KR100466250B1 - Manufacturing Method for Colloidal Crystals with Variable Form and Multi-Pore Structure Using Said Colloidal Crystals - Google Patents

Abstract

The present invention relates to a method for forming a colloidal crystal, which is provided as a material for the device industry, such as in the field of optical communication, comprising the steps of infiltrating a colloidal solution into a capillary tube, evaporating a solvent in the colloidal solution to crystallize the colloid, and Disclosed is a method of preparing a colloidal crystal comprising the step of removing.

In another aspect, the present invention is to penetrate the colloidal solution into the capillary, to evaporate the solvent in the colloidal solution to crystallize, to penetrate the polymer precursor or inorganic precursor inside the capillary to polymerize or mineralize, and the capillary Disclosed is a method of preparing a porous structure using colloidal crystals, including removing colloidal crystals.

Description

Manufacturing Method for Colloidal Crystals with Variable Form and Multi-Pore Structure Using Said Colloidal Crystals

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing colloidal crystals, which is provided as a material for the device industry, such as the optical communication field. More specifically, the shape of the colloidal crystal can be freely controlled, and various applications can be made to small devices required for the optical communication field. It relates to a possible colloidal crystal and a method for producing a porous structure having the template.

Colloidal crystals are those in which spherical particles of a uniform size of polymer or inorganic are arranged in a crystal structure. In this case, a general crystal structure obtained from self-array has a face-centered cubic structure. Colloidal crystals are called photonic crystals because they affect the propagation of light, such that they do not transmit through a specific wavelength of light because the crystal structure has a periodicity of a size similar to the wavelength of light. In particular, the wavelength region of light that cannot pass through the photonic crystal is called a photonic band gap. At present, many attempts have been made to use such photonic crystals industrially, and one of them is to control the appearance of colloidal crystals, and such an attempt is to manufacture optical devices such as optical waveguides and lenses.

Photonic crystals can utilize not only colloidal crystal structures but also inverted structures of colloidal crystals. The production of photonic crystals using colloids is variously disclosed in US Pat. No. 6,339,030. In this patent, photonic crystals of colloidal crystal structure are fabricated using uniformly sized spherical particles of several hundred nanometers in size, and inverted by filling nanometer-sized inorganic and semiconductor particles and removing colloidal crystals therebetween. Photonic crystal of structure was prepared.

The application of the photonic crystal structure has been introduced in various patents, and US Patent 6,343,167 has been disclosed in the photonic signal delay device using a photonic crystal structure of the two-dimensional periodic form. In addition, US Pat. No. 6,175,671 discloses an application as an optical switch device using a waveguide device, and US Pat. No. 5,740,287 uses a laminated structure of materials having different dielectric constants.

Such a patent is possible to manufacture a photonic crystal using a colloid, but the appearance is not controlled to apply to the device, and even in the case of an optical device using a photonic crystal, a simple one-dimensional, not three-dimensional, such as that made through the colloidal method. It differs from this invention in the point which has a structure.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method of manufacturing a colloidal crystal in which the form of the colloidal crystal is freely controlled, and which can be variously applied to small devices required in the field of optical communication.

Another object of the present invention is to provide a method for producing an inverted porous structure having the colloidal crystal as a template so as to change the properties of the optical bandgap to be very useful in the optical communication field.

1 is a principle diagram for explaining the manufacturing process of the colloidal crystal and porous structure according to the present invention

FIG. 2 is an optical micrograph of a colloidal solution penetrated into a capillary

3 is an electron scanning micrograph of a thin cylindrical colloidal crystal composed of polymer particles

4 is an electron scanning micrograph of a thin cylindrical colloidal crystal composed of silica particles;

5 is an electron scanning micrograph of a porous structure made of silica prepared using colloidal crystals as a template

6 is an electron scanning micrograph of a porous structure made of a polymeric material prepared using a colloidal crystal as a template

7 is a result of measuring the reflectivity according to the size of the polymer particles in the colloidal crystal of the thin cylinder form

The present invention is a method for producing colloidal crystals,

Penetrating the colloidal solution into the capillary; and evaporating the solvent in the colloidal solution to crystallize the colloid; and removing the capillary.

