KR101745558B1 - A substrate for surface enhanced raman scattering and fabricating method of the same and analyzing method using the same - Google Patents

Abstract

A surface enhanced Raman scattering substrate is disclosed. The surface enhanced Raman scattering substrate according to an embodiment of the present invention includes a flexible substrate on which a protruding structure is formed, a metal nanostructure formed on a flexible substrate, and a flexible substrate on which the metal nanostructure is formed, Lt; RTI ID = 0.0 > layer. ≪ / RTI >

Description

[0001] The present invention relates to a surface enhanced Raman scattering substrate, a method of manufacturing the same, and an analysis method using the surface enhanced Raman scattering substrate,

The present invention relates to a surface enhanced Raman scattering substrate, a method of manufacturing the same, and an analysis method using the same.

When light enters the surface of metal nanoparticles, free electrons on the surface of metal nanoparticles or metal nanostructures oscillate collectively due to the electromagnetic field of the specific energy of the light and the resonance of the metal nanoparticles. This is called local surface plasmon resonance (LSPR, localized surface plasmon resonance).

Surface-enhanced Raman spectroscopy (SERS) is a technique that can amplify the Raman signal of a molecule using local surface plasmon resonance, and the surface-enhanced Raman scattering substrate (SERS substrate) Quot; refers to a metal nanoparticle or a metal nanostructure capable of amplifying the Raman signal of the metal nanoparticle.

The surface enhanced Raman scattering substrate can be used for various sensors because it can detect trace amounts of pathogens, toxic substances, environmental hormones and chemical / biomaterials such as DNA using SERS signal.

In addition, since the surface enhanced Raman scattering substrate exhibits a signal inherent to a molecule regardless of humidity or temperature change, the reliability of the molecular detection is high.

A first prior art of the present invention is a method for forming a metal cap on a flexible column and encapsulating a coating material on a metal cap, which is disclosed in US Patent Application Publication No. US2013-0195721 (METALLIC-NANOFINGER DEVICE FOR CHEMICAL SENSING) .

Such a sealing technique does not disclose a technique of sealing the entire substrate as a technique of sealing only the metal cap portion.

The principle of amplifying the Raman signal of the first prior art is that a metal cap is formed on the polymer rod, and the mechanical flexibility of the polymer rod is utilized so that the upper metal cap is capillary force by liquid evaporation We use the phenomenon that we gather together.

As the metal cap is gathered, a nanogap is formed, and a sample is trapped in the nanogap, so that the Raman signal of the sample captured in the nanogap can be amplified.

The first prior art does not disclose a technique for collecting or filtering molecules using the swelling property of a solvent.

The second prior art of the present invention is US Pat. No. 4,876, 399 (Surfaced enhanced Raman spectroscopy substrates), which states that a protective coating can selectively adsorb only specific surfaces.

However, while the second conventional technique is a technique of adsorbing only a chemically specific substance by a protective coating, the present invention does not induce chemical adsorption, but a polymer acting as a protective film expands in volume by a solvent, And differs from the second conventional technique in that it functions to selectively densify only molecules having a small molecular weight physically into the polymer layer.

A third prior art of the present invention is the US Apparatus for Performing SERS (US 8665432), which discloses a surface enhanced Raman scattering substrate in which metal nanoparticles are coated on the body portion of polymer nanopillars .

The surface enhancement Raman scattering substrate according to the third prior art is a technique using the principle of amplifying the SERS effect as the nano gap is reduced as the gap between the polymer nanoparticles is reduced by expanding the polymer nanoparticles by the solvent.

The third conventional technique is to apply metal nanoparticles to polymer nanoparticles. However, the present invention is a structure in which a SERS substrate is embedded as a polymer material, It is different from the invention.

A fourth prior art of the present invention is US Patent No. US7588827 (SERS-active composite nanoparticles, methods of fabrication thereof, and methods of use thereof), which adsorbs reporter molecules to metal nanoparticles and protects reporter molecules This is a technique for sealing the protective layer.

The fourth prior art does not disclose a technology for collecting or filtering molecules using the swelling characteristics of a solvent.

A fifth conventional technique of the present invention is a method for preparing a SERS particle (US Patent No. US2013-0196057). This is different from the present invention in that a biocompatible protective layer is used as a protective layer in making SERS particles.

A sixth prior art of the present invention is US Patent Publication No. US2013-0273561 (Lipid encapsulation of SERS nanoparticles).

The sixth prior art does not disclose a technique of collecting or filtering molecules using the swelling characteristics of a solvent.

As a seventh prior art of the present invention, there is disclosed a Korean Patent Registration No. KR1511036 (Nano Plasmonic Biosensor) and a substrate for surface enhanced Raman spectroscopy comprising a first metal nanostructure-stimulus-sensitive polymer layer-second metal nanostructure have.

