WO2019059423A1 - Procédé de production de nanostructure poreuse, électrode tridimensionnelle et capteur ayant une nanostructure poreuse produite par ce dernier, et appareil de production de nanostructure poreuse - Google Patents

Procédé de production de nanostructure poreuse, électrode tridimensionnelle et capteur ayant une nanostructure poreuse produite par ce dernier, et appareil de production de nanostructure poreuse Download PDF

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WO2019059423A1
WO2019059423A1 PCT/KR2017/010230 KR2017010230W WO2019059423A1 WO 2019059423 A1 WO2019059423 A1 WO 2019059423A1 KR 2017010230 W KR2017010230 W KR 2017010230W WO 2019059423 A1 WO2019059423 A1 WO 2019059423A1
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conductive substrate
nanostructure
porous
producing
porous nanostructure
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PCT/KR2017/010230
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English (en)
Korean (ko)
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양성
권희정
홍성아
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주식회사 라디안큐바이오
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Priority to PCT/KR2017/010230 priority Critical patent/WO2019059423A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/623—Porosity of the layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/02—Tanks; Installations therefor
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/20—Electroplating using ultrasonics, vibrations
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys

Definitions

  • the present invention relates to a method of manufacturing a porous nanostructure, and more particularly, to a method of manufacturing a porous nanostructure using electrochemical deposition, a three-dimensional electrode and a sensor including the porous nanostructure manufactured thereby, .
  • Nanoscale materials ie, particles at the nanoscale level, can vary in surface area, chemical reactivity due to surface energy, and magnetic / magnetic properties or optical properties as they control size or shape. Nanostructures having such physical and chemical properties are widely used in a wide range of fields such as chemical, biological, mechanical, electronic, and communication. Particularly, a business that is applied to a chemical catalyst, an electromagnetic material, and an optical sensor device by using a nanostructure having improved sensitivity and high selectivity is gradually expanding.
  • nanostructures having various shapes as disclosed in Korean Patent Publication No. 10-2014-0014069 are manufactured by gas-phase deposition or hydrothermal method under a high temperature atmosphere.
  • a high-quality nanostructure can be produced through a vapor deposition method, there is a disadvantage that manufacturing cost is increased due to a high-temperature composition and it is difficult to manufacture the nanostructure in a large area.
  • the hydrothermal synthesis method is easier to control the process than the vapor deposition method and can be applied to a large area, but it takes a long time to reduce the production yield.
  • the noble metal including gold (Au) and silver (Ag) among the various metals used as the material of the nanostructure has a standard measurement principle for measuring the adsorption degree of the sample due to the characteristics of surface plasmon resonance and quantitative and qualitative It is possible to measure and is used for biosensor and so on.
  • gold nanoparticles have advantages of high biostability and low cytotoxicity, and various attempts have been made to form nanostructures having a surface with high sensitivity using gold.
  • the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a method of manufacturing a porous nanostructure having a relatively small cost and a short time,
  • the present invention provides a three-dimensional electrode, a sensor, and a porous nanostructure manufacturing apparatus.
  • a method of fabricating a porous nanostructure comprising: preparing a conductive substrate; and performing electrochemical deposition on the conductive substrate in an atmosphere in which an electrolyte is supplied, A foaming step of forming a metal structure having a plurality of pores by bubbles generated in the electrochemical deposition process and an electrochemical deposition process in an atmosphere in which the electrolyte is supplied to the metal structure, And a coating step of forming a first nanostructure.
  • the electrolyte solution contains a metallic base metal capable of performing an electrochemical deposition process on the metal structure.
  • the metallic base metal may be at least one of copper, zinc, gold, and platinum.
  • the foam forming step includes a reaction tank preparation step of preparing a deposition reaction tank containing the electrolytic solution therein, a first immersion step of installing the reference electrode, the counter electrode, and the conductive substrate in the deposition reaction tank so as to be immersed in the electrolyte solution, And performing a deposition process of applying a predetermined voltage to the conductive substrate and the reference electrode immersed in the electrolyte so that bubbles may be generated on the conductive substrate.
