WO2019059423A1

WO2019059423A1 - Method for producing porous nanostructure, three-dimensional electrode and sensor having porous nanostructure produced thereby, and apparatus for producing porous nanostructure

Info

Publication number: WO2019059423A1
Application number: PCT/KR2017/010230
Authority: WO
Inventors: 양성; 권희정; 홍성아
Original assignee: 주식회사 라디안큐바이오
Priority date: 2017-09-19
Filing date: 2017-09-19
Publication date: 2019-03-28

Abstract

The present invention relates to a method for producing a porous nanostructure and, in more detail, comprises: a preparation step for preparing an electrically conductive substrate; a foam forming step wherein an electrochemical deposition process is performed on the electrically conductive substrate in an atmosphere supplied with an electrolytic solution, and wherein a metallic structure having a plurality of pores due to bubbles generated during the electrochemical deposition process is formed on the electrically conductive substrate; and a coating step for forming a first nanostructure on the metallic structure by performing an electrochemical deposition process on the metallic structure in the atmosphere supplied with the electrolytic solution.

Description

Method for producing porous nanostructure, three-dimensional electrode and sensor having porous nanostructure produced by the method, apparatus for manufacturing porous nanostructure

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, .

Recently, researches on various nanostructured materials such as nanorods, nanotubes, and nanowires have been conducted according to the development of nanotechnology. 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.

In general, 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. Although 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.

On the other hand, 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. In particular, 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.

According to an aspect of the present invention, there is provided 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.

Wherein 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.

In the deposition step, a voltage of -2.7 V to -3.3 V is applied to the conductive substrate.

Wherein 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.

Meanwhile, 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.

Wherein 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.

It is preferable that the coating step and the additional deposition step apply a voltage of -0.005 V to -0.015 V to the conductive substrate.

In the pattern layer forming step, 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 according to the present invention 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 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.

BRIEF DESCRIPTION OF THE DRAWINGS 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,

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.

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,

8 to 10 are SEM photographs taken immediately after the fabrication, 24 hours after the fabrication, and 48 hours after the fabrication of the fabricated porous structure according to the present invention,

11 is a SEM photograph of the same magnification of the metal structure produced by performing only the foam forming step and the metal structure carried to the coating step of the porous nanostructure manufacturing method of the present invention,

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,

17 is a cross-sectional view of an apparatus for manufacturing a porous nanostructure according to another embodiment of the present invention.

Hereinafter, a method for manufacturing a porous nanostructure according to an embodiment of the present invention, a three-dimensional electrode having the porous nanostructure, a sensor, and an apparatus for manufacturing a porous nanostructure will be described in detail with reference to the accompanying drawings. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. Like reference numerals are used for like elements in describing each drawing. In the accompanying drawings, the dimensions of the structures are enlarged to illustrate the present invention in order to clarify the present invention.

The terms 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. For example, without departing from the scope of the present invention, the 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 terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "comprises", "having", and the like are used to specify that a feature, a number, a step, an operation, an element, a part or a combination thereof is described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

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. At this time, 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.

More specifically, 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.

On the other hand, 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. For example, 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 reference electrode 102 and a counter electrode 103 formed on the conductive substrate 105 and a conductive metal layer 105 formed on the conductive substrate 105 to form a nanostructure on the porous metal structure, And 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.

At this time, 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 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.

In the first immersion step, 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. At this time, 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. At this time, 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.

At this time, the voltage of the power source applied to the conductive substrate 105 is preferably -2.7 V to -3.3 V. When 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.

As described above, 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. At this time, 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. At this time, since 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.

In 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.

At this time, the first nanostructure is formed by depositing base metal particles of the electrolyte on the metal structure exposed by the micropattern layer. At this time, it is preferable to change the voltage of the power source applied to the conductive substrate 105 from -0.005V to -0.015V. When a voltage is applied to the conductive substrate 105 at less than -0.005 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.

Since the first nanostructures deposited on the porous metal structure through the coating step are formed on the porous metal structure exposed by the micropattern layer and formed between the patterns of the micropattern layer, 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.

Meanwhile, 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. After the coating step is completed, the conductive substrate 105 is taken out of the deposition reaction tank 101 and immersed in the etching solution. At this time, 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.

In the additional deposition step, 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.

At this time, the voltage of the power source applied to the conductive substrate 105 is preferably -0.005 V to -0.015 V. When a voltage is applied to the conductive substrate 105 at less than -0.005 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.

