KR101688212B1 - Process for preparing photonic crystal polymer substrate for florescence signal amplication - Google Patents

Abstract

The present invention modifies the intensity and shape of the fluorescence spectrum of a fluorescent polymer by using a photonic crystal polymer film. The photocrystalline film is used to control the fluorescence path of the fluorescent material, Can be achieved without changing the structure or amount.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for manufacturing a photonic crystal polymer substrate for amplifying a fluorescence signal,

The present invention relates to a method of manufacturing a photonic crystal polymer substrate for amplifying a fluorescence signal, and more particularly, to a method of manufacturing a photonic crystal polymer substrate for amplifying a fluorescence signal, To a method for manufacturing a photonic crystal polymer substrate.

Microarray Biochip is a high-density integration of biomaterials such as DNA, proteins, and cells on the surface of a solid substrate. By using the microarray bio-chip, biological information can be used to identify gene expression patterns, genetic defects, DNA-Protein interactions, Protein- Chemical-protein interactions, disease diagnosis, and the like.

The microarray biochip analysis device can use detection technology such as fluorescence, chemiluminescence, mass spectrometry, and SPR.

Fluorescent labeling assay, which involves labeling a sample with a fluorescent material and analyzing it with a fluorescent scanner, is commonly used in the microarray biochip analysis device.

In analyzing a microarray biochip, conventionally, a bioreceptor was attached to a plate-shaped substrate and a sample labeled with a fluorescent material was introduced, and analysis was performed. At this time, since the surface area of the plate type substrate is limited, the amount of the bioreceptor attached on the substrate is limited, and thus the fluorescent signal emitted is limited, which makes it difficult to detect low concentration biomaterials. Accordingly, in order to modify the intensity and shape of the fluorescence spectrum of the fluorescent polymer, a method of changing the chemical structure or amount of the fluorescent material has been inevitable. However, in recent years, it has been known that nanoparticles of metal can amplify the fluorescence intensity (Bardhan et al., ACS NANO VOL. 3, No. 3, 744-752, 2009) There is a problem that quenching of the fluorescent material occurs depending on the kind of the particles and the fluorescent signal is killed.

Therefore, it is necessary to study the process of manufacturing a photonic crystal polymer substrate for fluorescence signal amplification, efficiently controlling the path of the fluorescent light without the quenching problem of the fluorescent material without changing the chemical structure of the fluorescent material.

The present invention provides a method for manufacturing a photonic crystal polymer substrate for amplifying a fluorescence signal, which can amplify and convert a fluorescence signal using a photonic crystal film without changing the chemical structure of the phosphor or the like.

The present invention also provides a photonic crystal polymer substrate for amplifying a fluorescence signal, which is produced by such a method.

The present invention provides a method of producing a photonic crystal polymer film, comprising: producing a photonic crystal polymer film using a photonic crystal dispersion composition comprising a photocurable monomer containing an acrylate group, spherical photonic crystal particles, and a photoinitiator; And applying a fluorescent material onto the film. The present invention also provides a method of manufacturing a photonic crystal polymer substrate for amplifying a fluorescence signal.

The present invention also provides a photonic crystal polymer substrate for amplifying a fluorescence signal, which is produced according to the above method.

Hereinafter, a method for fabricating a photonic crystal polymer substrate for amplifying a fluorescence signal according to a specific embodiment of the present invention, a photonic crystal polymer substrate for amplifying a fluorescence signal manufactured therefrom, etc. will be described in detail.

The inventors of the present invention have been studying a fluorescence signal amplification substrate capable of amplifying the intensity of a fluorescence spectrum. However, what has been possible only by changing the chemical structure of a conventional phosphor is that a photonic crystal film is used as a substrate, Can be achieved without changing the structure or the amount of the phosphor, thereby completing the present invention.

According to one embodiment of the present invention, a method of manufacturing a photonic crystal polymer substrate for amplifying a fluorescence signal is provided. The method for producing a photonic crystal polymer substrate for amplifying a fluorescence signal includes the steps of: producing a photonic crystal polymer film using a photonic crystal dispersion composition comprising a photocurable monomer containing an acrylate group, spherical photonic crystal particles, and a photoinitiator; And applying a fluorescent material onto the film.