  • the foam forming step further includes a bubble reducing step of reducing the size of the bubble generated during the electrochemical deposition process.
  • the bubble reducing step applies ultrasonic waves to the conductive substrate immersed in the electrolytic solution.
  • the bubble reduction step includes a water tank preparation step of preparing a water tank in which immersion water is contained, a second immersion step of immersing the deposition reaction tank in the immersion index held in the water tank, and a second immersion step of immersing the immersion water immersed in the deposition reaction tank in an ultrasonic oscillator And the ultrasound wave oscillator is operated to generate ultrasonic waves in the deposition reaction tank.
  • the bubble reduction step may irradiate the conductive substrate immersed in the electrolyte with light having a predetermined wavelength.
  • a voltage of -2.7 V to -3.3 V is applied to the conductive substrate.
  • the coating step is a step of applying a predetermined voltage to the conductive substrate and the reference electrode provided in the deposition reaction tank so that the nanostructure can be formed on the metal structure, A lower voltage is applied.
  • the coating step preferably applies a voltage of -0.005 V to -0.015 V to the conductive substrate.
  • the method of fabricating a porous nanostructure according to the present invention may further comprise a pattern layer forming step of forming a micropattern layer on the conductive substrate between the preparing step and the foam forming step, wherein a micropattern layer is exposed on a part of the conductive substrate ,
  • the coating step forms the first nanostructure on which the base metal particles of the electrolyte are deposited on the metal structure exposed by the micropattern layer.
  • the method for fabricating a porous structure according to the present invention may further include a removing step of selectively removing the micropattern layer after the coating step is completed and a step of removing the micropattern layer from the microstructure layer, Further comprising performing an electrochemical deposition process to form a second nanostructure on which the base metal particles of the electrolyte are deposited on the first nanostructure.
  • the coating step and the additional deposition step apply a voltage to the conductive substrate and the reference electrode in a state where the conductive substrate having the metal nano body is immersed in the electrolyte solution together with the reference electrode and the counter electrode, And the applied voltage and the low voltage are applied in the deposition process.
  • the coating step and the additional deposition step apply a voltage of -0.005 V to -0.015 V to the conductive substrate.
  • a patterned photoresist is deposited on the metal structure at regular intervals.
  • the reference electrode is silver-silver chloride (Ag / AgCl), and the counter electrode uses platinum (Pt).
  • the porous nanostructure according to the present invention may further include a heat treatment step of performing heat treatment by applying heat to the metal structure having the nanostructure formed thereon after the coating step is completed.
  • Another aspect of the present invention includes a three-dimensional electrode having a porous nanostructure prepared by the above-described method for producing a porous nanostructure.
  • Yet another aspect of the present invention includes a sensor having a porous matrix structure produced by the above-described method for producing a porous nanostructure.
  • the apparatus for manufacturing a porous nanostructure includes a deposition reaction tank in which an electrolyte is contained and in which a conductive substrate is immersed so as to be immersed in the electrolyte, a reference electrode and a counter electrode provided in the deposition reaction tank to be immersed in the electrolyte, A voltage applying member for forming a porous metal structure on the conductive substrate and applying a voltage to the conductive substrate and the reference electrode to perform an electrochemical deposition process on the conductive substrate to form a nanostructure on the porous metal structure, And a bubble reduction unit that reduces the size of bubbles formed on the conductive substrate when a voltage is applied to the conductive substrate.
  • the bubble reducing unit applies ultrasonic waves to the conductive substrate immersed in the electrolytic solution.
  • the bubbling reducing portion includes a water tank in which immersion water is contained and immersed in the immersion index, and an ultrasonic oscillator installed in the water tank to generate ultrasonic waves in the deposition tank so as to be immersed in the immersion index .
  • the bubble reduction unit may irradiate the conductive substrate immersed in the electrolyte with light having a predetermined wavelength.
  • the electrolyte solution contains a metallic base metal capable of performing an electrochemical deposition process on the metal structure.
  • the base metal is preferably at least one of copper, zinc, gold, and platinum.
