WO2023080536A1 - Capteur de glycémie sans enzyme et son procédé de fabrication - Google Patents

Capteur de glycémie sans enzyme et son procédé de fabrication Download PDF

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WO2023080536A1
WO2023080536A1 PCT/KR2022/016514 KR2022016514W WO2023080536A1 WO 2023080536 A1 WO2023080536 A1 WO 2023080536A1 KR 2022016514 W KR2022016514 W KR 2022016514W WO 2023080536 A1 WO2023080536 A1 WO 2023080536A1
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Prior art keywords
electrode
photoresist
porous carbon
blood glucose
palladium
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PCT/KR2022/016514
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English (en)
Korean (ko)
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신흥주
김범상
정우재
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울산과학기술원
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Priority claimed from KR1020220134870A external-priority patent/KR20230063861A/ko
Application filed by 울산과학기술원 filed Critical 울산과학기술원
Publication of WO2023080536A1 publication Critical patent/WO2023080536A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
    • A61B5/1468—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using chemical or electrochemical methods, e.g. by polarographic means
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/15—Devices for taking samples of blood
    • A61B5/155—Devices specially adapted for continuous or multiple sampling, e.g. at predetermined intervals

Definitions

  • the present invention relates to an enzyme-free blood glucose sensor and a manufacturing method thereof.
  • a sensor that measures blood glucose from these bodily fluids is a glucose that selectively reacts sensitively with glucose.
  • Techniques using oxidative enzymes are widely used. However, these enzyme-based sensors are highly affected by the surrounding environment (pH, temperature, humidity, etc.) and have poor stability.
  • Enzyme-based blood glucose sensors which are actively used to measure blood glucose, use enzymes that selectively react with glucose (e.g., glucose oxidase Gox). pH, temperature, humidity, etc.).
  • an enzyme-free blood glucose sensor that can be used for a long time without using enzymes. Since the enzyme-free blood glucose sensor detects glucose using a metal/metal oxide catalyst instead of an enzyme, it can be relatively stable in the surrounding environment. However, metal/metal oxide catalysts have poor sensitivity to glucose at neutral pH, making it difficult to detect blood glucose contained in bodily fluids such as blood, saliva, sweat, and tears.
  • the present disclosure raises the pH of the solution with strong basicity to form a reactive hydrous oxide (OH ads ) layer on the surface of the metal / metal oxide catalyst to oxidize glucose and release it Generated electrons can be sensitively sensed.
  • OH ads reactive hydrous oxide
  • An object of the present disclosure is to provide a sensor capable of sensitively detecting glucose by locally increasing the pH of a solution near a metal/metal oxide catalyst.
  • the enzyme-free blood glucose sensor includes a substrate; An insulating layer formed by depositing on a substrate; Porous carbon electrode formed by depositing on the insulating layer; a metal material region formed on at least a portion of a surface of the porous carbon electrode; and a palladium electrode deposited on the insulating layer to be spaced apart from the porous carbon electrode.
  • a negative voltage is applied to the palladium electrode to locally increase the concentration of hydroxide ions around the palladium electrode, and blood glucose is measured by measuring a current signal difference according to glucose concentration using a metal material region.
  • the metal material region may include metal nanoparticles, metal thin films, or both.
  • the metal may include a metal including at least one of gold, platinum, silver, palladium, nickel, copper, or a combination thereof, an alloy, or a composite.
  • the metal material region may include metal nanoparticles formed on the porous carbon electrode.
  • the metal nanoparticles are formed on the top surface of the porous carbon electrode, and the size of the metal nanoparticles may be 1 nm to 1 ⁇ m, or the metal nanoparticles may form a layer having a thickness of 1 nm to 10 ⁇ m.
  • the metal material region may include a metal thin film formed on at least a portion of the porous carbon electrode, and the metal thin film may include an infiltration region within pores of the porous carbon electrode.
  • the porous carbon electrode may have a width of 1 ⁇ m to 1 mm and a thickness of 10 nm or more to 500 ⁇ m.
  • the width of the palladium electrode may be 1 ⁇ m or more to 1 mm, and the thickness of the palladium electrode may be 10 nm or more to 1 ⁇ m.
  • the porous carbon electrode is a comb pattern pair electrode, a polygonal electrode, a circular electrode, a polygonal column electrode, a cylindrical electrode, a conical electrode with a flat top cut, a polygonal pyramid electrode with a flat top cut, and a 3D multi-layer structure. It may include at least one of an electrode and a combination thereof.
  • the palladium electrode may be formed to surround the porous carbon electrode, or the palladium electrode may be spaced apart from the porous carbon electrode and may include a space therebetween.
  • the palladium electrode is a comb pattern pair electrode, a line electrode, a polygonal electrode, a circular electrode, a polygonal column electrode, a cylindrical electrode, a conical electrode with a top cut flat, a polygonal pyramid electrode with a top cut flat, and a 3D double layer. It may include at least one of a structural electrode, a ring electrode, and a combination thereof. According to an embodiment, the palladium electrode may include an open area in which a portion is cut. According to one embodiment, the palladium electrode may be a ring-shaped electrode in which a part is cut.
  • the enzyme-free blood glucose sensor may further include a pH sensing electrode.
  • the pH sensing electrode may include a carbon electrode, a silver/silver chloride electrode, or an oxide-based electrode.
  • the pH sensing electrode may adjust or stop the negative voltage applied to the palladium electrode through the feedback loop when a feedback loop is formed with the palladium electrode and the detected pH is out of a certain range.
  • the pH sensing electrode is a comb pattern pair electrode, a polygonal electrode, a circular electrode, a polygonal column electrode, a cylindrical electrode, a conical electrode with a flat top cut, a polygonal pyramid electrode with a flat top cut, and a 3D multilayer structure. It may include at least one of an electrode and a combination thereof.
  • a metal electrode (counter electrode) for electricity flow may further include.
  • an insulating layer may be formed on at least a portion of the surface of the metal electrode for electric flow.
