WO2022169090A1 - Procédé de préparation de nanostructure métallique - Google Patents

Procédé de préparation de nanostructure métallique Download PDF

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WO2022169090A1
WO2022169090A1 PCT/KR2021/018704 KR2021018704W WO2022169090A1 WO 2022169090 A1 WO2022169090 A1 WO 2022169090A1 KR 2021018704 W KR2021018704 W KR 2021018704W WO 2022169090 A1 WO2022169090 A1 WO 2022169090A1
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metal
substrate
nanostructure
nanoparticles
fluorocarbon
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PCT/KR2021/018704
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English (en)
Korean (ko)
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이성도
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이성도
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Priority claimed from KR1020210172965A external-priority patent/KR20220114469A/ko
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Publication of WO2022169090A1 publication Critical patent/WO2022169090A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/44—Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering

Definitions

  • the present invention relates to a method for manufacturing a novel metal nanostructure providing an enhanced Raman signal.
  • Raman scattering is a phenomenon in which the energy (hv) of an incident photon is scattered with energy (hv') of a different frequency while changing the vibrational state of the molecule, and the scattering at this time belongs to inelastic scattering. Since Raman scattering exhibits a unique photon energy change (Raman shift) form depending on a molecular structure that interacts with photons to induce scattering, it can be effectively used for detection, confirmation and analysis of molecules. By using Raman spectroscopy using Raman scattering, a signal can be obtained even for a non-polar molecule with an induced polarization change of the molecule, and virtually all organic molecules have an inherent Raman shift. In addition, since it is not affected by interference by water molecules, it is more suitable for the detection of biomolecules such as proteins and genes.
  • the analysis target material can be directly analyzed by analyzing such a Raman signal.
  • Raman scattering is inherently weak in signal, so a long time exposure to a high-power laser is required to detect molecules.
  • Raman scattering (SERS) spectroscopy SERS
  • SERS surface-enhanced Raman scattering
  • SERS Surface-enhanced Raman scattering
  • LSPR localized surface plasmon resonance
  • surface-enhanced Raman spectroscopy is capable of detecting the intensity of a signal down to the level of a single molecule when molecules emitting a Raman signal are on the surface of a metal nanostructured substrate. It is a measurement method that uses a phenomenon that is augmented to the extent that there is. In general, the smaller the distance between nanoparticles constituting the metal nanostructure, that is, the nanogap, the higher the intensity of the Raman signal generated by surface-enhanced Raman spectroscopy (SERS). Therefore, it is preferable to minimize the nanogap.
  • the nanostructure for forming the nanogap is a conventional representative technique, (1) forming a mask on a silicon substrate through an exposure process and forming silicon and metal nanorods through plasma etching, (2) nanoimprint ( nanoimprint) process to form high-aspect-ratio polymers and metal nanorods.
  • nanoimprint nanoimprint
  • noble metal nanostructures are manufactured by applying various nanoprocesses, such as (3) a technique for forming uniform metal nanorods by metal nanowires.
  • the number (density) of silicon/noble metal nanorods per unit area is up to 18 pieces/ ⁇ m 2 , which is tens of nm away from neighboring nanorods, so that a nanogap that is a hot spot is not formed. Therefore, in order to form a nanogap, a nanogap can be formed using the high aspect ratio metal nanorod closing phenomenon by applying a capillary force of a solvent.
  • the method of (2) is characterized in that the density of the noble metal nanorods is at most 25/ ⁇ m 2 and the distance between the nanorods is separated by several tens of nm. Therefore, as in (1), it is possible to form a nanogap using the closing phenomenon of the high aspect ratio metal nanorods by applying a capillary force.
  • Au is vacuum-deposited on the polymer nanorods formed through .
  • another technical problem to be solved by the present invention is a method of manufacturing a metal nanostructure that controls the surface energy of the substrate through surface treatment of the substrate, deposits a metal mask thereon, and provides an improved Raman signal according to the surface energy, and To provide a metal nanostructure manufactured through this.
