WO2023106624A1 - Substrat polymère sur lequel sont formées des nanostructures et capteur le comprenant - Google Patents

Substrat polymère sur lequel sont formées des nanostructures et capteur le comprenant Download PDF

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WO2023106624A1
WO2023106624A1 PCT/KR2022/016590 KR2022016590W WO2023106624A1 WO 2023106624 A1 WO2023106624 A1 WO 2023106624A1 KR 2022016590 W KR2022016590 W KR 2022016590W WO 2023106624 A1 WO2023106624 A1 WO 2023106624A1
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nanostructure
plasmonic
nanostructures
polymer substrate
ion beam
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Korean (ko)
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정성훈
박성규
이승훈
나종주
양준영
김도근
박주영
변은연
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한국재료연구원
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • 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
    • C23C14/20—Metallic material, boron or silicon on organic substrates
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    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
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    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3435—Applying energy to the substrate during sputtering
    • C23C14/3442—Applying energy to the substrate during sputtering using an ion beam
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    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
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    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
    • 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
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/645—Specially adapted constructive features of fluorimeters
    • G01N21/648—Specially adapted constructive features of fluorimeters using evanescent coupling or surface plasmon coupling for the excitation of fluorescence
    • 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
    • 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
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to a polymer substrate on which nanostructures are formed and a sensor including the same. More specifically, the present invention relates to a polymer substrate having a nanostructure that can be used as a sensor by depositing a metal or metal oxide without a separate surface coating treatment by modifying the surface of the polymer substrate, and a sensor including the same.
  • Biosensors may be classified into electrochemical, piezoelectric, thermal, nanomechanical, and optical biosensors according to technical fields.
  • optical biosensors include calorimetry, fluorescence, plasma resonance-based sensors, surface enhanced Raman scattering or surface enhanced Raman spectroscopy (SERS) sensors, and the like.
  • SERS technology is a technology that enhances an electric field by using ultrafine surface nanostructures and amplifies Raman spectrum signals through it. It is a technology related to a biosensor using a greatly increased phenomenon.
  • ultrafine nanostructures since hotspots, which are regions in which an electric field is locally enhanced, exist mainly in nanogaps due to ultrafine nanostructures, a technique for making ultrafine nanostructures is important.
  • Conventional representative technologies for forming a nanogap by ultrafine nanostructures include (1) a technology of forming high aspect ratio silicon and metal nanorods by plasma etching of a silicon substrate, and (2) nanoimprint There are methods of forming high aspect ratio polymers and metal nanorods by applying an etching process.
  • (3) metal nanostructures were prepared by applying various nanoetching processes, such as a technique of forming a uniform metal nanorod by optical interference lithography.
  • nanoprotrusions on the polymer substrate, depositing a metal such as Au on the surface of the nanoprotrusions to form a metal thin film.
  • a metal thin film depositing metal nanoparticles on the nanostructure on which the surface-treated metal thin film is formed, Since it has to go through a step of forming an approximately spherical final nanostructure, the process is complicated and expensive.
  • Korean Patent Registration No. 10-1932195 discloses a method for manufacturing a substrate for surface-enhanced Raman spectroscopy.
  • the present inventors have developed a polymer substrate that can be used for a high-sensitivity optical biosensor, etc. with ultrafine nanostructures formed, and a polymer substrate that can be used for a high-sensitivity optical biosensor, etc. with a simplified process by omitting a separate surface coating step such as PFDT. I tried to invent a way to make it.
  • An object of the present invention is to provide a polymer substrate on which a nanostructure is formed, which can be utilized in a highly sensitive optical biosensor or the like, on which an ultrafine nanostructure is formed.
  • Another object of the present invention is to provide a highly sensitive sensor including a polymer substrate on which the nanostructure is formed.
  • Another object of the present invention is to provide a method for manufacturing a polymer substrate having a nanostructure formed with a simplified manufacturing process step by omitting a separate surface coating step such as PFDT.
  • a polymer layer on which a plurality of nanostructures are formed wherein the polymer layer is made of a fluorine-based polymer, and the nanostructure is formed by ion beam treatment with an energy of 50 to 2000eV, wherein the nanostructure is formed.
  • a polymer substrate is provided.
