KR102737564B1 - Porous patterned substrate for surface enhanced raman scattering and manufacturing method therefor - Google Patents

Abstract

The present invention relates to a porous patterned surface-enhanced Raman scattering substrate and a method for manufacturing the same, and more specifically, to a method for manufacturing a substrate for surface-enhanced Raman scattering, the method including: a step of depositing a pretreatment metal and a plasmonic metal on a patterned substrate to manufacture a patterned plasmonic metal substrate; a step of reducing the plasmonic metal on the patterned plasmonic metal substrate with a plasmonic metal precursor solution containing polymer micelles by an electrochemical deposition method to manufacture a micelle-plasmonic metal thin film; and a step of washing the patterned plasmonic metal substrate on which the micelle-plasmonic metal thin film is formed with an organic solvent to form pores.
In addition, the present invention provides a substrate for surface-enhanced Raman scattering manufactured by the above-described manufacturing method.

Description

{POROUS PATTERNED SUBSTRATE FOR SURFACE ENHANCED RAMAN SCATTERING AND MANUFACTURING METHOD THEREFOR}

The present invention relates to a porous patterned surface-enhanced Raman scattering substrate and a method for manufacturing the same.

Surface-enhanced Raman scattering (SERS) technology has recently attracted attention in the field of detection due to its high sensitivity and specificity for the detection target. SERS technology is based on the principle that the intensity of the signal is amplified by the electromagnetic resonance phenomenon, which is caused by the surface plasmon resonance phenomenon excited by electromagnetic waves. Surface plasmon refers to the collective oscillation of free electrons in a metal at the surface between the metal and the dielectric, and the phenomenon in which this surface plasmon absorbs light in the visible to near-infrared range and causes a resonance phenomenon is called surface plasmon resonance (SPR). SERS activity can significantly enhance the intensity of the Raman spectrum by the absorbed energy at the plasmonic metal surface. When the analyte to be detected is dropped on the SERS substrate and Raman analysis is performed, the analyte molecule shows its own Raman scattering spectrum depending on the vibration of electrons generated on the metal surface and the electrical interaction of the analyte existing around the metal surface. In this SERS-based sensor, the biggest factor that determines the sensitivity and stability of the sensor is the metal substrate, which plays a role in amplifying the signal generated from the analyte, and the localized plasmon resonance phenomenon (LSPR) that occurs on the surface of the nano-scale metal structure improves the intensity and stability of the signal. A commonly used SERS substrate is an aggregate obtained by agglomerating gold or silver nanoparticles using a salt, etc., which can form a large number of hot spots between the nanoparticles and greatly amplify the Raman signal.

Various nanomanipulation techniques have been used to introduce nanostructures such as nanometer-scale columns, repetitive linear irregularities, or nanoparticles into the substrate surface to introduce roughness and hot spots. The most widely used technique at present is to form plasmon patterns on silicon-based substrates through a photolithography process. However, it has been difficult to commercialize due to disadvantages such as high manufacturing costs, highly toxic etching solutions, and high-temperature processes.

In order to solve these problems, a technology for manufacturing a substrate for surface-enhanced Raman scattering spectroscopy by using a flexible and porous paper substrate to adsorb plasmonic metals has been introduced. However, since a general paper substrate has a micro-scale porosity along with surface roughness, there is a problem of aggregation of metal molecules and non-uniformity of distribution in the adsorption of plasmonic metals having nano-scales, which significantly reduces the reproducibility of analysis results and causes deviation of the substrate during substrate manufacturing. In addition, the texture of the paper surface is due to irregularly arranged fibers, and due to this irregularity, the metal nanoparticles introduced to the surface are non-uniformly distributed, for example, they are densely accumulated in recessed areas and sparsely present in protruding areas, making it difficult to detect reproducible signals, or the signals are reduced due to offset caused by phase mismatch of the generated signals. In addition, the paper-based plasmonic pattern formation method has limitations such as having to use a plasmonic metal that can be inked, problems with the stability of the dispersion, and the substrate that can be printed is limited to general paper. In addition, despite being a SERS technology that is not affected by moisture, there are problems such as the substrate being damaged by moisture by using a paper substrate (Non-patent Document 0001).

0001: US Patent Publication No. 2012-0300203

The purpose of the present invention is to provide a porous patterned surface-enhanced Raman scattering substrate and a method for manufacturing the same.