  • the present invention comprises the steps of surface-treating a template substrate or a base substrate;
  • LSPR localized surface plasmon resonance
  • the present invention provides a metal nanostructure manufactured by the method for manufacturing the metal nanostructure.
  • the present invention provides a substrate for surface-enhanced Raman scattering spectroscopy, characterized in that it comprises a metal nanostructure manufactured according to a method for manufacturing a metal nanostructure.
  • the high-density nanostructured surface-enhanced Raman spectroscopy substrate structure using a low surface energy substrate and a metal mask according to the present invention consists of a nanostructured metal deposition thin film of various designs formed through an etching (etching) process on the upper portion of the substrate, and As for the nanostructure, a metal mask having nanometal particles of different shapes is generated according to the surface treatment of the substrate, and nanostructures having different shapes can be formed depending on the metal mask.
  • a method for manufacturing a surface-enhanced Raman spectrometer having a high-density nanostructure using a low-surface-energy substrate and a metal mask according to the present invention is a water-repellent coating with low surface energy using a process chamber and a resistance heating boat installed inside the process chamber.
  • a method of generating a metal nanoparticle mask by performing metal deposition with A surface-enhanced Raman spectroscopy substrate having a high-density nanostructure by resistance heating coating or sputtering is performed.
  • 2 is an embodiment of the structure of a nanostructure surface-enhanced Raman spectroscopy substrate using a plurality of metal nanoparticle masks according to the present invention.
  • 2 is a cross-sectional image of a metal nanostructure analyzed by a field emission scanning electron microscope (FE-SEM) of the metal nanostructure, and the bottom of FIG. 2 is a metal nanostructure analyzed by a field emission scanning electron microscope (FE-SEM) It is a surface image.
  • FE-SEM field emission scanning electron microscope
  • 3 shows the shape of the metal nanoparticle mask according to the difference in surface energy of the substrate taken with a field emission scanning electron microscope (FE-SEM).
  • 3 (a) is a shape of a metal nanoparticle mask having a triangular structure manufactured by the method of Comparative Example 1
  • FIG. 3 (b) is a shape of a metal nanoparticle mask having a rectangular structure manufactured by the method of Comparative Example 2
  • 3(c) is a shape of a metal nanoparticle mask having a mushroom structure manufactured by the method of Example 1.
  • each figure is a cross-sectional image analyzed with a field scanning electron microscope (FE-SEM), and the contact angle between the substrate and the metal nanoparticle mask is shown, and the right side is a metal nanoparticle analyzed with a field emission scanning electron microscope (FE-SEM). This is the surface image of the particle mask.
  • FE-SEM field scanning electron microscope
  • FIG. 4 shows that the etching process was performed using a metal nanoparticle mask according to the difference in surface energy of the substrate, and the nanostructures manufactured through this were taken with a field emission scanning electron microscope (FE-SEM).
  • FE-SEM field emission scanning electron microscope
  • FIG. 7 shows that the shape of metal nanoparticles is changed according to the surface treatment of the substrate, and a nanostructure having a specific structure can be prepared through etching.
  • the present invention provides a novel metal nanostructure manufacturing method providing an enhanced Raman signal, a metal nanostructure manufactured using the novel metal nanostructure manufacturing method, and a Raman signal by using the metal nanostructure is significantly improved. It relates to a surface-enhanced Raman scattering spectroscopy method with significantly improved detection sensitivity.
  • the technical core of the present invention is to form a surface treatment coating film having different surface energy on the upper portion of the substrate, to create a metal nanoparticle mask through deposition, and to form nanostructures of different sizes and shapes through an etching process.
  • various nanostructures are made through a plurality of metal nanoparticle masks having different sizes, heights, intervals or shapes, and metals such as gold, silver, and copper are deposited to form metal nanostructures and nanogap can be precisely controlled, and through this, optimization can be carried out according to the target material to be analyzed, thereby optimizing the detection sensitivity of the sample by improving the Raman signal.
  • the present invention comprises the steps of surface-treating a substrate
  • LSPR localized surface plasmon resonance
  • FIG. 1 shows the principle and advantages of surface-enhanced Raman spectroscopy
  • FIG. 2 shows the structure of a surface-enhanced Raman spectroscopy substrate for metal nanostructures using a metal nanoparticle mask according to the present invention.