  • the fluorine-based polymer may be made of one or more of PTFE, FEP, PFA, PVDF, ETFE, and PVF.
  • the shape of the nanostructure may be one or more of a wrinkle shape, a cone shape, and a protrusion shape.
  • a plasmonic layer formed by depositing a metal or metal oxide on the polymer layer may be further provided.
  • a plasmonic nanostructure including the nanostructure and a plasmonic layer of metal or metal oxide deposited on the nanostructure is formed, and the shape of the plasmonic nanostructure is one of a projection shape and a sphere shape. There may be more than one species.
  • the average thickness of the plasmonic layer may be greater than or equal to 100 nm and less than 500 nm.
  • the average diameter of the plasmonic nanostructures may be 50 to 200 nm.
  • the average spacing of the plasmonic nanostructures may be 1 to 30 nm.
  • the density of the plasmonic nanostructures may be 10 to 100/ ⁇ m 2 .
  • a sensor including a polymer substrate on which the nanostructure described herein is formed is provided.
  • the senor may be a surface enhanced Raman scattering (SERS) sensor, a plasmon-enhanced fluorescence (PEF) sensor, or an electrochemical sensor.
  • SERS surface enhanced Raman scattering
  • PEF plasmon-enhanced fluorescence
  • the gas used during the ion beam treatment in step i) may include at least one of argon and oxygen.
  • a plasmonic nanostructure including the nanostructure and a plasmonic layer of a metal or metal oxide deposited on the nanostructure is formed, and the shape of the plasmonic nanostructure is a projection shape and It may be one or more of spherical shapes.
  • the step of forming a plasmonic layer by depositing a metal or metal oxide on the polymer layer on which the nanostructure is formed in step ii) is performed by sputtering, vacuum thermal evaporation, or electron beam evaporation (E-beam evaporation). It may be formed by one or more of evaporation, evaporation, chemical vapor deposition, and atomic layer deposition.
  • the steps may be performed in a roll-to-roll process.
  • the process speed of the roll-to-roll process may be 0.1 to 1 mpm.
  • ultrafine nanostructures are formed by ion beam treatment using low surface energy characteristics of fluorine-based polymers to provide a polymer substrate with nanostructures that can be used for high-sensitivity optical biosensors and the like without a separate surface coating layer. there is.
  • a highly sensitive sensor including a polymer substrate on which ultra-fine nanostructures are formed by ion beam treatment using low surface energy characteristics of fluorine-based polymers.
  • ultrafine nanostructures are formed by ion beam treatment using low surface energy characteristics of fluorine-based polymers to efficiently manufacture a polymer substrate having plasmonic nanostructures that can be used for high-sensitivity optical biosensors and the like without a surface coating layer. can do.
  • a polymer substrate on which plasmonic nanostructures are formed can be manufactured in only two steps: an ion beam treatment step for a fluorine-based polymer and a metal or metal oxide deposition step, without requiring a separate surface coating treatment process, Productivity of the polymer substrate on which the plasmonic nanostructure is formed can be dramatically improved through the simplification of the manufacturing process.
  • FIG. 1 is a view schematically showing a polymer substrate on which a nanostructure is formed according to an embodiment of the present invention.
  • FIG. 2 is a view schematically showing a method for manufacturing a polymer substrate having nanostructures according to an embodiment of the present invention.
  • FIG. 3 is a schematic diagram schematically showing changes in the surface shape of a substrate in a method for manufacturing a polymer substrate on which nanostructures are formed according to an embodiment of the present invention.
  • FIG. 4 is a photograph showing the surface of a PTFE substrate after ion beam treatment under different ion beam treatment conditions and the surface after Cu is deposited on the ion beam treated PTFE substrate according to an embodiment of the present invention.
  • FIG. 5 is a photograph showing the surface after ion beam treatment on an FEP substrate according to an embodiment of the present invention under different ion beam treatment conditions and the surface after Cu is deposited on the ion beam treated FEP substrate.
  • FIG. 6 is a photograph showing a surface after ion beam treatment by varying ion beam treatment conditions on a PFA substrate according to an embodiment of the present invention and a surface after Cu is deposited on the ion beam treated PFA substrate.