  • the present invention is advantageous in that a nanostructure having a three-dimensional nanosurface can be manufactured at a relatively low cost by using an electrochemical deposition method.
  • the present invention can produce an electrode having a relatively large surface area by forming multiple nanostructures in a porous metal structure, and can be utilized for a sensing means such as a sensor requiring high sensitivity, and the nanostructure can be used as a structure of the porous metal structure And maintains the porous structure firmly even after a lapse of time, so that there is an advantage that the performance reliability is high.
  • FIG. 1 is a schematic view of a patterned layer of an amorphous silicon layer used in a method for producing a porous nanostructure according to the present invention
  • FIG. 2 is a view showing an apparatus for manufacturing a porous nanostructure according to the present invention
  • FIG. 3 is a photograph showing the production of a nanostructure according to a method of manufacturing a porous nanostructure according to the present invention using an actual nanostructure manufacturing apparatus.
  • FIG. 4 is a graph showing changes in roughness factor with time after the metal structure manufactured by performing only the foam forming step of the porous nanostructure manufacturing method of the present invention and the metal structure performed up to the coating step,
  • 5 to 7 are SEM photographs taken immediately after the fabrication of the fabricated structure, 24 hours after the fabrication, and 48 hours after the fabrication, respectively, of the porous nanostructure fabricating method of the present invention.
  • FIG. 12 is a cross-sectional view of a porous nanostructure manufacturing apparatus according to another embodiment of the present invention.
  • FIG. 13 is a photograph showing the production of a nanostructure according to the method of manufacturing a porous nanostructure according to the present invention using the apparatus for producing a nanostructure of FIG. 17,
  • FIG. 14 is a cross-sectional view of a metal structure (Nominal) fabricated by performing only a foam forming step, a metallic structure (Sonication 1,2) fabricated by applying ultrasonic waves in the manufacture of a metal structure, (Degassing 1, 2)
  • 15 and 16 are SEM and FE-SEM photographs of the metal structure obtained by performing both the coating step and the heat treatment step of the porous nanostructure of the present invention.
  • FIG. 17 is a cross-sectional view of an apparatus for manufacturing a porous nanostructure according to another embodiment of the present invention.
  • first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.
  • first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.
  • the method for producing a porous nanostructure according to the present invention comprises a preparation step, a pattern layer forming step, a foam forming step, a coating step, a removing step and an additional deposition step.
  • the preparation step is a step of preparing a conductive substrate.
  • the conductive substrate may be platinum, silver, copper, gold, titanium, nickel, ruthenium or the like, and carbon materials such as graghite, carbon nanotube and fullerene may be used.
  • the pattern layer forming step is a step of forming, on the conductive substrate, a micropattern layer in which a part of the conductive substrate is exposed.
  • the micropattern layer is formed on a conductive substrate, and a part of the conductive substrate may be exposed at regular intervals or in a constant shape between patterns of the micropattern layer by the micropattern layer.
  • 1 shows an embodiment of a patterned layer of an amide.
  • the pattern layer forming step may deposit photoresist patterned at regular intervals on a conductive substrate.
  • the patterned photoresist is formed by applying a photoresist on a conductive substrate to form a photoresist film, covering the photoresist film with a mask having a pattern of a predetermined interval or a predetermined shape, A patterned photoresist having a desired pattern is formed on the conductive substrate.
  • a gold (Au) seed layer may be formed on the conductive substrate before the pattern layer forming step.
  • the gold (Au) seed layer may be a thin film layer made of only gold particles, and may be a thin film layer made of an alloy containing conductive metal particles other than gold particles according to an embodiment.
  • the conductive metal particles may be at least one selected from the group consisting of Au, Pt, Fe, Co, Ti, V, Al, Mo, (Cu), and silver (Ag).
  • the gold (Au) seed layer may be formed on the metal structure by a method such as evaporation, sputtering, wet coating, electrolytic plating, or electroless plating. , It can be formed by a sputtering method.
  • the foam forming step is a step of performing an electrochemical deposition process on the conductive substrate in an atmosphere where an electrolyte is supplied, and a metal structure having a plurality of pores is formed on the conductive substrate by bubbles generated during the electrochemical deposition process .
