of the hydrophilic polymer domain (P _b ) in accordance with the introduction of the oxide. As described above, the thickness adjustment of such a hydrophilic polymer domain (P _b) can be carried out by controlling the amount of metal oxide that is selectively introducing within the hydrophilic polymer domains (P _b).

As such, the block copolymer film in which the metal oxide (MO) is selectively introduced into the hydrophilic polymer domain (P _b ) may serve as a photonic crystal that reflects a specific wavelength. In addition, by adjusting the thickness of the hydrophilic polymer domain (P _b ), the wavelength (λ) of the reflected light can be varied. The selectively reflected wavelength λ is called an optical band gap, and the optical band gap is easily set to a desired band among all wavelength bands of the ultraviolet-visible-infrared ray through the thickness control of the hydrophilic polymer domain P _b . Can be.

On the other hand, in forming the photonic crystal using the block copolymer, the increase in the thickness of the polymer domain may be performed by increasing the molecular weight of the polymer (> 1Mg / mol). However, as the molecular weight increases, the viscosity of the polymer increases, which makes it difficult to self-assemble and thus it is very difficult to arrange the domains regularly. In contrast, in the present embodiment, the photocrystal may be formed using a block copolymer having polymer blocks having a relatively low molecular weight. In other words, a block copolymer having a relatively low molecular weight may be used as compared to the molecular weight (˜10 ⁶ g / mol) theoretically required to have an optical band gap in the block copolymer photonic crystal. Therefore, in addition to having an advantage in terms of synthesis of the block copolymer, there is an advantage in improving the alignment of the hydrophobic polymer domain and the hydrophilic polymer domain by lowering the viscosity and increasing the mobility in the self-assembly process.

Hereinafter, preferred examples are provided to aid the understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited to the following experimental examples.

Organic weapons hybrid Photonic Produce

Polystyrene-b-poly (2-vinylpyridine) copolymer (polystyrene-b-poly (2-vinyl pyridine copolymer, PS-b-P2VP) PS₁₉₀-b-P2VP₁₉₀ (M_n × 10³ = 190/190, PDI = 1.10, purchased from Polymer Source Inc, Dorval, Canada), dissolved in 5 wt% of propylene glycol monomethyl ether acetate (PGMEA) to contain an organic hydrophobic-hydrophilic block copolymer. The solution was prepared. This organic solution was spin coated on slide glass at 600 rpm for 1 minute. The film coated on the slide glass was solvent annealed with chloroform vapor at 50 ° C. for 7 days to prepare a block copolymer film well arranged in a layered structure.

The prepared block copolymer film was placed in a container (100 ml) containing methanol (50 ml), and then slowly added TEOS (tetraethoxysilane) (5 ml) and NH ₄ OH (1 ml) while stirring at about 600 rpm. After stirring for about 20 minutes, HCl (0.2 ml) was further added, and after a certain time, the block copolymer film was taken out of the container and dried.

Here, the time taken to remove the block copolymer film from the addition of HCl, that is, the aging time (τ _a ) was set to 15 minutes.

An organic-inorganic hybrid photonic crystal was manufactured in the same manner as in Preparation Example 1, except that τ _a = 30 minutes.

An organic-inorganic hybrid photonic crystal was manufactured in the same manner as in Preparation Example 1, except that τ _a = 40 minutes.

An organic-inorganic hybrid photonic crystal was manufactured in the same manner as in Preparation Example 1, except that τ _a = 60 minutes.

Production Example 5

An organic-inorganic hybrid photonic crystal was manufactured in the same manner as in Preparation Example 1, except that τ _a = 90 minutes.

An organic-inorganic hybrid photonic crystal was manufactured in the same manner as in Preparation Example 1, except that τ _a = 120 minutes.

4 is a transmission spectrum of organic-inorganic hybrid photonic crystals prepared according to Preparation Examples 1 to 6, respectively, and FIG. 5 is a aging time (τ) of organic-inorganic hybrid photonic crystals prepared according to Preparation Examples 1 to 6, respectively. _{It is a} graph showing the maximum reflection wavelength (λ _max ) for a), Figure 6 is a photograph taken under the white light of the organic-inorganic hybrid photonic crystals prepared according to Preparation Examples 1 to 6. The downward peak in FIG. 4 represents a wavelength band in which reflection occurs by the photonic crystal.

4, 5 and 6, it can be seen that the organic-inorganic hybrid photonic crystal also has a wavelength at which reflection occurs as the aging time τ _a increases. From this, it can be seen that the thickness of the hydrophilic polymer domain is increased as the aging time (τ _a ) is increased, and the increase in the thickness of the hydrophilic polymer domain is due to the increase of the amount of metal oxide introduced into the hydrophilic polymer domain. It is feed.

FIG. 7 is an SEM image of a block copolymer film before introducing a metal oxide, and FIGS. 8, 9, and 10 are SEM images of organic-inorganic hybrid photonic crystals prepared according to Preparation Example 1, Preparation Example 3, and Preparation Example 6, respectively. .