  • FIG. 7 is a photograph showing the surface of a fluorine-based polymer after ion beam treatment according to the type of gas according to an embodiment of the present invention.
  • FIG 8 is a graph showing the water contact angle of the surface of the fluorine-based polymer after ion beam treatment according to the type of gas according to an embodiment of the present invention.
  • FIG. 9 is a photograph showing a surface on which Cu is deposited after ion beam treatment according to gas types according to an embodiment of the present invention.
  • FIG. 10 is a graph showing SERS signals of sensors including various fluorine-based polymer substrates on which nanostructures are formed according to an embodiment of the present invention.
  • FIG. 11 is a photograph showing a surface on which Ag of various thicknesses is deposited on a PTFE substrate after ion beam treatment according to an embodiment of the present invention.
  • FIG. 12 is a graph showing the average diameter of nanostructures and the average distance between nanostructures according to the deposition thickness after Ag deposition on a PTFE substrate after ion beam treatment according to an embodiment of the present invention.
  • FIG. 13 is a photograph showing a surface on which Ag of various thicknesses is deposited after ion beam treatment on a FEP substrate according to an embodiment of the present invention.
  • FIG. 14 is a graph showing the average diameter of nanostructures and the average distance between nanostructures according to the deposition thickness after Ag deposition on a FEP substrate after ion beam treatment according to an embodiment of the present invention.
  • 15 is a photograph showing the surface on which Ag of various thicknesses is deposited after ion beam treatment on a PFA substrate according to an embodiment of the present invention.
  • 16 is a graph showing the average diameter of nanostructures and the average distance between nanostructures according to the deposition thickness after Ag deposition after ion beam treatment on a PFA substrate according to an embodiment of the present invention.
  • first and second may be used to describe various components, but the components should not be limited by the terms. These terms are only used for the purpose of distinguishing one component from another.
  • a polymer layer in which a plurality of nanostructures are formed including, wherein the polymer layer is made of a fluorine-based polymer, and the nanostructure is formed by ion beam treatment having an energy of 50 to 2000 eV, nano A polymer substrate on which a structure is formed is provided.
  • the fluorine-based polymer may be composed of various known fluorine-based materials.
  • the fluorine-based polymer is polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), perfluoroalkoxy (PFA), polyvinylidene fluoride (Polyvinylidene fluoride (PVDF), ethylene tetrafluoroethylene (ETFE), and polyvinyl fluoride (PVF).
  • PTFE polytetrafluoroethylene
  • FEP fluorinated ethylene propylene
  • PFA perfluoroalkoxy
  • PVDF polyvinylidene fluoride
  • ETFE ethylene tetrafluoroethylene
  • PVF polyvinyl fluoride
  • the polymer substrate on which the nanostructure of the present application is formed is a plasmonic nanostructure of a metal or metal oxide having at least one type of protrusion or sphere in a simple process by using a fluorine-based polymer as a polymer layer, using the low surface energy characteristics of the fluorine-based polymer. can be easily formed and used for sensors.
  • the nanostructure is formed by ion beam treatment of a fluorine-based polymer layer with energy of 50 to 2000 eV. If the energy of the ion beam is less than 50 eV, the formation of nanostructures on the fluorine-based polymer layer may not be smooth, and if the ion beam energy exceeds 2000 eV, deformation such as twisting and contraction occurs in the substrate including the fluorine-based polymer layer, resulting in deformation of the sensor substrate. cannot be used as
  • the shape of the nanostructure may be one or more of a wrinkle shape, a cone shape, and a protrusion shape.
  • a plasmonic layer formed by depositing a metal or metal oxide on the polymer layer may be further provided.
  • the metal or metal oxide may include one or more of copper (Cu), silver (Ag), gold (Au), platinum (Pt), palladium (Pd), and aluminum (Al). .
  • Plasmonic means that when a metal material with high conductivity forms an interface with a dielectric material, electrons on the surface of the metal thin film oscillate collectively by an applied electric field and proceed with a certain period along the interface.
  • Metal plasmonic nanostructures such as gold and silver induce a resonance phenomenon (localized surface plasmon resonance, LSPR) between incident light and free electrons present inside the metal nanostructure, and the incident light is converted into metal plasmonic It can be focused on the sharp tips of nanostructures or local spaces of nanogaps between nanostructures.