In particular, the method of manufacturing a photonic crystal polymer substrate for amplifying a fluorescence signal according to the present invention uses a photonic crystal polymer film as a substrate to control the path of a fluorescent light by using a photonic crystal polymer film, So that it can be achieved without changing the structure or amount of the phosphor.

The photocatalytic polymer film used as the substrate in the present invention can be produced by processing a photocatalyst dispersion composition containing a photocurable monomer containing an acrylate group, spherical photonic crystal particles, and a photoinitiator into a film and irradiating light.

The photo-curable monomer having an acrylate group in the photochemical dispersion composition has two or more double bonds, preferably two or more acrylate groups, and is liquid at room temperature. The photocurable monomer may be selected from the group consisting of ethoxylated trimethylolpropane triacrylate (ETPTA), di (trimethylolpropane) tetracrylate, glycerol propoxylate triacrylate, (meth) acrylate, triacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane ethoxylate triacrylate, and trimethylolpropane ethoxylate triacrylate. Gt; and / or < / RTI >

In addition, the photonic crystal dispersion composition includes spherical photonic crystal particles together with the photocurable monomer containing the acrylate group. The spherical photonic crystal particles are characterized by containing a hydrophilic group on the surface and may be selected from the group consisting of silica, polystyrene, polymethylmethacrylate, titanium dioxide, iron oxide, aluminum oxide, zirconium oxide, and zinc oxide ). ≪ / RTI > Of these, silica, polystyrene, polymethylmethacrylate and the like are preferable from the viewpoint of preventing light transmission loss due to scattering.

The size of the spherical photonic crystal particles may be 5 to 2,000 nm, preferably 50 to 1,000 nm, more preferably 100 to 500 nm. The size of the spherical photonic crystal particles can be kept within the range described above in order to form a photonic crystal that efficiently reflects the visible light and the near-infrared light. In addition, the photonic crystal particles must be spherical. However, if the difference between the refractive index of the particles and the refractive index of the photonic crystal polymer film is large, the reflection signal due to the photonic crystal increases, but at this time, the background signal also increases due to scattering by the particles. That is, if the refractive index difference between the particles and the film is too small to be about 0.01 or less, the transparent signal may be weak but the reflection signal may be weak and the amplification effect of the fluorescence signal may not be remarkable. If the refractive index difference is about 0.05 or more, the film itself becomes opaque. There is a drawback that it falls.

The spherical photonic crystal particles may have a volume ratio of 0.1 to 0.7, preferably 0.15 to 0.6, more preferably 0.2 to 0.5, based on the total volume of photocurable monomers. The spherical photonic crystal particles may have a volume ratio of 0.1 or more in terms of high diffraction of light and a volume ratio of 0.7 or less in terms of viscosity of the dispersion.