Wherein the stimulable-sensitive polymer layer is made of a hydrogel having a swelling property by any one of external stimulation of pH, temperature (heat), electric field, magnetic field and light (i.e., active control by external stimulation) It is a feature technology.

And a second metal nanostructure in which a vertical interval between the first metal nanostructure and the first metal nanostructure is controlled by an external stimulus, thereby realizing a nanoplasmonic biosensor.

However, the seventh related art does not disclose the filtering of the substance to be detected and the detection of the substance to be detected by the expansion of the solvent.

U.S. Published Patent Application No. 2013-0195721 (entitled METALLIC-NANOFINGER DEVICE FOR CHEMICAL SENSING)

According to an embodiment of the present invention, there is provided an ultrasensitive surface enhanced Raman scattering substrate capable of detecting a trace amount of chemical / biomaterial and a method of manufacturing the same.

According to another embodiment of the present invention, there is provided a surface enhanced Raman scattering substrate capable of molecular filtering and a method of manufacturing the same.

According to another embodiment of the present invention, there is provided a surface enhanced Raman scattering substrate capable of molecular filtering and an analysis method thereof.

According to an aspect of the present invention, there is provided a semiconductor device comprising: a flexible substrate on which a protruding structure is formed; a metal nanostructure formed on a flexible substrate; and an insulating layer formed of a sensitive material swelling by a solvent, To provide a surface enhanced Raman scattering substrate.

The sensitizer may be selected from the group consisting of PDMS (polydimethylsiloxane), SiGMA (2-prphenolic acid, 2-methyl-, 2-hydroxy-3- [3- [ Bis (trimethylsilyl) oxy] disiloxanyl] propoxy] propyl ester),?,? - bismethacryloxypropylpolydimethylsiloxane, mPDMS (monomethacryloxypropyl terminated mono-en- Terminal polydimethylsiloxane) and TRJS (3-methacryloxypropyl tris (trimethylsiloxy) silane).

The sensitive material may be selected from the group consisting of poly (ethylene oxide), poly (propylene oxide), poly (vinylmethylether), poly (hydropropyl acrylate), hydroxypropylcellulose, methylcellulose, (N-substituted acrylamides), poly (N-isopropylacrylamide), poly (N-acrylolypyrrolidines), poly Acryl-L-amino acid amide) and poly (methacrylic acid).

The pore size of the insulating layer may be different depending on the position.

The insulating layer may be formed to have a height lower than a height formed from the upper end to the upper end of the metal nanostructure from the lower end to the lower end of the flexible substrate.

The insulating layer may be formed to have a height higher than a height formed from a lower end to a lower portion of the flexible substrate to an upper portion of the metal nanostructure.

The protruding structure may be formed so that a slope is formed with respect to the flexible substrate, and a distance between the protruding structures becomes narrower toward the upper part.

The metal nanostructure may be composed of one or more alloys in the group consisting of gold, silver, platinum, aluminum, iron, zinc, copper, tin, bronze, brass and nickel.

The metal nanostructure may be selected from metal nanoparticles, metal nanorods, metal islands and metal pastes, metal caps, and metal nanowires.

According to another aspect of the present invention, there is provided a method for fabricating a metal nanostructure, including: forming a protruding structure on a flexible substrate; forming a metal nanostructure on the protruding structure; And forming an insulating layer on the Raman scattering layer.

The step of forming the protruding structure on the flexible substrate may include a step of forming the flexible substrate by a plasma etching, a lithography method, a nanoimprint method, or the like.

The step of forming the insulating layer may include forming an insensitive material solution having a characteristic of being swollen in a solvent, forming an insensitive material layer using the insensitive material solution, arranging the metal nanostructure on one surface of the insulative material layer Impregnating the sensitive material layer and the metal nanostructure with the sensitive material solution, and curing the sensitive material solution.

The step of curing the sensitive material solution may include repeatedly performing the step of impregnating the sensitive material film and the metal nanostructure into the sensitive material solution and the step of curing the sensitive material solution, .

According to another aspect of the present invention, there is provided a method of manufacturing a surface enhanced Raman scattering substrate, comprising: preparing a surface enhanced Raman scattering substrate; preparing a solvent capable of swelling the insulating layer of the surface enhanced Raman scattering substrate; Forming a solution, dipping the surface-enhanced Raman scattering substrate into the solution to swell the insulating layer, drying the surface-enhanced Raman scattering substrate, and measuring the Raman signal of the dried surface- The method comprising the steps of:

The step of mixing the detection substance with the solvent to form the detection substance mixture solution may include mixing the plurality of detection substances.

According to an embodiment of the present invention, a surface enhanced Raman scattering substrate capable of detecting a trace amount of chemical / biomolecule material and a method of manufacturing the same can be provided.

According to another embodiment of the present invention, a surface enhanced Raman scattering substrate capable of molecular filtering and a method of manufacturing the same can be provided.