  • a high-sensitivity sensor can be utilized by using the local electric field enhancement region, that is, the hotspot, which is the local space.
  • ultra-sensitive surface-enhanced Raman spectroscopy capable of detecting trace amounts of hazardous chemicals or disease-related biomarkers by amplifying the Raman signal of molecules adsorbed to plasmonic hotspots by more than 10 6 times.
  • -Enhanced Raman spectroscopy can provide a substrate.
  • the form of the metal or metal oxide deposited on the nanostructure formed on the polymer layer may be composed of various types of nanostructures. Although not limited thereto, a plasmonic nanostructure composed of the nanostructure and a plasmonic layer of metal or metal oxide deposited on the nanostructure is formed, and the shape of the plasmonic nanostructure is one of a protrusion shape and a spherical shape. There may be more than one species.
  • the average thickness of the plasmonic layer may be greater than or equal to 100 nm and less than 500 nm.
  • the polymer substrate on which the nanostructures of the present application are formed is applied as a SERS sensor, when the average thickness of the plasmonic layer is out of the above range, the spacing of the plasmonic nanostructures is too far to form a nanogap, or a plasmonic nanostructure is not formed. Intervals between the structures may be too close to form a nanogap.
  • an average diameter of 50 to 200 nm of the plasmonic nanostructures may be suitable for electrical signal enhancement and SERS signal enhancement in local electric field enhancement regions (hotspots), and the average diameter of the plasmonic nanostructures
  • the diameter may be more preferably 65 to 190 nm, the average diameter of the plasmonic nanostructures may be more preferably 70 to 190 nm, and the average diameter of the plasmonic nanostructures may be more preferably 80 to 150 nm. It may be more suitable that the average diameter of the plasmonic nanostructure is 90 to 140 nm.
  • an average spacing of 10 to 30 nm of the plasmonic nanostructures may be suitable for electrical signal enhancement and SERS signal enhancement in local electric field enhancement regions (hotspots), and the average spacing of the plasmonic nanostructures A spacing of 10 to 20 nm may be more suitable.
  • the density of the plasmonic nanostructures is 10 to 100 / ⁇ m 2 , which may be suitable for electrical signal enhancement and SERS signal enhancement in local electric field enhancement regions (hotspots), and the plasmonic nanostructures It may be more suitable that the density of the structure is 15 to 65 / ⁇ m 2 , and the density of the plasmonic nanostructure may be more suitable to be 25 to 65 / ⁇ m 2 , and the density of the plasmonic nanostructure may be more suitable. 25 to 55 pieces/ ⁇ m 2 may be more suitable.
  • a sensor including a polymer substrate on which the nanostructure described herein is formed is provided.
  • the senor may be a biosensor that detects a biomaterial by adsorbing DNA, cells, biomolecules, or reagents and then using changes in electrical and optical properties of a metal or metal oxide thin film.
  • the biosensor may include an electrochemical biosensor and an optical biosensor.
  • the optical biosensor may be a surface enhanced Raman scattering (SERS) sensor or a plasmon-enhanced fluorescence (PEF) sensor.
  • forming a plurality of nanostructures by treating the fluorine-based polymer layer with an ion beam having an energy of 50 to 2000 eV; And forming a plasmonic layer by depositing a metal or metal oxide on the polymer layer on which the nanostructure is formed; a method for manufacturing a polymer substrate having a nanostructure is provided.
  • the ion beam treatment is a step of modifying the surface of the polymer layer to form a nanostructure on the surface of the fluorine-based polymer layer.
  • ion beam energy of 50 to 2000 eV may be suitable for forming nanostructures on the surface of the polymer layer, 50 to 1500 eV may be more suitable, 50 to 1000 eV may be more suitable, and 50 to 500 eV may be more suitable. may be more suitable.
  • the surface modification effect may be insufficient, and when the ion beam energy exceeds 2000 eV, deformation such as twisting and contraction occurs in the substrate including the fluorine-based polymer layer, which can be used as a sensor substrate.
  • the gas used during the ion beam treatment may include at least one of argon and oxygen suitable for forming nanostructures on the surface of the polymer layer.