In addition, the photonic crystal dispersion composition further comprises a photoinitiator. The photoinitiator is characterized in that a radical is generated by irradiation with UV light. In particular, the photoinitiator has a wavelength in the ultraviolet wavelength range of 320 to 380 nm, preferably 330 to 375 nm, more preferably 340 to 370 nm Radicals are generated during light irradiation and the photo-curing reaction starts. For example, the photoinitiator may be selected from the group consisting of anthraquinone, anthraquinone-2-sulfonic acid, sodium salt monohydrate, benzene tricarbonylchromium, benzoin ethyl ether, benzoin isobutyl ether, benzoin methyl ether, benzophenone, 4-benzoylbiphenyl, and the like. ), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone [ benzophenone, dibenzosuberenone, 2,2-dimethoxy-2-phenylacetophenone, 3,4-dimethylbenzophenone, 3'-hydroxyacetophenone, 2-hydroxy-2-methyl propiophenone, 2-hydroxy- (2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl propiophenone], 1-hydroxycyclohexyphenyl ketone (1- hydroxycyclohexyphenyl ketone, methylbenzoyl formate, diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, phosphine oxide phenylbis (2,4,6-trimethylbenzoyl), 2-methyl-1- [4- (methylthio) phenyl] -2- 2- (4-morpholinyl) -1-propanone}, 2-benzyl-2- (dimethylamino) -1- [ (4-morpholinyl) phenyl] -1-butanone}, 2-dimethylamino- 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-methyl-benzyl) -morpholin-4-yl-phenyl) -butan-1-one], bis (5-2,4-cyclopentadien- Yl) -bis (2,6-difluoro-3 (1 H-pyrrol-l- yl) -phenyl] titanium, 2-isopropyl thioxanthone, 2-ethyl anthraquinone, 2,4-dihexyl thioxanthone Benzyl dimethyl ketal, benzophenone, 4-chloro benzophenone, methyl-2-benzoylbenzoate, 4-phenylbenzophenone 4-phenyl benzophenone, 2,2'-bis (2-chlorophenyl) -4,4'-5,5'-tetraphenyl- -chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole], 2,2', 4-tris (2- chlorophenyl) -5- (3,4- Phenyl) -4 ', 5'-diphenyl-1,1'-biimidazole [2,2', 4-tris (2-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenyl-1,1'-biimidazole], 4-phenoxy-2 ', 2'-dichloro acetophenone, ethyl 4- (dimethylamino) benzoate ethyl-4- (dimethylamino) benzoate], isoamyl 4- (dimethylamino) benzoate, 2-ethylhexyl- 4- (dimethylamino) benzoate], 4,4'-bis (diethylamino) benzophenone, 4- (4'-methylphenylthio) 4-methylphenylthio) -benzophenone], 1,7-bis (9-acridinyl) heptane, n-phenyl glycine, and 2- And 2-hydroxy-2-methylpropiophenone may be used. Among them, anthraquinone-2-sulfonic acid (sodium salt monohydrate), benzoin ethyl ether, benzoin isobutyl ether benzoin isobutyl ether, benzoin methyl ether, dibenzosuberenone, 2,2-dimethoxy-2-phenylacetophenone, 3, 3,4-dimethylbenzophenone, 3'-hydroxyacetophenone, 2-hydroxy-2-methyl propiophenone, and the like, desirable.

The photoinitiator may be used in an amount of 0.1 wt% to 10 wt%, preferably 0.5 wt% to 5 wt%, more preferably 0.75 wt% to 1.5 wt%, based on the total amount of photocurable monomer. The photoinitiator may be used in an amount of 0.1% by weight or more from the viewpoint of allowing sufficient photo-curing reaction to proceed when irradiated with ultraviolet (UV) light. However, when the photoinitiator is used in an excess amount exceeding 10% by weight, the light transmittance of the photonic crystal polymer film can be reduced by absorbing light in the visible light region.

In addition, the photocatalyst dispersion composition may further include a dispersing agent capable of dispersing photonic crystal particles such as silica. Examples of such a dispersing agent include a component which can be removed through volatilization or evaporation such as ethanol, distilled water and methanol, or a dispersion monomer capable of forming a polymer film through photocuring reaction together with the photocurable monomer. Here, the dispersion monomer has a (meth) acrylate-based dispersion-use monomeric silica having a terminal hydroxyl group and a hydroxyl group capable of dispersing silica through hydrogen bonding, and a double bond contained in the polymeric film through a photoreaction (Meth) acrylate-based dispersion monomer having a terminal hydroxy group, and the like.

The dispersing monomer may be selected from the group consisting of 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, Hydroxybutyl methacrylate, 2-hydroxy-3- {3- [2,4,6,8-tetramethyl-4,6,8-tris (propylglycidyl ether) -2- 2-Hydroxy-3- {3- [2,4,6,8-tetramethyl-4,6,8-tris (propyl glycidyl ether) -2-cyclotetrasiloxanyl] propyl methacrylate propoxy} propyl methacrylate, and caprolactone 2- (methacryloyloxy) ethyl ester). These may be used alone or in combination of two or more. Among them, 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (2-hydroxyethyl acrylate), and 4-hydroxybutyl acrylate 4-hydroxybutyl acrylate, and hydroxybutyl methacrylate.

When a dispersant such as ethanol is used in the photocrystalline dispersion composition of the present invention, a dispersing agent is mixed with a photocurable monomer, a spherical photonic crystal particle, and a photoinitiator, processed into a suspension, and then a volatilization step is added so as to remove a dispersant such as ethanol . At this time, the dispersing agent such as ethanol is used in a mass ratio of 1: 0.01 to 1:20, preferably 1: 0.05 to 1:10, more preferably 1: 0.1 to 1: 5 Can be used.