  • the structure of the surface-enhanced Raman spectroscopy substrate using the metal nanoparticle mask according to the present invention is characterized in that the nanostructure is formed on the upper portion of the substrate through the metal nanoparticle mask, and the metal deposition film is sequentially arranged thereon.
  • the substrate is made of at least one non-metal material selected from the group consisting of glass, silicon (Si), gallium arsenide (GaAs), glass, quartz, and polymer.
  • non-metal material selected from the group consisting of glass, silicon (Si), gallium arsenide (GaAs), glass, quartz, and polymer.
  • the surface energy of the coating film in the surface energy coating step is 18 mN/m or less, 17 mN/m or less, 3 to 17 mN/m, 3 to 18 mN/m, 5 to 17 mN/m, 5 to 18 mN/m , may be characterized as 13 to 18 mN/m, 13 to 32 mN/m, preferably 13 to 17 mN/m.
  • a low surface energy coating having a uniform and excellent adhesion can be performed through the atmospheric pressure plasma treatment process of the glass substrate.
  • the metal nanospheres prepared by the method of the present invention include a low surface energy coating film formed on the substrate and a metal nanoparticle mask formed on the low surface energy coating film, and the surface of the low surface energy coating film formed on the substrate. It may be characterized in that the difference in surface energy of the mask on which the metal nanoparticles are deposited compared to the energy is 100 mN/m or more.
  • a low surface energy coating film may be formed through a coating agent treatment, and the coating agent is perfluoropolyether (PFPE), fluorocarbon carboxylic acid, hydrocarbon thiol (alkanethiol) ), hydrocarbon disulfide (alkyldisulfide), fluorocarbon thiol, fluorocarbon silane, chlorocarbon silane, fluorocarbon amine, fluorocarbon carboxylic acid, carbonization It may be characterized in that at least one selected from the group consisting of fluorocarbon polymers and derivatives thereof.
  • PFPE perfluoropolyether
  • fluorocarbon carboxylic acid hydrocarbon thiol (alkanethiol) ), hydrocarbon disulfide (alkyldisulfide), fluorocarbon thiol, fluorocarbon silane, chlorocarbon silane, fluorocarbon amine, fluorocarbon carboxylic acid, carbonization It may be characterized in that at least one selected from the group consisting of flu
  • the water contact angle of the substrate on which the low surface energy coating film is formed may be 80° or more, and the thickness of the low surface energy coating film may be 100 nm or less.
  • the low surface energy coating film may be formed by vacuum deposition or vapor deposition or a solution process.
  • the nanoparticle mask can be manufactured by depositing a metal on the low surface energy coating film formed in the step of surface energy coating the substrate.
  • the metal is any one or more nanoparticles selected from the group consisting of silver, gold, platinum, aluminum, copper, chromium, lead, nickel, iron, tungsten and cobalt. can be characterized.
  • the nanomask may be manufactured through a resistance heating method or a sputtering method.
  • the metal nanoparticles are deposited at a deposition rate of 1.0 ⁇ /sec or less, and the thickness may be 30 nm or less.
  • the metal nanoparticle mask may be formed in a spherical or hemispherical shape according to a difference in surface energy with the low surface energy coating film.
  • the contact angle between the substrate and the metal-nanoparticles may be 50 to 150 ⁇ , preferably 115 to 150 ⁇ .
  • the thickness between the metal and the substrate may be 5 to 30 nm.
  • the metal nanoparticles may have a diameter of 30 to 170 nm.
  • etching is performed using the metal nanoparticles prepared through the step of depositing the metal nanoparticles on the coated substrate as a mask. have.
  • the etching energy may be 60 j/cm 2 to 360 j/cm 2 It may be characterized.
  • the density of RF plasma power used for etching of 1.0 W/cm 2 can be converted to 60 J/min/cm 2 . If this is multiplied by the time (min), the etching energy (j/cm 2 ) can be obtained.