  • the gas used during the ion beam treatment may include at least one of argon and oxygen suitable for forming nanostructures on the surface of the polymer layer.
  • it may be suitable for forming a plasmonic nanostructure during deposition of metal or metal oxide without separate surface treatment.
  • the step of forming a plasmonic layer by depositing a metal or metal oxide on the polymer layer on which the nanostructure is formed is, but is not limited to, the nanostructure and a plasmonic layer of the metal or metal oxide deposited on the nanostructure.
  • a plasmonic nanostructure consisting of may be formed.
  • the shape of the plasmonic nanostructure may be at least one of a protrusion shape and a spherical shape.
  • Forming a plasmonic layer by depositing a metal or metal oxide on the polymer layer on which the nanostructure is formed is performed by sputtering of metal or metal oxide particles, vacuum thermal evaporation, or electron beam evaporation (E-beam evaporation). It can be carried out using various known techniques such as evaporation, evaporation, chemical vapor deposition, and atomic layer deposition.
  • the forming of the plasmonic layer by depositing a metal or metal oxide on the polymer layer on which the nanostructures are formed may be performed by sputtering, particularly ion beam-assisted sputtering.
  • the metal or metal oxide is deposited by ion beam-assisted sputtering
  • the plasmonic nanostructure may be more suitable for forming at least one of a protrusion shape and a spherical shape.
  • the metal or metal oxide When the metal or metal oxide is deposited on the polymer layer and the nanostructure, the metal or metal oxide is uniformly deposited initially, but may be deposited intensively on top of the nanostructure as the deposition progresses.
  • the intensive deposition on the top of the nanostructure as described above is due to the shadow effect of the metal or metal oxide particles already deposited on the top of the nanostructure as the deposition progresses. Accordingly, the size of the nanogap can be appropriately adjusted by controlling the deposition conditions.
  • the above steps may be performed in a roll-to-roll process.
  • the process speed of the roll-to-roll process is 0.1 to 10 mpm.
  • FIG. 3 is a schematic diagram schematically showing changes in the surface shape of a substrate in a method for manufacturing a polymer substrate on which nanostructures are formed according to an embodiment of the present invention.
  • Table 1 shows process conditions for forming a polymer substrate on which nanostructures are formed according to an embodiment of the present invention.
  • Ion beam treatment was performed on the surfaces of PTFE, FEP, and PFA under the process conditions in Table 1 using argon or argon and oxygen gas, respectively. Then, Cu was deposited using ion beam assisted sputtering.
  • FIG. 4 is a photograph showing the surface after ion beam treatment under different ion beam treatment conditions (sample 1-4) on a PTFE substrate according to an embodiment of the present invention and the surface after Cu is deposited on the ion beam treated PTFE substrate. am.
  • FIG. 5 is a photograph showing the surface after ion beam treatment on an FEP substrate according to an embodiment of the present invention under different ion beam treatment conditions (sample 1-4) and Cu deposited on the ion beam treated FEP substrate. am.
  • FIG. 6 is a photograph showing the surface after ion beam treatment by varying the ion beam treatment conditions (sample 1-4) on the PFA substrate according to an embodiment of the present invention and the surface after Cu is deposited on the ion beam treated PFA substrate. am.
  • Fluorine-based polymer PTFE, FEP, and PFA substrates are prepared, and ion beam treatment is performed on the surface of each polymer substrate using a different type of gas under the following conditions to form a surface modification layer, and the surface modification layer is formed on the polymer.
  • the water contact angle of the substrate surface was measured. Since the energy of the ion beam used to form the surface modification layer is distributed in the range of 30% - 80% of the ion beam anode voltage, it generally has a Gaussian distribution, so the specimen is irradiated with an ion beam with energy of 300 to 1000 eV. To do this, an ion beam anode voltage of 0.6 to 1.2 kV was used.
  • FIG. 7 is a photograph showing the surface of a fluorine-based polymer after ion beam treatment according to the type of gas according to an embodiment of the present invention.
  • FIG 8 is a graph showing the water contact angle of the surface of the fluorine-based polymer after ion beam treatment according to the type of gas according to an embodiment of the present invention.