According to another embodiment of the present invention, a surface enhanced Raman scattering substrate capable of molecular filtering and an analysis method thereof can be provided.

1 is a view showing a surface enhanced Raman scattering substrate according to a first embodiment of the present invention.
2 is a view showing a surface enhanced Raman scattering substrate according to a second embodiment of the present invention.
3 is a view showing a surface enhanced Raman scattering substrate according to a third embodiment of the present invention.
4 is a view showing a surface enhanced Raman scattering substrate according to a fourth embodiment of the present invention.
5 is a flowchart illustrating a method of manufacturing a surface enhanced Raman scattering substrate according to an embodiment of the present invention.
6 is a schematic view illustrating a method of manufacturing a surface enhanced Raman scattering substrate according to an embodiment of the present invention.
7 is a flowchart illustrating a Raman signal analysis method using a surface enhanced Raman scattering substrate according to an embodiment of the present invention.
8 is a TEM image of a surface enhanced Raman scattering substrate according to the first embodiment of the present invention.
9 is a photograph showing the discoloration process of the surface enhanced Raman scattering substrate according to Experimental Examples 1 and 2 of the present invention.
10 is a Raman spectrum graph according to Experimental Examples 1 and 2 of the present invention.
11 is a photograph showing a discoloration process of a surface enhanced Raman scattering substrate according to Experimental Example 3 of the present invention.
12 is a Raman spectrum graph according to Experimental Example 3 of the present invention.
13 is a view illustrating a process of analyzing a detection substance using a surface enhanced Raman scattering substrate according to a third embodiment of the present invention.
14 is a view illustrating a process of analyzing a detection substance using a surface enhanced Raman scattering substrate according to a fourth embodiment of the present invention.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise.

In the present application, when a component is referred to as "comprising ", it means that it can include other components as well, without excluding other components unless specifically stated otherwise. Also, throughout the specification, the term "on" means to be located above or below the object portion, and does not necessarily mean that the object is located on the upper side with respect to the gravitational direction.

In addition, the term " joining " is used not only in the case of directly bonding physically directly between the constituent elements in the bonding relationship between the constituent elements, but also means that other constituent elements are interposed between the constituent elements, It should be used as a concept to cover the case where they are connected to each other.

The sizes and thicknesses of the respective components shown in the drawings are arbitrarily shown for convenience of explanation, and thus the present invention is not necessarily limited to those shown in the drawings.

Hereinafter, a surface enhanced Raman scattering substrate and a method of manufacturing the same according to embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description, the same or corresponding components are denoted by the same reference numerals, And redundant explanations thereof will be omitted.

Surface Enhancement In order to realize a technique for directly sensing in situ using a Raman scattering substrate, surface treatment technology of surface enhanced Raman scattering capable of selectively capturing only specific molecules in a mixed sample is required. In the prior art, the principle of imparting selectivity through an antigen-antibody reaction, an enzyme reaction, and a ligand-receptor reaction by coating a metal surface with an antibody, an enzyme, or a ligand in order to identify and detect a specific detection substance .

Such a technique of increasing the molecular selectivity by coating of chemical and biomaterials is a technique in which the Raman signals of the detection substance can be overlapped with each other by the surface treatment substance and the probability that the detection substance is adsorbed in the hot spot is separated by the surface treatment substance It is impossible to measure the Raman signal of the detection substance. Therefore, there is a limitation in realizing high sensitivity sensing, and there is also a problem in the reproducibility of the Raman signal due to the degradation of the stability of the enzyme and the antibody.

According to the embodiment of the present invention, by using an insulating material having a swelling property in a solvent, it is possible to obtain a detection target (a target object) within a hot spot (a nanogap existing between metal structures) according to the swelling degree and the molecular weight of the molecule contained in the solvent A surface enhanced Raman scattering substrate capable of selectively capturing molecules, and a method of manufacturing the same.

In addition, according to the embodiment of the present invention, the metal nanostructure is encapsulated in an insulator, thereby selectively detecting a specific detection substance and enhancing the durability of the surface enhanced Raman scattering substrate. can do.

Hereinafter, a surface enhanced Raman scattering substrate according to an embodiment of the present invention will be described in detail with reference to the drawings.

1 is a view showing a surface enhanced Raman scattering substrate 100 according to an embodiment of the present invention.

1, a flexible substrate 5 on which a protruding structure 3 is formed, a metal nanostructure 10 formed on a flexible substrate 5, and a flexible substrate 5 formed of a sensitive material which is swollen by a solvent, ) And an insulating layer 15 formed so as to contain the metal nanostructure 10 can be identified.

The flexible substrate 5 can be formed of a flexible material that is not damaged even when an external force such as bending is applied, and is a concept including silicon, polymer, and paper.

When light is incident on the surface of the metal nanostructure 10, the metal nanostructure 10 is excited by light to generate a strong photoelectric field, thereby generating a Raman scattering signal.

