WO2015054775A1 - Électrodes, détecteurs, leurs utilisations et leurs procédés de fabrication - Google Patents

Électrodes, détecteurs, leurs utilisations et leurs procédés de fabrication Download PDF

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Publication number
WO2015054775A1
WO2015054775A1 PCT/CA2014/000748 CA2014000748W WO2015054775A1 WO 2015054775 A1 WO2015054775 A1 WO 2015054775A1 CA 2014000748 W CA2014000748 W CA 2014000748W WO 2015054775 A1 WO2015054775 A1 WO 2015054775A1
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WIPO (PCT)
Prior art keywords
electrode
region
sub
detector
conductive pattern
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Application number
PCT/CA2014/000748
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English (en)
Inventor
Ricardo Izquierdo
Philippe Juneau
Florent LEFÈVRE
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Transfert Plus, S.E.C.
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Application filed by Transfert Plus, S.E.C. filed Critical Transfert Plus, S.E.C.
Publication of WO2015054775A1 publication Critical patent/WO2015054775A1/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
    • A61B5/68—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient
    • A61B5/6801—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be attached to or worn on the body surface
    • A61B5/6813—Specially adapted to be attached to a specific body part
    • A61B5/6814—Head
    • A61B5/6821—Eye
    • 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
    • A61B5/1455—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 optical sensors, e.g. spectral photometrical oximeters
    • 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
    • A61B5/145—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
    • A61B5/1486—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 enzyme electrodes, e.g. with immobilised oxidase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/307—Disposable laminated or multilayered electrodes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
    • A61B2562/02—Details of sensors specially adapted for in-vivo measurements
    • A61B2562/0233—Special features of optical sensors or probes classified in A61B5/00
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
    • A61B2562/12—Manufacturing methods specially adapted for producing sensors for in-vivo measurements
    • A61B2562/125—Manufacturing methods specially adapted for producing sensors for in-vivo measurements characterised by the manufacture of electrodes
    • 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
    • A61B5/14532—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 for measuring glucose, e.g. by tissue impedance measurement
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3271—Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04—Contact lenses for the eyes

Definitions

  • the present subject-matter relates to electrodes, detectors uses thereof, and methods of preparation thereof, and more particularly to an electrode fabricated using conductive nanomaterial members.
  • Electrochemical sensors or detectors capable of sensing or detecting a level of particular analytes in a gas or liquid have various applications.
  • use of currently available electrochemical sensor or detectors is limited by their properties, such as non-transparency or inflexibility of the sensors.
  • electrochemical sensors often require costly fabrication processes, for example requiring evaporation and vacuum pulverization.
  • an electrode comprising a plurality of nanomaterial members defining a plurality of pores, wherein said electrode allows passage of at least 60 % of light in the about 390 nm to about 1200 nm wavelength range.
  • the electrode for measuring capacitance, resistance, inductance, electrochemical properties and/or photoelectric properties of an element to be analyzed.
  • a detector comprising: a working electrode; a counter electrode; and a reference electrode.
  • a process for fabricating at least one electrode comprising: forming on a substrate a conductive pattern comprising a plurality of conductive nanomaterial members;
  • the conductive pattern comprises a plurality of pores, wherein said electrode allows passage of at least 60% of light in the about 390 nm to about 1200 nm wavelength range.
  • a detector comprising a first electrode having a sensing sub-region functionalized by a first material sensitive to at least a first type of analyte and a second electrode having a substrate and a conductive pattern comprising a plurality of conductive nanomaterial members, the second electrode forming a reference or a counter electrode.
  • a detector comprising :
  • At least one of the electrodes comprises a plurality of nanomaterials defining a plurality of pores.
  • FIG. 1 illustrates a side elevation view of an exemplary substrate coated with conductive nanomaterial members
  • FIG. 2 illustrates a plan view of an exemplary substrate coated with conductive nanomaterial members
  • FIG. 3A illustrates a plan view of an exemplary substrate during an exemplary lithography process
  • FIG. 3B illustrates a plan view of an exemplary substrate having formed thereon a conductive pattern
  • FIG. 4 illustrates a plan view of an exemplary electrode during a functionalizing process
  • FIG. 5 illustrates a plan view of an exemplary electrode after functionalizing of a sub-region
  • FIG. 6 illustrates a plan view of an exemplary electrode after removal of the protective layer
  • FIG. 7A illustrates a plan view of an exemplary multi-electrode detector during an exemplary lithography process
  • FIG. 7B illustrates a plan view of an exemplary non-functionalized multi- electrode detector
  • FIG. 8 illustrates a plan view of the exemplary multi-electrode detector during functionalization of one of the electrodes
  • FIG. 9 illustrates a plan view of the exemplary multi-electrode detector following functionalization of one of the electrodes
  • FIG. 10 illustrates a plan view of the exemplary multi-electrode detector after removal of the protective layer
  • FIG. 11 illustrates a plan view of the exemplary multi-electrode detector during functionalization of another of the electrodes
  • FIG. 12 illustrates a plan view of the exemplary multi-electrode detector following functionalization of the other of the electrodes
  • FIG. 13 illustrates a plan view of the exemplary multi-electrode detector following removal of the protective layer
  • FIG. 14 illustrates a plan view of the exemplary multi-electrode detector having functionalized electrodes
  • FIG. 15A illustrates a plan view of an exemplary multi-electrode detector during an exemplary lithography process
  • FIG. 15B illustrates a plan view of an exemplary substrate having formed thereon a conductive pattern having a contiguous region
  • FIG. 16 illustrates a plan view of an exemplary multi-electrode detector flowing functionalization of the contiguous region.
  • FIG. 17 illustrates a plan view of the exemplary multi-electrode detector after removal of the protective layer
  • FIG. 18 illustrates a plan view of the exemplary multi-electrode detector while forming an insulating region
  • FIG. 19 illustrates a plan view of the exemplary multi-electrode detector following forming of the insulating region
  • FIG. 20 illustrates a plan view of the an exemplary substrate having formed thereon a plurality of multi-electrode detectors
  • FIG. 21A illustrates a side elevation view of an exemplary multi-electrode detector supported within walls of a fluidic channel
  • FIG. 2 B illustrates a side elevation view of an exemplary multi-electrode detector supported within walls of a fluidic channel
  • FIG. 22 illustrates a side elevation view of an exemplary multi-electrode detector applied for spectral measurement
  • FIG. 23 illustrates a cross section view of an exemplary apparatus applying an exemplary multi-electrode detector
  • FIG. 24 illustrates a plan view of an exemplary multi-electrode detector being formed of different nanomaterials.
  • FIG. 25 is a graph showing the current response of an exemplary detector when varying voltage is applied thereto;
  • FIG. 26 is a graph showing current response measured by an exemplary detector for varying concentrations of hydrogen peroxide
  • FIG. 27 is a graph showing current response measured by an exemplary detector for a solution having no cell culture and another solution having algae/bacteria over different voltage levels;
  • FIG. 28 is a graph showing voltage response measured by an exemplary detector using different voltage sweep speeds in a solution having benzoquinone;
  • FIG. 29 shows microscope images according to example deposits of silver nanofilaments at transparencies of 91 %, 86%, 82%, 44% and 30%;
  • FIG. 30 is a graph showing effective surface of an electrode at different transparency levels for two example fabrications
  • FIG. 31 shows a microscope image according to example deposits of silver nanofilaments coated with platinum
  • FIG. 32 is a graph showing transparency over a range of wavelengths of an electrode having silver nanofilaments coated with platinum.
  • FIG. 33 is a side elevation view of a contact lens according to an exemplary embodiment.
  • nanoofilament refers to a material that exhibits a length to width ratio of at least 10, at least 100 or at least 1000.
  • nanowire refers to a material that exhibits a length to width ratio of at least 10, at least 100 or at least 1000.
  • substantially transparent refers to a material or element that allows passage of at least 80 %, 90 % or 95 % of light in the about 390 nm to about 1200 nm wavelength range. . In some exemplary embodiments, the passage of light may be limited to about 390 nm to about 800 nm wavelength range.
  • At least one of the electrodes can be semi-transparent.
  • at least one of the electrodes can be porous.
  • the at least one electrode can comprise a plurality of nanomaterial members defining a plurality of pores.
  • the at least one electrode can be formed of a plurality of nanomaterial members defining a plurality of pores.
  • the at least one of the electrodes can have a transparency greater than about 60%, about 65 % or about 70 %.
  • the sheet resistance of the at least one of the electrodes can be less than about 10 ohms/square or less than about 20 ohms/square and the transparency can be less than about 65 %, about 75% or about 80 %.
  • the nanomaterial members can be nanofilaments that are formed of silver.
  • the nanofilaments can be coated with platinum, nickel copper, palladium, gold or mixtures thereof.
  • At least one electrode can be coated with platinum, nickel, copper, palladium, gold or mixtures thereof.
  • the transparency of the at least one electrode can be of about
  • the sheet resistance of the at least one electrode can be about 0.3 ohms/square to about 30 ohms/square.
  • the at least one property detected by the electric detector can be chosen from current, voltage, resistivity, capacity and conductivity.
  • the at least one property detected by the electric detector can be oxygen concentration.
  • the electric detector can comprise a working electrode, a counter electrode; and a reference electrode; and each of the electrodes can be formed of a plurality of nanofilaments defining a plurality of pores.
  • the nanofilaments can be formed of silver; and the nanofilaments forming the working electrode and the counter electrode can be coated with platinum.
  • the nanofilaments can be formed of gold; and the nanofilaments forming the working electrode and the counter electrode can be coated with platinum, silver, copper or other materials.
  • the nanofilaments can be formed of platinum; and the nanofilaments forming the working electrode and the counter electrode can be coated with gold, silver, copper or other materials.
  • the nanofilaments can be formed of copper; and the nanofilaments forming the working electrode and the counter electrode can be coated with gold, platinum, silver, copper or other materials.
  • the nanofilaments can be coated with a polymer.
  • the electrodes can be coated with a polymer.
  • the electrode can be semi-transparent or substantially transparent to allow light to pass through it.
  • the electrode can comprise a nanomaterial including plurality of members defining a plurality of pores for allowing passage of light and water therethrough.
  • the nanomaterial members can be conductive and can have a diameter in the range of the nanometer.
  • the nanomaterial members associated with the filter can be interweaved to define a plurality of porous openings having width/area in the range of about 0.01 to about 100pm.
  • the water sample can pass through the porous openings. Additionally, a substantial amount of light can pass through the porous openings or be transmitted by the nanomaterial members.
  • the nanomaterial members comprised in the electrode 14 can be in the form of nanotubes, nanofilaments, nanowires, nanorods etc.
  • the nanomaterial can be carbon, silver, platinum, nickel, palladium, copper, gold or other suitable metals, alloys or derivatives thereof.