  • the foam forming step uses the porous nanostructure manufacturing apparatus 100 shown in FIG. 2, and includes a reactor preparation step, a first immersion step, and a deposition step.
  • the apparatus for manufacturing a porous nanostructure 100 includes a deposition reaction tank 101 in which an electrolyte is contained and in which a conductive substrate 105 is immersed so as to be immersed in the electrolyte solution and a deposition reaction tank 101 installed in the deposition reaction tank 101 to be immersed in the electrolyte solution.
  • a voltage applying member 104 for applying a voltage to the conductive substrate 105 and the reference electrode 102 in order to perform the process.
  • the electrolyte solution contains a metallic base metal capable of performing an electrochemical deposition process on the base metal structure, and the metallic base metal is at least one of copper, zinc, gold, and platinum. More preferably, the electrolyte is yeomhwageum (III) hydrate (Gold (III) chloride hydrate; AuCl 3 ⁇ H 2 O), chloroauric acid (Hydrogen Tetrachloroaurate (III); HAuCl 4 ⁇ H 2 O), chloroauric acid, potassium ( KAuCl 4 ), sodium tetrachloroaurate (III) dihydrate, NaAuCl 4 ⁇ H 2 O, gold (III) bromide hydrate, AuBr 3 ⁇ H 2 O), and gold (III) chloride (AuCl 3 ).
  • the electrolyte is yeomhwageum (III) hydrate (Gold (III) chloride hydrate; AuCl 3 ⁇ H 2 O), chloroauric acid (Hydrog
  • the concentration of the electrolytic solution may be 0.1M to 0.5M. When the concentration of the electrolytic solution is less than 0.1M, the base metal particles of the electrolytic solution are difficult to deposit sufficiently on the conductive substrate 105. When the concentration of the electrolytic solution exceeds 1M, Or may not be formed into a nanostructure of a desired shape.
  • the reference electrode 102 is silver-silver chloride (Ag / AgCl), and the counter electrode 103 is made of platinum (Pt). Further, the voltage applying member 104 is a voltage supplying means for applying a voltage to the electrodes conventionally used in the electrochemical vapor deposition process, and a detailed description thereof will be omitted.
  • the reactor preparation step is a step of preparing a deposition reaction vessel 101 containing an electrolyte therein. At this time, it is preferable that the deposition reaction tank 101 is formed of a transparent material so as to easily grasp the internal state from the outside.
  • the reference electrode 102, the counter electrode 103, and the conductive substrate 105 are installed in the deposition reaction tank 101 so as to be immersed in the electrolyte solution.
  • the conductive substrate 105 is connected to the cathode of the voltage applying member 104, and the counter electrode 103 is connected to the anode.
  • the conductive substrate 105 becomes a working electrode during the electrochemical deposition process.
  • the step of performing the deposition process may be performed by performing an electrochemical deposition process on the conductive substrate 105.
  • the conductive substrate 105 and the reference electrode 102 which are immersed in the electrolyte solution, To a predetermined voltage.
  • the voltage of the power source applied to the conductive substrate 105 is preferably -2.7 V to -3.3 V.
  • the voltage is applied to the conductive substrate 105 at less than -3.0 V, plating is not performed on the conductive substrate 105, and when the applied voltage exceeds -4.0 V, cracks are generated in the deposited porous metal structure. May occur.
  • the metal particles precipitated on the conductive substrate 105 can obtain a porous metal structure having many pores inside or on the surface of the metal particles due to hydrogen generated during the electrochemical deposition process.
  • the hydrogen bubbles are generated from the negative electrode reaction on the conductive substrate 105, and are continuously generated during the electrochemical deposition process.
  • the metal structure is formed on the conductive metal substrate between the hydrogen bubbles because the metal structure is not formed at the portion where the hydrogen bubble is present because the metal ion is hardly present.
  • the micropattern layer is formed on the conductive substrate 105, the porous metal structure is formed in a part of the conductive substrate 105 exposed by the micropattern layer.