The present invention comprises:

A step of manufacturing a patterned plasmonic metal substrate by depositing a pretreatment metal and a plasmonic metal on a patterned substrate;

A step of producing a micelle-plasmonic metal thin film by reducing a plasmonic metal on a patterned plasmonic metal substrate with a plasmonic metal precursor solution containing polymer micelles using an electrochemical deposition method; and

A method for manufacturing a substrate for surface-enhanced Raman scattering is provided, comprising the step of washing a patterned plasmonic metal substrate on which a micelle-plasmonic metal thin film is formed with an organic solvent to form pores.

In addition, the present invention provides a substrate for surface-enhanced Raman scattering manufactured by the above-described manufacturing method.

A substrate manufactured by the manufacturing method according to the present invention can be used as a surface-enhanced Raman scattering substrate having very high detection sensitivity and reproducibility by forming a plasmonic metal thin film with uniformly formed pores (porous) on a nano-patterned plasmonic metal substrate.

FIG. 1 is a schematic diagram of a method for manufacturing a porous patterned plasmonic metal substrate according to an embodiment of the present invention.
Figure 2 is a schematic diagram showing the process of forming a porous plasmonic metal thin film on a patterned plasmonic metal substrate of the present invention.
FIG. 3 is a schematic diagram for explaining surface-enhanced Raman scattering according to a hot spot of a porous metal formed on a nanopattern of a substrate for surface-enhanced Raman scattering of the present invention.
FIG. 4 is a photograph of a patterned PDMS stamp manufactured according to an embodiment of the present invention.
FIG. 5 is a photograph of a patterned polymer substrate manufactured according to an embodiment of the present invention.
FIG. 6 is a photograph of a patterned gold electrode manufactured according to an embodiment of the present invention.
FIG. 7 is a photograph of a porous patterned gold electrode manufactured according to an embodiment of the present invention.
Figure 8 is a surface scanning electron microscope image of Comparative Example 1 of the present invention.
Figure 9 is a surface scanning electron microscope image of Example 1 of the present invention.
Figure 10 is a cross-sectional scanning electron microscope image of Example 1 of the present invention.
Figure 11 is a graph showing the analysis results for rhodamine 6G of Comparative Example 1 and Example 1 of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention

A step of manufacturing a patterned plasmonic metal substrate by depositing a pretreatment metal and a plasmonic metal on a patterned substrate;

A step of producing a micelle-plasmonic metal thin film by reducing a plasmonic metal on a patterned plasmonic metal substrate with a plasmonic metal precursor solution containing polymer micelles using an electrochemical deposition method; and

A method for manufacturing a substrate for surface-enhanced Raman scattering is provided, comprising the step of washing a patterned plasmonic metal substrate on which a micelle-plasmonic metal thin film is formed with an organic solvent to form pores.

The above patterned substrate

It is manufactured by pressing a substrate coated with photoresist with a patterned stamp and then photocuring it, or

or

It can be manufactured using a photolithography process on a silicon wafer substrate, but is not limited thereto, and any method for manufacturing a pattern on a substrate commonly used in the technical field of the present invention is possible.

A method for manufacturing the above porous patterned plasmonic metal substrate is schematically illustrated in Fig. 1. The pattern includes all pattern shapes applicable using a mask aligner, including a line, a square, and a hexagonal shape, and the period and depth of the pattern can be 100 nm to 10 micrometers, respectively. The pattern can be regular or irregular. Such a pattern can form a hot spot that induces surface plasmon resonance.

The above photocuring may be UV curing, and may be performed at an intensity of 200 to 500 W for 30 seconds to 5 minutes. After photocuring, post-baking may be performed and heat treatment may be performed at a temperature of 100 to 200°C to remove any remaining solvent.

The term "photoresist (PR)" of the present invention refers to a photosensitive resin that is a photoreactive material used in various processes such as photolithography (exposure process) and photolithography to form a patterned coating on a surface. Polymethyl methacrylate (PMMA), epoxy, silicate, and thiolein series are mainly used. In the present invention, an epoxy-based photoresist (SU-8 50 from KAYAKU (MICROCHEM)) was used.

The term "micelle" of the present invention means a coherent nanostructure formed by amphiphilic molecules having a uniform size and shape. The shape of micelles is usually observed to be very diverse, ranging from spheres to ellipsoids, cylinders, rings, and lamellas, and typically exists in a size of 10 to 200 nm.