  • a method of manufacturing an enzyme-free blood glucose sensor may include depositing an insulating layer on a substrate; coating a photoresist on the insulating layer; Exposing the coated photoresist to ultraviolet rays; forming a plurality of photoresist polymer structures by developing the exposed photoresist; forming a plurality of porous polymer structures by performing an oxygen plasma treatment on the plurality of photoresist polymer structures; Forming a plurality of porous carbon electrodes by applying a thermal decomposition process to the plurality of porous structure polymer structures; depositing a metal thin film on at least one of the plurality of porous carbon electrodes; and depositing a palladium thin film on the insulating layer; can include
  • forming metal nanoparticles by applying a heat treatment process to the porous carbon electrode on which the metal thin film is deposited may further include.
  • a method of manufacturing an enzyme-free blood glucose sensor includes depositing an insulating layer on a silicon substrate; first coating a photoresist on the insulating layer; first exposing the coated photoresist to ultraviolet rays; forming a first photoresist polymer structure by developing the exposed photoresist; forming a first porous polymer structure by performing an oxygen plasma treatment on the first photoresist polymer structure; coating a second photoresist on a silicon substrate; Exposing the coated photoresist to ultraviolet rays for a second time; forming a second photoresist polymer structure by developing the exposed photoresist; forming a first porous carbon electrode and a pH sensing electrode by subjecting the first porous structure polymer structure and the second photoresist polymer structure to a thermal decomposition process; depositing a metal thin film on the first porous carbon electrode; forming metal nanoparticles by applying a heat treatment process to the first porous carbon electrode on which the metal thin film is deposited
  • a method of manufacturing an enzyme-free blood glucose sensor may include depositing an insulating layer on a silicon substrate; first coating a photoresist on the insulating layer; first exposing the coated photoresist to ultraviolet rays; forming a first photoresist polymer structure by developing the exposed photoresist; forming a first porous polymer structure by performing an oxygen plasma treatment on the first photoresist polymer structure; coating a second photoresist on a silicon substrate; Exposing the coated photoresist to ultraviolet rays for a second time; forming a second photoresist polymer structure by developing the exposed photoresist; forming a first porous carbon electrode and a pH sensing electrode by subjecting the first porous structure polymer structure and the second photoresist polymer structure to a thermal decomposition process; depositing a palladium thin film on a silicon substrate; and depositing a metal thin film on the first porous carbon electrode.
  • a method of manufacturing an enzyme-free blood glucose sensor includes forming metal nanoparticles by applying a heat treatment process to a first porous carbon electrode on which a metal thin film is deposited; It may further include.
  • a method of manufacturing an enzyme-free blood glucose sensor may include depositing an insulating layer on a silicon substrate; first coating a photoresist on the insulating layer; first exposing the coated photoresist to ultraviolet rays; forming a first photoresist polymer structure by developing the exposed photoresist; forming a first porous polymer structure by performing an oxygen plasma treatment on the first photoresist polymer structure; coating a second photoresist on a silicon substrate; Exposing the coated photoresist to ultraviolet rays for a second time; forming a second photoresist polymer structure by developing the exposed photoresist; forming a first porous carbon electrode and a pH sensing electrode by subjecting the first porous structure polymer structure and the second photoresist polymer structure to a thermal decomposition process; depositing a palladium thin film on the insulating layer; forming metal nanoparticles on the first porous carbon electrode; can include
  • the forming of the metal nanoparticles on the first porous carbon electrode may include forming the metal nanoparticles through an electroplating process.
  • a method of manufacturing an enzyme-free blood glucose sensor includes forming metal nanoparticles by applying a heat treatment process to a first porous carbon electrode on which a metal thin film is deposited; It may further include.
  • a method of manufacturing an enzyme free blood glucose sensor according to embodiments of the present disclosure (eg, the enzyme free blood glucose sensor of FIG. 1, FIG. 2, FIG. 3, FIG. 4 or FIG. 5 ( 1) can be produced.
  • the present disclosure relates to an enzyme-free blood glucose sensor, and provides a sensor using a metal-based nanocatalyst (eg, a metal catalyst or a metal oxide catalyst) on which an active hydrogen oxide layer is formed on a surface by locally controlling pH, according to one embodiment.
  • a metal-based nanocatalyst eg, a metal catalyst or a metal oxide catalyst
  • the enzyme-free blood glucose sensor can effectively detect glucose without pretreatment of a neutral solution by integrating a working electrode and a pH sensor electrode, and adjusting the size of a palladium electrode, and can provide a blood glucose sensor suitable for a living body. .
  • FIG. 1 is a conceptual top view of an enzyme-free blood glucose sensor according to an embodiment.
  • FIG. 2 is a conceptual cross-sectional view of an enzyme-free blood glucose sensor according to an embodiment.
  • FIG. 3 is a conceptual cross-sectional view of an enzyme-free blood glucose sensor according to an embodiment.
  • FIG. 4 is a conceptual cross-sectional view of an enzyme-free blood glucose sensor according to an embodiment.
  • FIG. 5 is a conceptual cross-sectional view of an enzyme-free blood glucose sensor according to an embodiment.
  • 6A illustrates a process of a method of manufacturing an enzyme-free blood glucose sensor according to an embodiment.
  • FIG. 6B illustrates a process of a manufacturing method of an enzyme-free blood glucose sensor according to an embodiment, and corresponds to a process sequential to FIG. 6A.
  • 7A is a glucose measurement graph of an enzyme-free blood glucose sensor, according to an embodiment, and a current and voltage curve according to glucose concentration.
  • 7B is a glucose measurement graph of an enzyme-free blood glucose sensor according to an embodiment, and is a curve showing a relationship between glucose concentration and current corresponding to the curve of FIG. 7A.
  • first, second, A, B, (a), (b) may be used. These terms are only used to distinguish the component from other components, and the nature, sequence, or order of the corresponding component is not limited by the term.
  • FIG. 1 is a conceptual top view of an enzyme-free blood glucose sensor 1 according to an embodiment.
  • 2, 3, 4, and 5 are cross-sectional conceptual views of the enzyme-free blood glucose sensor 1 according to example embodiments.
  • the enzyme-free blood glucose sensor 1 includes a substrate 100, an insulating layer 110, a porous carbon electrode 200, and a palladium electrode. 300 and a metal material region 500 .