  • the RF plasma power density is 1.0 W/cm 2 , and the optimum etching time under the above conditions is 2 to 5 minutes. If the RF plasma power density is multiplied by 1 to 6 minutes, etching energy of 360 j/cm 2 can be obtained from 60 j/cm 2 .
  • the process of processing the nanostructure using the metal nanoparticles as a mask may be performed through plasma etching (etching).
  • the nanostructure When plasma etching (etching) the nanostructure is used, it may be characterized by using any one or more gases selected from the group consisting of argon, oxygen, hydrogen, helium, nitrogen, fluorine and chlorine gas.
  • the metal is silver, gold, platinum, It may be characterized in that it is any one or more metals or metal thin films selected from the group consisting of aluminum, copper, chromium, lead, nickel, iron, tungsten, cobalt, and alloys thereof.
  • the metal exhibiting the local surface plasmon resonance it may be characterized in that the surface plasmon resonance is strengthened by the nano-gap between the metal nanostructures.
  • the metal thin film on the nanostructure is formed by vacuum deposition, and is uniformly deposited on the nanostructure, but may tend to be concentrated on the upper portion as the deposition proceeds.
  • the vacuum deposition may use any one of sputtering, evaporation, chemical vapor deposition, and atomic layer deposition, but is not limited thereto.
  • the metal thin film may use any one of Al, Au, Ag, Cu, Pt, Pd, and alloys thereof, but is not limited thereto. It may be suitable for the metal thin film to apply Au or Ag.
  • the metal thin film may be formed by vacuum-depositing the Au, Ag, or an alloy thereof to a thickness of 10 nm or more, and the optimized thickness may vary according to the spacing of the nanostructures.
  • the optimized thickness is determined by the size of the nanogap.
  • the size of the nanogap is suitable to be formed to be 10 nm or less, and at this time, plasmonic coupling occurs between the metal-containing nanostructures to remarkably improve the sensitivity of the substrate for surface-enhanced Raman scattering.
  • the metal nanostructure may be characterized in that it provides an increased Raman signal in a surface-enhanced Raman scattering (SERS) analysis.
  • SERS surface-enhanced Raman scattering
  • the metal nanostructure may be characterized in that it is for a surface-enhanced Raman scattering (SERS) substrate.
  • SERS surface-enhanced Raman scattering
  • the present invention provides a metal nanostructure manufactured by the method for manufacturing the metal nanostructure.
  • the metal nanostructure may be characterized in that it provides an increased Raman signal.
  • the present invention provides a substrate for surface-enhanced Raman scattering spectroscopy, characterized in that it comprises a metal nanostructure.
  • the present invention comprises the steps of: i) functionalizing a biomolecule complementary to a nucleic acid to be detected on the surface of the metal nanostructure;
  • the sample expected to contain the nucleic acid to be detected may be used as the collected sample itself, or used by separating, purifying, or amplifying the nucleic acid to be detected therefrom.
  • the nucleic acid detection method may be characterized as a nucleic acid detection method for the diagnosis of disease, identification, confirmation of blood ties, identification of bacteria or cells, or confirmation of origin of animals and plants.
  • the nucleic acid detection method may be characterized as a single nucleotide polymorphism (SNP) detection method.
  • SNP single nucleotide polymorphism
  • FIG. 3 is a SEM photograph of a metal nanoparticle mask according to an embodiment of the present invention.
  • FIG. 3 (a) is a shape of a metal nanoparticle mask having a triangular structure manufactured by the method of Comparative Example 1
  • FIG. 3 (b) is a shape of a metal nanoparticle mask having a rectangular structure manufactured by the method of Comparative Example 2
  • 3(c) is a shape of a metal nanoparticle mask having a mushroom structure manufactured by the method of Example 1.
  • the left side of each figure is a cross-sectional image analyzed with a field scanning electron microscope (FE-SEM), and the contact angle between the substrate and the metal nanoparticle mask is shown, and the right side is a metal nanoparticle analyzed with a field emission scanning electron microscope (FE-SEM). This is the surface image of the particle mask.