The term "plasmon metal" of the present invention refers to a metal capable of causing a surface plasmon resonance (SPR) phenomenon. The collective oscillation of delocalized free electrons within a metal at the surface between the metal and the dielectric is called surface plasmon, and the phenomenon in which this surface plasmon absorbs light in the visible to near-infrared range and causes a resonance phenomenon is called surface plasmon resonance.

The above plasmonic metal may be a metal including at least one selected from the group consisting of Ag, Al, Au, Co, Cu, Fe, Li, Ni, Pd, Rh, Ru and Pt. Preferably, it may be a metal including Cu, Ag, Au and Pt, and most preferably, it may be a metal including Ag and Au.

The above pores may have a diameter of 10 nm to 100 nm, preferably 10 nm to 50 nm, and most preferably 10 nm to 40 nm. The pores can be controlled depending on the type and size (molecular weight) of the polymer micelles added to the precursor solution, and swelling of the micelles due to addition of a cosolvent.

The plasmonic metal thin film having the above pores may have a thickness of 10 nm to 600 nm, preferably 100 nm to 400 nm, and most preferably 150 nm to 300 nm. If the thickness of the plasmonic metal thin film is less than 10 nm, the thin film may not be properly formed and may not function as a plasmonic nanostructure, and if the thickness is more than 600 nm, the porous metal thin film may clump together or the pattern may be blurred, and since there was no significant change in the SRES signal, a further thickness may not be meaningful. The thickness of the plasmonic metal thin film can be controlled by controlling the electrochemical deposition time and potential.

The above polymer micelle may be selected from the group consisting of polystyrene, polymethyl methacrylate, polyurethane, polyacrylamide, polydimethylsiloxane, polyvinylidene fluoride, polyethylene, polyethylene oxide, polyacrylate, polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone, polyphenylene oxide, polyolefin, and polystyrene-b-polyethylene oxide (PS-b-PEO), most preferably polystyrene-b-polyethylene oxide (PS-b-PEO), but any amphiphilic polymer composed of a block copolymer may be used. The molecular weight of each polymer of the polymer micelle may be 1,000 to 400,000, preferably 1,000 to 100,000. For polymer micelles, the closer the polydispersity index (PDI) is to 1, the more constant the length of the polymer chain is, and the more constant the size of the pores created by the polymer micelle is, the more uniform hot spots are formed, which can have a positive effect on the quality of the plasmonic metal substrate.

The above plasmonic metal precursor solution may contain the plasmonic metal precursor at a concentration of 1 mM to 125 mM, preferably 2 mM to 62.5 mM, and most preferably 3 mM to 32 mM. If the concentration of the plasmonic metal precursor in the plasmonic metal precursor solution is less than 1 mM, reduction may hardly occur and thus a porous metal substrate may not be formed, and if the concentration exceeds 125 mM, the metal may be indiscriminately reduced, thereby generating a non-porous, flat substrate.

The above plasmonic metal precursor solution may contain polymer micelles at a concentration of 0.1 mg/ml to 50 mg/ml, preferably 0.3 mg/ml to 25 mg/ml, and most preferably 0.5 mg/ml to 12.5 mg/ml. If the concentration of the polymer micelles in the plasmonic metal precursor solution is less than 0.1 mg/ml, micelles may not be formed, thereby forming a non-porous metal substrate, and if the concentration exceeds 50 mg/ml, micelles of a shape other than spherical micelles may be formed in the solution, thereby hindering the formation of a porous metal.

The above electrochemical deposition method can be performed using a plasmonic metal substrate as a working electrode, a platinum electrode as a counter electrode, and an Ag/AgCl electrode as a reference electrode. Electrochemical deposition can be performed with a system (two-electrode system) typically used in the electroplating field where electrochemical deposition is used. In the electrochemical deposition method, the potential range can be -0.2 V to -0.6 V, preferably -0.3 V to -0.5 V. If a lower potential (less than -0.6 V) is applied for the same time, the thickness is thicker, but pores may be created unevenly. In the electrochemical deposition method, the deposition time can be 500 seconds to 5000 seconds, preferably 1500 seconds to 3000 seconds. If the deposition time exceeds 3000 seconds, the thickness of the porous metal substrate may become thicker. The deposition conditions can be changed in consideration of the target SERS performance.