  • the substrate 100 may be a rigid or flexible substrate in terms of physical properties, for example, a rigid or flexible substrate having a wafer or film shape.
  • the substrate 100 may be crystalline or amorphous, or may be a mixture of crystalline and amorphous phases.
  • a crystalline body may be monocrystal or polycrystal.
  • the substrate 100 may include a semiconductor.
  • the substrate 100 may include a group 4 semiconductor including silicon (Si), germanium (Ge), or silicon carbide (SiC); Group 3 to 5 semiconductors including gallium nitride (GaN), gallium arsenide (GaAs), indium phosphide (InP) or gallium phosphate (GaP); And it may include at least one or more selected from combinations thereof, but is not limited thereto.
  • it may include a substrate layer including at least two or more of the materials described, or a plurality of substrate layers.
  • each layer of the plurality of substrate layers may include the same or different materials or different material combinations.
  • each layer of the plurality of substrate layers may have the same or different thicknesses.
  • the substrate 100 may have a thickness of about 100 ⁇ m (micrometer) to about 1 mm (millimeter) in the case of a rigid substrate, and about 30 ⁇ m (micrometer) to about 1 mm in the case of a flexible substrate. mm (millimeter).
  • the insulating layer 110 may be included on at least a portion of the substrate 100 (eg, at least a portion or the entire surface of the substrate 100). According to an embodiment, the insulating layer 110 may be formed on at least a portion of the substrate 100 (eg, at least a portion or the entire surface of the substrate 100). In some embodiments, the insulating layer 110 may be formed on at least a portion of the substrate 100 by a deposition process.
  • the deposition process includes sputtering, thermal evaporation, E-beam evaporation, atomic layer deposition, chemical vapor deposition (CVD), and low pressure chemical vapor deposition.
  • the insulating layer 110 may include an insulating material.
  • an oxide, a nitride, a mixture thereof, and a composite thereof may be included.
  • the insulating layer 110 is at least one of silicon oxide, silicon nitride, hafnium oxide, aluminum oxide, tungsten oxide, zinc oxide, titanium oxide, tin oxide, a composite thereof, and a mixture thereof. The above may include, but are not limited to.
  • the thickness of the insulating layer 110 may be 20 nm (nanometer) to 10 ⁇ m (micrometer).
  • the palladium electrode 300 may be included on at least a portion of the insulating layer 110 (eg, at least a portion of an outer surface of the insulating layer 110).
  • the concentration of hydroxide ions may be locally increased around the palladium electrode 300.
  • an active hydrogen oxide layer may be effectively formed on the surface of the metal material region 500 (eg, metal nanoparticles) through the palladium electrode 300 integrated on the insulating layer 110 .
  • H + ions in the solution are absorbed to form palladium hydride (PdH x ), and the absorption of H + ions in the solution improves the concentration of hydroxide ions.
  • an active hydrogen oxide layer may be formed on the surface of adjacent metal materials 500 (eg, metal nanoparticles) due to the enhancement of the concentration of hydroxide ions.
  • blood glucose can be measured by measuring a current signal difference according to glucose concentration (eg, in body fluid) using the metal material region 500 (eg, metal nanoparticles).
  • the palladium electrode 300 is used as a pH control electrode, which can locally adjust the pH of a solution (eg, bodily fluid).
  • the palladium electrode 300 may be formed on at least a portion (eg, at least a portion of an outer surface of the insulating layer 110) on the insulating layer 110 near the porous carbon electrode 200 through a deposition process.
  • the deposition process may be conventional deposition known in the art such as sputtering, E-beam evaporation, atomic layer deposition, or chemical vapor deposition (CVD). process may be used, but is not limited thereto.
  • the palladium electrode 300 may be formed near the porous carbon electrode 200 .
  • the palladium electrode 300 and the porous carbon electrode 200 may be spaced apart from each other and may include a spaced space between them.
  • the palladium electrode 300 includes a spaced space between the palladium electrode 300 and the porous carbon electrode 200 and forms an outer circumference of the porous carbon electrode 200 (or porous carbon electrode 200). on the surface of the insulating layer 110 close to the outer circumference of the electrode 200).
  • an open area S-1 may be included for connection with other components of the sensor 1.
  • the size (eg, diameter, radius, thickness, etc.) of the separation space may define a separation distance between the palladium electrode 300 and the porous carbon electrode 200.
  • the palladium microelectrode 300 surrounds a porous carbon working electrode having a metallic material region (eg, porous carbon electrode 200/metal material region 500). structure, which allows the entire working electrode to be included within the range of adjusting the hydroxide ion concentration through hydrogen ion absorption of the palladium microelectrode 300.
  • the concentration of hydroxide ions in the vicinity of the working electrode is locally increased to activate oxidation on the surface of the nano-sized metal material region 500 (eg, metal nanoparticles). It can improve glucose sensitivity by effectively forming an OH ads layer.
  • the palladium electrode 300 may have a one-dimensional, two-dimensional or three-dimensional shape.
  • the palladium electrode 300 is a comb pattern pair electrode, a line electrode (eg, straight or oblique), a polygonal electrode, a circular (eg, dot) electrode, a polygonal electrode, a cylindrical electrode, and a flat top. It may include at least one of a truncated cone electrode, a polygonal pyramid electrode with a flat top cut, a 3D multi-layered electrode, a ring electrode, and combinations thereof. Referring to FIG.
  • an electrode of the form described in some embodiments is hollow to surround a porous carbon electrode 200 (eg, a circular shape in the top view of FIG. 1 ).
  • a porous carbon electrode 200 eg, a circular shape in the top view of FIG. 1 .
  • the palladium electrode 300 including a space (eg, a central region or a region including the central region is an empty space) (eg, a hollow circular shape) and having an open region in a portion thereof.
  • the palladium electrode 300 may be a ring-shaped electrode having a part cut (eg, an open region S-1). Referring to FIG.
  • an electrode of the form described in an embodiment constitutes a plurality of unit patterns and surrounds a porous carbon electrode 200 (eg, a circular shape in the top view of FIG. 1 ) and an open area (eg, an open area ( S-1)) may be arranged to form a palladium electrode 300 .