  • the nanomaterial members can comprise carbon nanotubes, including single-walled or multi-walled carbon nanotubes.
  • the nanomaterials can be graphene, a mixture of nanowires and carbon nanotubes or composite nanowire formed from a mixture of metals.
  • the electrode can comprises a plurality of nanomaterial members defining a plurality of pores, wherein said electrode allows passage of at least 60 % of light in the about 390 nm to about 1200 nm wavelength range.
  • the electrode can be formed of said nanomaterial members.
  • the electrode can be flexible.
  • a flexible electrode can withstand from about 10% to about 80%, about 20 % to about 70 %, or about 25 % to about 65 % bending strain (%) without a substantial change in electrical characteristics.
  • a flexible electrode can withstand up to about 80% bending strain (%) without a substantial change in electrical characteristics.
  • the electrode can be flexible.
  • a flexible electrode can withstand from about 10% to about 80%, about 20 % to about 70 %, or about 25 % to about 65 % bending strain (%) without a substantial change in electrical characteristics after coming back to its initial state.
  • a flexible electrode can withstand up to about 80% bending strain (%) without a substantial change in electrical characteristics after coming back to its initial state.
  • the electrode can be extensible.
  • the electrode can withstand a tensile strength of up to about 15 %.
  • the nanomaterial members can be chosen from nanotubes, nanofilaments, nanowires, and nanorods.
  • the nanomaterial members can be chosen from nanofilaments or nanowires.
  • the material can be chosen from carbon, silver, platinum, nickel, palladium, copper and gold.
  • the electrode can comprise silver nanofilaments or silver nanowires.
  • the silver nanofilaments have an average length of about 1 to about 500 ⁇
  • the silver nanowires have an average length of about 1 to about 500 ⁇ .
  • the silver nanofilaments can have an average length of about 1 to about 10 ⁇ .
  • the silver nanofilaments can have an average length of about 10 to about 500 ⁇ .
  • the silver nanofilaments can have an average length of about 10 to about 100 ⁇ .
  • the silver nanofilaments can have an average length of about 50 to about 500 ⁇ .
  • the silver nanowires have an average length of about 10 to about 100 ⁇ .
  • the electrode can be coated with platinum, nickel copper, palladium, gold or mixtures thereof.
  • the electrode can have silver nanowires or silver nanofilaments that are coated with platinum, nickel copper, palladium, gold or mixtures thereof.
  • the electrode can have gold nanofilaments or gold nanowires.
  • the gold nanofilaments have an average length of about 1 to about 500 ⁇ .
  • the gold nanofilaments have an average length of about 1 to about 100 ⁇ .
  • the gold nanofilaments have an average length of about 1 to about 10 ⁇ .
  • the electrode can be coated with platinum, nickel copper, palladium, silver or mixtures thereof.
  • the electrode can have gold nanowires or gold nanofilaments that are coated with platinum, nickel copper, palladium, silver or mixtures thereof.
  • the electrode can comprise platinum nanofilaments or platinum nanowires.
  • the platinum nanofilaments can have an average length of about 1 to about 10 ⁇ .
  • the platinum nanofilaments can have an average length of about 1 to about 100 ⁇ .
  • the platinum nanofilaments can have an average length of about 1 to about 500 ⁇ .
  • the electrode can be coated with gold, nickel copper, palladium, silver or mixtures thereof.
  • the electrode can have platinum nanowires or platinum nanofilaments that are coated with gold, nickel copper, palladium, silver or mixtures thereof.
  • the electrode can comprise copper nanofilaments or copper nanowires.
  • the copper nanofilaments have an average length of about 1 to about 500 ⁇ .
  • the copper nanowires have an average length of about 1 to about 500 ⁇ .
  • the copper nanofilaments can have an average length of about 1 to about 10 ⁇ .
  • the copper nanofilaments can have an average length of about 10 to about 100 ⁇ .
  • the copper nanofilaments can have an average length of about 50 to about 500 ⁇
  • the copper nanowires have an average length of about 10 to about 100 ⁇ .
  • the electrode can be coated with platinum, nickel silver, palladium, gold or mixtures thereof.
  • the electrode can have copper nanowires or copper nanofilaments that are coated with platinum, nickel silver, palladium, gold or mixtures thereof.
  • the electrode can allow passage of at least 70 % of light in the about 390 nm to about 800 nm wavelength range.
  • the electrode can allow passage of at least 80 % of light in the about 390 nm to about 800 nm wavelength range.
  • the electrode can allow passage of at least 90 % of light in the about 390 nm to about 800 nm wavelength range.
  • the electrode can allow passage of at least 95 % of light in the about 390 nm to about 800 nm wavelength range.
  • the electrode can be disposed on a substrate.
  • the substrate can allow passage at least 60 % of light in the about 390 nm to about 800 nm wavelength range.
  • the substrate can allow passage at least 70 % of light in the about 390 nm to about 800 nm wavelength range.
  • the substrate can allow passage at least 80 % of light in the about 390 nm to about 800 nm wavelength range.
  • the substrate can allow passage at least 90 % of light in the about 390 nm to about 800 nm wavelength range.
  • the substrate can allow passage at least 95 % of light in the about 390 nm to about 800 nm wavelength range.
  • the electrode can allow passage of at least 70 % of light in the about 390 nm to about 1200 nm wavelength range.
  • the electrode can allow passage of at least 80 % of light in the about 390 nm to about 1200 nm wavelength range.
  • the electrode can allow passage of at least 90 % of light in the about 390 nm to about 200 nm wavelength range.
  • the electrode can allow passage of at least 95 % of light in the about 390 nm to about 1200 nm wavelength range.
  • the electrode can be disposed on a substrate.
  • the substrate can allow passage at least 60 % of light in the about 390 nm to about 1200 nm wavelength range.
  • the substrate can allow passage at least 70 % of light in the about 390 nm to about 1200 nm wavelength range.
  • the substrate can allow passage at least 80 % of light in the about 390 nm to about 1200 nm wavelength range.
  • the substrate can allow passage at least 90 % of light in the about 390 nm to about 1200 nm wavelength range.
  • the substrate can allow passage at least 95 % of light in the about 390 nm to about 1200 nm wavelength range.
  • the substrate can be flexible.
  • a flexible substrate can withstand from about 10% to about 80%, about 20 % to about 70 %, or about 25 % to about 65 % of bending strain (%) without a substantial change in electrical characteristics.
  • an electrode can withstand up to about 80% bending strain (%) without a substantial change in electrical characteristics.
  • the substrate can be flexible.
  • a flexible substrate can withstand from about 10% up to about 80%, about 20 % to about 70 %, or about 25 % to about 65 % of bending strain (%).
  • an electrode can withstand up to about 80% of bending strain (%).
  • the electrode can allow passage of at least 70 % of light in the about 390 nm to about 800 nm wavelength range.
  • the electrode can allow passage of at least 80 % of light in the about 390 nm to about 800 nm wavelength range.
  • the electrode can allow passage of at least 90 % of light in the about 390 nm to about 800 nm wavelength range.
  • the electrode can allow passage of at least 95 % of light in the about 390 nm to about 800 nm wavelength range.
  • the substrate can allow passage of at least 60 % of light in the about 390 nm to about 800 nm wavelength range.
  • the substrate can allow passage of at least 70 % of light in the about 390 nm to about 800 nm wavelength range.
  • the substrate can allow passage of at least 80 % of light in the about 390 nm to about 800 nm wavelength range.
  • the substrate can allow passage of at least 90 % of light in the about 390 nm to about 800 nm wavelength range.
  • the substrate can allow passage of at least 95 % of light in the about 390 nm to about 800 nm wavelength range.
  • one surface of the electrode can be functionalized with a functionalizing agent chosen from oxides, metals, metal oxides, metal ions, polymers, biological molecules and nanomaterials.
  • a functionalizing agent chosen from oxides, metals, metal oxides, metal ions, polymers, biological molecules and nanomaterials.
  • one surface of the electrode can be functionalized with a member chosen from enzymes (ex: peroxidase, tyrosinase, cholesterol oxidase, cholesterol esteral, Glucose oxidase, choline oxidase, horseradish peroxidase, glutamate dehydrogenase, fructose dehydrogenase, NADH dehydrogenase, urease, uricase), molecules (ex: FAD, GoxFAD, Prussian Blue and Its Analogues), DNA, RNA, antigen, conductive polymer (ex: PEDOT, polyaniline, polyindole, poliquinone, polythiophene, polypyrrole, their derivatives, and mixture of thereof), conductive oxide (ex: ZnO, ITO, and derivates), metals (ex : Ag, Pt, Au, Ni, Pd, Cu, TL), metal ions (ex: Ag + , Pt + , Au +
  • enzymes ex:
  • these materials could be entrapped in ZnO, Ti0 2 , silica, polymer (ex: PVP, PEDOT, polypyrrole, polyaniline, nafion).
  • the plurality of nanomaterial members define a conductive pattern, a sensing sub-region of the conductive pattern being functionalized with a material sensitive to at least one type of analyte.
  • the functionalized sub-region can produce an electrical signal when in presence of the at least first type of analyte.
  • the electrical signal can indicate a level of the at least first type of analyte.
  • the conductive pattern can comprise a conductive portion and a connecting portion, the electrical signal flowing from the functionalized sub-region via the conductive portion to the connecting portion.
  • the connecting portion can be for connecting to an external measurement device.
  • the connecting portion can be for connecting to an external voltage or current source.
  • the functionalized sub-region can be functionalized with a functionalizing agent chosen from oxides, metals, metal ions, metal oxides, polymers, biological molecules and nanomaterials.
  • a functionalizing agent chosen from oxides, metals, metal ions, metal oxides, polymers, biological molecules and nanomaterials.
  • the functionalized sub-region can be functionalized with a member chosen from enzymes (ex: peroxidase, tyrosinase, cholesterol oxidase, cholesterol esteral, Glucose oxidase, choline oxidase, horseradish peroxidase, glutamate dehydrogenase, fructose dehydrogenase, NADH dehydrogenase, urease, uricase ), molecules (ex: FAD, GoxFAD, Prussian Blue and Its Analogues), graphite, DNA, RNA, antigen, conductive polymer (ex: PEDOT, polyaniline, polyindole, poliquinone, polythiophene, polypyrrole, their derivatives, and mixture of thereof), conductive oxide (ex: ZnO, ITO, and derivates), metals (ex : Ag, Pt, Au, Ni, Pd, Cu, TL), metal ions (ex: Ag + , P
  • the conductive pattern can formed by coating the plurality of conductive nanomaterial members onto the substrate through a process chosen from filtration, electrochemical bonding, chemical vapor deposition, humid deposition, spin coating, and printing; and forming the conductive pattern by lithography.
  • the material sensitive to at least a first type of analyte can be chosen from, but not limited to these examples, inorganic substances (As, Ba, B, bromates, Cd, chloranines, Cr, Cu, CN, Ni, Zn, F, nitrate, nitrite, Hg, Pb, Se, U, ...