7 to 10, it can be seen that the thickness of the P2VP domain was selectively increased after the introduction of the metal oxide (SiO ₂ ) compared to the block copolymer film before the introduction of the metal oxide. In addition, it can be seen that the thickness of the P2VP domain increases as the amount of SiO ₂ introduced increases. Thus, it can be seen that by adjusting the thickness of the hydrophilic polymer domain according to the amount of introduction of the metal oxide, the organic-inorganic hybrid photonic crystal can be adjusted to have a specific band optical band gap.

In particular, in FIG. 10, a unique structure in which P2VP chains, which were originally entangled with each other, is divided into two regions to form an empty space between the two regions, and the two regions are connected by silica bridges.

In the above production example, only a photonic crystal having an optical band gap in the visible light region was manufactured, but this is only to make it easy to confirm the completion of the invention through visual verification. In addition, it is apparent that by changing the thickness of the hydrophilic polymer region, an organic-inorganic hybrid photonic crystal having an optical band gap can be produced not only in the visible region but also in the ultraviolet and infrared regions.

As described above, according to the present invention, an organic-inorganic hybrid photonic crystal having an optical band gap of a desired wavelength band among a wide wavelength band of ultraviolet-visible-ultraviolet rays is obtained by using a swelling-fixing method from one self-assembled block copolymer film. Easy to manufacture

In the above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications and changes by those skilled in the art within the spirit and scope of the present invention. Changes are possible.

Claims

Hydrophobic-hydrophilic block copolymer films having a structure in which hydrophobic polymer domains and hydrophilic polymer domains are alternately repeated; And

An organic-inorganic hybrid photonic crystal comprising a metal oxide introduced into the hydrophilic polymer domain of the film.
The method of claim 1,

The block copolymer film may be made of polystyrene-poly (vinylpyridine) copolymer, polystyrene-polymethylmethacrylate (poly (methylmethacrylate)) copolymer, polystyrene-poly (t-butylacrylate) ( poly (tert-butylacrylate) copolymer, polyisoprene-poly (ethyleneoxide) copolymer, polystyrene-polylactide copolymer, polycyclohexylethylene An organic-inorganic hybrid photonic crystal containing a polylactide copolymer or a polymethylstyrene-polyhydroxystyrene copolymer.
The method of claim 1,

The block copolymer film is a polystyrene-polyvinylpyridine copolymer film organic-inorganic hybrid photonic crystal.
The method of claim 1,

The structure in which the hydrophobic polymer domain and the hydrophilic polymer domain are alternately repeated is a lamellar structure.
The method of claim 1,

The metal oxide is any one selected from the group consisting of SiO 2 , TiO 2 , ZnO, Al 2 O 3 and ZrO 2 organic-inorganic hybrid photonic crystal.
Self-assembling a block copolymer having a hydrophobic polymer block and a hydrophilic polymer block to form a hydrophobic-hydrophilic block copolymer film having a structure in which the hydrophobic polymer domain and the hydrophilic polymer domain are alternately repeated;

Dipping the block copolymer film in a hydrophilic solvent to swell the hydrophilic polymer domain; And

Introducing a metal oxide into the swollen hydrophilic polymer domain.
The method of claim 6,

The block copolymer may be polystyrene-polyvinylpyridine copolymer, polystyrene-polymethylmethacrylate copolymer, polystyrene-poly (t-butylacrylate) copolymer, polyisoprene-poly (ethylene oxide) copolymer, polystyrene-poly A method for producing an organic-inorganic hybrid photonic crystal, which is a lactide copolymer, a polycyclohexylethylene-polylactide copolymer, or a polymethylstyrene-polyhydroxystyrene copolymer.
The method of claim 6,

The block copolymer is a polystyrene-polyvinylpyridine copolymer organic-inorganic hybrid photonic crystal manufacturing method.
The method of claim 6,

The hydrophobic polymer domain and the hydrophilic polymer domain alternately repeated structure is a lamellar structure organic-inorganic hybrid photonic crystal manufacturing method.
The method of claim 6, wherein forming the block copolymer film,

Preparing a solution containing the block copolymer;

Applying the solution onto a substrate to form a film; And

An organic-inorganic hybrid photonic crystal manufacturing method comprising the step of annealing the film.
The method of claim 6,

An organic-inorganic hybrid photonic crystal manufacturing method of adding haloalkane (haloalkane) in the hydrophilic solvent.
The method of claim 11,

The haloalkaine is methyl iodide organic-inorganic hybrid photonic crystal manufacturing method.
The method of claim 6,

The glass transition temperature of the hydrophobic polymer domain is higher than the temperature at which the swelling step is performed.
The method of claim 6,

The metal oxide is any one selected from the group consisting of SiO 2 , TiO 2 , ZnO, Al 2 O 3 and ZrO 2 organic-inorganic hybrid photonic crystal manufacturing method.
The method of claim 6, wherein introducing the metal oxide comprises:

Adding a metal oxide precursor into a hydrophilic solvent in which the block copolymer film is dipped; And

Organic-inorganic hybrid photonic crystal manufacturing method comprising the step of sol-gel (sol-gel) reaction of the added metal oxide precursor.