  • the palladium electrode 300 may be an electrode in which a plurality of unit patterns are arranged in a ring shape in which a portion is cut (eg, an open region S-1).
  • the size of the palladium electrode 300 may be about 1 nm to about several tens of millimeters (mm). eg, from about 1 nm to less than about 100 mm; from about 1 ⁇ m to less than about 100 mm; about 1 nm to about 80 mm; about 1 nm to about 40 mm; about 1 nm to about 20 mm; about 1 nm to about 10 mm; about 1 nm to about 1 mm; about 1 nm to about 500 ⁇ m (micrometer); about 1 nm to about 100 ⁇ m; about 1 nm to about 50 ⁇ m; about 1 nm to about 10 ⁇ m; about 1 nm to about 5 ⁇ m; about 1 nm to about 1 ⁇ m; about 1 nm to about 800 nm; about 1 nm to about 500 nm; about 1 nm to about 500 nm; 50 nm to about 200 nm; or 100 nm to about 200 nm.
  • the size of the palladium electrode 300 may mean length, diameter, radius, width, thickness, height, etc. depending on the shape, and the size may mean maximum, minimum, or average value.
  • the size of the palladium electrode 300 may be the width or diameter excluding the width or diameter of the hollow region, or the thickness.
  • the palladium electrode 300 may have a thickness or width of about 10 nm to about 1 mm.
  • the palladium electrode 300 may have a width of about 1 ⁇ m to about 1 mm and a thickness of about 10 nm to about 1 ⁇ m.
  • the pH adjustment range can be controlled by adjusting the thickness, width, or both of the palladium electrode. For example, adjusting the size (eg, reducing the size) of the working electrode (eg, porous carbon electrode 200/metal nanoparticle 500) and the palladium microelectrode (eg, palladium electrode 300). It is possible to minimize the pH range controlled by the solution compared to the entire solution, and to include the working electrode within the pH range controlled by the palladium microelectrode.
  • the working electrode eg, porous carbon electrode 200/metal nanoparticle 500
  • the palladium microelectrode eg, palladium electrode 300
  • the palladium electrode 300 includes an adhesion layer (eg, a chromium layer) for bonding with an insulating layer and a conductive metal layer (eg, a conductive material such as gold, silver, platinum, etc.) for electrical connection. may further include.
  • an adhesive layer, a conductive metal layer on the adhesive layer, and a palladium electrode layer may be formed on the conductive metal layer.
  • the conductive metal layer and the adhesive layer each have a thickness of about 5 nm to about 100 nm; about 5 nm to about 50 nm; or from about 10 nm to about 50 nm.
  • the porous carbon electrode 200 may be included in at least a portion of the insulating layer 110 (eg, at least a portion on a surface of the insulating layer 110).
  • the porous carbon electrode 200 includes a comb pattern pair electrode, a polygonal electrode, a circular electrode, a polygonal column electrode, a cylindrical electrode, a conical electrode with a flat top cut, a polygonal pyramid electrode with a flat top cut, and a 3D It may include at least one of a dual layer structure electrode, a 3D multi-layer structure ((Multi-Layers) electrode, and a combination thereof.
  • a dual layer structure electrode a 3D multi-layer structure ((Multi-Layers) electrode, and a combination thereof.
  • a 3D dual layer structure and a 3D multi-layer structure may be a three-dimensional structure each having two or more layers or a three-dimensional porous structure (eg, a mesh structure or a combined structure of a mesh structure and a flat structure (eg, film, sheet, etc.)).
  • the porous carbon electrode 200 in FIGS. 1 and 2 to 5 may be a porous structure in which pores P are formed from the outer surface toward the inside. In some embodiments, at least about 5% of the total volume of the porous carbon electrode 200; about 10% or more; about 30% or more; about 50% or more; or greater than about 60% pore volume.
  • the minimum and maximum values can be selected from the previously described values.
  • the porous carbon electrode 200 includes a pore distribution region (eg, a pore layer) in which pores are formed in a direction from the outer surface to the inside, and the thickness of the pore distribution region (eg, the pore layer) is the porous carbon electrode at least about 5% of the thickness of (200); about 10% or more; about 30% or more; about 50% or more; or about 60% or more.
  • the minimum and maximum values can be selected from the previously described values.
  • the pores in the porous carbon electrode 200 may include at least one of micropores, mesopores, and macropores.
  • the ratio of micropores and mesopores is about 50% or more of the total pores; more than about 60%; about 70% or more; about 80% or more; about 90% or more; or about 100%.
  • the size of the porous carbon electrode 200 may be 1 nm to several tens of millimeters (mm). eg, from about 1 nm to less than about 100 mm; from about 1 ⁇ m to less than about 100 mm; about 1 nm to about 80 mm; about 1 nm to about 40 mm; about 1 nm to about 20 mm; about 1 nm to about 10 mm; about 1 nm to about 1 mm; about 1 nm to about 500 ⁇ m (micrometer); about 1 nm to about 100 ⁇ m; about 1 nm to about 50 ⁇ m; about 1 nm to about 10 ⁇ m; about 1 nm to about 5 ⁇ m; about 1 nm to about 1 ⁇ m; about 1 nm to about 800 nm; about 1 nm to about 500 nm; about 1 nm to about 500 nm; 10 nm to about 200 nm; 50 nm to about 200 nm; or 100 nm to
  • the size of the porous carbon electrode 200 may mean length, diameter, radius, width, thickness, height, etc. depending on the shape, and the size may mean maximum, minimum, or average value.
  • the width and thickness of the porous carbon electrode 200 may be 10 nm to 1 mm, respectively.
  • the width of the porous carbon electrode 200 may be 1 ⁇ m to 1 mm, and the thickness of the porous carbon electrode 200 may be about 10 nm to about 500 ⁇ m.
  • the size of the working electrode (eg, the porous carbon electrode 200/metal material region 500) and the palladium microelectrode (eg, the palladium electrode 300) is adjusted (eg, reduced in size).
  • the pH range controlled by the microelectrode is minimized compared to the entire solution, and the working electrode can be included within the adjusted pH range.