  • the first sensing sub-region can be functionalized by at least one of electrical deposition, chemical reaction, adsorption, oxidation, and radiation.
  • forming the conductive pattern can comprise coating a surface of the substrate with the plurality of conductive nanomaterial members; and forming the conductive pattern from the conductive nanomaterial members coating by lithography.
  • coating of the surface of the substrate with the plurality of conductive nanomaterial members can be performed by a process chosen from filtration, electrochemical bonding, chemical vapor deposition, humid deposition, spin coating, dip coating, rod meyer, Langmuir Blodgett and printing.
  • the coating of the substrate with the plurality of conductive nanomaterial members can be performed by printing techniques chosen from inkjet, spray, and roll to roll.
  • the conductive nanomaterial members can comprise a material chosen from gold, silver, platinum, copper, and nickel.
  • forming the conductive pattern by lithography can comprise: covering the conductive nanomaterial coating with a protective layer; removing at least one sub-region of the protective layer to expose at least one sub-region of the conductive nanomaterial coating, the unexposed sub-region of the conductive nanomaterial coating corresponding to the conductive pattern to be formed; removing the at least one exposed sub-region of the conductive nanomaterial coating from the substrate; and removing the protective layer from the unexposed sub-region of the conductive nanomaterial coating.
  • removing the at least one exposed sub-region of the conductive nanomaterial coating can be performed by etching.
  • the protective layer can comprise polymer resin.
  • material sensitive to at least a first type of analyte is chosen from oxides, metals, metal ions, polymers, biological molecules, and nanomaterials.
  • functionalizing the sub-region of the conductive pattern can comprise covering the conductive pattern with a protective layer; removing at least one sub-region of the protective layer to expose at least one sub-region of the conductive pattern corresponding to the sub-region to be functionalized; functionalizing the at least one exposed sub-region of the conductive pattern with the material sensitive to the at least one type of analyte.
  • functionalization can include at least one of electrical deposition, chemical reaction, adsorption, oxidation, and radiation.
  • the functionalized sub-region of the conductive pattern can form a sensing portion of a first electrode.
  • the process can further comprise forming an insulating region separating the functionalized sub-region of the conductive pattern into a first portion and a second portion, wherein the first portion forms a sensing portion of a first electrode and the second portion forms a sensing portion of a second electrode.
  • the insulating region can be formed by lithography.
  • forming the insulating region can comprise covering at least the functionalized sub-region of the conductive pattern with a protective layer; removing at least one sub-region of the protective layer to expose at least a third portion of the functionalized sub-region corresponding to the insulating region to be formed; and removing the exposed third portion of the functionalized sub-region from the substrate.
  • removing the exposed third portion of the functionalized sub- region can be performed by etching.
  • the process can further comprise functionalizing a second sub-region of the conductive pattern with a material sensitive to at least a second type of analyte, wherein the second functionalized sub-region of the conductive pattern forms a sensing portion of a second electrode.
  • the first sub-region and the second sub-region can be functionalized with the same material and the at least first type of analyte and the at least second type of analyte can be the same.
  • the at least first type of analyte and the at least second type of analyte are different.
  • functionalizing the second sub-region can be carried out after functionalizing the first sub-region.
  • one of the first and second electrodes can be a working electrode and the other of the first and second electrodes can be a counter electrode.
  • a third sub-region of the conductive pattern is non- functionalized and can form a sensing portion of a third reference electrode.
  • the conductive pattern can comprise a sensing portion, a conducting portion and a connecting portion, and the process further comprises covering at least the conducting portion and the connecting portion with an additional protective layer.
  • the substrate can be porous, at least partially transparent, and flexible.
  • a flexible substrate can withstand from about 10% to about 80%, about 20 % to about 70 %, or about 25 % to about 65 % of bending strain (%).
  • the substrate can be porous, at least partially transparent, and flexible.
  • a flexible substrate can withstand from about 10% to about 80%, about 20 % to about 70 %, or about 25 % to about 65 % of bending strain (%) without a substantial change in electrical characteristics.
  • one of the first and second electrodes can be a working electrode and the other of the first and second electrodes is a counter electrode.
  • first material and the second material can be the same and wherein the at least first type of analyte and the at least second type of analyte can be the same.
  • first sub-region and the second sub-region can be functionalized with the different materials and wherein the at least first type of analyte and the at least second type of analyte can be different.
  • the detector can further comprise a third electrode having a substrate and a conductive pattern comprising a plurality of conductive nanomaterial members.
  • nanomaterial members can comprise a material chosen from gold, silver, platinum, copper, and nickel.
  • the detector can comprise a substrate; a conductive pattern comprising the plurality of nanomaterial members, the nanomaterial members coating a surface of the substrate; a first sensing sub-region of the conductive pattern being functionalized with a first material sensitive to at least a first type of analyte, said sensing sub-region forming a sensing portion of the working electrode; a second sensing sub-region of the conductive pattern being functionalized with a second material sensitive to at least a second type of analyte, said sensing sub-region forming a sensing portion of the counter electrode; a third sensing sub-region of the conductive pattern being non-functionalized, the third sensing sub-region forming a sensing portion of the reference electrode.
  • the substrate can be flexible and the conductive pattern can be flexible.
  • the flexible substrate and flexible conductive pattern can withstand from about 10% to about 80%, about 20 % to about 70 %, or about 25 % to about 65 % of bending strain without a substantial change in electrical characteristics.
  • the substrate can be porous and the conductive nanofilaments can define a plurality of pores.
  • the substrate can be at least partially transparent and the conductive pattern is at least partially transparent.
  • the conductive pattern can define a first conducting portion and first connecting portion of the working electrode, the first connecting portion being electrically connected to the first sensing sub-region via the first conducting portion; and wherein the conductive pattern defines a second conducting portion and a second connecting portion of the counter electrode, the second connecting portion being electrically connected to the second sensing sub-region via the second conducting portion.
  • the first connecting portion can be for connecting to at least one of an external measurement device and a voltage or current source; and the second connecting portion can be for connecting to at least one of the measurement device and the voltage or current source.
  • the conductive pattern can be formed by coating the plurality of conductive nanomaterial members onto the substrate through a process chosen from filtration, electrochemical bonding, chemical vapor deposition, humid deposition, spin coating and printing; and forming the conductive pattern by lithography.
  • the first sensing sub-region and the second sensing sub- region can be functionalized by at least one of electrical deposition, chemical reaction, adsorption, oxidation, and radiation.
  • At least one of the electrodes can define a plurality of pores and allows passage of at least 60% of light in the about 390 nm to about 1200 nm wavelength range.
  • a suitable substrate is provided and a surface of the substrate is coated with a plurality of conductive nanomaterial members.
  • the nanomaterial members can be any of nanotubes, nanofilaments, nanowires, nanorods, etc.
  • the nanomaterial can comprise carbon nanotubes, including single-walled or multi-walled carbon nanotubes.
  • the nanomaterials can be graphene, a mixture of nanowires and carbon nanotubes or composite nanowire formed from a mixture of metals.
  • the conductive nanomaterial members can have a resistance below microorganism or biological material.
  • the electrodes of the present disclosure can be used for for measuring oxygen concentration; determining toxicity of water; for measuring capacitance, resistance, inductance, electrochemical properties and/or photoelectric properties of an element to be analyzed; for carrying out amperometric measurments optionally coupled with optic measurement; as a freshness sensor; in an electronic patch network; or in an electronic patch.
  • the detectors of the present disclosure can be used for for measuring oxygen concentration; determining toxicity of water; for measuring capacitance, resistance, inductance, electrochemical properties and/or photoelectric properties of an element to be analyzed; for carrying out amperometric measurments optionally coupled with optic measurement; as a freshness sensor; in an electronic patch network; or in an electronic patch.
  • FIG. 1 therein illustrated is a side elevation view of a substrate 100 having been coated with a layer of plurality of conductive nanomaterial members 104 on one the surfaces thereof.
  • the substrate 100 can be porous, semi-transparent or substantially transparent, flexible, malleable, elastic or a combination thereof.
  • the substrate 100 can be porous, semi-transparent or substantially flexible, flexible and malleable.
  • the substrate 100 can be formed of plastic, PET, PEN, PS, PDMS, Teflon, alumina, glass or cellulose.
  • the flexible and malleable substrate can withstand from about 10% to about 80%, about 20 % to about 70 %, or about 25 % to about 65 % of bending strain without a substantial change in electrical characteristics.
  • the conductive nanomaterial members 104 can comprise at least one material chosen from gold, silver, platinum, copper, nickel, other suitable metals, alloys or derivatives thereof or a mixture thereof.
  • the conductive nanomaterial members 104 can each comprise at least one of gold, silver, platinum, copper, nickel, palladium, and zinc oxide,
  • silver nanofilaments or nanowires have an average length of about 1 to about 500 ⁇ .
  • the silver nanofilaments or nanowires have an average length of about 10 to about 00 ⁇ .
  • gold nanofilaments or nanowires have an average length of about 1 to about 10 ⁇ .
  • platinum nanofilaments or nanowires have an average length of about 1 to about 10 ⁇ .
  • copper nanofilaments or nanowires have an average length of about 1 to about 100 ⁇ .
  • FIG. 2 therein illustrated is a plan view of an exemplary substrate 100 having been coated with a plurality of conductive nanomaterial members 104 forming a coating 106. Due to their thread-like structure, neighboring nanomaterial members 104 are in physical contact with one another while defining a plurality of pores 108. For example, the plurality of pores 108 can each have a size of about 0.01 pm to about 10 ⁇ . Due to this physical contacting of the conductive nanomaterial members 104, the coating 106 of the conductive nanomaterial members 104 forms a conductive path through which electrical current can flow. Due to the conductive nanomaterial members 104 defining a plurality of pores, fluid can flow through the coating 106. For example, fluid can flow through the coating 06 in a direction generally transverse to a plane defined by the conductive nanomaterial coating 106.
  • the coating 106 is semi-transparent or substantially transparent. For example, at least some of the light incident on a first surface on the coating 106 passes through the pores defined by the conductive nanomaterial members 104 and exits an opposite surface of the coating 106. It will be appreciated that the degree of transparency of the coating 106 can depend on the density of conductive nanomaterial members 104 coated onto the substrate 100.
  • the coating of the substrate 100 with the conductive nanomaterial members 104 can be performed by a process chosen from filtration, electrochemical bonding, chemical vapor deposition, humid deposition, dip coating, spin coating, rod meyer, Langmuir Blodgett, printing process (spray, inkjet, roll to roll, gravure, screen printing).
  • conductive nanomaterial members 104 are synthesized and cleaned.
  • the synthesized nanomaterial members 104 are then dispersed in a suitable carrier solution, such as alcohol, water or other solvent to form a nanomaterial mixture.