The above electrochemical deposition method can be performed at a temperature of 25 to 45° C., preferably 30 to 45° C., and most preferably 35 to 45° C. When the temperature is less than 25° C., the reactivity of the electrochemical deposition process is reduced, so that the degree of deposition of the porous plasmonic metal substrate is reduced, and thus a uniform porous plasmonic metal substrate may not be created. In addition, when the temperature during the electrochemical polymerization reaction exceeds 45° C., the physical properties of the substrate may be affected in the aqueous solution phase.

The above organic solvent may be dichloromethane, acetone, diethyl ether, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, N-methylpyrrolidone or chloroform.

In an embodiment of the present invention, a schematic diagram of a method for manufacturing a plasmonic metal substrate on which a porous patterned plasmonic metal thin film is deposited is shown in Fig. 1 and can be explained as follows.

1. Step of manufacturing a patterned plasmonic metal substrate;

2. Step of forming micelle-plasmonic metal,

3. A step of depositing a micelle-plasmonic metal thin film on a plasmonic metal substrate, and

4. Step of removing polymer micelles with an organic solvent.

In the first step, PDMS is poured onto a silicon (Si) master pattern substrate on which a nanopattern is formed, cured, and then removed to manufacture a patterned PDMS stamp. Next, a photoresist is coated on the substrate, and the patterned PDMS stamp is placed on the substrate and pressed down with pressure. The photoresist is photocured with UV wavelength and heat-treated to manufacture a patterned polymer substrate. Titanium (Ti) and a plasmonic metal are deposited on the patterned polymer substrate thus manufactured to manufacture a patterned plasmonic metal substrate. In the second step, a micelle-plasmonic metal precursor solution in which a polymer and a plasmonic metal compound are mixed in a solution phase to form a micelle-metal is manufactured (used as an electrolyte in the following electrochemical deposition method). The molecular weight and concentration of the polymer affect the size of the micelle, which is directly related to the size of the pores in the porous plasmonic metal thin film. In the third step, a three-electrode system using the patterned plasmonic metal substrate manufactured as a working electrode, a platinum electrode as a counter electrode, a Ag/Agcl electrode as a reference electrode, and the micelle-plasmonic metal precursor solution manufactured as an electrolyte is used to apply a reduction voltage to the micelle-metal, thereby manufacturing a micelle-plasmonic metal thin film on the surface of the patterned plasmonic metal substrate. The reduction potential can be adjusted according to the plasmonic metal used, and the thickness of the micelle-plasmonic metal thin film can be controlled by controlling the time for which the current is passed. In the fourth step, micelles in the micelle-plasmonic metal thin film are dissolved and removed using an organic solvent, thereby manufacturing a porous patterned plasmonic metal thin film. The metal substrate on which the micelle-plasmonic metal thin film is deposited is immersed in the organic solvent for a sufficient time to remove micelles, and the residue is removed by washing several times with distilled water or an organic solvent capable of dissolving a polymer. After a sufficient drying process, a patterned plasmonic metal substrate having a porous plasmonic metal thin film deposited thereon can be obtained.

The material of the above substrate may be PET, polyimide, silicon, glass or quartz. Most preferably, it may be silicon, but any material that can be used to manufacture a plasmonic metal substrate by depositing or adsorbing a plasmonic metal may be used.

The above pretreatment metal may be a metal including at least one selected from the group consisting of Ti and Cr.

The above pattern may or may not be constant. The more constant the pattern, the higher the optical properties may be.

A schematic diagram of a surface-enhanced Raman scattering substrate manufactured by the above method is shown in Fig. 3. A porous plasmonic metal thin film was formed on the nanopattern, showing the formation of a hot spot.

The present invention provides a substrate for surface-enhanced Raman scattering manufactured by a method according to the present invention.

The substrate may have pores having a diameter of from 10 nm to 100 nm, preferably from 10 nm to 50 nm, and most preferably from 10 nm to 40 nm.

The above substrate may have a plasmonic metal thin film having a thickness of 10 nm to 600 nm, preferably 100 nm to 400 nm, and most preferably 150 nm to 300 nm. If the thickness of the plasmonic metal thin film is less than 10 nm, there is a problem that the thin film is not properly formed and thus cannot function as a plasmonic nanostructure, and if the thickness exceeds 600 nm, the porous metal thin film may clump together or the pattern may become blurred, and since there was no significant change in the SRES signal, a further thickness may not be meaningful.

Hereinafter, the present invention will be described in detail by the following experimental examples and/or manufacturing examples. However, the following experimental examples and/or manufacturing examples are only intended to illustrate the present invention, and the content of the present invention is not limited by the following experimental examples and/or manufacturing examples. In addition, since these experimental examples and/or manufacturing examples are only intended to aid understanding of the present invention, the scope of the present invention is not limited by them in any sense.