  • FIG. 9 is a photograph showing a surface on which Cu is deposited after ion beam treatment according to gas types according to an embodiment of the present invention.
  • nanostructures were not formed on the surfaces of PTFE, FEP, and PFA when ion beam treatment was not performed, and thus protrusions or spherical plasmonic nanostructures were not formed after copper deposition.
  • nanostructures were not formed, or even though nanostructures were formed, protrusions or spherical plasmonic nanostructures were not formed after copper deposition. This is because the surfaces of PTFE, FEP, and PFA have high surface energy by hydrogen or argon and hydrogen ion beam treatment.
  • nanostructures were formed on the surfaces of PTFE, FEP, and PFA treated with argon or oxygen ion beams, and plasmonic nanostructures in the form of projections or spheres were formed after copper deposition. This is because the surfaces of PTFE, FEP, and PFA have low surface energy by argon or oxygen ion beam treatment.
  • the contact angles of argon or oxygen ion beam-treated PTFE, FEP, and PFA substrate surfaces with water are all 100° or more, and hydrogen ion beam or argon and hydrogen ion beam-treated PTFE, FEP, and PFA substrate surfaces have water and water contact angles. All of the contact angles were less than 50°. This is a result that can be seen that the contact angle with water is remarkably high in the case of argon ion beam treatment or oxygen ion beam treatment.
  • a high contact angle with water means that the surface energy is low, which indicates that it is suitable for forming plasmonic nanostructures in the form of projections or spheres when depositing metal or metal oxide on the surface of the ion beam pretreated polymer layer. .
  • the nanostructure formed on the surface of the polymer and the low surface energy it is possible to form a protrusion or spherical plasmonic nanostructure without any surface treatment, so that the polymer substrate on which the nanostructure of the present application is formed can be applied to a SERS sensor. It was confirmed that it could be suitable.
  • ion beam treatment was performed on the surfaces of PTFE, FEP and PFA under conditions of 1 kV, 70 mA, 0.1 mpm, once. Thereafter, Ag was deposited to a thickness of 100 nm, 300 nm, and 500 nm using ion beam-assisted sputtering, and then the SERS signal was measured under the following conditions.
  • FIG. 10 is a graph showing SERS signals of sensors including various fluorine-based polymer substrates on which nanostructures are formed according to an embodiment of the present invention.
  • Table 2 is a table showing the SERS signal amplification rate of the polymer substrate on which the nanostructure is formed according to an embodiment of the present invention.
  • the thickness of Ag deposited after ion beam treatment showed high signal amplification in the order of 100 nm, 300 nm, and 500 nm.
  • the highest signal amplification rate was shown when the Ag thickness deposited after the oxygen ion beam treatment was 100 nm.
  • the thickness of deposited Ag after ion beam treatment showed high signal amplification in the order of 300 nm, 100 nm, and 500 nm.
  • the signal amplification rate was the highest, and the signal amplification rate was significantly higher than that of PTFE and PFA.
  • the thickness of deposited Ag after ion beam treatment showed high signal amplification in the order of 300 nm, 100 nm, and 500 nm.
  • the highest signal amplification rate was shown when the thickness of Ag deposited after the oxygen ion beam treatment was 300 nm.
  • Ion beam treatment was performed on the surfaces of PTFE, FEP and PFA under the same conditions using argon or oxygen gas. Then, Ag was deposited using ion beam assisted sputtering. In order to measure the shape and average diameter of Ag plasmonic nanostructures and the average distance between nanostructures, SPIP analysis was performed using FE-SEM images.
  • FIG. 11 is a photograph showing a surface on which Ag of various thicknesses is deposited on a PTFE substrate after ion beam treatment according to an embodiment of the present invention.
  • FIG. 12 is a graph showing the diameter of plasmonic nanostructures and the average distance between plasmonic nanostructures according to the deposition thickness after Ag deposition on a PTFE substrate after ion beam treatment according to an embodiment of the present invention.
  • Table 3 shows the average diameter of Ag plasmonic nanostructures formed after ion beam treatment and Ag deposition on PTFE, average distance between plasmonic nanostructures, average gap size, and plasmonic nanostructures. Density is indicated.