  • a suitable carrier solution such as alcohol, water or other solvent
  • the synthesized nanomaterial mixture forms an ink which may be applied onto the substrate 100 using known printing techniques such as inkjet, spray, roll to roll or langmuir.
  • the nanomaterial mixture is filtered over a filtration membrane and the conductive nanomaterial members 104 to form a first porous coating on the surface of the filtration membrane.
  • the first porous coating is then transferred by stamping onto a glass plate.
  • the pressure and temperature of the stamping is appropriately controlled.
  • the glass plate is pre-treated to improve adhesion of the conductive nanomaterial members 104 to the glass plate.
  • a surface of the glass plate is functionalized with silane to improve adhesion.
  • the stamped conductive nanomaterial coating 106 on the glass plate can be further washed and cooked to further improve adhesion.
  • cooking of the coating is carried out by a laser.
  • the coating 106 of conductive nanomaterial members 104 adhered to the substrate 100 is also semi-transparent or substantially transparent, flexible, malleable, elastic or a combination thereof. This is due to the conductive nanomaterial members 104 also being flexible and malleable.
  • the coating 106 and the substrate 100 together form a layer having a transparency greater than 60%. It will be understood that the transparency of the layer may depend on the length of the nanomaterials used.
  • Figure 32 shows transparency over a range of wavelengths of an electrode having silver nanowires and another electrode having silver nanowires coated with platinum. It will be appreciated that transparency was around 80% and 60% respectively over the range of wavelengths.
  • a conductive pattern 112 is formed from the conductive nanomaterial coating 106. For example, portions of the conductive nanomaterial coating 106 are removed and the remaining conductive nanomaterial coating 106 define the conductive pattern.
  • the conductive pattern 1 12 is formed from the conductive nanomaterial coating 106 by lithography.
  • the lithography process further includes etching.
  • the conductive nanomaterial coating 106 (ex: FIG. 2) is covered by a protective layer.
  • the protective layer is a photosensitive layer.
  • the protective layer is formed of polymer resin.
  • the protective layer covers the whole surface of the conductive nanomaterial coating 106.
  • conductive nanomaterial members 104 are synthesized and cleaned.
  • the synthesized nanomaterial members 104 are then dispersed in a suitable carrier solution, such as alcohol, water or other solvent to form a nanomaterial mixture.
  • the synthesized nanomaterial mixture forms an ink, which may be applied onto the substrate 100 using known printing techniques such as inkjet, spray, gravure, screen printing, roll to roll forming the conductive pattern 12.
  • FIG. 3A therein illustrated is a plan view of the exemplary substrate 100 during the exemplary lithography process.
  • At least one sub-region 116 of the protective layer is removed to expose at least one sub-region of the conductive nanomaterial coating 106.
  • the at least one sub-region of the protective layer is removed by exposing it to a suitable light.
  • the exposed portions of the conductive nanomaterial coating 106 correspond to portions of the coating 106 that are to be removed.
  • the unexposed portions of the conductive nanomaterial coating 106 remain covered by the remaining protective layer 18 and correspond to the conductive pattern to be formed. It will be understood that the unremoved portions of the protective layer 118 will have the same shape as the conductive pattern 112 to be formed.
  • the at least one exposed sub-region of the conductive nanomaterial coating 106 is removed.
  • the exposed sub-region can be removed by performing etching of the exposed sub-region. The etching process removes the exposed sub-region of the conductive nanomaterial coating 106 while leaving portions of the coating 106 still covered by the protective layer unaffected.
  • the remainder of the protective layer which corresponds to the unexposed sub-region of the conductive nanomaterial coating 106 is removed.
  • the remainder of the protective layer is removed by exposing it to a suitable light source. It will be appreciated that once the remainder is protective layer is removed, only the previously unexposed sub-region of the conductive nanomaterial coating 106 remains adhered to the substrate 100, which forms the conductive pattern 1 12. Accordingly, the conductive pattern 1 12 is porous and semi-transparent or substantially transparent.
  • FIG. 3B therein illustrated is a plan view of the substrate 100 having formed thereon a conductive pattern 12. As shown, the exposed sub-region of the conductive nanomaterial coating 106 has been removed and only the conductive pattern 1 12 remains on the substrate 100.
  • the conductive pattern 1 12 constitutes a non-functionalized electrode 120.
  • the conductive pattern 1 12 includes a sensing portion 122, a conducting portion 124 and a connecting portion 128.
  • the conducting portion 124 forms an electrical path between the sensing portion 122 and the connecting portion 128.
  • the non-functionalized electrode 120 can be used to sense a property of the environment (ex: gas or liquid) surrounding the electrode.
  • the non- functionalized electrode 120 can take a measurement of the capacitance, resistance, inductance, electrochemical properties or photoelectric properties of the environment.
  • a measurement of oxygen concentration can be obtained.
  • a first and a second non-functionalized electrodes 120 are provided for measuring a property of an environment surrounding the electrodes.
  • the first and second non-functionalized electrodes 120 can be for measuring a property of a solution.
  • the sensing portions 122 of each of the first and second electrodes are placed in the solution and spaced apart from one another.
  • the connecting portions of the first and second electrodes may be connected to two leads of a measuring device, such as voltmeter or ammeter. A voltage potential difference between the sensing portions of the first and second electrodes or a current flowing through the solution can then be measured using the two electrodes.
  • a sub-region of the conductive pattern 1 12 can be functionalized with a functionalizing material.
  • the functionalizing material at the functionalized sub-region of the conductive pattern 1 12 is sensitive to at least one type of analyte.
  • the functionalized sub-region of the conductive pattern 12 produces an electrical signal when in the presence of the at least one type of analyte.
  • the electrical signal can indicate a level of the at least one type of analyte.
  • the electrical signal can further flow from the functionalized sub-region to the connecting portion 128 via the conducting portion 124.
  • the functionalizing material is chosen from oxides, metals, metal ions, metal oxides, polymers, biological molecules and nanomaterials.
  • the functionalizing material can be one or more of enzymes (ex: peroxidase, tyrosinase, cholesterol oxidase, cholesterol esteral, Glucose oxidase, choline oxidase, horseradish peroxidase, glutamate dehydrogenase, fructose dehydrogenase, NADH dehydrogenase, urease, uricase ), molecules (ex: FAD, GoxFAD, Prussian Blue and Its Analogues), DNA, RNA, antigen, conductive polymer (ex: PEDOT, polyaniline, polyindole, polypyrrole, their derivatives, and mixture of thereof), conductive oxide (ex: ZnO, ITO, and derivates), metals (ex : Ag, Pt, Au, Ni, P
  • the conductive pattern 1 12 is covered by a protective layer.
  • the protective layer is a photosensitive layer.
  • the protective layer is formed of polymer resin.
  • the protective layer covers the conductive pattern 1 12 and the substrate 100.
  • At least one sub- region of the protective layer is removed to expose at least one sub-region of the conductive pattern 1 12.
  • the at least one sub-region of the protective layer is removed by exposing it to a suitable light.
  • the exposed sub-region of the conductive pattern 112 corresponds to the portion of the conductive pattern 1 12 that is to be functionalized.
  • the exposed sub-region of the conductive pattern 12 corresponds to the sensing portion 122 of the conductive pattern 1 12.
  • FIG. 4 therein illustrated is a plan view of the substrate 100 and conductive pattern 1 12 during the exemplary functionalizing process after removal of the at least one sub-region of the protective layer.
  • the substrate 100 and conductive pattern 1 12 is covered by protective layer 132 over their entire surface except for sub-region 136 where the protective layer has been removed. Removal of the protection layer at the sub-region 136 exposes the conductive pattern 1 12 underneath. For example, the sensing portion 122 of the conductive pattern 1 12 is exposed.
  • the at least one exposed sub-region 136 of the conductive pattern 1 12 is then functionalized with the material sensitive to the at least one type of analyte.
  • the functionalizing with the sensitive material only causes the exposed sub-regions 136 to be functionalized while regions 132 covered by the protective layer remain non-functionalized.
  • the functionalizing of the exposed sub-region 136 may include at least one of an electrical depositing, chemical reaction, adsorption, oxidation, and radiation. Functionalizing the exposed sub-region 136 forms a functionalized sensing portion 122' of the conductive pattern 1 12.
  • FIG. 5 therein illustrated is a plan view of the exemplary substrate 100 and conductive pattern 1 12 after functionalizing the exposed sub-region 136 prior to removal of the protective layer.
  • the exposed sub-region 136 of FIG. 4 has now been functionalized with the functionalizing material sensitive to the at least one type of analyte.
  • This sub-region now forms the functionalized sensing portion 122' of a functionalized conductive pattern 1 2'.
  • FIG. 6 therein illustrated is a plan view of the exemplary substrate 100 and the functionalized conductive pattern 1 12' after removal of the protective layer.
  • the functionalized conductive pattern 1 12' and the substrate 100 are no longer covered by the protective layer and the functionalized sensing portion 122', conductive portion 124 and connecting portion 128 of the functionalized conductive pattern 112' are exposed.
  • the functionalized conductive pattern 1 12' and the substrate constitute a functionalized electrode 120'.
  • the functionalized electrode 120' can be semi-transparent and flexible.
  • the functionalized electrode 120' can be substantially transparent and flexible
  • portions of the conductive pattern 1 12 or functionalized conductive pattern 1 12' are further coated with an additional protective layer.
  • the additional protective layer serves to protect portions of the conductive pattern 1 12 or functionalized conductive pattern 1 12' from damage and wear and tear.
  • the additional protective layer restricts portions of the conductive pattern 12 or functionalized conductive pattern 12' from contacting an environment being tested.
  • the conductive portion 124 and connecting portion 128 are coated with the additional protective layer so as to prevent contact thereof with the environment being tested.
  • the non-functionalized sensing portion 122 or functionalized sensing portion 122' is left exposed. This causes only the sensing portion 122 or 122' of the conductive pattern 1 12 or functionalized conductive pattern 1 12' to be sensitive to analytes while preventing false readings from being generated by the conductive portion 124 or connecting portion 128.
  • the protective layer can be ZnO, Ti0 2 , silica, PVP, PEDOT, polypyrrole, polyaniline, poliquinone, polythiophene or nafion.
  • the functionalized electrode 120' formed according to the exemplary processes described herein comprises the substrate 100 and the functionalized conductive pattern 1 12'.
  • the functionalized conductive pattern 1 12' comprises the plurality of conductive nanomaterial members 104 that coat a surface of the substrate 100.
  • the functionalized conductive pattern 1 12' defines a sensing portion or sub-region 122', a conducting portion or sub-region 124, and the connecting portion or sub-region 128.
  • a sensing sub-region of the functionalized conductive pattern 1 12' is functionalized with a material sensitive to the at least one type of analyte.