<Manufacturing Example 1> Manufacturing of a patterned plasmonic metal substrate with pores (porous)

PDMS base and curing agent are mixed in a ratio of 20:3 and the generated air bubbles are removed by placing them in a desiccator. Then, PDMS is poured on a silicon (Si) master pattern substrate on which nano patterns have been formed and placed in an oven at 90 degrees for 2 hours to manufacture a patterned PDMS stamp and then removed. The patterned PDMS stamp produced at this time can be used multiple times, which increases the efficiency of substrate production.

The patterned polymer substrate was fabricated by the nanoimprint patterning method. After spin-coating photoresist (PR) on the substrate, a PDMS stamp was placed on top and pressure was applied so that the stamp completely adhered to the PR. The PR was photocured with UV light and the remaining solvent was removed through heat treatment to fabricate the patterned polymer substrate. The PR was spin-coated at 500 rpm for 10 seconds and at 2000 rpm for 30 seconds. In the case of a relatively inexpensive glass substrate, the adhesion properties with the cured PR were poor, so the thickness of the cured PR thin film was uneven and the thin film easily peeled off from the glass after curing. Therefore, a silicon substrate was used for the fabrication.

Patterned gold electrodes were obtained by depositing titanium (Ti) and gold (Au) to a thickness of 30 nm and 80 nm, respectively, on a patterned polymer substrate using a thermal evaporator. Titanium is essential for enhancing the adhesion between the gold film and the photoresist. The patterned gold electrodes could be manufactured in a large area according to the PDMS pattern, and exhibited excellent characteristics in that the pattern was distributed very uniformly. The patterned gold electrodes manufactured by the above method were later used as electrodes for the electrochemical deposition of porous metal films using polymer micelles.

A three-electrode system is used, in which the patterned gold electrode serves as the working electrode, the platinum electrode serves as the counter electrode, the Ag/AgCl electrode serves as the reference electrode, and a plasmonic metal precursor solution made by mixing HAuCl ₄ and Poly(styrene)-b-Poly(ethylene oxide) (PS molecular weight: 18,000. PEO molecular weight: 7,500, PS-b-PEO) as the electrolyte, to apply a constant voltage by the chronoamperometric method to reduce the metal and manufacture a gold thin film with pores. To manufacture the electrolyte, add 10 mg of PS-b-PEO and 3 ml of THF to a 10 ml vial and dissolve in a water bath having a temperature of 40 degrees Celsius or higher. When the PS-b-PEO is completely dissolved, add 1.5 ml of ethanol, 1 ml of a 40 mM HAuCl ₄ aqueous solution, and 2.5 ml of triple-distilled water in that order, and stir for approximately 30 minutes. In the electrolyte solution manufactured in this way, PS-b-PEO is present at a concentration of 1.25 mg/mL based on the total electrolyte solution, and HAuCl ₄ is present at a concentration of 5 mM. By applying a constant reduction voltage (-0.5 V vs. Ag/AgCl) for 1000 s through an electrochemical deposition method, gold ions of the working electrode, the gold electrode, were reduced to PS-b-PEO-HAuCl ₄ in the electrolyte solution to manufacture a micelle-gold thin film, which was then washed with an organic solvent to remove the PS-b-PEO micelles, thereby manufacturing a porous patterned gold electrode (Example 1). FIGS. 4 to 7 show photographs of a patterned polymer film, a patterned gold electrode, and a porous patterned gold electrode manufactured by the above-mentioned manufacturing method, respectively.

<Manufacturing Example 2> Manufacturing of a porous gold electrode without a pattern

In the above Manufacturing Example 1, a pattern-free porous gold electrode (Comparative Example 1) was manufactured in the same manner as in the previous Manufacturing Example 1 except that the patterned polymer substrate was changed to an unpatterned silicon substrate. In order to match the thickness of the porous gold thin film as much as possible, the voltage application time was made shorter in the unpatterned gold electrode than in the patterned gold electrode.

<Experimental Example 1> Evaluation of surface properties of gold electrodes with gold nanoparticles adsorbed

The surfaces of Comparative Example 1 and Example 1 were photographed using a scanning electron microscope (SEM) and a normal microscope.