In the photocatalyst dispersion composition of the present invention, when the dispersing monomer is used as the dispersing agent, the content of the photoinitiator and the photonic crystal particle may be adjusted based on the total amount of the photocurable monomer and the dispersing monomer. The photocurable monomer and the dispersing monomer may be mixed in a volume ratio of 0.1: 9.9 to 9: 1, preferably 0.5: 9.5 to 8.5: 1.5, more preferably 1: 9 to 8: have. In particular, it is more preferable that the volume ratio of the photocurable monomer and the dispersing monomer is 1: 9 to 8: 2 in terms of effective dispersion of silica. In particular, in the free standing photocrystalline polymer film according to the present invention, the photocurable monomer and the dispersing monomer have a volume ratio of 9: 1 to 3: 7, preferably 8.5: 1.5 to 3: 7, Preferably in a volume ratio of 8: 2 to 3: 7.

Meanwhile, the photocatalytic dispersion composition is prepared by mixing the photocurable monomer, spherical photonic crystal particles, and photoinitiator as described above, dispersing the mixture at room temperature for 30 minutes, and then dispersing the dispersion in a UV / Vis spectrometer at a wavelength of 400 nm to 800 nm The measured transparency can be 80% or more, preferably 85% or more, more preferably 90% or more at the wavelength except for the region where the reflection occurs by the photonic crystal.

The photocatalyst polymer film according to the present invention can be produced by applying the photonic crystal dispersion composition on a separate substrate such as a glass substrate in the form of a film and conducting light irradiation. Further, before applying the photonic crystal dispersion composition to a separate substrate, ultrasonic irradiation may be further performed for 30 minutes at room temperature. The light irradiation step may be performed by irradiating a 365 nm wavelength under a nitrogen condition.

The photocrystalline polymer film thus produced can be produced in the form of a free standing film. Such a free standing film can be easily peeled off from the glass substrate with weak adhesive force with the glass substrate after photo-curing, Quot; In addition, the photonic crystal polymer film may have a thickness of 10 to 1,000 mu m. The thickness of the photonic crystal polymer film is preferably 20 to 500 mu m, more preferably 30 to 400 mu m. If the thickness of the photonic crystal polymer film is too thin, the signal reflected by the photonic crystal is weak and too thick, but the reflectivity due to the photonic crystal does not increase.

The photonic crystal polymer film may have a reflectivity of 5 to 100, preferably 10 to 97.5, and more preferably 20 to 95 as a photonic crystal peak measured by regular reflection. The reflectivity of such a photonic crystal polymer film can maintain the above-described range in terms of efficient modulation of the fluorescence signal. The reflection peak of the photocatalytic polymer film may appear at a wavelength of 200 nm to 2000 nm, preferably 300 nm to 1000 nm, more preferably 380 nm to 780 nm. Such a photonic crystal polymer film can control the intensity of the fluorescence peak in the same region as the position of the reflection peak.

In addition, the transmittance of the photo-curable polymer film measured by a UV / Vis spectrometer may show a transmittance degradation peak in the opposite phase to the reflectance peak in the same region as the reflectance peak as described above. That is, the photocurable polymer film may exhibit a transmittance degradation peak at a wavelength of 200 nm to 2000 nm, preferably 300 nm to 1000 nm, more preferably 380 nm to 780 nm, corresponding to the reflection wavelength. In addition, the photocurable polymer film exhibits a transmittance of 85% or more, 90% or more, or 95% or more in a wavelength region larger than the peak of transmittance degradation and 80 Or less, or 75% or less, or 50% or less. For example, when the transmittance lowering peak is centered at 560 nm, the transmittance is 80% or less in a wavelength region of 540 nm or less and the transmittance is 85% or more in a wavelength region of 580 nm or more. Particularly, as the transmittance becomes lower in the wavelength region smaller than the transmittance lowering peak, the transmittance of the wavelength region becomes lower as the wavelength region becomes lower.