The metal nanostructure 10 is preferably formed of a nanostructure such as a metal nanoparticle, a metal nanorod, a metal nano island and a metal paste, a metal cap, or a metal nanowire, Aluminum, iron, zinc, copper, tin, bronze, brass and nickel.

The insulating layer 15 may contain the entire metal nanostructure 10 or the metal nanostructure 10 and the substrate 5 to form a protective layer around the metal nanostructure 10 and the substrate 5 .

It is possible to prevent the insulating layer 15 from being denatured from moisture and air contact by forming the protective layer around the metal nanostructure 10 and the substrate 5. [

Therefore, it is possible to minimize the damage of the substrate during the field diagnosis, and to improve the durability of the apparatus.

In the insulating layer 15, it is known that a hot spot 20 in which a LSPR phenomenon occurs strongly in the nanogap between metal nanostructures in the surface enhanced Raman scattering substrate 100 is present.

In order to increase the detection sensitivity of molecules, it is required to capture the detection substance into the insulating layer 15.

The insulating layer 15 according to an embodiment of the present invention is characterized in that the insulating layer 15 is formed of a sensitive material which is swollen by a solvent to capture a detection substance therein.

When the insulating layer 15 is formed of the sensitive material which swells in the solvent, the detection material may be trapped in the insulating layer 15 by using a solution in which the detection material is dissolved in a solvent capable of swelling the sensitive material.

The detection material may be trapped in the insulating layer 15 by being infiltrated into the insulating layer 15 in the process of swelling the solvent penetrating into the insulating layer 15 and swelling the solvent capable of swelling the sensitive substance.

In the process of swelling of the insulating layer 15 by the solvent, the pores formed between the sensitive material chains are expanded by capturing the detection material into the insulating layer 15, So that the detection substance can be introduced into the hot spot 20 as a result.

The detection substance introduced into the hot spot 20 is dried while the solvent is dried, and the pores are again reduced, leaving only the solvent, and the detection substance remains trapped in the hot spot 20.

When the Raman signal is measured while being captured in the hot spot 20, the signal is largely output, and the intensity of the sensing can be increased.

On the other hand, the insulating layer 15 can detect the substance to be detected without limiting the detection substance by selectively using the substance sensitive to the property of the substance to be dissolved in the solvent.

For example, the insulating layer 15 can be formed by using an irritating substance which is swollen in an organic solvent when the detecting substance is dissolved in an organic solvent, and by using an irritating substance swelling in an inorganic solvent when dissolved in an inorganic solvent, Depending on the dissolution characteristics of the material.

Specifically, the sensitizing substance is selected from the group consisting of PDMS (polydimethylsiloxane), SiGMA (2-prphenolic acid, 2-methyl-, 2-hydroxy-3- [3- [ (3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl] propoxy] propyl ester), α, ω-bismethacryloxypropylpolydimethylsiloxane, mPDMS (monomethacryloxypropyl terminated mono-ene -Butyl-terminated polydimethylsiloxane) and TRJS (3-methacryloxypropyltris (trimethylsiloxy) silane).

Also, the sensitive substance may be selected from poly (ethylene oxide), poly (propylene oxide), poly (vinyl methyl ether), poly (hydro propyl acrylate), hydroxypropyl cellulose, methyl cellulose, hydroxypropyl methyl (Polyvinyl alcohol), poly (N-substituted acrylamide), poly (N-isopropylacrylamide), poly (N-acrylolypyrrolidine) (Acrylic-L-amino acid amide) and poly (methacrylic acid).

Therefore, the detection substance can be detected without limitation by forming the insulating layer 15 by selecting the sensitive substance in consideration of the dissolution characteristics of the detection substance.

2 is a view showing a surface enhanced Raman scattering substrate 200 according to another embodiment of the present invention.

2, it is preferable that the surface enhanced Raman scattering substrate 200 is formed such that the metal nanostructure 10 is dispersed in the insulator 15. FIG.

It is preferable that the single surface enhanced Raman scattering substrate 200 is formed so that the metallic nanostructure 10 is dispersed in the insulator 15 so as to be advantageous for detecting a plurality of detection materials.

Referring to FIG. 2, the insulating layer 15 of the surface-enhanced Raman scattering substrate 200 may have different pore sizes depending on the heights to simultaneously detect the detection materials having different molecular weights.

For example, the insulating layer 15 can be formed by forming the pore size differently as needed so that the size of the pores gradually increases or decreases with height of each of the insulating layers 11, 12, The substance can be formed so that the detection substance having a small molecular weight at a large porosity can be detected simultaneously in a small pore size region.

Therefore, there is an effect that a plurality of detection substances can be simultaneously detected using a single surface-enhanced Raman scattering substrate 200. [

3 is a view showing a surface enhanced Raman scattering substrate 300 according to a third embodiment of the present invention.