  • the sensing sub-region 122' corresponds to the functionalized sensing portion 122' of the electrode 120.
  • the substrate 100 is flexible and the functionalized electrode 120' is also flexible. This is due to the malleability of the conductive nanomaterial members 104, which offer flexibility while maintaining electrical conductivity.
  • the functionalized conductive pattern 1 12' is resistant to wear from torsion.
  • the printing of the nanomaterial members 104 onto the substrate 100 causes the functionalized electrode 120' to be porous and rough. This further property increases the surface area of the functionalized electrode 120', thereby increasing sensitivity.
  • the porosity of the functionalized conductive pattern 112' allows the functionalized electrode 120' to be semi-transparent or substantially transparent.
  • the electrical signal indicates a level of the at least first type of analyte.
  • the electrical signal flows from the functionalized sub-region 122' via the conducting portion 124 to the connecting portion 128.
  • the connecting portion can be connected to an external measurement device to measure the electrical signal, from which a level of the analyte can be obtained. Since the functionalized conductive pattern 1 12' defines each of the sensing portion 122', conducting portion 124 and the connecting portion 128, these portions of the functionalized electrode 120' can be formed together (i.e. the printing of the conductive nanomaterial members and the removal of the nanomaterial members by lithography), instead of having to be fabricated separately.
  • At least two electrodes can be fabricated onto a single substrate to form a multi-electrode detector.
  • exemplary processes for fabricating one electrode described herein can be repeated on the substrate 100 to fabricate electrodes in addition to the first electrode that is fabricated.
  • a second electrode fabricated according to various exemplary processes described herein can be functionalized with the same functionalizing material as the first electrode.
  • the second electrode can be functionalized with a second functionalizing material that is different from the functionalizing material of the first electrode to be sensitive to a second type of analyte.
  • one of the first electrode and second electrode is a working electrode and the other of the first and second electrode is a counter electrode.
  • a third electrode fabricated according to various exemplary processes described herein is non-functionalized and acts as reference.
  • the conductive pattern 12 formed on the substrate 100 from the conductive nanomaterial coating 106 includes portions of at least two electrodes to be formed.
  • the lithography process for removal of portions of the conductive nanomaterial coating 106 sub-regions of protective layer are removed so that the unexposed portions of the conductive nanomaterial coating 106 correspond to portions of the at least two electrodes to be formed.
  • FIG. 7A therein illustrated is a plan view of a substrate 100 during the exemplary lithography process.
  • portions of the substrate 100 that are coated with conductive nanomaterial 104 are shown in solid coloring.
  • the sub-region 1 16 represent the at least one sub-region of the protective layer that is removed and the sub-region of the coating 106 that is to be removed in order to form a conductive pattern.
  • the unexposed portions of the conductive nanomaterial coating 106 remain covered by the remaining protective layer 1 18 and correspond to the conductive pattern to be formed. It will be understood that the un-removed portions of the protective layer 18 will have the same shape as the conductive pattern to be formed.
  • FIG. 7B therein illustrated is a plan view of the exemplary substrate 100 having formed thereon on a conductive pattern 133.
  • the conductive pattern 133 shown in FIG. 7B defines portions of a first electrode 134, a second electrode 136, and a third electrode 140.
  • the conductive pattern 1 12 can define at least two electrodes according to various exemplary embodiments.
  • none of the plurality of electrodes defined by the conductive pattern 133 are functionalized.
  • the conductive pattern 133 and the substrate 100 form a non-functionalized multi-electrode detector 141.
  • the multi-electrode detector can be porous, semi-transparent and flexible.
  • the multi-electrode detector can be porous, substantially transparent and flexible
  • the first electrode 134 defined by the conductive pattern 133 includes a sensing portion 142, a conducting portion 143 and a connecting portion 144.
  • the second electrode 136 defined by the conductive pattern 133 includes a sensing portion 145, a conducting portion 148 and a connecting portion 52.
  • the third electrode 140 defined by the conductive pattern 133 includes a sensing portion 156, a conducting portion 160 and a connection portion 164.
  • the sensing portion 142 of the first electrode 134 extends along a path to substantially contour the sensing portion 145 of the second electrode 136.
  • the multi-electrode detector 141 having non-functionalized electrodes can be used to measure a property of the environment.
  • the multi-electrode detector is 141 placed in an environment to be measured.
  • the connecting portion 144 of the first electrode 134 and the connecting portion 152 of the second electrodes 136 may be connected to two leads of a measuring device, such as voltmeter or ammeter.
  • a voltage potential difference between the sensing portions of the first and second electrodes 134, 136 or a current following through the environment can then be measured using the multi-electrode detector 141.
  • the detector 141 can further measure current, voltage, resistivity, capacitance, conductivity and oxygen concentration.
  • At least one sub-region of the conductive pattern 33 is functionalized with a material sensitive to at least a first type of analyte.
  • the at least one sub- region is functionalized according to various exemplary processes described herein for fabricating one electrode.
  • the sensing portion of a first electrode defined by the conductive pattern 133 is functionalized while the sensing portion of a second electrode defined by the conductive pattern 1 12 is non-functionalized. Accordingly, the first electrode forms a working electrode while the second electrode forms a reference electrode.
  • the sensing portions of at least two electrodes defined by the conductive pattern 133 are functionalized within a single functionalizing step. Accordingly, the conductive pattern 133 is covered by a protective layer.
  • the protective layer is a photosensitive layer.
  • the protective layer is formed of polymer resin.
  • the protective layer covers the conductive pattern 133 and the substrate 100. A first sub-region of the protective layer is removed to expose a sub-region of a first electrode defined by the conductive pattern 133. A second sub-region of the protective layer is removed to expose a sub-region of a second electrode defined by the conductive pattern 133. For example, the sensing portions of the first and second electrodes are exposed.
  • the exposed sub-region of the first electrode and the exposed sub-region of the second electrode are then functionalized with the material sensitive to at least one type of analyte.
  • the functionalizing of the exposed sub-regions may include at least one of an electrical depositing, chemical reaction, adsorption, oxidation, and radiation. Consequently, both the first and second electrodes defined by the conductive pattern 133 will have functionalized portions that are sensitive to the at least one type of analyte.
  • the protective layer can be removed.
  • the sensing portions of at least two electrodes defined by the conductive pattern 133 are functionalized in more than one functionalizing steps. Accordingly, to functionalize a first electrode the conductive pattern 133 is covered by a first protective layer.
  • the protective layer is a photosensitive layer.
  • the protective layer is formed of polymer resin.
  • the protective layer covers the conductive pattern 133 and the substrate 100. A first sub-region of the protective layer is removed to expose a sub-region of a first electrode defined by the conductive pattern 133.
  • FIG. 8 therein illustrated is a plan view of the exemplary multi-electrode detector 141 during functionalization of the first electrode 134.
  • a sub-region of the protective layer corresponding to the sensing portion 142 of the first electrode 134 is removed to expose the sensing portion 142.
  • the exposed sub-region of the first electrode 134 is then functionalized with a first functionalizing material sensitive to at least a first type of analyte.
  • FIG. 9 therein illustrated is a plan view of the multi- electrode detector 141 following functionalization of the first electrode.
  • sensing portion 142 of the first electrode 134 has been functionalized by the first functionalizing material to become a functionalized sensing portion 142' and to form a functionalized first electrode 134'.
  • the protective layer can be removed.
  • FIG. 10 therein illustrated is a plan view of the multi- electrode detector 141 after functionalization of the first electrode 134. It will be appreciated that at this stage, only one of the electrodes defined by the conductive pattern 1 12 has been functionalized and second electrode 136 and third electrode 140 remain non-functionalized.
  • the conductive pattern 133 is covered by a second protective layer.
  • the protective layer is a photosensitive layer.
  • the protective layer is formed of polymer resin.
  • the protective layer covers the conductive pattern 133 and the substrate 100. A second sub-region of the protective layer is removed to expose a sub-region of a second electrode defined by the conductive pattern 133.
  • FIG. 1 1 therein illustrated is a plan view of the exemplary multi-electrode detector 141 prior to functionalization of the second electrode.
  • a sub-region of the protective layer corresponding to the sensing portion 145 of the second electrode 136 is removed to expose the sensing portion 145.
  • the exposed sub-region of the second electrode 136 is then functionalized with a second functionalizing material sensitive to at least a second type of analyte.
  • FIG. 12 therein illustrated is a plan view of the exemplary multi-electrode detector following functionalization of the second electrode 136.
  • sensing portion 145 of the second electrode 140 has been functionalized by the second functionalizing material to form a functionalized sensing portion 145'.
  • the protective layer can be removed.
  • the first functionalizing material of the first electrode 134 and the second functionalizing material of the second electrode 136 are the same and are sensitive to the same type of analyte.
  • the first functionalizing material and the second functionalizing material can be different and can be sensitive to different types of analytes.
  • FIG. 13 therein illustrated is a plan view of the exemplary multi-electrode detector 141 after functionalizing of the second electrode 136.
  • the first electrode 134 and the second electrode 136 defined by the conductive pattern 133 have both been functionalized.
  • the third electrode 140 remains non-functionalized.
  • the first, second and third electrodes 134, 136, 140 can be coated with an additional protective layer.
  • the additional protective layer serves to protect portions of the electrodes 134, 136, 140 from damage and wear and tear. Furthermore, the additional protective layer restricts portions of the electrodes from contacting a solution being tested.
  • one of the first electrode 134 and the second electrode 136 is a working electrode and the other of the first electrode 134 and the second electrode 136 is a counter electrode.
  • the non-functionalized third electrode 140 acts as a reference electrode.
  • the multi-electrode detector 141 can be porous, semi- transparent and flexible.
  • the multi-electrode detector 141 can be porous, substantially transparent and flexible
  • the third electrode 140 is also functionalized with a functionalizing material.
  • the functionalizing of the third electrode 140 can be carried out in a similar manner as the first electrode 134 or second electrode 136 as described herein.
  • the multi- electrode detector 141 includes the first electrode 134, which may be a working electrode, the second electrode 136, which may be a counter electrode, and a third electrode 140, which may be a reference electrode. Each of the electrodes are formed a plurality of conductive nanomaterial members 104 defining a plurality of pores 108.
  • the multi-electrode detector 141 further includes a substrate 100.
  • a conductive pattern 133 comprising the plurality of conductive nanomaterial members 104 coats a surface of the substrate and defines the first electrode 134, second electrode 136 and third electrode 140.
  • the conductive pattern 133 defines a functionalized sensing portion 142', conducting portion 124 and connecting portion 128 of the first electrode 136.
  • the conductive pattern 133 further defines a functionalized sensing portion 145', conducting portion 148 and connecting portion 152 of the second electrode 136.
  • the conductive pattern 133 further defines a functionalized sensing portion 156', connecting portion 160 and connecting portion 164 of the third electrode 140.