According to the present invention, as described above, the photocrystalline dispersion composition is used to prepare a free standing film through light irradiation or the like, and the fluorescent material is coated on the substrate using the photoresist as a substrate to form a photonic crystal polymer A substrate can be manufactured. The fluorescent material may be at least one selected from the group consisting of a polyvinylene compound, a cinnamate compound, a coumarin compound, a naphthalene compound, a cyanide compound, an anthracene compound, a pyrene compound, a rhodamine compound, a heterocyclic compound, And at least one selected from the group consisting of Examples of the fluorescent material include poly (p-phenylenevinylene), poly (2,5-thienylenevinylene), 3,6-bis-dimethylaminoacridine, 9-aminoacridine, 9 - (4-diethylamino-1-methylbutylamino) -3-chloro-7-methoxyacridine, aryl-naphthalene-sulfonate, N- p-toluidinyl-naphthalene-6-sulfonate, 1,1'-dihexyl-2,2'-oxacarbocyanine, 3,3'-dipropylthia-dicarbocyanine (iodide) (3H) -benzoxazolylidene) -2-butenylidene] -1,3-dibutyl-2-thiabarbituric acid, tetramethyldiaminodiphenyl-keto Imine hydrochloride, 1,6-diphenyl-1,3,5-hexatriene, 2 ', 4', 5 ', 7'-tetrabromofluorescein, 2,7- Benzoylamido-4'-aminostilbene-2,2'-di (3-hydroxyphenyl) (5)] pentamethine oxonol, [alpha] (9,11 [beta] -dihydroxybis , 13,15-cis, trans, trans, cis) octadecatetraenoic acid beta (9,11,13,15-all-trans) -octadecatetraenoic acid, perylene (dibenz [de, kl] anthracene Phenyl-1-naphthylamine, pyrene (benzo [def] phenanthrene), 2,8-dimethyl-3,7-diamino-5-phenylphenazium chloride, 4- -2 (3H), 1'-futtalan] -3,3'-dione, o-phthalic dicarboxaldehyde, 1 -dimethylaminophthalene-5-sulfonyl chloride, fluorescein isothiocyanate N-dodecyl aziridine, N- (1-anilinonaphthyl-4) maleimide, 7-dimethylamino- (2,5-bis- (5- tert -butyl-2-benz-oxazolyl) thiophene), N- (3-pyrene) maleimide, , Rubrene, nile red, etc. The can. Examples of the inorganic fluorescent material include II-VI group compounds such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, and HgTe; Group III-V compounds such as GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP and InAs; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HggZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, InAlN, InAlN, InAlN, InAlN, InAlN, InAlN, InAlN, InAlN, InAlN, InAlN, InAlN, InAlN, InAlN, InGaN, InGaN, InGaN, InGaN, Of these, a polyvinylene-based compound, a rhodamine-based compound and the like are preferable from the viewpoint of the coating.

The fluorescent material may be applied by a method such as spin coating, spraying, inkjet printer, dipping, casting, gravure coating, bar coating, roll coating, wire bar coating, screen coating, Process can be performed.

The coating layer of the fluorescent substance formed on the photonic crystal polymer film may have a thickness of 1 to 2,000 nm. The thickness of the fluorescent material coating layer may preferably be 2 to 1,000 nm, more preferably 5 to 500 nm. The thickness of the fluorescent substance coating layer may be 1 nm or more, more preferably 5 nm or more, to obtain a sufficient fluorescence signal, and 2,000 nm or less for the amplification of the fluorescent signal to be performed by the photonic crystal film, And may be 500 nm or less.

According to another embodiment of the present invention, there is provided a photonic crystal polymer substrate for amplifying a fluorescence signal, which is produced by the above-described method.

The photocatalyst polymer substrate for amplifying a fluorescent signal of the present invention can change the intensity and shape of a fluorescence spectrum without changing the chemical structure of the fluorescent material and the like. In particular, by adjusting the reflectivity of a polymer film itself used as a substrate to which a fluorescent material is applied And the position, shape, and shape of the fluorescent peak can be variously adjusted in the final photoluminescence polymer substrate for fluorescence amplification.

The photonic crystal polymer substrate for fluorescence signal amplification may exhibit fluorescence peaks at a wavelength of 200 nm to 2,000 nm, preferably 300 nm to 1,000 nm, more preferably 380 nm to 780 nm. In particular, such fluorescence peaks can exhibit wavelengths of more than 380 nm and less than 780 nm, which are human visible visible light regions.

The photocatalyst polymer substrate for amplifying a fluorescent signal of the present invention can exhibit a fluorescence spectrum amplified by about 1.2 times or more, about 1.8 times or more, and about 2.2 times or more as compared with the case where a fluorescent substance is applied under the same conditions using a glass substrate have. However, as described above, the photonic crystal polymer substrate for signal amplification of the present invention can not only amplify the fluorescence peak intensity and area, but also can control the shape of the fluorescence spectrum, the position and intensity of the fluorescence peak, .