According to the present invention, it is possible to produce colloidal crystals of various shapes depending on the shape of the capillary tube to be used, and also to invert the structure of the colloidal crystals by using this as a template.

The capillary provides a space of a predetermined shape for filling the colloidal solution, in which case the specific shape does not require special limitation. Thus, depending on the desired shape of the final crystals, the shape of the capillary can be variable. The following preferred embodiment described below discloses a cylindrical cylinder structure, but it should be noted that this is only one aspect of various shapes provided to explain the contents of the present invention.

The capillary tube should be of a material that is easy to remove after the colloidal crystals are formed. The material that satisfies these requirements is preferably a material that can be removed by sintering with a polymer or inorganic material that can be dissolved in a specific solvent. Whether to remove with a solvent or sintering can be appropriately selected by those skilled in the art in consideration of the characteristics of the colloidal crystal therein.

Specifically, the polymer and inorganic materials that can be used as the material of the capillary are listed. Polymers include polystyrene, polymethylmethacrylate, polyphenylmethacrylate, polyacrylate, polyalphamethylstyrene, poly1-methylcyclohexyl methacrylate, polycyclohexyl methacrylate, polybenzyl methacrylate, poly Chlorobenzyl methacrylate, poly1-phenylcyclohexyl methacrylate, poly1-phenylethyl methacrylate, polyperfuryl methacrylate, poly1,2-diphenylethyl methacrylate, polypentabromophenyl methacrylate There are homopolymers, such as acrylate, polydiphenylmethyl methacrylate, and polypentachlorophenyl methacrylate, and the copolymer comprised from these.

Inorganic materials include fused synthetic silica, fused quartz, borosilicate, titania, zirconia, and the like.

Particles contained in the colloidal solution is a substance capable of crystallization through self-assembly by evaporation of the solvent and need not be limited to a particular kind as long as the crystal is industrially useful. Examples of possible particles are organic polymer particles or inorganic particles, and examples of polymer particles include polystyrene, polymethylmethacrylate, polyphenylmethacrylate, polyacrylate, polyalphamethylstyrene, poly1-methylcyclohexylmetha. Acrylate, polycyclohexyl methacrylate, polybenzyl methacrylate, polychlorobenzyl methacrylate, poly1-phenylcyclohexyl methacrylate, poly1-phenylethyl methacrylate, polyperfuryl methacrylate, poly Methyl methacrylate as a homopolymer or copolymer composed of 1,2-diphenylethyl methacrylate, polypentabromophenyl methacrylate, polydiphenylmethyl methacrylate, and polypentachlorophenyl methacrylate Acrylate-benzyl methacrylate copolymer, styrene-acrylonitrile copolymer, MMA-TFEMA (2,2,2-tri Fluoroethyl methacrylate) copolymer, MMA-PFPMA (2,2,3,3,3-pentafluoropropylmethacrylate) copolymer, MMA-HFIPMA (1,1,1,3,3,3 Hexafluoroisomethacrylate) copolymer, MMA-HFBMA (2,2,3,3,4,4,4-heptafluorobutylmethacrylate) copolymer, TFEMA-PFPMA copolymer, TFEMA-HFIPMA Copolymers, styrene-methylmethacrylate (SM) copolymers, and TFEMA-HFBMA copolymers.

Examples of inorganic particles include fused synthetic silica, fused quartz, borosilicate, titania, zirconia, and the like.

The solvent is capable of self-assembly and is preferably selected from materials larger than the effective density of the selected particles. Usable as such solvents, for example, water, methanol, ethanol, ethylene glycol, glycerol, perfluorodecalin, perfluoromethyldecalin, perfluorononane, perfluoroisoacid, perfluorocyclohexane, perfluoro1,2-dimethyl There is one kind selected from the group consisting of cyclohexane, perfluoro2-methyl2-pentene and perfluorokerosene.

The evaporation of the solvent is typically required to be carried out below the boiling point of the solvent. The faster the evaporation rate of the solvent, the shorter the time taken for photonic crystals to form on the surface of the solvent. It can cause problems. In the present invention, the optimum evaporation conditions for the crystal formation are different depending on the type of particles and the solvent used, and these are merely matters that can be easily selected by those skilled in the art from the description of the present invention, and thus no specific specification of these conditions is required. .