  • FE-SEM field scanning electron microscope
  • FIG. 4 is an SEM photograph of a substrate on which a nanostructure is formed according to an embodiment of the present invention. It has a triangular structure (Comparative Example 1), a rectangular structure (Comparative Example 2), and a mushroom structure (Example 1) depending on the process conditions.
  • 4(a) is a nanostructure having a triangular structure prepared by the method of Comparative Example 1
  • FIG. 4(b) is a nanostructure having a rectangular structure prepared by the method of Comparative Example 2
  • FIG. 4(c) is an Example It is a nanostructure having a mushroom structure prepared by the method of 1.
  • the metal nanoparticle mask process conditions (refer to Comparative Example 1) for forming the triangular nanostructure are illustratively as follows.
  • the water contact angle of the substrate is made 90-100°, and Ag is vacuum-deposited by the resistance heating method.
  • the vacuum deposition rate may be 0.5 ⁇ /sec or less, and the deposition thickness may be 7 to 10 nm.
  • 3(a) shows the shape of a metal nanoparticle mask having a triangular structure manufactured by the method of Comparative Example 1, and it can be confirmed that the metal nanoparticle mask is formed in a hemispherical shape as a metal nanoparticle mask for forming a triangular nanostructure.
  • these hemispherical metal nanoparticles are subjected to a reactive ion etching process using CF 4 gas for 3 minutes, the nanostructure of FIG. 4(a) can be formed.
  • the metal nanoparticle mask process conditions (refer to Comparative Example 2) for forming the rectangular nanostructure are illustratively as follows.
  • the water contact angle of the substrate is made 100 ⁇ 110°, and Ag is vacuum-deposited by the resistance heating method.
  • the vacuum deposition rate may be 0.5 ⁇ /sec or less, and the deposition thickness may be 12 to 15 nm.
  • 3(b) shows the shape of the metal nanoparticle mask having a rectangular structure manufactured by the method of Comparative Example 2, and it can be confirmed that the contact angle of the metal nanoparticle mask for the formation of the rectangular structure nanostructure is formed at 107°. have.
  • these metal nanoparticles are subjected to a reactive ion etching process using CF 4 gas for 3 minutes, the nanostructure of FIG. 4(b) can be formed.
  • the metal nanoparticle mask process conditions (refer to Example 1) for forming the mushroom-structured nanostructure are illustratively as follows.
  • the water contact angle of the substrate is made 110 ⁇ 120°, and Ag is vacuum-deposited by the resistance heating method.
  • the vacuum deposition rate may be 0.5 ⁇ /sec or less, and the deposition thickness may be 20 nm.
  • the water contact angle may mean a contact angle between water and the substrate measured using water before metal nanoparticles are deposited.
  • Figure 3(c) shows the shape of the metal nanoparticle mask having a mushroom structure manufactured by the method of Example 1, and it can be confirmed that the metal nanoparticle mask for forming the mushroom structure nanostructure was formed in a spherical shape.
  • these spherical metal nanoparticles are subjected to a reactive ion etching process using CF 4 gas for 3 minutes, the nanostructure of FIG. 4(c) can be formed.
  • Reactive ion etching (RIE) process conditions for forming the nanostructures are illustratively as follows.
  • FIG. 7 is a schematic view showing that the shape of metal nanoparticles is changed according to the surface treatment of the substrate, and a nanostructure having a specific structure can be prepared through etching.
  • FIG. 5 is a view showing the results of evaluation by comparing the Raman spectroscopic characteristics of the multi-nanostructure surface-enhanced Raman spectrometer substrate according to an embodiment of the present invention according to the shape of each nanostructure.
  • Example 6 is a Raman Shift (Raman Shift, cm -1 ) of a nanostructure surface-enhanced Raman spectroscopic substrate (Example 1) and a flat substrate having a mushroom structure according to an embodiment of the present invention (Comparative Example 3) The results of comparing the signal intensities according to the following are shown.