In the present invention, matters other than those described above can be added or subtracted as required, and therefore, the present invention is not particularly limited thereto.

According to the present invention, there is an excellent effect that the photocrystalline polymer film can be used as a substrate to control the path of the fluorescent light and can be achieved without changing the structure and amount of the phosphor, which has been possible only by changing the chemical structure of the conventional phosphor.

Further, the photonic crystal polymer substrate for amplifying a fluorescence signal of the present invention has an advantage that it can be manufactured by adjusting the intensity and shape of a fluorescence spectrum according to a desired one.

1 is an SEM image (size: 190 nm ± 10 nm) of silica particles synthesized according to Example 1 of the present invention.
2 is a specular reflection diagram according to the thickness of the photonic crystal film synthesized according to Examples 1 to 3 and Comparative Example 1 of the present invention.
3 is a graph showing the transmittance according to the thickness of the photonic crystal film synthesized according to Examples 1 to 3 and Comparative Example 1 of the present invention.
4 is a specular reflection diagram according to the thickness of a photonic crystal film synthesized according to Examples 4 to 7 of the present invention.
5 is a schematic diagram showing a fluorescence spectrum measurement method for a photonic crystal polymer substrate for amplifying a fluorescence signal finally prepared according to Examples 1 to 3 and Comparative Example 1 of the present invention.
6 is a graph showing changes in fluorescence spectra according to the thickness of the photonic crystal film synthesized according to Examples 1 to 3 and Comparative Example 1 of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example 1]

Spherical silica synthesis

Distilled water (94 mL, 5M), ethanol (980 mL) and ammonium hydroxide (43 mL, 0.23 M) were placed in a two-neck round flask and stirred at 350 rpm. TEOS (95 mL, 0.314 M) and ethanol (380 mL) were diluted in a total ethanol: TEOS ratio of 4: 1 and then placed in a round flask and stirred at room temperature for 2 hours. After completion of the reaction, the suspension was filled up to 40 mL in a 50 mL centrifuge tube and centrifuged at 3800 rpm for 30 minutes. In the centrifuge tube, pelletized silica and solution remained. After the solution was discarded, the solution was filled with pure ethanol, sonicated until the silica pellet was dispersed in ethanol, and then washed with a centrifuge. When ammonium hydroxide, distilled water, and unreacted TEOS remaining in silica particles were completely removed, they were dried in a convection oven at 70 ° C. The size of the synthesized silica particles was analyzed by a scanning electron microscope (SEM), and spherical particles having an average particle size of 174.4 ± 2.6 nm (PDI 0.066) were identified as shown in FIG.

Fabrication of photonic crystal polymer substrate

2.72 g (1 wt% of photoinitiator to ETPTA) of ethoxylated trimethylolpropane triacrylate (ETPTA) and 2-hydroxy-2-methyl propiophenone as photoinitiator , Silica particles (3.34 g) and ethanol (3 mL). Then, ethanol was volatilized at 70 ° C for 24 hours to prepare a photocatalyst dispersion. The photocatalyst dispersion was coated on the glass substrate to a thickness of 50 μm and then irradiated with 365 nm wavelength for 3 minutes. The formed coating film was easily peeled off from the glass substrate to form a photonic crystal free standing film. The prepared photonic crystal free standing film was used as a substrate for applying a fluorescent polymer.

Fabrication of Photonic Crystal Polymer Substrate for Fluorescence Signal Amplification

Further, a fluorescent polymer solution was prepared by dissolving 0.04 g of fluorescent polymer poly (para-phenylenevinylene) (Super Yellow from Merck) in 9.96 g of toluene so as to be 0.4 wt%.

The fluorescent polymer solution thus prepared was coated on a photonic crystal free standing film substrate at 2,000 rpm for 30 seconds using a spin coater to form a fluorescent coating layer having a thickness of 50 nm.

[Example 2]

A photonic crystal polymer substrate for fluorescence signal amplification was prepared in the same manner as in Example 1, except that a photocatalyst dispersion (silica volume ratio: 0.4) was coated on a glass substrate to a thickness of 100 μm to prepare a photonic crystal free standing film.