1 is a schematic diagram of a process of manufacturing the colloidal crystal, the colloidal solution penetrates into a cylindrical capillary and the solvent is evaporated to form a colloidal crystal in the form of a cylinder by densification in a face-centered cubic structure by a self-assembly process. Is shown.

The present invention comprises the steps of infiltrating the colloidal solution into the capillary, evaporating the solvent in the colloidal solution to crystallize the colloid, infiltrating the polymer precursor into the capillary and polymerizing, and removing the capillary and colloidal crystals It includes a method for producing a porous structure using a colloidal crystal comprising a.

Since the capillary and colloidal solution is the same as described above, only the process of forming the porous structure will be described below.

Colloids are not coated on the inner wall due to the low concentration and surface tension of the solution in the capillary. Therefore, when the polymer precursor solution is penetrated into the crystal and the capillary together with the initiator in the capillary to polymerize the polymer, a new composite structure having the crystal as a template can be obtained. The composite structure is an intermediate for obtaining a porous structure, and when the capillary and colloidal crystals are removed in the future, the final porous structure as shown in FIG. 1 is obtained.

The polymer precursor that penetrates into the capillary in which the colloidal crystal is formed is a monomer used in conventional polymer synthesis, and includes styrene, urethane, methyl methacrylate, phenyl methacrylate, acrylate, alphamethyl styrene, and 1-methylcyclohexyl methacryl. Latex, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, 1-phenylcyclohexyl methacrylate, 1-phenylethyl methacrylate, perfuryl methacrylate, 1,2-diphenylethyl methacrylate Acrylate, pentabromophenyl methacrylate, diphenylmethyl methacrylate, pentachlorophenyl methacrylate, and the like.

In this case, as a conventional initiator for polymer polymerization, azo-bis-iso-butylnitrile (AIBN), azobisdimethylvelonitrile, benzoyl peroxide, t-butylhydroperoxide, t-butylperoxyoctanoate, t -Butyl peroxybenzoate, cumin hydroperoxide, cumyl peroxide and the like can be penetrated with the monomer.

In another aspect, the present invention is to penetrate the colloidal solution into the capillary, to evaporate the solvent in the colloidal solution to crystallize, to penetrate the mineral precursor in the capillary and mineralization (mineralization), and capillary and colloidal crystals It includes a method for producing a porous structure using a colloidal crystal comprising the step of removing.

Examples of the inorganic precursors include tetramethylorthosilicate, tetraethylorthosilicate, titanium butoxide, zirconium butoxide and the like. Mineralization reactions using these precursors include conventional sol-gel preparation.

Capillary and colloidal crystals can be removed by dissolving or sintering in a specific solvent (eg hydrofluoric acid). Whether to remove with a solvent or sintering can be appropriately selected by those skilled in the art in consideration of the characteristics of the colloidal crystal therein.

The colloidal crystal and the inverted structure manufactured through the above process may be provided in the manufacture of a laser, a piezoelectric sensor, an actuator, a separation membrane of chromatography, a catalyst carrier, an optical integrated circuit, an optical filter, an optical sensor, a display device, and the like. .

Hereinafter, the content of the present invention will be described in more detail with reference to Examples. However, these examples are only presented to understand the content of the present invention, and the scope of the present invention should not be construed as being limited to these embodiments.

The colloidal solution used in this example was a dispersion of monodisperse polymer polystyrene or silica particles of several hundred nanometers in size, and the concentration was 10%. The polystyrene spherical particles were polymerized according to the emulsion polymerization method without an emulsifier which is a known method, and the silica spherical particles were prepared by a multi-step sol-gel according to the Stover-pink-this method which is similarly known. As the capillary, a cylindrical shape made of silica material or polymethyl methacrylate was used.

Example 1 Colloidal Crystal Form I

The 10% silica colloidal solution was permeated into a cylindrical capillary made of polymethylmethacrylate (FIG. 2A). The capillary infiltrated with the colloidal solution was placed in an oven at 40 ° C. and the solvent in the solution was completely evaporated. The evaporated capillary was sintered at 500 ° C. for 3 hours to obtain colloidal crystals as shown in FIG. 3. According to FIG. 3, colloidal crystals having a thin cylinder form can be observed that particles having a uniform size of 200 to 300 nm are densely formed in a face centered cubic structure. The length of the crystals is determined by the colloidal solution and can be made up to several millimeters. The diameter of the colloidal crystal is determined by the diameter of the capillary tube and shows that the diameter of the crystal according to this embodiment is approximately 5 to 10 μm.