  • the sensing portion 142' of the first electrode 134 has an area of 4 mm 2
  • the sensing portion 145' of the second electrode 136 has an area of 10mm 2
  • the sensing portion 56 of the third electrode 140 has of 1 .6mm 2 .
  • a first sensing sub-region of the conductive pattern 133 is functionalized with a first material sensitive to at least a first type of analyte.
  • the first sensing sub-region corresponds to the sensing portion 142' of the first electrode 34.
  • a second sensing sub-region of the conductive pattern 133 is functionalized with a second material sensitive to the at least second type of analyte.
  • the second sensing sub-region corresponds to the sensing portion 145' of the second electrode 136.
  • a third sensing sub-region of the conductive pattern 133 corresponding to the sensing portion 156 of the third electrode 140 is non-functionalized (FIG. 13).
  • the third sensing sub-region of the conductive pattern 133 is functionalized with a third material sensitive to at least a third type of analyte and forms a third sensing portion 156'.
  • the first functionalizing material and the second functionalizing material can be the same.
  • the first functionalizing material and the second functionalizing material are sensitive to different types of analytes.
  • the conducting portion 143 of the first electrode 134 provides an electrical path between the sensing portion 142' and the connecting portion 144 of the first electrode 134.
  • the conducting portion 148 of the second electrode 136 provides an electrical path between the functionalized sensing portion 145' and the connecting portion 152 of the second electrode 136.
  • the conducting portion 160 of the third electrode 140 provides an electrical path between the functionalized sensing portion 156' and the connecting portion 164 of the third electrode 140.
  • the connecting portions 144, 152, 164 act as leads of the electrodes 134, 136, and 140.
  • one or more of a voltage source, current source, voltmeter or ammeter can be connected to the connecting portions 144, 152, 164 of the first, second, and third electrode 134, 136, 140 respectively for measuring a property of a solution according to known configurations.
  • first electrode 134 is illustrated for example purposes in the figures as extending about the perimeter of a rectangle.
  • second electrode 136 is illustrated for example purposes as having a rectangular shape, whereby the first electrode 134 extends to partially surround the second electrode 136.
  • the third electrode 140 is illustrated for example purposes as being offset from the first electrode 134 and the second electrode 136.
  • first electrode 134, second electrode 136 and the third electrode 140 may have various other shapes and arrangements while maintaining detecting properties described herein.
  • at least one of the electrode may be substantially circular while at least one of the other electrodes defines an arc that surrounds the substantially circular electrode.
  • an intermediate conductive pattern formed on the substrate 100 from the conductive nanomaterial coating 106 includes a contiguous region from which the sensing portions of at least two electrodes can be formed.
  • the sub-regions of protective layer are removed so that the unexposed portions of the conductive nanomaterial coating 106 correspond to portions of the at least two electrodes to be formed and includes the contiguous region.
  • FIG. 15A therein illustrated is a plan view of an exemplary substrate 100 during the exemplary lithography process.
  • the shaded sub- region 1 16 represent the at least one sub-region of the protective layer that is removed and the sub-region of the coating 106 that is to be removed in order to form the conductive pattern 1 12.
  • the unexposed portions of the conductive nanomaterial coating 106 remain covered by the remaining protective layer 1 18 and correspond to the intermediate conductive pattern to be formed. It will be understood that the unremoved portions of the protective layer 1 8 will have the same shape as the conductive pattern 1 12 to be formed.
  • FIG. 15B therein illustrated is a plan view of the exemplary substrate 100 having formed thereon an intermediate conductive pattern 170 that includes the contiguous region 168. As shown in FIG. 15B, sub-regions of the 00748
  • conductive nanomaterial coating 106 are removed so as to form the intermediate conductive pattern 170 defining the contiguous region 168, conducting portion 143 and connecting portion 1 4 of a first electrode 34 to be formed, conducting portion 148 and connecting portion 152 of a second electrode 136, and sensing portion 156, conducting portion 160 and connecting portion 164 of a third electrode to be formed.
  • the sensing portion of the first electrode 134 and the sensing portion of the second electrode 136 are to be formed from the contiguous portion 168.
  • the sensing portion 156 of the third electrode 140 is not electrically connected to the contiguous region 168.
  • the contiguous region 168 is functionalized with a material sensitive to at least a first type of analyte.
  • the at least one contiguous region 168 is functionalized according to various exemplary processes described herein for fabricating one electrode.
  • the intermediate conductive pattern 170 is covered by a protective layer.
  • the protective layer is a photosensitive layer.
  • the protective layer is formed of polymer resin.
  • the protective layer covers the intermediate conductive pattern 170 and the substrate 100. A sub-region of the protective layer is removed to expose the contiguous region 168 of the conductive pattern.
  • the exposed contiguous region 168 is then functionalized with the material sensitive to the at least one type of analyte.
  • the functionalizing of the exposed sub-regions may include at least one of an electrical depositing, chemical reaction, adsorption, oxidation, and radiation. Consequently, the surface of the contiguous region 168 is functionalized to form a functionalized contiguous region 168'.
  • FIG. 16 therein illustrated is a plan view of the substrate 100 and intermediate conductive pattern 170 following functionalization of the contiguous region 168. As shown in FIG. 16, the contiguous region 168' has been functionalized. After functionalizing the exposed contiguous region 168', the protective layer can be removed.
  • FIG. 7 therein illustrated is a plan view of the exemplary multi-electrode detector 141 after functionalization of the contiguous region 168' and removal of the protective layer. It will be appreciated that both the conducting portion 143 of the first electrode 134 to be formed and the conducting portion 148 of the second electrode 136 to be formed are connected to the functionalized contiguous region 168'. 0748
  • an insulating region separating the functionalized contiguous region 168' into non-contiguous first and second portions is formed. That is, the first portion and the second portion of the separated contiguous region 168 are not electrically connected with one another due to the forming of the insulating region.
  • the first portion of the functionalized contiguous region 168' corresponds to the sensing portion 142 of the first electrode 134 to be formed and the second portion of the functionalized contiguous region 168' corresponds to the sensing portion 144 of the second electrode 136 to be formed.
  • the insulating region is formed by lithography.
  • FIG. 18 therein illustrated is a plan view of the exemplary substrate 100 in an intermediate state while forming the insulating region.
  • the protective layer is a photosensitive layer.
  • the protective layer is formed of polymer resin.
  • a sub-region of the protective layer 1 16 corresponding to the insulating region to be formed is removed to expose a sub-region 172 of the functionalized contiguous region 168'.
  • the exposed sub-region 172 of the contiguous region 168' is then removed to form the insulating region.
  • the exposed sub-region 172 can be removed by performing etching.
  • the etching process removes the exposed sub-region of the functionalized contiguous region 168' while leaving portions of the coating 106 still covered by the protective layer unaffected. The remainder of the protective layer is the removed.
  • FIG. 19 therein illustrated is a plan view of the exemplary multi-electrode detector following forming of the insulating region.
  • the functionalized contiguous region 168' has been separated into a first portion forming a functionalized sensing portion 142' of the first electrode and into a second portion forming a functionalized sensing portion 145' of the second electrode 140.
  • the first and second portions of the functionalized contiguous region 168' are separated by the insulating region 174 which forms a gap between the two portions. For example, removal by etching of the portions of the conductive pattern to form the insulating region 174 causes the first and second portions 142', 145' to no longer be electrically connected.
  • the electrodes are further coated with an additional protective layer.
  • the additional protective layer serves to protect portions of the electrodes from damage and wear and tear. Furthermore, the additional protective layer restricts portions of the electrodes from contacting an environment being tested. For example, the conductive portions and connecting portions of the electrodes are coated with the additional protective layer so as to prevent contact thereof with the solution being tested. Meanwhile, the sensing portions are left exposed. This causes only the sensing portions of the electrodes to be sensitive to analytes while preventing false readings from being generated by the conductive portions or connecting portions. For example, and as illustrated in FIG. 19, portions of the multi-electrode detector have been coated by a protective layer 101. In particular, conducting portions of the first, second and third electrodes have been coated by the protective layer.
  • a plurality of multi-electrode detectors 141 can be formed with a single fabrication process.
  • a substrate 100 having a planar surface area sufficient for accommodating a plurality of detectors 141 is first provided.
  • the substrate 100 is then coated with conductive nanomaterial members 104 to form a conductive nanomaterial coating 106 according to various exemplary processes described herein.
  • a plurality of conductive patterns can then be formed from the conductive nanomaterial coating 106 through removal appropriate sub- regions of the coating 106 according to various exemplary processes described herein.
  • the plurality of conductive patterns can be formed through lithography and etching. Sub-regions of each of the plurality of conductive patterns can then be functionalized according to various exemplary processes described herein.
  • FIG. 20 therein illustrated is a plan view of exemplary three multi-electrode detectors 141a, 141 b, and 141c having been fabricated on a single substrate 100.
  • the substrate 100 can then be appropriately cut to separate the three multi-electrode detectors 141 a, 141 b and 141c.
  • FIG. 21 A therein illustrated is an elevated section view of an exemplary two-electrode detector 141 being applied for measurements of analytes in a fluid.
  • the two electrode detector 141 includes a conductive pattern covering a porous substrate 100.
  • the conductive pattern defines a sensing portion 142, a conducting 2014/000748
  • the detector 141 is generally supported within walls 200 defining a fluidic channel 204.
  • the detector 141 is oriented transversely to a direction of flow of fluid through the channel 204.
  • the direction of the flow of fluid is denoted by arrow 208.
  • the particular analytes 212 having sizes larger than the pores of the substrate or the pores 108 defined by the conductive nanomaterial members 104 will be collected the porous detector 141 .
  • the bunching of the particular analytes 212 forms a path between the sensing portion 142 of the first electrode 134 and the sensing portion 145 of the second electrode 136.
  • the path is an electrically conductive path.
  • FIG. 21 B therein illustrated is an elevated section view of an exemplary alternative two-electrode detector 141 being applied for measurements of analytes in a fluid.
  • FIG. 22 therein illustrated is a side elevation view of an exemplary two-electrode detector 141 being applied for opto-electronic measurement.
  • the opto-electronic measurement can obtain both optical measurements (ex: fluorescence, absorbance) and electronic measurements (ex: conductivity, electromchemical properties, capacitance, etc.).
  • the two electrode detector 141 is positioned between a light source 216 and a light sensor 220.
  • the two-electrode detector 141 is aligned with the light source 216 and the light sensor 220.
  • the two-electrode detector 141 is positioned transverse or generally perpendicular to the light emitted from the light source 216.
  • Incident light 222 emitted from the light source 216 reaches the detector 141 and a portion of the incident light 222 passes through the at least partially transparent detector 141 as transmitted light 224.
  • analytes 212 collected at the porous detector 141 becomes excited and exhibits fluorescence.