  • the metal material region 500 may be included on at least a portion of the surface of the porous carbon electrode 200 (eg, at least a portion or the entire outer surface). In some embodiments, the metal material region 500 may be included in an upper region of the surface of the porous carbon electrode 200 (eg, an upper surface and a lateral or peripheral region close to the upper surface; or an upper surface).
  • the enzyme-free glucose sensor 1 includes a metal material region 500 (eg, metal nanoparticles or a metal thin film) formed on at least a portion of the porous carbon electrode 200 as an enzyme-free glucose sensing working electrode.
  • the sensor 1 may measure blood sugar by measuring a current signal difference according to a glucose concentration using the metal material region 500 .
  • glucose glucose
  • a metal catalyst e.g., metal nanoparticles or metal thin films
  • the senor 1 is a solution (eg, sweat, saliva, tears, etc.) It can measure the concentration of glucose in body fluids) and improve the sensitivity to glucose.
  • a solution eg, sweat, saliva, tears, etc.
  • the metal material region 500 may be formed on at least a portion of the surface of the porous carbon electrode 200, for example, on a top surface, a circumferential surface (or side surface), or both. there is. In some instances it may be formed on the top surface. In some instances it may be formed around the top and sides.
  • the metal material region 500 may include metal nanoparticles, metal thin films, or both. Referring to FIGS. 2 and 3 , the metal material region 500 may include metal nanoparticles.
  • the particle size of the metal nanoparticles may be about 1 nm to about 1 ⁇ m.
  • the metal nanoparticles may form a layer having a thickness of about 1 nm to about 10 ⁇ m. According to an embodiment, the metal nanoparticles may have a single layer or multiple layers.
  • the metal nanoparticle may include a metal, alloy, or composite including at least one of gold, platinum, silver, palladium, nickel, copper, and combinations thereof, but is not limited thereto.
  • the metal nanoparticle 500 may include gold or platinum.
  • the metal nanoparticles may be formed using a pyrolysis process (eg, a rapid pyrolysis process), an electroplating process, or both.
  • 2 to 3 are metal nanoparticles formed through a thermal decomposition process
  • FIG. 5 is a metal nanoparticle formed through an electroplating process.
  • the metal material region 500 may include a metal thin film.
  • the thickness of the metal thin film may be about 1 nm to about 10 ⁇ m.
  • the thickness may be measured based on the surface of the porous carbon structure.
  • the metal thin film in the metal material region 500 may include a region penetrated into the porous carbon structure. In some instances, it can penetrate into the pores of the porous carbon structure. In some instances, the thickness of the infiltrated region is from about 1 nm to about 10 ⁇ m; about 1 nm to about 1 ⁇ m; about 1 nm to about 0.8 ⁇ m; or about 10 nm to about 0.5 ⁇ m.
  • the metal thin film may include a metal including at least one of gold, platinum, silver, palladium, nickel, copper, and combinations thereof, an alloy, or a composite, but is not limited thereto.
  • the metal thin film may include gold or platinum.
  • the metal thin film may be formed by vapor deposition or electroplating.
  • the enzyme-free blood glucose sensor 1 may further include a pH sensing electrode 400 for sensing pH.
  • the enzyme-free blood glucose sensor 1 integrates a palladium electrode 300 around a working electrode using metal nanoparticles 500 (eg, porous carbon electrode 200/metal nanoparticles 500).
  • metal nanoparticles 500 eg, porous carbon electrode 200/metal nanoparticles 500.
  • an active hydrogen oxide layer eg, gold nanoparticles.
  • the size of the pH sensing electrode 400 is about 20 ⁇ m to about 200 ⁇ m, about 20 ⁇ m to about 150 ⁇ m; about 20 ⁇ m to about 100 ⁇ m; about 20 ⁇ m to about 50 ⁇ m; about 20 ⁇ m to about 40 ⁇ m; or about 20 ⁇ m to about 30 ⁇ m.
  • the size of the pH sensing electrode 400 may mean length, diameter, radius, width, thickness, height, etc. depending on the shape, and may be a minimum value, a maximum value, or an average value.
  • the pH sensing electrode 400 may have a width of about 20 ⁇ m to about 200 ⁇ m.
  • the pH sensing electrode 400 may include a material capable of sensing pH, such as a carbon-based material, an oxide, a metal/metal salt, or a metal.
  • the pH sensing electrode 400 may include a carbon electrode, a porous carbon electrode, a silver/silver chloride (eg, Ag/AgCl) electrode, or an oxide-based electrode such as IrO 2 , WO 2 or TiO 2 . Not limited.
  • the pH sensing electrode 400 includes a comb pattern pair electrode, a polygonal electrode, a circular electrode, a polygonal column electrode, a cylindrical electrode, a conical electrode with a flat top cut, a polygonal pyramid electrode with a flat top cut, and a 3D It may include at least one of a dual layer structure electrode, a 3D multi-layer structure ((Multi-Layers) electrode, and a combination thereof.
  • a 3D dual layer structure and a 3D multi-layer structure (( Multi-Layers) may be a three-dimensional structure or a three-dimensional porous structure (eg, mesh structure) each having two or more layers.
  • the pH sensing electrode 400 may form a feedback loop with the palladium electrode 300 by integrating the pH sensing carbon electrode around the working electrode and the palladium electrode 300 . That is, when the pH detected by the pH sensing electrode 400 is out of a certain range, the application of negative voltage to the palladium electrode 300 may be adjusted or stopped through a feedback loop.
  • the pH sensing electrode 400 may detect the pH of an area adjacent to the porous carbon electrode 200 and the palladium electrode 300 . According to an embodiment, the pH sensing electrode 400 may sense to return the detected pH to a normal range when it detects that the detected pH does not reach an appropriate range or rises higher than that.
  • the pH of the solution locally adjusted by the palladium electrode 300 in the enzyme-free blood glucose sensor 1 is fed back through the pH sensor electrode to prevent the pH of the entire solution from being out of the biocompatible range.
  • the concentration of hydroxide ions near the working electrode is locally increased by using the hydrogen absorption property of palladium.
  • Glucose sensitivity can be improved by effectively forming an active hydrogen oxide layer (OHads layer) on the surface of nano-sized metal particles (eg gold particles).