  • the average spacing between the plasmonic nanostructures is a value obtained by subtracting the average diameter of the plasmonic nanostructures from the average distance between the plasmonic nanostructures.
  • the average distance between the plasmonic nanostructures refers to the distance between the centers of adjacent plasmonic nanostructures
  • the average diameter of the plasmonic nanostructures refers to the average diameter of cross sections of the plasmonic nanostructures.
  • the spacing between plasmonic nanostructures refers to the distance between adjacent plasmonic nanostructures.
  • the density of Ag plasmonic nanostructures is the highest at 58.8/ ⁇ m 2 , but the average spacing between nanostructures is the widest at 25.2 nm. .
  • the deposition thickness of Ag was 500 nm, many overlapping Ag plasmonic nanostructures were generated, and the density was the lowest at 17.0/ ⁇ m 2 , and the average spacing between the plasmonic nanostructures was -3.0 nm.
  • the deposition thickness of Ag is 300 nm
  • the density of Ag plasmonic nanostructures is 26.7 pieces/ ⁇ m 2
  • the average spacing between plasmonic nanostructures is 14.0 nm, which is the most suitable value for the density and signal enhancement of the hot spot. can be expected to be the highest.
  • FIG. 13 is a photograph showing a surface on which Ag of various thicknesses is deposited after ion beam treatment on a FEP substrate according to an embodiment of the present invention.
  • FIG. 14 is a graph showing the diameter of nanostructures and the average distance between nanostructures according to the deposition thickness after Ag deposition on a FEP substrate after ion beam treatment according to an embodiment of the present invention.
  • Table 4 shows the average diameter of the Ag plasmonic nanostructures formed after ion beam treatment and Ag deposition on the FEP, the average distance between the plasmonic nanostructures, the average spacing, and the density of the plasmonic nanostructures.
  • the average distance between the plasmonic nanostructures is a value obtained by subtracting the average diameter of the plasmonic nanostructures from the average distance between the plasmonic nanostructures.
  • the density of Ag plasmonic nanostructures is 38.4 pieces/ ⁇ m 2
  • the average spacing between plasmonic nanostructures is 14.6 nm, which is the most suitable value for the density and signal enhancement of the hot spot. can be expected to be the highest.
  • 15 is a photograph showing the surface on which Ag of various thicknesses is deposited after ion beam treatment on a PFA substrate according to an embodiment of the present invention.
  • 16 is a graph showing the diameter of nanostructures and the average distance between nanostructures according to the deposition thickness after Ag deposition after ion beam treatment on a PFA substrate according to an embodiment of the present invention.
  • Table 5 shows the average diameter of Ag plasmonic nanostructures formed after ion beam treatment and Ag deposition on PFA, the average distance between plasmonic nanostructures, the average spacing, and the density of plasmonic nanostructures.
  • the average distance between the plasmonic nanostructures is a value obtained by subtracting the average diameter of the plasmonic nanostructures from the average distance between the plasmonic nanostructures.
  • the density of Ag plasmonic nanostructures is 26.3 pieces/ ⁇ m 2
  • the average spacing between plasmonic nanostructures is 12.2 nm, which is the most suitable value for the density and signal enhancement of the hot spot. can be expected to be the highest.
  • the polymer substrate on which the nanostructure is formed according to the present invention is formed by ion beam treatment on a fluorine-based polymer substrate under appropriate conditions to form a nanostructure, and depositing a metal or metal oxide on the nanostructure formed to form a metal or metal oxide. It was confirmed that a plasmonic nanostructure can be formed and used as a highly sensitive sensor including a SERS sensor that can effectively amplify a signal using the plasmonic nanostructure.

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Abstract

La présente invention concerne un substrat polymère sur lequel sont formées des nanostructures et un capteur le comprenant. Plus particulièrement, la présente invention concerne : un substrat polymère sur lequel sont formées des nanostructures, qui peuvent être utilisées en tant que capteur par modification de surface du substrat polymère pour déposer un métal ou un oxyde métallique sans traitement de revêtement de surface séparé; et un capteur le comprenant.
PCT/KR2022/016590 2021-12-10 2022-10-27 Substrat polymère sur lequel sont formées des nanostructures et capteur le comprenant WO2023106624A1 (fr)

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