  • Raman Shift Raman Shift, cm -1
  • Table 2 shows the contact angle of the silver-nanoparticle mask according to each surface energy. According to Table 2, when surface-treated with a surface energy of 35 N/m or higher, the silver-nanoparticle mask was not formed and deposited in the form of a film, and silver (Ag) deposition was not done at all When the film is deposited in the form of a film or silver (Ag) is not deposited, a silver-nanoparticle mask is not generated, so that a nanostructure manufacturing using the same cannot be performed.
  • Table 3 shows the results of measuring and analyzing Raman signals according to each etching time. As shown in Table 3, when the etching was performed in 2 minutes or less, there was a problem that the Raman signal enhancement was not smooth because the height of the nanostructure was too small. In addition, if excessive etching is performed for more than 5 minutes, first, all the silver-nanoparticle masks are etched away and the nanostructures created through etching are also etched, so that the height of the nanostructures decreases again, and accordingly, the Raman signal enhancement is also has decreased
  • the etching gas used CF4 gas which is advantageous for Si etching and is not harmful to the human body.
  • the pressure may be adjustable with the amount of process gas injected and a throttle valve.
  • the process pressure increases, the etching rate decreases, and when the process pressure is high, it is difficult to form a desired structure through fast etching with strong straightness.
  • a process pressure of 150 mTorr 100 nm is etched at an etching rate of 33 nm/min for 3 minutes.
  • Sodalime Glass substrate (TASCO, 100 X 100 X 1.1 mmTh) was prepared and the process was carried out with atmospheric plasma (APP Co., Ltd., ILP-450S) equipment.
  • Ar O 2 gas is injected at atmospheric pressure through atmospheric plasma equipment to generate plasma with RF power.
  • the atmospheric plasma process conditions were 330 W RF power, Ar 4 L/min and O 2 A linear plasma was floated at a flow rate of 30 mL/min and exposed four times at a rate of 2 m/min.
  • the low surface energy coating agent was prepared through the following synthesis process.
  • the glass substrate Since PFPE contains fluorine, the glass substrate has a very low surface energy, and the silane group helps to increase the adhesion between the glass substrate and the low surface energy coating agent. Coating was carried out on the glass substrate subjected to atmospheric pressure plasma treatment in the 1-1 surface treatment process using the low surface energy coating agent obtained through the above synthesis process and a spin coater (Rhabdos, SE-150LED). The spin coater dropped 5 mL of the low surface energy coating agent onto the glass substrate and proceeded for 10 seconds at a speed of 2000 rpm, forming a thin and uniform film with a thickness of 10 to 20 nm.
  • the substrate coated with low surface energy is coated with silver (Ag) (TASCO, EAG0LT0006) was deposited to a thickness of 20 nm at a deposition rate of 0.5 ⁇ /sec or less.
  • Ag silver
  • the Ag deposition was not formed as a thin film but as nanoparticles.
  • FE-SEM field emission scanning microscope
  • etching process silver-nanoparticles having a high contact angle of 120 to 135 ⁇ manufactured through the 1-3 nano mask process were used as a mask.
  • This etching process was performed using reactive ion etching (Artek System, RIE) equipment.
  • RIE reactive ion etching
  • the silver-nano-particles on the glass substrate act as a mask, so that where silver-nano-particles are formed, etching is not performed, and where silver-nano-particles are not formed, etching proceeds to form nanostructures.
  • a mushroom-shaped nanostructure was prepared due to the spherical silver-nanoparticle mask having a high contact angle (Fig. 4(c)).
  • etching process conditions using RIE equipment are as follows. At the initial vacuum degree of 10 mtorr of the RIE equipment, CF 4 (MS gas, CF 4 ), a process gas suitable for glass etching, was injected 40 sccm to create a process pressure of 150 mtorr, 1-3. The substrate calculated in the nanomask process was etched for 3 minutes at an RF plasma power density of 1.0 W/cm 2 .
  • the glass substrate was etched with an average of 100 nm at an etching rate of 33 nm/min to form a mushroom-shaped nanostructure (FIG. 4(C)).
  • a surface-enhanced Raman spectrometer was manufactured by depositing gold (Au) (TASCO, EAU0KI0001) on the nano mushroom structure formed through the 1-4 etching process.