Fig. 8 is a surface SEM photograph of Comparative Example 1, and Fig. 9 is a surface SEM photograph of Example 1. Compared to Fig. 8, it can be confirmed that a rough pattern exists in Fig. 9, and a hot spot is formed due to this pattern. Fig. 10 is a cross-sectional SEM photograph of Example 1. It can be confirmed that the pattern confirmed on the surface exists.

<Experimental Example 2> Surface-enhanced Raman scattering signal analysis results of patterned or unpatterned porous gold electrodes

A solution was prepared by dispersing rhodamine 6G in ethanol at a concentration of 10 μM, and the solution was dropped on the surfaces of Comparative Example 1 and Example 1 obtained through the above process, dried, and sampled. The surface-enhanced Raman scattering signal was then measured using a 532 nm laser and a Raman analyzer, and the results are shown in Fig. 11. From the graph, it can be confirmed that the intensity of the peak of Example 1 is greater, demonstrating that the presence of a pattern can form a hot spot and increase the detection sensitivity.

Claims (16)

A step of manufacturing a patterned plasmonic metal substrate by depositing a pretreatment metal and a plasmonic metal on a patterned substrate;
A step of producing a micelle-plasmonic metal thin film by reducing a plasmonic metal on a patterned plasmonic metal substrate with a plasmonic metal precursor solution containing polymer micelles using an electrochemical deposition method; and
A method for manufacturing a substrate for surface-enhanced Raman scattering, comprising the step of washing a patterned plasmonic metal substrate on which a micelle-plasmonic metal thin film is formed with an organic solvent to form pores. In paragraph 1,
The above patterned substrate
It is manufactured by pressing a substrate coated with photoresist with a patterned stamp and then photocuring it, or
or
A method for manufacturing a substrate for surface-enhanced Raman scattering using a photolithography process on a silicon wafer substrate. In paragraph 1,
A method for manufacturing a substrate for surface-enhanced Raman scattering, wherein the plasmonic metal is a metal including at least one selected from the group consisting of Ag, Al, Au, Co, Cu, Fe, Li, Ni, Pd, Rh, Ru, and Pt. In paragraph 1,
A method for manufacturing a substrate for surface-enhanced Raman scattering, wherein the pores have a diameter of 10 nm to 100 nm. In paragraph 1,
A method for manufacturing a substrate for surface-enhanced Raman scattering, wherein the above plasmonic metal thin film has a thickness of 10 nm to 600 nm. In paragraph 1,
A method for manufacturing a substrate for surface-enhanced Raman scattering, wherein the polymer micelle is selected from the group consisting of polystyrene, polymethyl methacrylate, polyurethane, polyacrylamide, polydimethylsiloxane, polyvinylidene fluoride, polyethylene, polyethylene oxide, polyacrylic acid, polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone, polyphenylene oxide, polyolefin, and polystyrene-b-polyethylene oxide (PS-b-PEO). In paragraph 1,
The above plasmonic metal precursor solution is a method for manufacturing a substrate for surface-enhanced Raman scattering, wherein the plasmonic metal precursor is contained in a concentration of 1 mM to 125 mM. In paragraph 1,
A method for producing a substrate for surface-enhanced Raman scattering, wherein the above plasmonic metal precursor solution comprises polymer micelles at a concentration of 0.1 mg/ml to 50 mg/ml. In paragraph 1,
The above electrochemical deposition method is a method for manufacturing a substrate for surface-enhanced Raman scattering, which is performed at a temperature of 25 to 45°C. In paragraph 1,
A method for producing a substrate for surface-enhanced Raman scattering, wherein the organic solvent is dichloromethane, acetone, diethyl ether, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, N-methylpyrrolidone or chloroform. In paragraph 1,
A method for manufacturing a substrate for surface-enhanced Raman scattering, wherein the material of the substrate is PET, polyimide, silicon, glass or quartz. In paragraph 1,
A method for manufacturing a substrate for surface-enhanced Raman scattering, wherein the above pretreatment metal comprises at least one metal selected from the group consisting of Ti and Cr. In paragraph 1,
A method for manufacturing a substrate for surface-enhanced Raman scattering, wherein the above pattern may or may not be constant. A substrate for surface-enhanced Raman scattering manufactured by the method according to claim 1. In Article 14,
The above substrate is a surface-enhanced Raman scattering substrate having pores with a diameter of 10 nm to 100 nm. In Article 14,
The above substrate is a surface-enhanced Raman scattering substrate having a plasmonic metal thin film with a thickness of 10 nm to 600 nm.