In the additional deposition step, as described above, 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.

At this time, 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. Accordingly, a structure in which fine grains having nanosurfaces are three-dimensionally connected can be formed, and 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. In addition, 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. In 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. At this time, the heat treatment step may be performed between the coating step and the removing step, or may be performed after the additional deposition step.

In addition, 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.

Experiments conducted through the method for producing porous nanostructures according to the present invention will be described in detail as follows. 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.

At this time, in the 2M ammonium chloride in 0.1M chloroauric acid (HAucl ₄₎ (NH ₄ Cl) was used as the respective mixed electrolyte, the reference electrode 102 Ag / AgCl, the counter electrode 103 is Pt mesh, a conductive substrate Is a Pt / Ti / Glass electrode, and the voltage application time is 20 seconds. Further, 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. In this case, Nominal is a metal structure manufactured by performing only the foam forming step, Gold coating is a metal structure carried to the coating step, and Rf is a roughness factor. Here, 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.

Referring to the drawing, roughness factors of Nominal and Gold coating are almost similar immediately after the fabrication of the metal structure. However, after 12 hours of manufacture, the roughness factor is steadily decreased in case of Nominal, The factor remains constant and has a value greater than Nominal.

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 according to another embodiment of the present invention will be described in more detail as follows. The foam forming step 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.

At this time, 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.

Referring to FIG. 1, 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. At this time, 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.

In the ultrasonic wave application step, 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.

Meanwhile, the foam forming step according to the present invention may include a degassing step in the deposition step instead of the bubble reducing step. In the deposition step, the gas generated during the electrochemical deposition process is forcibly discharged to the outside of the deposition reaction tank.

Experiments conducted through the method for producing porous nanostructures according to the present invention will be described in detail as follows. 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.

At this time, in the 2M ammonium chloride in 0.1M chloroauric acid (HAucl ₄₎ (NH ₄ Cl) was used as the respective mixed electrolyte, the reference electrode 102 Ag / AgCl, the counter electrode 103 is Pt mesh, a conductive substrate Is a Pt / Ti / Glass electrode, and 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. At this time, in the metal structure, 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. . In addition, 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.

Accordingly, in order to manufacture the most stable and excellent metal structure, 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 캜.

The bubble reduction step according to another embodiment of the present invention will be described in more detail as follows. The bubble reducing step is a step of irradiating the conductive substrate 105 immersed in the electrolyte with light having a predetermined wavelength. At this time, 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.

According to another aspect of the present invention, there is provided a three-dimensional electrode including a nanostructure produced by the method of manufacturing a porous nanostructure as described above. Specifically, 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 >

According to another aspect of the present invention, there is provided a sensor including the nanostructure fabricated by the method of manufacturing a porous nanostructure described above in one aspect of the present invention. The sensor 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. At this time, the sensor including the nanostructure may be a norovirus measuring sensor.

The description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features presented herein.

Claims

Preparing a conductive substrate;

Forming a metal structure having a plurality of pores by bubbles generated in the electrochemical deposition process on the conductive substrate by performing an electrochemical deposition process on the conductive substrate in an atmosphere in which an electrolyte is supplied;

And a coating step of performing an electrochemical deposition process in an atmosphere in which the electrolyte solution is supplied to the metal structure to form a first nanostructure on the metal structure,

A method for producing a porous nanostructure.
The method according to claim 1,

Wherein the electrolytic solution contains a metallic base metal capable of performing an electrochemical deposition process on the metal structure,

A method for producing a porous nanostructure.
3. The method of claim 2,

Wherein the metallic base metal is at least one of copper, zinc, gold and platinum,

A method for producing a porous nanostructure.
The method according to claim 1,

The foam forming step

A reaction tank preparation step of preparing a deposition reaction tank containing the electrolytic solution therein,

A first immersion step in which the reference electrode, the counter electrode, and the conductive substrate are installed in the deposition reaction tank so as to be immersed in the electrolytic 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 by performing an electrochemical deposition process on the conductive substrate,

A method for producing a porous nanostructure.
The method according to claim 1,

Wherein the foaming step further comprises a bubble reduction step of reducing the size of bubbles generated during the electrochemical deposition process.