[Example 3]

A photonic crystal polymer substrate for fluorescence signal amplification was prepared in the same manner as in Example 1, except that a photocatalyst dispersion (silica volume ratio: 0.4) was coated on a glass substrate to a thickness of 200 μm to prepare a photonic crystal free standing film.

[Example 4]

(PDI 0.211) having an average particle size of 132.9 ± 4.0 nm was synthesized by using ammonium hydroxide (43 mL, 0.165 M) to prepare a photonic crystal polymer substrate with a photonic crystal dispersion (silica volume ratio of 0.33) A photonic crystal polymer substrate for fluorescence signal amplification was prepared in the same manner as in Example 1.

[Example 5]

Except that a photonic crystal polymer substrate was prepared from photonic crystal dispersion (silica volume ratio of 0.33) by synthesizing spherical silica particles (PDI 0.136) having an average particle size of 148.6 ± 4.3 nm using ammonium hydroxide (43 mL, 0.19 M) A photonic crystal polymer substrate for fluorescence signal amplification was prepared in the same manner as in Example 1.

[Example 6]

(PDI 0.114) having an average particle size of 168.4 +/- 4.7 nm was prepared by using ammonium hydroxide (43 mL, 0.21 M), and a photocatalytic polymer substrate was produced from the photonic crystal dispersion (silica volume ratio of 0.33) A photonic crystal polymer substrate for fluorescence signal amplification was prepared in the same manner as in Example 1.

[Example 7]

(PDI 0.040) having an average particle size of 191.6 ± 3.3 nm was synthesized using ammonium hydroxide (43 mL, 0.25 M) to prepare a photonic crystal polymer substrate with a photonic crystal dispersion (silica volume ratio of 0.33) A photonic crystal polymer substrate for fluorescence signal amplification was prepared in the same manner as in Example 1.

[Comparative Example 1]

A fluorescent polymer solution was prepared by dissolving 0.04 g of fluorescent polymer poly (para-phenylenevinylene) (Super Yellow from Merck) in 9.96 g of toluene so as to be 0.4 wt%. The prepared fluorescent polymer solution was applied on a 2 mm thick glass substrate at 2,000 rpm for 30 seconds using a spin coater.

[Experimental Example]

Evaluation of physical properties of the photonic crystal polymer substrate and the glass substrate produced according to Examples 1 to 7 and Comparative Example 1 and fluorescent spectrum measurement after application of the fluorescent material were carried out in the following manner.

a) specular reflectance and transmittance

The specular reflection and transmittance of the photonic crystal free standing films of Examples 1 to 3 and the organic substrate of Comparative Example 1 were measured using a reflectometer (USB 4000, Ocean Optics) and a UV / Vis spectrometer, respectively, 3.

The specular reflectance of the photonic crystal free standing films of Examples 4 to 7 was measured using a reflectometer (USB 4000, Ocean Optics), and the results are shown in FIG.

b) Fluorescence spectral film

Fluorescence spectral change of the fluorescent polymer according to the type or thickness of the substrate on the fluorescent substance-coated substrate according to Examples 1 to 3 and Comparative Example 1 was observed in a parallel mode as shown in Fig. Particularly, the fluorescence spectra are obtained by irradiating a sample made of a substrate coated with a fluorescent substance with light from an excitation filter, a dichroic beam-splitter, and an objective lens through an excitation light After irradiating the excitation light, the emitted fluorescence light was measured with a detector through a mirror. Here, in order to generate fluorescence, a wavelength of 446 nm was vertically incident on the substrate, and the fluorescence spectrum of the fluorescent polymer was also measured at an angle perpendicular to the substrate, and the measurement result thereof is shown in FIG.

Among them, the physical properties of the photocrystalline polymer substrate and the glass substrate produced according to Examples 1 to 3 and Comparative Example 1 were evaluated, and the fluorescence spectrum measurement results after application of the fluorescent material were as shown in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Substrate type ETPTA polymer film ETPTA polymer film ETPTA polymer film Glass substrate Silica particle size (nm) 174.4 ± 2.6 174.4 ± 2.6 174.4 ± 2.6 174.4 ± 2.6 Silica content (by volume) 0.4 0.4 0.4 0.4 Film / substrate thickness (탆) 50 100 200 2000 The degree of specular reflection of the film (%) 62 75 90 8 Reflection peak wavelength of film (nm) 562 562 562 - Decrease in transmittance of film Peak wavelength (nm) 562 562 562 - Transmittance (%) of the film at a wavelength of 500 nm below the reflection wavelength 88.6 78.1 58.05 96 Transmittance (%) of the film at a wavelength of 600 nm or more above the reflection wavelength 97.56 94.28 90.78 96.09 The thickness (nm) of the fluorescent coating layer 50 50 50 50 Fluorescence peak wavelength (nm) 562 562 562 592 Fluorescence peak intensity (a.u.) 600 605 608 599 Fluorescent peak shape double double double single