3, the insulating layer 15 has a height h1 (hereinafter referred to as a lower height) formed from the lower end to the lower end of the flexible substrate 5 at an upper portion from the upper end of the metal nanostructure 10 (H1 > h2) higher than the height (h2 or less, referred to as the upper height).

On the other hand, the protruding structure 3 of the surface enhanced Raman scattering substrate 300 according to the third embodiment is inclined with respect to the flexible substrate 5 so that the distance between the protruding structures 3 becomes narrower toward the upper side As shown in FIG.

As the distance between the metal nanostructures 10 becomes narrower, the protruding structure 3 may become narrower toward the upper part.

In order to maximize the Raman signal, the spacing formed between the metal nanostructures 10, that is, the size of the nanogap, should be as small as 1 nm, preferably as small as 0.5 nm.

As a method for forming the hot spot 20, which is the nano gap of the metal nanostructure 10, to be 1 nm or less, there is a capillary-force method.

Specifically, the capillary-force method is a method in which a liquid is dropped onto the metal nanostructure 10, and the metal nanostructure 10 is gathered by the cohesive force between the liquids.

At this time, the protruding structure 3 can be inclined simultaneously with the metal nanostructure 10 due to its flexible nature.

When the insulating layer 15 is cured around the metal nanostructure 10, the protruding structure 3 may be inclined. As a result, a hot spot 20 of 1 nm or less is formed on the surface-enhanced Raman scattering substrate . When the height h1 of the lower portion is formed to be higher than the height h2 of the upper portion as described above, the force pushing upward from the lower portion when the insulation layer 15 expands is relatively larger.

4 is a view showing a surface enhanced Raman scattering substrate 400 according to a fourth embodiment of the present invention.

4, the insulating layer 15 is formed to have a height h1 formed at a lower portion to a lower portion of the flexible substrate 5 smaller than a height h2 formed at an upper portion of the upper portion of the metal nanostructure 10 (h1 < h2).

When the height h1 of the lower portion is formed to be smaller than the height h2 of the upper portion as described above, a force pressing downward from the upper portion of the insulating layer 15 is relatively large when the insulating layer 15 expands.

In the surface enhanced Raman scattering substrate 400, a force pushing downward from the upper part of the insulating layer 15 is formed to be relatively large during the expansion of the insulating layer 15, and is bent downward convexly.

When the surface enhanced Raman scattering substrate 400 is bent downward, the spacing of the hot spots 20 in the metal nanostructure 10 can be reduced.

Therefore, the surface enhanced Raman scattering substrate 400 according to the fourth embodiment can measure a more amplified Raman signal.

Hereinafter, a method for manufacturing a surface enhanced Raman scattering substrate according to an embodiment of the present invention will be described.

FIG. 5 is a flowchart illustrating a method of manufacturing a surface enhanced Raman scattering substrate according to an embodiment of the present invention, and FIG. 6 is a view schematically illustrating a method of manufacturing a surface enhanced Raman scattering substrate according to an embodiment of the present invention.

5 to 6, a method for fabricating a surface enhanced Raman scattering substrate includes the steps of forming a protruding structure 3 on a flexible substrate 5, forming a metal nanostructure 10 on the protruding structure 3, (S200) of forming the metal nanostructure 10 and a step (S300) of forming the insulating layer 15 by embedding the flexible substrate 5 on which the metal nanostructure 10 is formed with the sensitive material which is swollen by the solvent .

The step S100 of forming the protruding structure 3 on the flexible substrate 5 includes the steps of forming the protruding structure 3 on the flexible substrate 5 by plasma etching, lithography, or nanoimprinting S105).

A metal nano-particle, a metal nano-rod, or a metal such as a metal nano-island is formed on the protruding structure 3 in the step (S200) of forming the metal nano-structure 10 on the flexible substrate 5 on which the protruding structure 3 is formed And forming the nanostructure 10.

Step S300 of forming the insulating layer 15 may include forming a susceptible material solution having a property of swelling in a solvent 305, forming a susceptive material layer using the susceptive material solution S310, A step S320 of impregnating the sensitive material layer 12 and the metal nanostructure layer 10 with a sensitive material solution and a step S325 of curing the sensitive material solution ).

Referring to FIG. 6, a method of forming a structure in which the metal nanostructure 10 is encapsulated in an insulator in the step of forming the insulating layer 15 (S300) includes the steps of preparing a sensitive material layer, It can be confirmed that the flexible substrate 5 on which the metal nanostructure 10 is formed is disposed in the sensitive material layer and is impregnated with the sensitive material solution.

Next, the step (S325) of curing the sensitive material solution can be preferably performed in an oven ranging from 90 to 100 degrees for from 110 minutes to 130 minutes.

However, the step of curing the sensitive material solution (S325) does not limit only the temperature range and the curing time depending on the substance to be detected.