  • Au gold
  • 120 nm deposition was performed at a deposition rate of 1.5 ⁇ /sec through a resistance heating deposition method (Thermal Evaporator (ULTECH, EasyDEP-3)) in a high vacuum of 1.0 x 10 -5 Torr or less.
  • Thermal Evaporator UTECH, EasyDEP-3
  • the performance as a surface-enhanced Raman spectroscopy substrate is improved. It is known that the enhancement index increases to 108 when the spacing between nanostructures is narrowed to 1 nm.
  • the enhancement factor increases, and then the gap between the nanostructures disappears above a certain thickness and is deposited in the form of a film rather than a nanostructure.
  • the thickness of the deposited gold was optimized to be 120 nm.
  • Raman signal measurement was carried out using a surface-enhanced Raman spectrometer having a mushroom structure prepared in the same manner as in Example 1.
  • Methylene blue (MB) (Samjeon pure medicine, M0796) was diluted in ethanol (Samjeon pure medicine, EtOH 99%) to make a concentration of 20 ⁇ M, and as a result of Raman analysis, a signal strength of about 69000 can be confirmed at the main peak, 1624 cm -1 . There was (Test Example 1 and FIG. 5).
  • Thickness 120 nm
  • a nanostructure was prepared in the same manner as in Example 1, but 1-2 After the low surface energy coating process, the surface energy was set to 25 mN/m through 1-1 atmospheric pressure plasma treatment.
  • the atmospheric pressure plasma process conditions were 330 W RF power, Ar 4 L/min and O 2
  • a linear plasma was floated at a flow rate of 30 mL/min and exposed to the plasma twice at a rate of 10 m/min.
  • a difference in surface energy was made by using the characteristic of increasing surface energy, and in the 1-3 nano mask process of Example 1, 20 nm silver (Ag) deposition was reduced to a thickness of 10 nm and proceeded to 70 ⁇ 80 ⁇
  • a silver-nanoparticle mask having a contact angle of was fabricated (Fig. 3(a)).
  • a surface-enhanced Raman scattering nanostructure having a triangular structure was prepared.
  • a nanostructure was prepared in the same manner as in Example 1, but 1-2 After the low surface energy coating process, the surface energy was adjusted to 20 mN/m through 1-1 atmospheric pressure plasma treatment.
  • the atmospheric pressure plasma process conditions were 330 W RF power, Ar 4 L/min, and O 2
  • a linear plasma was floated at a flow rate of 30 mL/min and exposed to plasma once at a rate of 10 m/min.
  • the surface energy difference was made by using the property that the surface energy increases when exposed to plasma, and in the 1-3 nano mask process of Example 1, silver (Ag) 20 nm deposition was reduced to a thickness of 15 nm and proceeded to 100 ⁇ 110 ⁇
  • a silver-nanoparticle mask having a contact angle of was prepared (Fig. 3(b)).
  • Example 1-1 Surface treatment process, 1-2 low surface energy coating process, 1-3 nano mask process, and 1-4 etching process are omitted, and only 1-5 deposition process is performed to manufacture a gold substrate having a planar structure did.
  • Gold (Au) (TASCO, EAU0KI0001) was deposited at 120 nm on a Sodalime Glass substrate (TASCO, 100 X 100 X 1.1 mmTh). As a result, a gold substrate having a planar structure was manufactured.
  • Methylene blue (MB) (Samjeon Soonyak, M0796) was analyzed using the surface-enhanced Raman spectrometer of different nanostructures prepared above. Methylene blue was diluted in ethanol (Samjeon Pure Chemical, EtOH 99%) to a concentration of 20 ⁇ M to measure the Raman signal.
  • the measurement conditions in this example are as follows.
  • Raman spectrometer PRISM, NOST
  • the strongest Raman signal was confirmed in the mushroom-shaped nanostructure prepared in the same manner as in Example 1 (signal intensity of about 69000 at the main peak, 1624 cm -1 ), and a rectangular structure ( A strong Raman signal was confirmed in the order of Comparative Example 2) and the triangular structure (Comparative Example 1).