  • the enzyme-free blood glucose sensor 1 may further include a reference electrode 600 and a counter electrode 700 .
  • the reference electrode 600 and the counter electrode 700 may be included singly or in plural numbers for each sensor operation.
  • the reference electrode 600 and the counter electrode 700 may be included.
  • the reference electrode 600 may include a carbon-based material and may be a carbon electrode.
  • the counter electrode 700 may include a conductive material, for example, a metal-based electrode.
  • the first metal-based electrode is a metal or alloy (eg, binary or ternary) including at least one of gold, platinum, silver, palladium, nickel, copper, iridium, ruthenium, rhodium, and combinations thereof. or a quaternary alloy), an oxide or a composite, but is not limited thereto.
  • the enzyme-free blood glucose sensor 1 further includes second metal-based electrodes 700a, 700b, 700c and 700d for electricity flow, which correspond to the enzyme-free blood glucose sensor 1 for driving. It can be in contact with each electrode.
  • the second metal-based electrodes 700a, 700b, 700c, and 700d include the first metal-based electrode mentioned in the counter electrode 700, which may be the same as or different from the counter electrode 700.
  • grooves or protrusions may be formed on at least one of the electrodes of the sensor 1 to contact the second metal-based electrodes 700a, 700b, 700c, and 700d.
  • the second metal-based electrodes 700a, 700b, 700c, and 700d may be metal electrodes patterned for contact.
  • an insulating layer 710 may be further included on surfaces of the second metal-based electrodes 700a, 700b, 700c, and 700d in FIGS. 2 and 5 .
  • the insulating layer 710 may include a material mentioned in the insulating layer 110 , which may include the same material as or a different material from the insulating layer 110 .
  • the insulating layer 710 may be further formed on a portion of at least one or more of the electrodes of the sensor 1 .
  • an insulating layer 710 may be further included on the surfaces of the electrodes 200 and 700 in FIGS. 2 to 5 .
  • the insulating layer 710 may include a material mentioned in the insulating layer 110 , which may include the same material as or a different material from the insulating layer 110 .
  • the insulating layer 710 may be formed on at least a portion of the surface (porous electrode 200 of FIG. 2 ) of the lower circumference (or formed on the side surface) of the electrode.
  • the insulating layer 710 may not be formed on the porous electrode 200 .
  • an insulating layer 710 may be formed on a surface of a portion of the electrode 700 (eg, 700e in FIG. 1 ).
  • the enzyme-free blood glucose sensor 1 (eg, the enzyme-free blood glucose sensor 1 of FIGS. 1, 2, 3, 4, or 5) may be harmless to a living body.
  • the enzyme-free blood glucose sensor 1 (eg, the enzyme-free blood glucose sensor 1 of FIGS. 1, 2, 3, 4, or 5) is a non-invasive blood glucose sensor that is directly applied to the body. contact or direct contact with bodily fluids.
  • the palladium electrode 300 is applied to the pH of the surrounding area.
  • the pH of the surrounding area can be significantly increased locally, and the pH of the area in contact with the body may be maintained in a biocompatible range.
  • the enzyme-free blood glucose sensor 1 (eg, the enzyme-free blood glucose sensor 1 of FIGS. 1, 2, 3, 4, or 5) includes a pH sensing electrode 400 for detecting pH. ) and the palladium electrode 300, the entire solution (eg, body fluid) can be maintained within a biocompatible pH range.
  • a feedback loop system can be implemented by integrating a pH-sensing carbon electrode (400) around a glucose-sensing working electrode (eg, porous carbon electrode (200)/metal nanoparticles (500)) and a palladium microelectrode (300). there is. This can implement a glucose sensing system through a feedback loop of pH adjustment-glucose detection-pH control.
  • a method of manufacturing an enzyme-free blood glucose sensor includes depositing an insulating layer on a substrate; Coating a photoresist on the insulating layer, exposing the coated photoresist to ultraviolet rays, developing the exposed photoresist to form a plurality of photoresist polymer structures, treating the plurality of photoresist polymer structures with oxygen plasma to form a plurality of porous structure polymer structures, forming a plurality of porous carbon electrodes by applying a pyrolysis process to the plurality of porous structure polymer structures, depositing a metal thin film on at least one of the plurality of porous carbon electrodes , forming metal nanoparticles by applying a heat treatment process to the porous carbon electrode on which the metal thin film is deposited, and depositing a palladium thin film on the insulating layer.
  • a method of manufacturing an enzyme-free blood glucose sensor includes forming metal nanoparticles by applying a heat treatment process to a first porous carbon electrode on which a metal thin film is deposited; It may further include.
  • a method of manufacturing an enzyme-free blood glucose sensor includes depositing an insulating layer on a silicon substrate. , first coating a photoresist on the insulating layer, first exposing the coated photoresist to ultraviolet rays, developing the exposed photoresist to form a first photoresist polymer structure, first photoresist polymer Performing oxygen plasma treatment on the structure to form a first porous polymer structure, coating a second photoresist on a silicon substrate, second exposing the coated photoresist to ultraviolet rays, developing the exposed photoresist to form a second photoresist.
  • Forming a photoresist polymer structure applying a thermal decomposition process to each of the first porous structure polymer structure and the second photoresist polymer structure to form a first porous carbon electrode and a pH sensing electrode, a metal thin film on the first porous carbon electrode
  • the method may include depositing a metal nanoparticle, forming metal nanoparticles by applying a heat treatment process to the first porous carbon electrode on which the metal thin film is deposited, and depositing a palladium thin film on the insulating layer.
  • a method of manufacturing an enzyme-free blood glucose sensor includes depositing an insulating layer on a silicon substrate. ; first coating a photoresist on the insulating layer; first exposing the coated photoresist to ultraviolet rays; forming a first photoresist polymer structure by developing the exposed photoresist; forming a first porous structure polymer structure by performing an oxygen plasma treatment on the first photoresist polymer structure; coating a second photoresist on a silicon substrate; Exposing the coated photoresist to ultraviolet rays for a second time; forming a second photoresist polymer structure by developing the exposed photoresist; forming a first porous carbon electrode and a pH sensing electrode by subjecting the first porous structure polymer structure and the second photoresist polymer structure to a thermal decomposition process; depositing a palladium thin film on the insulating layer; and forming metal nano
  • the forming of the metal nanoparticles on the first porous carbon electrode may include forming the metal nanoparticles using an electroplating process.