In the step S300 of forming the insulating layer 15, the step of impregnating the sensitive material film and the metal nanostructure 10 with the sensitive material solution S320 and the step of hardening the sensitive material solution S325 are repeatedly performed But can be carried out with different curing times.

By repeating the step of forming the insulating layer 15 (S300), the size of the pores of the insulating layer 15 is gradually changed, or the insulating layer 15 having a different interlayer pore size is formed .

For example, the degree of curing of the central portion of the insulating layer 15 can be increased to reduce the size of the pores of the sensitive material, and the degree of curing of the outer portion can be reduced to increase the size of the pores of the sensitive material.

The surface enhancement Raman scattering substrate 100 capable of detecting a plurality of detection materials at the same time can be realized by forming the insulating layer 15 differently in the degree of curing.

Hereinafter, the method of analyzing the detection substance will be described with reference to the drawings, and the analysis result of the detection substance using the surface enhanced Raman scattering substrate 100 will be described.

7 is a flowchart illustrating a Raman signal analysis method using a surface enhanced Raman scattering substrate 100 according to an embodiment of the present invention.

Hereinafter, a method of analyzing a detected substance using the surface enhanced Raman scattering substrate 100 according to another aspect of the present invention will be described with reference to FIG.

The method for analyzing a detection substance using the surface enhanced Raman scattering substrate 100 includes the steps of preparing a surface enhanced Raman scattering substrate (S10), preparing a solvent capable of swelling the insulating layer 15 of the surface enhanced Raman scattering substrate A step S30 of dipping the surface-enhanced Raman scattering substrate in the solution to swell the insulating layer 15 (S40), a step of growing a surface-enhanced Raman scattering layer Drying the substrate (S50), and measuring the Raman signal of the dried surface-enhanced Raman scattering substrate (S60).

The step (S30) of mixing a detection substance with a solvent to form a detection substance mixture solution may include a step (S35) of mixing a plurality of detection substances.

The surface enhanced Raman scattering substrate 100 includes an insulating layer 15 having a different degree of interlayer curing and having different pore sizes.

The step of drying the surface enhanced Raman scattering substrate S50 may be omitted if the height of the upper portion of the insulating layer 15 is higher than the height of the lower portion. Since the surface enhanced Raman scattering substrate 400 according to the fourth embodiment forms a state in which the hot spot 20 is the narrowest in the dipping process, it is preferable to measure the signal only before it is dried.

8 is a TEM image of a surface-enhanced Raman scattering substrate according to the first embodiment of the present invention. It is confirmed that a silver metal nanostructure 10 is formed on a polymer substrate and a PDMS protective layer is formed .

FIG. 9 is a photograph showing the discoloration process of the surface-enhanced Raman scattering substrate according to Experimental Examples 1 and 2 of the present invention, and FIG. 10 is a Raman spectrum graph according to Experimental Examples 1 and 2 of the present invention.

<Manufacturing process>

Pre-cured PDMS film formation

Place the metal nanostructure on one side of the PDMS membrane

PDMS solution pouring such that the metal nanostructure is embedded in the PDMS

Curing in an oven at 100 ° C for 2 hours

<Experimental Method>

Each solution prepared by dissolving 1 mM methylene blue (molecular weight: 319.85 g / mol) in chloroform or water

10 minutes, 1 hour, 20 hours dipping in chloroform solution

Dipping in aqueous solution for 10 minutes, 1 hour, 20 hours

Drying in air for 30 minutes after dipping

Raman signal measurement

[Table 1] Experimental conditions

Referring to FIG. 9, it can be seen that the surface enhanced Raman scattering substrate immersed in chloroform is gradually discolored to blue by 10 minutes after the diffusion of methylene blue.

On the other hand, it can be confirmed that the color of the insulating layer 15 is not discolored even after 20 hours of surface enhanced Raman scattering substrate immersed in the aqueous solution.

According to the experimental results, it can be seen that in the chloroform solution in which PDMS can be swollen, methylene blue can be diffused to the inside of the insulating layer 15, and thus the Raman signal is amplified in the chloroform solution It can be deduced that the methylene blue exists in the hot spot 20.

FIG. 11 is a photograph showing a discoloration process of a surface enhanced Raman scattering substrate according to Experimental Example 3 of the present invention, and FIG. 12 is a Raman spectrum graph according to Experimental Example 3 of the present invention.

<Manufacturing process>

Pre-cured PDMS film formation

Place the metal nanostructure on one side of the PDMS membrane

PDMS solution pouring such that the metal nanostructure is embedded in the PDMS

Curing in an oven at 100 ° C for 2 hours

<Experimental Method>

Prepare a mixed solution of 1 mM methylene blue (molecular weight 319.85 g / mol) and Rhodamin 6G (R6G, molecular weight 497.02 g / mol) in chloroform

10 minutes and 20 minutes dipping in chloroform solution

Drying in air for 30 minutes after dipping

[Table 2] Experimental conditions

Referring to FIGS. 11 to 12, it can be seen that both methylene blue and R6G are dissolved in chloroform, but only the methylene blue Raman signal is detected, so that only the detection substance having a small molecular weight is diffused into the hot spot 20 .