  • the mushroom structure exhibited Raman signals of 69889 intensity (au), the rectangular structure 40175 intensity (au), and the triangular structure 6235 intensity (au).
  • the conditions for confirming the Raman signal on the flat gold substrate are as follows.
  • Raman spectrometer PRISM, NOST
  • Table 1 shows the Raman shift (Raman Shift, cm - The results of comparing the signal intensity according to 1 ) according to the shape of each nanostructure are shown.
  • the surface-enhanced Raman spectroscopy substrate manufactured by the present invention had a signal enhancement of 11 to 22 times compared to other nanostructures regardless of the Raman shift of MB.
  • a nanostructure was prepared in the same manner as in Example 1, but 1-2 After the low surface energy coating process, 1-1 atmospheric pressure plasma treatment was performed, and the surface energy treated at this time is shown in Table 2.
  • Surface-enhanced Raman spectroscopy substrates having different nanostructures were prepared using different silver-nanoparticles prepared respectively as masks, and Raman signals were measured and analyzed in the same manner as in Test Example 1.
  • a nanostructure was prepared in the same manner as in Example 1, but the etching times of the 1-4 etching processes were changed as shown in Table 3, respectively.
  • Surface-enhanced Raman spectroscopy substrates having different nanostructures were prepared using different silver-nanoparticles prepared respectively as masks, and Raman signals were measured and analyzed in the same manner as in Test Example 1.
  • the present invention relates to a method for manufacturing a novel metal nanostructure providing an enhanced Raman signal, and surface-enhanced Raman scattering spectroscopic analysis using the metal nanostructure prepared using the novel method for manufacturing a metal nanostructure of the present invention
  • a detection sensitivity is remarkably improved as the Raman signal is remarkably improved.

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Abstract

La présente invention concerne un nouveau procédé de préparation d'une nanostructure métallique fournissant un signal Raman amélioré, et si une spectroscopie de diffusion Raman exaltée de surface est réalisée à l'aide d'une nanostructure métallique préparée à l'aide du nouveau procédé de préparation d'une nanostructure métallique, de la présente invention, un signal Raman est remarquablement amélioré, et fournit donc un excellent effet pour remarquablement améliorer la sensibilité de détection.
PCT/KR2021/018704 2021-02-08 2021-12-10 Procédé de préparation de nanostructure métallique WO2022169090A1 (fr)

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KR1020210172965A KR20220114469A (ko) 2021-02-08 2021-12-06 금속 나노구조체의 제조방법

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101097205B1 (ko) * 2010-07-13 2011-12-21 포항공과대학교 산학협력단 표면증강라만산란 분광용 기판의 제조방법
KR20150044206A (ko) * 2013-10-16 2015-04-24 한국전자통신연구원 나노홀 어레이를 포함하는 표면 강화 라만 분광용 기판 및 그 제조방법
US20160223467A1 (en) * 2013-09-17 2016-08-04 Korea Institute Of Machinery & Materials Substrate for surface-enhanced raman spectroscopy and method for producing same
KR101932195B1 (ko) * 2017-10-27 2018-12-24 한국과학기술원 표면강화 라만 분광용 기판의 제조방법
KR20190124606A (ko) * 2018-04-26 2019-11-05 한국기계연구원 미끄럼 절연막을 포함하는 기판 및 이의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101097205B1 (ko) * 2010-07-13 2011-12-21 포항공과대학교 산학협력단 표면증강라만산란 분광용 기판의 제조방법
US20160223467A1 (en) * 2013-09-17 2016-08-04 Korea Institute Of Machinery & Materials Substrate for surface-enhanced raman spectroscopy and method for producing same
KR20150044206A (ko) * 2013-10-16 2015-04-24 한국전자통신연구원 나노홀 어레이를 포함하는 표면 강화 라만 분광용 기판 및 그 제조방법
KR101932195B1 (ko) * 2017-10-27 2018-12-24 한국과학기술원 표면강화 라만 분광용 기판의 제조방법
KR20190124606A (ko) * 2018-04-26 2019-11-05 한국기계연구원 미끄럼 절연막을 포함하는 기판 및 이의 제조방법

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