  • the fluorescent light transmitted to the light sensor 220 as transmitted light 224 can be measured to obtain a first measurement of a property of the analytes.
  • properties of the path formed by the excited analytes 212 can be measured. For example, capacitance, resistance, inductance, or electrochemical properties of the excited analytes 212 can be measured to obtain a second measurement of the property of the analytes 212.
  • Electrical contacts 176 and 180 of the first and second electrodes 134 and 136 can be connected to a measurement device 226.
  • the detector 141 may be placed within an apparatus allowing for optical and electrical measurements.
  • FIG. 23 therein illustrated is a section view of some exemplary embodiments of a measurement apparatus 300.
  • the apparatus 300 includes a chip 304 defining at least one microfluidic channels 306.
  • the microfluidic channels 306 are hollow and can extend a portion of the length of the chip 304.
  • the chip 304 can be a microelectromechanical systems (MEMS) formed of polydimenthylsiloxane material.
  • the chip 304 can also be formed of epoxy resin, such as SU8 - Microchem type, glass, or other suitable materials that allows forming of channels 306.
  • the microfluidic channels can be fabricated using standard soft lithography techniques. However other known techniques for forming suitable microfluidic channels 306 are hereby contemplated, and such techniques are intended to be covered by the present description.
  • the microfluidic channels 306 can be fabricated to have a depth in the micrometer range, up to 1 mm.
  • the chip 304 can be fabricated on a glass slide having a thickness in the millimeter range, which provides mechanical strength.
  • each microfluidic channel 306 can further define one or more microfluidic chambers 308a, 308b, 308c, and 308d.
  • the microfluidic chamber 308 can be a cavity within the microfluidic channel 308 having a greater cross-sectional area than other portions of the microfluidic channel 306.
  • Analytes 212 are received within the at least one microfluidic channels 306 of the chip 304.
  • the analytes 212 are microorganism or biological material.
  • the microorganism or biological material 212 can comprise at least one type of photosynthetic microorganism that undergoes photosynthesis when exposed to light in certain spectral ranges.
  • a water sample of water for which the pollution level is to be determined can also be received in the at least one microfluidic channels 306.
  • the water sample can be water polluted with chemical pollutant, organic or inorganic, like herbicides or other toxic substances.
  • the water sample can be collected from water drained from farmlands.
  • the microorganism or biological material 212 and the water sample received in the microfluidic channel 306 can be mixed in the microfluidic channel 306 to form a composition.
  • the microorganism or biological material 212 and the water sample can be mixed previously, before being introduced in the channel. Properties of the composition comprising the microorganism or biological material 212 and the water sample in each of the microfluidic channels 306 can then be determined.
  • Each microfluidic channels 306 can further define a first opening 310 at a first end of the microfluidic channel 306 and a second opening 312 at a second end of the microfluidic channel 306.
  • microfluidic chamber 308 of each microfluidic channels 306 are in fluid communication with outside space through both the first opening 310 and the second opening 312.
  • the microorganism or biological material 212 can be first inserted, or pre-inserted during fabrication of the chip, into the microfluidic channel 306.
  • the chip 304 can then be submerged into a volume of water for which the level of pollution is to be determined.
  • the chip 304 is submerged such that at least one of the first opening 3 0 or second opening 312 is in communication with the volume of water.
  • a sample of the volume of water then enters either the first opening 310 or second opening 312, or both, to be received in the microfluidic channel 306.
  • apparatus 300 comprise the least one light source 216.
  • the light source 216 can be supported by a substrate
  • the light source 216 can be horizontally arranged, for example within a same plane defined by the illuminating layer
  • the at least one light source 216 can be at least one organic light emitting diodes (OLEDs).
  • OLEDs organic light emitting diodes
  • Organic light emitting diodes can have a miniature size, thereby allowing the illuminating layer to have a very thin profile.
  • it is 2014/000748
  • the chip 304 can include microlenses to focus the emission light from the light source 216.
  • microlenses can be included into the light layer 332 or into the light filtering layer 336.
  • light emitted by the light source 216 can have specific spectral properties.
  • the light emitted by the light source 216 can cause certain reactions to the microorganism or biological material received within the microfluidic channel 306 and/or microfluidic chamber 308.
  • the microorganism or biological material 212 comprises at least one type of photosynthetic microorganism
  • exposing the at least one type of photosynthetic microorganism to the light emitted from light source 216 causes it to absorb the light and undergo photosynthesis.
  • Absorption of light by the at least one type of photosynthetic microorganism is due to its chlorophylls and its pigments (for example carotenoids, phycocyanins and phycoerythrins). Absorbed photons are used to perform photosynthesis. Any excess energy not used for photosynthesis is reemitted as heat or fluorescent light.
  • Exciting the photosynthetic microorganisms.
  • Light emitted from the light source 216 for exciting the at least one type of photosynthetic microorganism will herein be referred to as “excitation” light.
  • excitation light emitted from the light source 216 includes emitted photons having wavelengths in a spectral range corresponding to the spectral range wherein the received photosynthetic microorganisms are excited.
  • At least one first optical filter which can form a filtering sublayer of the illuminating layer 332 and is positioned between the substrate 331 supporting the light source 216 and the chip 304 to filter light emitted from the light source 216. Accordingly the light emitted by the at least one light source 216 having known spectral properties are filtered by the optical filter such that excitation light emitted from the top surface of the illuminating layer 332 has specific spectral properties for causing reaction in the microorganism or biological material 212.
  • the optical filters can exhibit limited auto-fluorescence, high transmittance at the desired spectral range, high attenuation in the unwanted spectral range, and is inexpensive to fabricate.
  • optical filter can be fabricated as a dye-doped resin.
  • the optical filter can be dichroic, absorbing, or polarizing.
  • the at least one light source 216 can be selected or configured to directly produce light having specific spectral properties for causing the microorganism or biological material 212 to be excited.
  • excitation light having specific spectral properties for exciting the microorganism or biological material 212 can be emitted by appropriately selecting the organic emissive layers of the OLED.
  • excitation light having specific spectral properties for exciting the photosynthetic microorganisms can be emitted by varying the intensities of differently colored OLED an array of OLED and/or different emission wavelength OLED. It will be appreciated that where the at least one light source 216 directly produces excitation light having desired specific spectral properties, it can be not necessary to have at least one optical filter within the illuminating layer 332.
  • a single light source 216 can be used to emit light to the microfluidic channels, and microfluidic chambers, of the chip 304.
  • the chip 304 and the at least one light source 216 can be positioned such that at least some of the at least one microfluidic chamber 308 is substantially aligned with at least one of the light source 216 in a direction transverse to the plane defined by the chip 304.
  • at least one microfluidic chamber 308 can be aligned with the at least one light source 216 in a direction orthogonal to the plane defined by the chip 304.
  • the substrate of chip 304 can be semi-transparent or substantially transparent at the locations of some of the microfluidic chambers 308. This restricts each microfluidic chamber 308 from being exposed to excitation light from a non-aligned light source 216.
  • chip 304 can be formed to be semi- transparent or substantially transparent to allow light emitted upwardly from the microfluidic channels 306 and/or microfluidic chambers 308 to reach other layers disposed above the chip 304.
  • chip 304 can be formed to be substantially opaque in an upper and in a lower portion of the chip 304 except for the at least one transparent gap.
  • chip 304 can comprise a substantially opaque sub-layer defining the at least one transparent gaps.
  • Light emitted from a the microfluidic chambers 308 after having have been exposed to excitation light emitted from the illuminating layer 332 can have varying spectral properties that can depend on the properties of the microorganism or biological material and/or water received in the microfluidic chamber 308.
  • the chip 304 can be fabricated to be semi-transparent or substantially transparent at top surface only at the locations of each of microfluidic chambers.
  • the apparatus 302 can comprise at least one second optical filter 340, which can form a filtering layer.
  • the filtering layer can be supported by the chip 304.
  • the at least one second optical filter 340 can have a longpass or a passband corresponding to the spectral range of fluorescent light emitted by the excited photosynthetic microorganisms received in the chip 304.
  • light emitted from the chip 304 can comprise a mixture of excitation light emitted from the at least one light source 216 not absorbed by the photosynthetic microorganisms and fluorescent light emitted from the plurality of photosynthetic microorganisms received in the chip 304.
  • light in the fluorescent light spectral range is transmitted while light outside this spectral range, for example excitation light from the illuminating layer 332 not absorbed, is attenuated.
  • the optical filter 340 exhibits limited auto-fluorescence, high transmittance at the desired spectral range, high attenuation in the unwanted spectral range, and is inexpensive to fabricate.
  • the optical filter can be fabricated as a dye-doped resin.
  • the optical filters 340 can be dichroic, absorbing, or polarizing.
  • the apparatus 300 can comprise the at least one light sensor or photodetector 220.
  • the at least one photodetector 220 can be any type of detector that determines the intensity of photons in light emitted from the chip 304 and being filtered by optical filters 340 where such optical filters 340 are used.
  • the at least one photodetector 220 can be supported on a semi-transparent or substantially transparent substrate 350.
  • the at least one photodetector 220 can be organic photodetector.
  • the organic photoddetector can be fabricated using semiconducting polymers with alternating thieno[-3,4-b]-thiophene and benzodithiophene or with phtalocyanin organic material and other semi-conducting material that absorbs at the desired wavelength.
  • the at least one photodetector 220 can be inorganic, such as being formed of silicon.
  • the at least one photodetector 220 can detect an intensity level of photons received by the at least one photodetector 220 and return an amplitude value, such as voltage or power value.
  • the at least one photodetector 220 can be an image sensor, such as a CCD or CMOS, sensor that returns electronic signal for the light sensed.
  • the electronic signal can be a frequency response of the detected light.
  • the at least one photodetector 220 can be any light detector that can detect properties of light emitted from the chip 304 that are in a spectral range corresponding to the spectral range of fluorescent light emitted by the excited photosynthetic microorganisms in the microfluidic channels.
  • the at least one photodetectors 220 can be optimized for detecting light in this spectral range.
  • the at least one photodetector 220 can be positioned to be substantially aligned with at least one one of the microfluidic chambers 308.
  • the at least one photodetector 220 can be aligned with the at least one microfluidic chamber 308 in a direction transverse to the planed defined by the chip 304.
  • the at least one photodetector 220, the at least one microfluidic chamber 308 and the at least one light source 216 can be aligned in a direction orthogonal to the plane defined by the chip 304.
  • the at least one light source 216 is not necessarily aligned with the at least one microfluidic chamber 308 and the at least one light source 216 can emit light into more than one microfluidic chamber 308.
  • the at least one light source 216 is an OLED, which has a very high index of refraction and wide angle of emission.
  • the at least one light source 216 can be aligned with the photodetector 220 and the microfluidic chamber 308 that are already aligned together.