Example 2 Colloidal Crystals II

The 10% polystyrene colloidal solution was penetrated into the cylindrical capillary made of silica (FIG. 2B). The capillary infiltrated with the colloidal solution was placed in an oven at 40 ° C. and the solvent in the solution was completely evaporated. The evaporated capillary was treated with 20% hydrofluoric acid to obtain colloidal crystals as shown in FIG. 4.

Example 3 Porous Structure I

A 10% silica colloidal solution was permeated into a cylindrical capillary made of silica. The capillary infiltrated with the colloidal solution was placed in an oven at 40 ° C. and the solvent in the solution was completely evaporated. A 99% styrene monomer solution, an ABIN as an initiator, was penetrated into the monomer solution by 0.1% by weight, and thermal polymerization was performed at 80 ° C. for 12 hours. The composite structure formed as above was removed with capillary and colloidal crystals with 20% hydrofluoric acid to obtain a colloidal crystal as shown in FIG.

Example 4 Porous Structure II

A 10% polystyrene colloidal solution was permeated into a cylindrical capillary made of polymethylmethacrylate. The capillary infiltrated with the colloidal solution was placed in an oven at 40 ° C. and the solvent in the solution was completely evaporated. 25% silica precursor solution (tetramethylorthosilicate + 1N hydrochloric acid) was infiltrated into the evaporated capillary and solidified through a sol-gel reaction. The composite structure formed as above was sintered at 500 ° C. for 3 hours to remove capillary and colloidal crystals together to obtain a colloidal crystal as shown in FIG. 6.

Test Example 1 Reflectance Analysis

The reflectivity of the colloidal crystals made of polymer particles having different sizes of 300 nm, 320 nm, and 400 nm obtained in Example 1 was analyzed according to the visible light wavelength of the cross section. The results are shown in FIG. 7, and it can be seen that the maximum reflection occurs at different wavelengths depending on the size of the particles. This result is consistent with the calculation of the maximum reflectance wavelength for each sample by Bragg scattering conditions. The experimental results show that the colloidal crystals can be usefully applied to small optical filters.

According to the present invention, colloidal crystals of various shapes can be prepared according to the shape of the capillary tube, and an inverted structure of colloidal crystals can be prepared by using this as a template. The colloidal crystal and the inverted structure manufactured by the above process are easy to control the optical properties, which is very useful for miniaturization of the device required in the optical communication field.

Claims (9)

In the method for producing a colloidal crystal, Penetrating the colloidal solution into the capillary, evaporating the solvent in the colloidal solution to crystallize the colloid, and removing the capillary. The method of claim 1, Method for producing a colloidal crystal, characterized in that the inorganic particles are dispersed colloidal solution. The method of claim 1, Method for producing a colloidal crystal, characterized in that the colloidal solution in which the polymer particles are dispersed. The method of claim 1, Capillary is a method for producing a colloidal crystal, characterized in that the predominantly polymer or inorganic. Penetrating the colloidal solution into the capillary, evaporating the solvent in the colloidal solution to crystallize the colloid, penetrating the polymer precursor into the capillary and polymerizing the polymer, and removing the capillary and the colloidal crystals. Method for producing a porous structure using colloidal crystals. Infiltrating the colloidal solution into the capillary, evaporating the solvent in the colloidal solution to crystallize the colloid, infiltrating the inorganic precursor into the capillary and mineralizing it, and removing the capillary and colloidal crystals. Method for producing a porous structure using colloidal crystals. The method according to any one of claims 1 to 4, Capillary is a method of producing a colloidal crystal, characterized in that the cylindrical shape. The method of claim 5, wherein Capillary is a method of producing a colloidal crystal, characterized in that the cylindrical shape. The method of claim 6, Capillary is a method of producing a colloidal crystal, characterized in that the cylindrical shape.