  • the electroplating process may select an appropriate electroplating solution, current density, voltage, temperature, time, etc. to provide the performance of the sensor 1 of the present disclosure.
  • the electroplating solution may be about 0.001% to about 50% by weight of the plating solution; from about 0.001% to about 20% by weight; Or about 0.1% by weight to about 10% by weight of a metal source (eg, metal salt) and in addition may include additives and solvents such as suitable acids, but is not limited thereto.
  • the current density may be from about 1 A/dm 2 to about 10 A/dm 2 ; about 2 A/dm 2 to about 5 A/dm 2 or about 2 A/dm 2 to about 3 A/dm 2 , but is not limited thereto.
  • the temperature of the electroplating solution is 10 °C to 50 °C; 20 °C to 40 °C; Or it may be 30 °C to 40 °C, but is not limited thereto.
  • an electroplating time of 1 hour or more; more than 2 hours; more than 5 hours; more than 10 hours; It may be 30 hours or more, but is not limited thereto.
  • the voltage may be 1 V to 20 V; 3 V to 10 V; or 5 V to 8 V; Or it may be 6 V to 7 V, but is not limited thereto.
  • oxygen plasma treatment may be oxygen plasma etching.
  • the "pyrolysis process” is a photocatalytic process under conditions in which oxidation does not occur (eg, a vacuum or inert gas atmosphere of 10 ⁇ -2 torr or less, a temperature of 500 ° C to 1000 ° C and a holding time of 2 hours to 24 hours). Heating the resist polymer structure can convert the photoresist polymer structure into a conductive carbon electrode.
  • the conductive carbon electrode obtained in the "pyrolysis process” can be used as a working electrode and a pH sensing electrode.
  • deposition may use a deposition process known in the art of the present disclosure, for example, sputtering, thermal evaporation, and electron layer evaporation (E-beam evaporation).
  • Techniques of the present disclosure such as Atomic Layer Deposition, Chemical Vapor Deposition (CVD), Low Pressure Chemical Vapor Deposition, Plasma Enhanced Chemical Vapor Deposition or Thermal Oxidation Deposition
  • CVD Chemical Vapor Deposition
  • Low Pressure Chemical Vapor Deposition Low Pressure Chemical Vapor Deposition
  • Plasma Enhanced Chemical Vapor Deposition or Thermal Oxidation Deposition
  • Conventional deposition processes known in the art may be used, but are not limited thereto.
  • the "heat treatment process” may be a "rapid heat treatment (RTA annealing)" process.
  • RTA annealing is a high-speed process under conditions where oxidation does not occur (e.g., vacuum or inert gas atmosphere below 10 ⁇ -2 torr, temperature of 700 °C to 1200 °C and holding time of 30 seconds to 1 hour).
  • heating the metal e.g., vacuum or inert gas atmosphere below 10 ⁇ -2 torr, temperature of 700 °C to 1200 °C and holding time of 30 seconds to 1 hour.
  • rapid cooling eg, a cooling rate of about 50 °C/min to about 150 °C/min
  • a heat treatment process eg, a rapid heat treatment process.
  • 6A and 6B are flowcharts of a manufacturing process of an enzyme-free blood glucose sensor according to embodiments.
  • a manufacturing method of an enzyme-free blood glucose sensor includes the following steps. can do:
  • a silicon oxide film (eg insulating layer) (eg insulating layer 110 of FIGS. 1 to 6 ), for example, by oxidizing a silicon wafer to form a SiO 2 insulating layer.
  • a photoresist photoresist
  • PR photoresist
  • a negative photoresist may be spin coated on the surface of the SiO 2 insulating layer.
  • a photoresist photoresist
  • a first photoresist used to generate a working electrode (eg, the porous carbon electrode 200 of FIGS. 1 to 3) through UV exposure;
  • a polymer structure (or pattern) can be formed.
  • developing a photoresist to form a polymer structure (or pattern) for example, developing a photoresist (photoresist) not exposed in step (4) to obtain a first photoresist polymer structure (or pattern) can do.
  • exposing the coated photoresist to ultraviolet light for example, a second photoresist used to generate a pH-sensing carbon electrode (eg, the pH-sensing electrode 400 of FIGS. 1 to 3) through UV exposure;
  • a polymer structure (or pattern) can be formed.
  • the unexposed photoresist may be developed to obtain a second photoresist polymer structure (or pattern).
  • (11) forming a first porous carbon electrode and a pH sensing electrode by subjecting the porous polymer structure and the second photoresist polymer structure to a pyrolysis process, for example, by heating the polymer under conditions in which oxidation does not occur;
  • the polymer can be converted into a conductive carbon electrode.
  • a photosensitizer for example, the first porous carbon electrode portion to be coated with a metal nano-thin film (eg, a gold (Au)-thin film) through UV exposure and development; can be exposed.
  • a metal thin film on the first porous carbon electrode for example, a metal nano-thin film (eg, gold (Au)-thin film) to be converted into gold (Au) nanoparticles through E-beam evaporation can be deposited.
  • a metal nano-thin film eg, gold (Au)-thin film
  • Au gold
  • Forming metal nanoparticles by applying a rapid heat treatment process to the metal thin film for example, gold (Au) nanoparticles may be formed by performing rapid heat treatment (RTA annealing) under conditions in which oxidation does not occur. .
  • RTA annealing rapid heat treatment
  • the formation of nanoparticles can be effectively achieved by heating the metal at a rapid rate (heating rate: about 700 °C/min to about 1000 °C/min) under conditions where such oxidation does not occur.
  • rapid cooling eg, a cooling rate of about 50° C./min to about 150° C. may be performed after the rapid heat treatment process.
  • the step of developing the photoresist for example, (19) and (20) may expose a portion (eg, an insulating layer portion) where the palladium microelectrode is to be deposited through UV exposure and development.