  • the pores generated by the hydrogen may be variously formed depending on the metal material contained in the electrolyte, the concentration of the metal material, and the pore size may be from several tens nanometers to several tens of microseconds. At this time, the pores formed in the metal structure are preferably 10 micrometers to 20 m chrome.
  • the coating step an electrochemical deposition process is performed in an atmosphere in which the electrolyte solution is supplied to the metal structure to form a first nanostructure on the metal structure.
  • the coating step is a step of applying a predetermined voltage to the conductive substrate 105 and the reference electrode 102 provided in the deposition reaction tank 101 so that the nanostructure can be formed on the metal structure, 105 in the deposition process step.
  • the first nanostructure is formed by depositing base metal particles of the electrolyte on the metal structure exposed by the micropattern layer.
  • the electrochemical deposition process itself is not performed. If the applied voltage exceeds -0.015 V, cracks may be generated in the deposited nanostructure have.
  • the side regions of the structure may be deposited in a limited manner by the pattern of the micropattern layer.
  • the first nanostructure may be formed of a nanostructured crystal while particles are intensively deposited in an upper region of the metal structure where no pattern of the micropattern layer is formed.
  • the method of manufacturing a porous nanostructure according to the present invention may be repeated several times in the deposition step and coating step. That is, when the coating step is completed, the conductive substrate 105 having the metal nano body is immersed in the electrolyte together with the reference electrode 102 and the counter electrode 103, A voltage of -2.7 V to -3.3 V is applied to the conductive substrate 105 for a predetermined time and then a voltage of -0.005 V to -0.015 V is applied to the conductive substrate 105 Repeat the process.
  • the removing step is a step of selectively removing the micropattern layer after the coating step is completed.
  • the micropattern layer may be selectively removed by performing an etching process on the metal structure having the first nanostructure formed thereon.
  • the conductive substrate 105 is taken out of the deposition reaction tank 101 and immersed in the etching solution.
  • the etching solution is a solution of (CH 3) 2 CHOH (acetone), HF (hydrofluoric acid), BHF (buffered hydrofluoric acid), H 2 SO 4 (sulfuric acid), H 2 O 2 (hydrogen peroxide) But is not limited to, any one selected from NH 4 OH (ammonia), HCl (hydrochloric acid), H 3 PO 4 (phosphoric acid), and stripper.
  • an electrochemical deposition process is performed in an atmosphere in which the electrolyte is supplied to the metal structure from which the micropattern layer is removed, thereby forming a second nanostructure on which the base metal particles of the electrolyte are deposited on the first nanostructure .
  • the conductive substrate 105 having the metal structure is connected to the negative electrode of the voltage applying member 104 and then installed in the deposition reaction tank 101 so as to be immersed in the electrolytic solution, A power source is applied to the deposition reaction tank 101 to perform an electrochemical deposition process.
  • the voltage of the power source applied to the conductive substrate 105 is preferably -0.005 V to -0.015 V.
  • the electrochemical deposition process itself is not performed. If the applied voltage exceeds -0.015 V, cracks may be generated in the deposited nanostructure have.
  • the conductive substrate 105 on which the first nanostructure is formed is used as a working electrode, and the base metal particles of the electrolyte are reduced and further deposited on the first nanostructure, To form a structure.
  • the second nanostructure has a flower-like three-dimensional nanosurface structure, which is different from the first nanostructure in that the micro-pattern layer is removed by the removing step Accordingly, the particles deposited by performing the additional deposition step are also deposited on the lateral region of the first nanostructure, so that the gold particles are deposited and grown on the porous metal structure in all directions, and the three- A second nanostructure on a microscale scale is formed. More specifically, the flower-like nanostructure is formed by connecting fine grains in the form of nano-rod or nano-needle like branches and forming a crystal grains such as a leaf of a coniferous tree, And the like.
  • each of the second nanostructures having such a flower-shaped three-dimensional nanosurface structure has a microscale size.
  • the particles deposited by the additional deposition step may be deposited on the surface of the first nanostructure as well as on the surface of the porous metal structure by reducing the gold particles.