On the other hand, as shown in FIG. 4, it can be seen that when the spherical silica particles are applied differently according to Examples 4 to 7, the wavelength region where the reflection peak of the photonic crystal free staining film used as the substrate is located can be controlled. Here, the respective reflection peaks were 420 nm for Example 4, 507 nm for Example 5, 576 nm for Example 6, and 642 nm for Example 7, respectively. Accordingly, there is an advantage in that the position, intensity, and shape of the fluorescent peak of the finally prepared photonic crystal polymer substrate for fluorescence signal amplification can be controlled.

As shown in Table 1, the fluorescence spectra of the fluorescent polymer varied according to the type of the substrate measured when the photonic crystal free standing film was used as the substrate according to Examples 1 to 3, when the glass substrate was used according to Comparative Example 1 It can be seen that the intensity of the fluorescence peak is increased due to the increase of the amount of light scattered by the silica particles and the intensity of the fluorescence peak can be controlled in the same region as the reflection peak of the photonic crystal film (See FIG. 6). This means that the fluorescence spectrum can be freely adjusted. As shown in this example, the change in the fluorescence spectrum in the visible light region means a change in color, so that it can be applied to an information electronic material optimized for human eyes.

Claims (10)

Producing a photonic crystal polymer film having a thickness of 10 to 1,000 mu m using a photonic crystal dispersion composition comprising a photocurable monomer containing an acrylate group, a spherical photonic crystal particle, and a photoinitiator; And
Applying a fluorescent material on the film to a thickness of 1 to 2,000 mu m;
Lt; / RTI >
Wherein the photonic crystal polymer film has a reflection peak at a wavelength of 200 nm to 2,000 nm and the reflectance of the reflection peak measured at a regular reflection is 20% to 95%. The method according to claim 1,
The photocurable monomer may be selected from the group consisting of ethoxylated trimethylolpropane triacrylate (ETPTA), di (trimethylolpropane) tetracrylate, glycerol propoxylate triacrylate, (meth) acrylate, triacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane ethoxylate triacrylate, and trimethylolpropane ethoxylate triacrylate. Wherein the at least one photocatalyst polymer is at least one selected from the group consisting of photocatalysts. The method according to claim 1,
The spherical photonic crystal particles may be at least one selected from the group consisting of silica, polystyrene, polymethylmethacrylate, titan dioxide, iron oxide, aluminum oxide, zirconium oxide, and zinc oxide. A method for manufacturing a photonic crystal polymer substrate for signal amplification. The method according to claim 1,
Wherein the photoinitiator is a compound that generates a radical by light irradiation at a wavelength of 320 to 380 nm. The method according to claim 1,
Wherein the fluorescent substance is selected from the group consisting of a polyvinylene compound, a cinnamate compound, a coumarin compound, a naphthalene compound, an anthracene compound, a pyrene compound, a rhodamine compound, a heterocyclic compound, Wherein at least one selected from the group consisting of photoresist and photoresist is used. The method according to claim 1,
Wherein the spherical photonic crystal particles are contained in a volume ratio of 0.1 to 0.7 based on the total volume of photocurable monomers. The method according to claim 1,
Wherein the spherical photonic crystal particles have a size of 5 to 2,000 nm. delete 8. Process according to any one of claims 1 to 7,
A photonic crystal polymer film having a thickness of 10 to 1,000 占 퐉, and a fluorescent substance coating layer having a thickness of 1 to 2,000 占 퐉,
Wherein the photonic crystal polymer film has a reflection peak at a wavelength of 200 nm to 2,000 nm and the reflectance of the reflection peak measured by regular reflection is 20% to 95%. 10. The method of claim 9,
A photonic crystal polymer substrate for amplifying a fluorescence signal exhibiting a fluorescence peak existing at a wavelength of 200 nm to 2,000 nm.

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