  • a palladium thin film for example, 50 nm of chromium (thickness) (not shown) as an adhesion layer with the substrate through E-beam evaporation, 10 nm of gold (thickness) for electrical connection ) (not shown) may be deposited after deposition of 100 nm (thickness) of a palladium microelectrode (Pd).
  • a palladium thin film for example, 50 nm of chromium (thickness) (not shown) as an adhesion layer with the substrate through E-beam evaporation, 10 nm of gold (thickness) for electrical connection ) (not shown) may be deposited after deposition of 100 nm (thickness) of a palladium microelectrode (Pd).
  • metal-based electrodes eg, the second metal-based electrodes 700a, 700b, 700c, and 700d of FIGS. 1 to 3 and the counter electrode 700
  • metal-based electrodes eg, the second metal-based electrodes 700a, 700b, 700c, and 700d of FIGS. 1 to 3 and the counter electrode 700
  • 6a and 6b show that a process can be selected and adjusted to manufacture the sensor 1 of FIGS. 1 to 3 .
  • M corresponds to a photomask.
  • An enzyme-free blood glucose sensor was manufactured according to the manufacturing process shown in FIGS. 6A and 6B. At this time, the palladium electrode, the porous carbon electrode, and the pH sensing electrode disposed on the silicon substrate had a disposition structure as shown in FIG. 2 .
  • the palladium electrode 300 is disposed to surround the porous carbon electrode 200, and forms a reference electrode 600 and a counter electrode 700 disposed to be spaced apart from the porous carbon electrode 200, thereby ineffective.
  • the performance of the bovine blood glucose sensor was measured according to the three-electrode method.
  • the enzyme-free blood glucose sensor according to the preparation example was brought into contact with solutions having various glucose concentrations, and current according to voltage was measured.
  • 7A and 7B are glucose measurement graphs of an enzyme-free blood glucose sensor according to an embodiment of the present invention.
  • FIG. 7A corresponds to a voltage-current graph for neutral solutions having various glucose concentrations of an enzyme-free blood glucose sensor according to an embodiment. Of these, the current according to the glucose concentration at about -0.2 V was measured and shown in FIG. 7B.
  • the enzyme-free blood glucose sensor according to the exemplary embodiments can sufficiently detect even a solution having a low glucose concentration.
  • the enzyme-free blood glucose sensor of the present disclosure (eg, the enzyme-free blood glucose sensor 1 of FIGS. 1 and 2 ) can effectively detect glucose without pretreatment of a neutral solution and is a biocompatible sensor. can provide
  • the enzyme-free blood glucose sensor (eg, the enzyme-free blood glucose sensor 1 of FIGS. 1 and 2) of the present disclosure controls local pH by integrating a palladium micro-electrode near a micro-working electrode on which an enzyme-free catalyst is formed. system can be provided. Furthermore, a pH sensing electrode may be added to provide an enzyme-free glucose sensor that includes both a pH control electrode and a pH sensing electrode (eg, a palladium microelectrode).
  • an in vitro glucose sensing system can be realized through a feedback loop of pH adjustment - glucose detection - pH detection - pH adjustment.

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Abstract

L'invention concerne un capteur de glycémie sans enzyme et son procédé de fabrication. Le capteur de glycémie sans enzyme comprend : un substrat ; une couche isolante déposée et formée sur le substrat ; une électrode en carbone poreux déposée et formée sur la couche isolante ; une région de matériau métallique formée sur au moins une partie de la surface de l'électrode en carbone poreux ; et une électrode en palladium déposée et formée sur la couche isolante pour être espacée de l'électrode en carbone poreux, dans l'électrode en palladium, une tension négative est appliquée pour augmenter localement la concentration d'ions hydroxyde autour de l'électrode en palladium, et une différence de signal de courant en fonction de la concentration de glucose peut être mesurée à l'aide de la région de matériau métallique, ce qui permet de mesurer le glycémie.
PCT/KR2022/016514 2021-11-02 2022-10-27 Capteur de glycémie sans enzyme et son procédé de fabrication WO2023080536A1 (fr)

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KR10-2021-0148873 2021-11-02
KR20210148873 2021-11-02
KR1020220134870A KR20230063861A (ko) 2021-11-02 2022-10-19 무효소 혈당 센서 및 이의 제조방법
KR10-2022-0134870 2022-10-19

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Citations (5)

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Publication number Priority date Publication date Assignee Title
US20090043227A1 (en) * 2006-01-31 2009-02-12 Matsushita Electric Industrial Co., Ltd. Blood sensor and blood test apparatus having the same
KR20090100588A (ko) * 2008-03-20 2009-09-24 광운대학교 산학협력단 무효소 바이오 센서 및 그 제조 방법
WO2019160932A1 (fr) * 2018-02-13 2019-08-22 The Regents Of The University Of California Architecture de dispositif de modulation de ph induisant la catalyse d'oxyde métallique pour la détection de métabolites
KR20200011369A (ko) * 2018-07-24 2020-02-03 가천대학교 산학협력단 비효소적으로 혈당을 측정하는 미세침 전극 센서 및 이의 제조하는 방법
KR20200136845A (ko) * 2019-05-28 2020-12-08 울산과학기술원 무효소 혈당센서 및 그 제조방법

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US20090043227A1 (en) * 2006-01-31 2009-02-12 Matsushita Electric Industrial Co., Ltd. Blood sensor and blood test apparatus having the same
KR20090100588A (ko) * 2008-03-20 2009-09-24 광운대학교 산학협력단 무효소 바이오 센서 및 그 제조 방법
WO2019160932A1 (fr) * 2018-02-13 2019-08-22 The Regents Of The University Of California Architecture de dispositif de modulation de ph induisant la catalyse d'oxyde métallique pour la détection de métabolites
KR20200011369A (ko) * 2018-07-24 2020-02-03 가천대학교 산학협력단 비효소적으로 혈당을 측정하는 미세침 전극 센서 및 이의 제조하는 방법
KR20200136845A (ko) * 2019-05-28 2020-12-08 울산과학기술원 무효소 혈당센서 및 그 제조방법

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