As a result, the surface enhanced Raman scattering substrate 100 according to an embodiment of the present invention can selectively detect a detection substance according to the molecular weight.

According to the experimental results, the surface enhanced Raman scattering substrate 100 can simultaneously detect the detection materials other than the detection materials shown in the experimental examples by differently forming the pores of the insulating layer 15.

The degree of curing of the sensitive material progressively changes from the center to the outside of the insulating layer 15, so that a plurality of detection materials can be detected using the single surface enhanced Raman scattering substrate 100.

2, it is preferable that the surface enhanced Raman scattering substrate 100 is formed such that the metal nanostructure 10 is dispersed in the insulator 15.

In addition, by controlling the dipping time, molecules having different molecular weights can be induced to be concentrated in the insulating layer 15, and then, by using a Raman microscope, by changing the focal distance, a unique Raman A signal may be derived.

13 is a view illustrating a process of analyzing a detection substance using the surface enhanced Raman scattering substrate 300 according to the third embodiment of the present invention.

Referring to FIG. 13, when the detection material 25 is analyzed using the surface enhanced Raman scattering substrate 300, it can be confirmed that the surface enhanced Raman scattering substrate 300 has a convex shape in the dipping process.

When the height of the lower portion of the insulating layer 15 is greater than the height of the upper portion of the surface enhanced Raman scattering substrate 300 according to the third embodiment (h1 &gt; h2), the volume at the time of expansion increases (h13> h23) So that the volume expansion of the lower portion having a higher height becomes larger.

At this time, if the thickness of the upper insulating film is small, the pushing force in the upward direction becomes large, and the surface enhancement Raman plate substrate 300 can be convex upward.

The surface-enhanced Raman scattering substrate 300 according to the third embodiment differs from the surface-enhanced Raman scattering substrate 300 according to the third embodiment in that the metal nanostructure 10 formed in the inside by the force pushing the insulating layer 15 upward in a state where the metal nanostructure 10 is inclined in the dipping process The mutual spacing between the first and second electrodes 10 can be widened.

When the mutual spacing of the metal nanostructures 10 is widened during the dipping process, the diffusion of the detection material 25 is more smoothly spread between the widened spaces, and in the process of drying the surface enhanced Raman scattering substrate 300, Is returned to the original state to form the hot spot 20, the Raman signal can be further amplified.

The surface enhancement Raman plate substrate 300 may be deformed upward in the dipping process, and the metal nanostructures 10 may be deformed into a gap between the metal nanostructures 10.

The pushing force from the lower part to the upper part during dipping acts to spread the space of the protruding structure 3 so that the detection material 25 is easily collected into the hot spot 20 at the gap interval .

The detection material 25 is collected between the open spots of the hot spot 20 and the surface enhanced Raman scattering substrate 400 is dried again so that the protruding structure 3 again measures the Raman signal in a state in which the narrow gap is formed toward the upper part .

The surface enhanced Raman scattering substrate 300 according to the third embodiment can more easily collect the detection material 25 in the expansion process and can form hot spots of 1 nm or less after the drying so that the Raman signal is more amplified Can be obtained.

FIG. 14 is a view illustrating an analysis process of a detection material 25 using a surface enhanced Raman scattering substrate 400 according to a fourth embodiment of the present invention.

It is also confirmed that the height of the upper portion of the insulating layer 15 is higher than the height of the lower portion (h1 &lt; h2).

In this case, when the height difference (h1 &lt; h2) is formed between the upper part and the lower part of the insulating layer 15 as described above, a strong pushing force from the upper part to the lower part during dipping is formed strongly, 400 can be formed.

The surface-enhanced Raman scattering substrate 400 having a downward convex shape may be deformed into a shape in which the upper portion is gathered by the pushing force from the upper portion to the lower portion during dipping, so that the interval of the metal nanostructures 10 can be narrower than before the deformation.

Therefore, the surface-enhanced Raman scattering substrate 400 according to the embodiment of the present invention can obtain a more amplified Raman signal of the detection molecule because the distance between the metal nanostructures 10 becomes narrower.

At this time, it is preferable that the Raman signal is measured in a state where the surface enhancement Raman scattering substrate 400 having the height above the insulating layer 15 is higher than the lower surface.

The surface enhanced Raman scattering substrate 400 according to the fourth embodiment recovers the spacing of the metal nanostructures 10 upon drying, so that it is preferable to measure the Raman scattering signal before drying.

The surface enhanced Raman scattering substrate according to the embodiment of the present invention can provide the optimal manufacturing method and analysis conditions according to each embodiment, and the hot spot 20 can be formed to 1 nm or less.