A method for producing a porous nanostructure.
6. The method of claim 5,

Wherein the bubble reduction step comprises applying ultrasonic waves to the conductive substrate immersed in the electrolyte solution,

A method for producing a porous nanostructure.
The method according to claim 6,

The bubble reduction step

A water tank preparing step of preparing a water tank containing immersion water therein,

A second immersion step of immersing the deposition reaction tank in a saliva index contained in the water tank,

And an ultrasonic wave application step of immersing the ultrasonic oscillator in the deposition index in which the deposition reaction bath is immersed and operating the ultra-wave oscillator to generate ultrasonic waves in the deposition reaction tank.

A method for producing a porous nanostructure.
6. The method of claim 5,

Wherein the bubble reduction step comprises irradiating the conductive substrate immersed in the electrolyte with light having a predetermined wavelength,

A method for producing a porous nanostructure.
5. The method of claim 4,

The performing of the deposition process may include applying a voltage of -2.7 V to -3.3 V to the conductive substrate,

A method for producing a porous nanostructure.
5. The method of claim 4,

Wherein 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, Applying a lower voltage,

A method for producing a porous nanostructure.
11. The method of claim 10,

Wherein the coating step comprises applying a voltage of -0.005 V to -0.015 V to the conductive substrate,

A method for producing a porous nanostructure.
5. The method of claim 4,

Forming a micropattern layer in which a part of the conductive substrate is exposed on the conductive substrate between the preparing step and the foam forming step,

Wherein 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

A method for producing a porous nanostructure.
13. The method of claim 12,

A removal step of selectively removing the micropattern layer after the coating step is completed;

An additional deposition step of performing an electrochemical deposition process in an atmosphere in which the electrolyte solution is supplied to the metal structure from which the micropattern layer has been removed to form a second nanostructure on which the base metal particles of the electrolyte are deposited on the first nanostructure; ; &Lt; / RTI >

A method for producing a porous nanostructure.
14. The method of claim 13,

Wherein 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 applying a voltage and a low voltage in the deposition process,

A method for producing a porous nanostructure.
15. The method of claim 14,

Wherein the coating step and the additional deposition step are performed by applying a voltage of -0.005 V to -0.015 V to the conductive substrate,

A method for producing a porous nanostructure.
13. The method of claim 12,

Wherein the pattern layer forming step comprises forming a patterned photoresist on the metal structure,

A method for producing a porous nanostructure.
13. The method of claim 12,

Wherein the reference electrode is silver-silver chloride (Ag / AgCl), and the counter electrode is made of platinum (Pt)

A method for producing a porous nanostructure.
13. The method of claim 12,

Further comprising a heat treatment step of performing heat treatment by applying heat to the metal structure on which the nanostructure is formed after the coating step is completed,

A method for producing a porous nanostructure.
A three-dimensional electrode having the porous nanostructure produced by any one of claims 1 to 18.
19. A sensor having a porous matrix structure produced by any one of claims 1 to 18.
A deposition reaction tank in which an electrolytic solution is contained, and a conductive substrate is immersed in the electrolytic solution;

A reference electrode and a counter electrode provided in the deposition reaction tank so as to be immersed in the electrolytic solution;

A voltage applying member for applying a voltage to the conductive substrate and the reference electrode to perform electrochemical deposition on the conductive substrate to form a porous metal structure on the conductive substrate and to form a nanostructure on the porous metal structure;

And a bubble reducing part that reduces the size of bubbles formed on the conductive substrate when a voltage is applied to the conductive substrate.

Porous nanostructure manufacturing apparatus.
22. The method of claim 21,

Wherein the bubble reducing unit applies ultrasonic waves to the conductive substrate immersed in the electrolytic solution,

Porous nanostructure manufacturing apparatus.
23. The method of claim 22,

The bubble reducing portion

A water tank in which immersion water is contained and in which the deposition reaction tank is immersed in the immersion index,

And an ultrasonic oscillator installed in the water tank so as to be immersed in the immersion index to generate ultrasonic waves in the deposition reaction tank,

Porous nanostructure manufacturing apparatus.
22. The method of claim 21,

Wherein the bubble reducing part irradiates light having a predetermined wavelength to the conductive substrate immersed in the electrolytic solution,

Porous nanostructure manufacturing apparatus.
22. The method of claim 21,

Wherein the electrolytic solution contains a metallic base metal capable of performing an electrochemical deposition process on the metal structure,

Porous nanostructure manufacturing apparatus.
26. The method of claim 25,

Wherein the base metal is at least one of copper, zinc, gold, and platinum,

Porous nanostructure manufacturing apparatus.