  • the second nanostructures may be connected to each other according to the magnitude of the voltage applied during the additional deposition step and the process execution time.
  • the porous nanostructure according to the present invention may further include a heat treatment step of performing heat treatment by applying heat to the metal structure having the nanostructure formed after the coating step is completed.
  • the heat treatment step the conductive substrate 105 on which the coating step has been completed is taken out of the electrolytic solution, and heat of 180 to 450 ° C is supplied to heat treatment.
  • the heat treatment step may be performed between the coating step and the removing step, or may be performed after the additional deposition step.
  • the method of manufacturing a porous nanostructure according to the present invention may omit the removing step and the additional deposition step depending on the type of the sensor and the electrode using the nanostructure.
  • FIG. 3 is a photograph illustrating a method of fabricating a nanostructure according to a method of manufacturing a porous nanostructure according to the present invention using an actual nanostructure manufacturing apparatus.
  • the reference electrode 102 Ag / AgCl the reference electrode 102 Ag / AgCl
  • the counter electrode 103 is Pt mesh
  • a conductive substrate Is a Pt / Ti / Glass electrode
  • the voltage application time is 20 seconds.
  • the foam forming step is performed at a voltage of -3 V applied to the conductive substrate, and a voltage of -0.01 V is applied in the coating step to perform an electrochemical deposition process.
  • FIG. 4 is a graph showing changes in roughness factor with time after the metal structure manufactured by performing only the foam forming step and the metal structure performed up to the coating step.
  • Nominal is a metal structure manufactured by performing only the foam forming step
  • Gold coating is a metal structure carried to the coating step
  • Rf is a roughness factor.
  • the roughness factor is an electrochemical area / geometrical area. The higher the roughness factor, the more the surface area exposed to the outside increases, so that the sensitivity of the sensor can be improved when applied to the sensor.
  • FIGS. 5 to 7 show SEM photographs taken immediately after the fabrication of the metal structure having the nominal conditions, 24 hours after the fabrication, 48 hours after the fabrication, and FIGS. 8 to 10 show the fabrication SEM photographs taken immediately after, 24 hours after, and 48 hours after production are shown.
  • 11 there is shown an SEM photograph of the same magnification of a metal structure having a nominal condition and a metal structure having a gold coating condition. Comparing the photographs, it can be seen that the surface area of the electrode is reduced to some extent over time in both the metal structure having the nominal condition and the metal structure having the gold coating condition. However, the metal structure with gold coating condition has a coarser structure due to the reduction of gold ion in the skeleton which maintains the porous structure compared to the metal structure with nominal condition. That is, it can be seen that the porous structure of the metal structure is more stably maintained as the skeleton forming the porous structure is thickened by the nanostructure formed through the coating step.
  • the foam forming process includes forming a metal structure on the substrate, and includes a reactor preparation step, a first immersion step, a bubble reduction step, and a deposition step. At this time, the steps of preparing the reaction tank, performing the first immersion step, and performing the deposition step are performed in the same manner as the foam formation step of the above-mentioned embodiment, and thus detailed description thereof will be omitted.
  • the bubble reduction step includes a water tank preparation step, a second immersion step, and an ultrasonic application step.
  • the foam forming step uses a nanostructure manufacturing apparatus according to another embodiment of the present invention shown in FIG. Elements having the same functions as those in the previous drawings are denoted by the same reference numerals.
  • the apparatus for fabricating a nanostructure further includes a bubble reducing unit 110 for reducing the size of bubbles formed on the conductive substrate 105 when a voltage is applied to the conductive substrate 105.
  • the bubble reduction unit 110 applies ultrasonic waves to the conductive substrate 105 immersed in the electrolyte solution and is configured to receive immersion water therein and to be immersed in the immersion index, And an ultrasonic oscillator 112 installed in the water tank 111 to generate ultrasonic waves in the deposition reaction tank 101 to be immersed in the immersion index.
  • the bubble reduction unit 110 indirectly transfers the ultrasonic waves generated by the ultrasonic oscillator 112 to the conductive substrate 105 through a needle index.