Meanwhile, since the surface enhanced Raman scattering substrate according to the embodiment of the present invention has a molecular filtering effect, only specific substances among various mixed samples can be selectively introduced into the hot spot 20.

Therefore, the surface enhanced Raman scattering substrate according to the embodiment of the present invention having a molecular filtering effect can enable field diagnosis sensing, and is highly likely to be practically used in a simple manufacturing process and economical aspect.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, many modifications and changes may be made by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims. The present invention can be variously modified and changed by those skilled in the art, and it is also within the scope of the present invention.

3: protruding structure
5: flexible substrate
10: metal nanostructure
15: Insulating layer
20: Hot Spot

Claims (15)

A flexible substrate on which a protruding structure is formed;
A metal nanostructure formed on a flexible substrate; And
And an insulating layer formed of a sensitive material which is swollen by the solvent and formed so as to contain the flexible substrate and the metal nanostructure therein
Surface enhanced Raman scattering substrate.
The method according to claim 1,
The sensitizer may be selected from the group consisting of PDMS (polydimethylsiloxane), SiGMA (2-prphenolic acid, 2-methyl-, 2-hydroxy-3- [3- [ Bis (trimethylsilyl) oxy] disiloxanyl] propoxy] propyl ester),?,? - bismethacryloxypropylpolydimethylsiloxane, mPDMS (monomethacryloxypropyl terminated mono-en- Terminal polydimethylsiloxane) and TRJS (3-methacryloxypropyl tris (trimethylsiloxy) silane).
The method according to claim 1,
The sensitive material may be selected from the group consisting of poly (ethylene oxide), poly (propylene oxide), poly (vinylmethylether), poly (hydropropyl acrylate), hydroxypropylcellulose, methylcellulose, (N-substituted acrylamides), poly (N-isopropylacrylamide), poly (N-acrylolypyrrolidines), poly Acryl-L-amino acid amide) and poly (methacrylic acid) are selected as the surface-enhanced Raman scattering substrate.
The method according to claim 1,
Wherein the insulating layer is formed to have different pore sizes depending on positions thereof.
The method according to claim 1,
Wherein the insulating layer
Wherein the insulating layer is formed to have a height higher than a height formed from a lower end to a lower portion of the flexible substrate to an upper portion of the metal nanostructure.
The method according to claim 1,
Wherein the insulating layer
Wherein a height formed from the lower end to the lower end of the flexible substrate is formed lower than a height formed from the upper end to the upper end of the metal nanostructure.
6. The method according to any one of claims 1 to 5,
The protruding structure
Wherein a slope is formed on the flexible substrate so that an interval between the protruding structures becomes narrower toward the upper side.
The method according to claim 1,
The metal nanostructure includes
Wherein the surface enhanced Raman scattering substrate is made of one or more alloys in the group consisting of gold, silver, platinum, aluminum, iron, zinc, copper, tin, bronze, brass and nickel.
The method according to claim 1,
The metal nanostructure includes
A surface enhanced Raman scattering substrate, wherein at least one of metal nanoparticles, metal nanorods, metal islands and metal pastes, metal caps, and metal nanowires is selected.
Forming a protruding structure on a flexible substrate;
Forming a metal nanostructure on the protruding structure;
And forming an insulating layer by impregnating the flexible substrate on which the metal nanostructure is formed with an irritating substance that is swollen by a solvent.
11. The method of claim 10,
Wherein the step of forming the protruding structure on the flexible substrate is a step of forming a flexible substrate by plasma etching, a lithography method, or a nanoimprint.
11. The method of claim 10,
The step of forming the insulating layer
Forming a solution of a sensitizing substance having a property of swelling in a solvent;
Forming a sensitive material layer using the sensitive material solution;
Disposing the metal nanostructure on one surface of the sensitive material layer;
Impregnating the sensitive material layer and the metal nanostructure with the sensitive material solution; And
And curing the sensitometric material solution. &Lt; Desc / Clms Page number 20 &gt;
13. The method of claim 12,
Wherein the step of curing the sensitive material solution comprises:
Impregnating the sensitive material layer and the metal nanostructure with the sensitive material solution; And
Curing the sensitive material solution is repeatedly performed,
Wherein the curing time is different from the initial curing time.
Preparing a surface enhanced Raman scattering substrate according to one of claims 1 or 9;
Preparing a solvent capable of swelling the insulating layer of the surface enhanced Raman scattering substrate;
Mixing the detection substance with the solvent to form a detection substance mixture solution;
Dipping the surface enhanced Raman scattering substrate into the solution to swell the insulating layer;
Drying the surface enhanced Raman scattering substrate; And
And measuring the Raman signal of the dried surface enhanced Raman scattering substrate.
15. The method of claim 14,
Wherein the step of mixing the detection substance with the solvent to form the detection substance mixture solution includes mixing the plurality of detection substances.

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