  • the bubble reduction unit 110 may include a vibrator installed in the water tub 111 to generate vibration, instead of the ultrasonic oscillator 112.
  • the water tank preparing step is a step of preparing a water tank 111 containing immersion water therein.
  • the second immersion step is a step of immersing the deposition reaction tank 101 in the immersion indices contained in the water tank 111.
  • the deposition reaction tank 101 is installed in the water tank 111 so that the lower part of the deposition reaction tank 101 is sufficiently immersed in the immersion index. It is preferable that the operator installs the deposition reaction tank 101 in the water tank 111 prior to the deposition process.
  • the ultrasonic oscillator 112 is immersed in the immersion index of the deposition reaction tank 101, and the ultrasonic oscillator 112 is operated to generate ultrasonic waves in the deposition reaction tank 101. At this time, an ultrasonic wave of 40 kHz is generated through the ultrasonic oscillator 112. The operator preferably stops the ultrasonic oscillator 112 after the deposition process step is completed. In place of the ultrasonic oscillator 112, a vibrator (not shown) provided in the water tank 111 may be operated to apply vibration to the conductive substrate.
  • the foam forming step according to the present invention may include a degassing step in the deposition step instead of the bubble reducing step.
  • the gas generated during the electrochemical deposition process is forcibly discharged to the outside of the deposition reaction tank.
  • FIG. 13 is a photograph showing a method of fabricating a nanostructure according to a method of manufacturing a porous nanostructure according to the present invention using an actual nanostructure manufacturing apparatus.
  • the reference electrode 102 Ag / AgCl the reference electrode 102 Ag / AgCl
  • the counter electrode 103 is Pt mesh
  • a conductive substrate Is a Pt / Ti / Glass electrode
  • the voltage application time is 20 seconds. Further, the voltage to be applied to the conductive substrate was set to -3V.
  • FIG. 14 shows a case where a metal structure (Nominal) manufactured by performing only a foam forming step, a metallic structure (Sonication 1, 2) fabricated by applying ultrasonic waves in the manufacture of a metal structure, and a metal structure (Degassing 1, 2).
  • the SEM photograph shows that the metal structure manufactured under the sonication condition is finer and has a larger number of pores than the nominal and degassing conditions.
  • 15 and 16 show an SEM photograph and an FE-SEM photograph of the metal structure obtained by performing both the coating step and the heat treatment step.
  • a voltage is applied to the conductive substrate 105 for 5 seconds during the deposition process, and a voltage is applied to the conductive substrate 105 for 20 seconds in the coating process.
  • the metal structure was manufactured by including a bubble reduction step in the foam forming step. Referring to the SEM photographs and the FE-SEM photographs, it can be seen that the particles of the metal structure subjected to both the coating step and the heat treatment step are relatively small and the surface is rough.
  • a process of applying a voltage to the conductive substrate 105 for 5 seconds in the deposition process step and applying a voltage to the conductive substrate 105 in the coating step for 20 seconds is referred to as 4 And then heat-treated at 450 ⁇ .
  • the bubble reduction step is a step of irradiating the conductive substrate 105 immersed in the electrolyte with light having a predetermined wavelength.
  • the apparatus for manufacturing a porous nanostructure shown in FIG. 17 is used.
  • the apparatus for manufacturing a porous nanostructure includes a bubble reduction unit 120 according to another embodiment of the present invention.
  • the bubble reduction unit 120 is installed at a position opposite to the deposition reaction tank 101, And a light irradiation member 121 for irradiating light having a predetermined wavelength.
  • the operator irradiates the conductive substrate 105 with light by activating the light irradiation member 121 when performing the electrochemical deposition process on the conductive substrate 105.
  • the hydrogen bubbles on the conductive substrate 105 are pulverized by the light to form a plurality of fine bubbles, and the metal structure has fine pores.
  • a three-dimensional electrode including a nanostructure produced by the method of manufacturing a porous nanostructure as described above.
  • the three-dimensional electrode may include the nanostructure on the surface. Accordingly, the three-dimensional electrode can have a wide surface area due to the structural characteristics of the gold nanostructure formed on the surface, and thus can be widely used as an electrode of a device requiring high sensitivity and high selectivity.
  • the three-dimensional gold electrode may have a surface area of 200 mm 2 to 800 mm 2 . This is because the gold nanostructure having a flower-like three-dimensional nano-surface formed in a predetermined pattern on the surface of the three-dimensional gold electrode has a significantly improved surface area compared to a conventional bare gold electrode having a flat surface Lt; / RTI >
  • a sensor including the nanostructure fabricated by the method of manufacturing a porous nanostructure described above in one aspect of the present invention can be applied to a sensing area of a sensor that requires high sensitivity to precisely measure the adsorption and concentration of the sample using the structural characteristics of the nanostructure composed of the three-dimensional nanosurface.
  • the sensor including the nanostructure may be a norovirus measuring sensor.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne un procédé de production d'une nanostructure poreuse, ledit procédé comprenant : une étape de préparation pour préparer un substrat électroconducteur ; une étape de formation de mousse dans laquelle une opération de dépôt électrochimique est réalisée sur le substrat électroconducteur dans une atmosphère alimentée par une solution électrolytique, et une structure métallique ayant une pluralité de pores dus à des bulles générées pendant l'opération de dépôt électrochimique est formée sur le substrat électroconducteur ; et une étape de revêtement pour former une première nanostructure sur la structure métallique par réalisation d'une opération de dépôt électrochimique sur la structure métallique dans l'atmosphère alimentée par la solution électrolytique.
PCT/KR2017/010230 2017-09-19 2017-09-19 Procédé de production de nanostructure poreuse, électrode tridimensionnelle et capteur ayant une nanostructure poreuse produite par ce dernier, et appareil de production de nanostructure poreuse WO2019059423A1 (fr)

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JP2008106315A (ja) * 2006-10-26 2008-05-08 National Institute Of Advanced Industrial & Technology 金属ナノ粒子及びその製造方法
KR20110001845A (ko) * 2009-06-29 2011-01-06 경상대학교산학협력단 3차원 나노 구조체 및 그의 제작 방법
KR101437289B1 (ko) * 2013-08-19 2014-09-02 성균관대학교산학협력단 3차원 그래핀 소자의 제작 방법 및 이를 포함한 센서
KR101463067B1 (ko) * 2014-01-07 2014-12-04 권지웅 초음파 조사에 의한 기공성을 갖는 금속입자 제조방법
KR20160013749A (ko) * 2014-07-28 2016-02-05 광주과학기술원 금 나노구조체의 제조방법, 이에 의해 제조된 금 나노구조체를 포함하는 3차원 골드 전극, 및 센서
KR20170130216A (ko) * 2016-05-18 2017-11-28 주식회사 큐바이오센스 다공성 나노구조체의 제조방법, 이에 의해 제조된 다공성 나노구조체를 갖는 3차원 전극 및 센서, 다공성 나노구조체 제조장치

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008106315A (ja) * 2006-10-26 2008-05-08 National Institute Of Advanced Industrial & Technology 金属ナノ粒子及びその製造方法
KR20110001845A (ko) * 2009-06-29 2011-01-06 경상대학교산학협력단 3차원 나노 구조체 및 그의 제작 방법
KR101437289B1 (ko) * 2013-08-19 2014-09-02 성균관대학교산학협력단 3차원 그래핀 소자의 제작 방법 및 이를 포함한 센서
KR101463067B1 (ko) * 2014-01-07 2014-12-04 권지웅 초음파 조사에 의한 기공성을 갖는 금속입자 제조방법
KR20160013749A (ko) * 2014-07-28 2016-02-05 광주과학기술원 금 나노구조체의 제조방법, 이에 의해 제조된 금 나노구조체를 포함하는 3차원 골드 전극, 및 센서
KR20170130216A (ko) * 2016-05-18 2017-11-28 주식회사 큐바이오센스 다공성 나노구조체의 제조방법, 이에 의해 제조된 다공성 나노구조체를 갖는 3차원 전극 및 센서, 다공성 나노구조체 제조장치

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