  • more than one light source 216 can be aligned with one photodetector 220 and one microfluidic chamber 308 that are already aligned together. Furthermore, each of the light sources 216 that are aligned can emit light in a different spectral range.
  • the multi-electrode detector 141 is positioned within the microfluidic chamber 308 to receive maximum exposure to light from the at least one light source 216.
  • the detector 141 can also be positioned such that the detector 141 of at least one of microfluidic chamber 308 can be substantially aligned with the at least one light source 216 in a direction transverse to the plane defined by the chip 304.
  • the at least one microfluidic chamber 308 can be aligned with the at least one light source 216 in a direction orthogonal to the plane defined by the chip 304.
  • the at least one photodetector 220 can be positioned to be further substantially aligned with the multi-electrode detector 141 of the at least one microfluidic chamber 308.
  • Photons in the emitted excitation light are absorbed by the microorganism or biological material 212 accumulated at the electrical detector 141 of the microfluidic chamber 308, causing the microorganism or biological material 212 to react.
  • the microorganism or biological material 212 is the at least one photosynthetic microorganism, photons within a specific spectral range will cause the microorganism or biological material 212 to be excited.
  • the multi-electrode detector 141 can be positioned to be parallel to the chip plane and transverse the direction of the light emitted from the at least one light source 216.
  • the multi-electrode detector 141 is positioned horizontally within the microfluidic chamber 308 and in parallel with the chip plane.
  • the multi-electrode detector 141 substantially restricts the flow of microorganism or biological material 212 such that the microorganism or biological material 2 2 is collected at the multi-electrode detector 141 according to this positioning, a large quantity of the members of the microorganism or biological material 212 are exposed to the light from the at least one light source 216.
  • the photons travel to the aligned microfluidic chamber 308 of the microfluidic channel 306 to expose the microorganism or biological material 212 received therein.
  • the multi-electrode detector 141 is positioned in the at least one microfluidic chamber 308 in alignment with the at least one microfluidic chamber 308 and the at least one light source 216. As the members defining the at least one microorganism or biological material 212 are collected at the multi-electrode detector 141 , the members defining the microorganism or biological material 212 are also exposed to the light from the at least one light source 216.
  • the multi-electrode detector 141 When the multi-electrode detector 141 is semi-transparent or substantially transparent, light from the at least one light source 216 passes through the multi-electrode detector 141 towards the at least one photodetector 220. Additionally, fluorescent light emitted from the members defining the microorganism or biological material 212 as they are excited also passes through the multi-electrode detector 141 towards the at least one photodetector 220.
  • the at least one photodetector 220 being further aligned with the at least one microfluidic chamber 308 and the at least one light source 216 detects intensity of light from the microfluidic chamber 308. In particular, it detects intensity of light in the spectral range corresponding to the fluorescent light emitted by the microorganism or biological material 212.
  • alignment of one photodetector, one microfluidic chamber and one light source in a direction transverse the chip plane in conjunction with placement of electrodes connected to the electric detector advantageously allows a plurality of measurements of properties to be taken of the composition in the same microfluidic chamber 308.
  • the level of fluorescent light that is emitted from the at least one microfluidic chamber 308 that is detected by the aligned at least one photodetector 220 allows for a determination of the amount, for example a concentration, of microorganisms in the composition. This provides a first indication of the pollution level of the water sample in the composition.
  • the microfluidic channel 306 comprises microfluidic chambers 308a, 308b, 308c and 308d.
  • Each microfluidic chamber can further have a multi-electrode detector 141.
  • microfluidic chambers 308a, 308b, 308c and 308d respectively have multi-electrode detector 141 a, 141 b, 141 c and 141 d.
  • the porous openings of the multi-electrode detector 141 a, 141 b, 141 c and 141d can become progressively smaller in the direction from first opening 310 towards second opening 312. It will be appreciated that the multi-electrode detector 141 a will only restrict flow of members of the at least one microorganism or biological material 212, with smaller members of microorganism or biological material 212 passing through the multi-electrode detector 141 a. As a result, the members of the at least one microorganism or biological material 212 found in each of microfluidic chambers 308a, 308b, 308c and 308d will have different sizes.
  • the multi-electrode detector 141 is positioned such that the plane defined by the co- planar first electrode 134, second electrode 136, and third electrode 140 are substantially parallel with the plane of the chip 304.
  • the first electrode 134 which may be a working electrode, of the multi-electrode detector 141 is positioned within the microfluidic chamber 308 to be substantially aligned with at least one of the light sources 216 in a direction transverse to the plane defined by the chip 304.
  • at least the first electrode 134 can be aligned with the at least one light source 216 in a direction orthogonal to the plane defined by the chip 304. Alignment of the first electrode 134 with the light source 216 positions the electrode 134 with a location where the microorganism or biological material will most likely undergo photoactivity.
  • at least the working electrode 134 is positioned proximate the filter where microorganisms or biological material received in the microfluidic chamber are entrapped.
  • the second electrode 136 which may be a counter electrode
  • the reference electrode 140 which may be a reference electrode
  • the second electrode 136 and the third electrode 140 are positioned within the microfluidic chamber 308 to be substantially aligned with at least one of the light source 216 in a direction transverse to the plane defined by the chip 304.
  • the second electrode 136 and the third electrode 140 can be aligned with the at least one light source 216 in a direction orthogonal to the plane defined by the chip 304.
  • Alignment of the second electrode 136 and the third electrode 140 with the light source 216 positions the electrodes 136 and 140 with a location where the microorganism or biological material will most likely undergo photoactivity.
  • at least the second electrode 136 and the third electrode 140 is positioned proximate the filter where microorganisms or biological material received in the microfluidic chamber are entrapped.
  • the electrodes described herein and fabricated according to various exemplary processes herein can be used for biomedical sensing.
  • the electrodes described herein can be used to detect the presence of microorganism or biological material.
  • biological material includes cells, such as algae, human cells, bacteria, DNA.
  • the electrodes described herein are used for taking both an electrical measurement as well as a spectral measurement. It has been found that platinum as a functionalization material increases electrical and chemical efficiency as well as chemical stability within an environment containing algae.
  • the biological material may also include muscle tissue or in vitro living cells.
  • the electrodes described herein and fabricated according to various exemplary processes herein can be used for measuring the presence or concentration of various gases.
  • the measurement of gases can be used to obtain an indication of the freshness of food produce.
  • the freshness measurement can be taken while the food produce is still in its packaging.
  • a multi-electrode detector 141 having electrodes functionalized to be sensitive to different types of analytes can be used.
  • the plurality of electrodes can be sensitive to oxygen, carbon dioxide, other gases, enzymes, or other oxidation indicators.
  • the semi-transparent characteristic of the electrodes improves aesthetics of the detector fabricated therefrom and placed in the food wrapping.
  • the electrodes described herein and fabricated according to various exemplary processes herein can be used for measurement of properties of a surface, such as skin or eyes.
  • the measurement can be an oxygen concentration on the surface.
  • these measurements can be used in cellulose patches.
  • an eye patch applied to an eye requires the patch to be transparent, which is provided by the electrodes described herein.
  • the electrode may also be used in contact lenses.
  • the electrode may also be embedded in a muscle. The porosity of the electrode provides respiration of the skin, eye or muscle.
  • the electrodes described herein and fabricated according to various exemplary processes described herein can be used for detecting presence of human fluid.
  • the electrode can be used to detect inorganic electrolytes (ex: K+, Na+, HCO2 " , Ca 2+ , Mg 2+ , CI " ), organic solution (ex: glucose, lactase), proteins and/or lipids.
  • the electrode or multi-electrode detector is first contacted with an environment to be measured or sensed. While contacting the environment, a response at the contacting portion of the electrode or contacting portions of the detector is measured, whereby the measured response represents a property of the environment.
  • the response may be an electrical parameter, such as current or voltage.
  • the environment may be a liquid solution and the electrode or detector is immersed in the solution.
  • the environment may be a gas and the electrode or detector is positioned within the volume of gas.
  • the environment may be a solid surface and the environment is contacted against the surface.
  • the property may be at least one of capacitance, resistance, inductance, electrochemical property and photoelectric property of the environment.
  • the property may be the oxygen concentration of the environment surrounding the electrode or detector.
  • the measured property may be toxicity of water.
  • the method of using the electrode or detector allows for biomedical sensing. Presence of microorganisms or biological material, such as cells, algae, human cells or bacteria may be sensed.
  • the biological material may also be muscle tissue or skin.
  • the property environment may be the presence of human fluid, such as inorganic electrolytic material, organic solution, protein or lipid.
  • the property of the environment may be the presence of oxygen, carbon dioxide, enzyme or oxidation or reduction.
  • the property may be freshness of a produce within the environment.
  • the first electrode 134 which may be a working electrode, is formed of gold.
  • the first electrode 134 may further be non-transparent.
  • the second electrode 136 which may be a counter electrode, is formed of at least one of silver and platinum.
  • the third electrode which may be a reference electrode, is formed of at least one of silver and platinum.
  • the second electrode 136 is substantially circular and the first electrode 134 extends to define an arc about the second electrode 136.
  • the third electrode also extends to define an arc between the first electrode 134 and the second electrode 136.
  • the conducting portions 143, 148, 160 and connecting portions 144, 152, 164 of each of the first electrode 34, second electrode 36 and third electrode 140 may also be formed of one of silver and platinum.
  • the contacting portions may have a size of about 50 urn to about 5 cm.
  • the working electrode, counter electrode and reference electrode may each have a size of about 10um 2 to about 20 mm 2 .
  • the working electrode, counter electrode and reference electrode may each have a size of about 100 urn 2 to about 10 mm 2 .
  • silver nanomaterial members are synthesized in ethylene glycol at about 160°C starting from polyvinyl pyrrolydone, silver nitrate, and copper sulfate. After cleaning, the nanomaterial members are dispersed in alcohol to form a stable mixture. For example, the cleaned nanomaterial members have lengths of about 10um to 100um and widths of about 100nm.
  • the mixture can be formulated differently according to desired physical properties adapted to different printing systems. For example, the mixture can be formulated using different solvents, T/CA2014/000748
  • the mixture is filtered over a filtration membrane to form a nanomaterial layer on the membrane.
  • the layer is then transferred by stamping onto a glass plate substrate.
  • the glass plate is functionalized with silane.
  • the nanomaterial layer thereby forms a nanomaterial coating on the glass plate substrate.
  • the nanomaterial coating can be washed and recooked in order to improve conductivity and adhesion.
  • the nanomaterial was cooked at 300 °C for 30 minutes.
  • a laser can be used so as to not damage the substrate.
  • FIG. 25 illustrates the current response of the detector when varying voltage is applied thereto. The response was measured when the detector is placed in a solution having oxygen and in a solution having added peroxide ( ⁇ 2 ⁇ 2) ⁇
  • the detector had a working electrode comprising silver nanofilaments; a reference electrode comprising silver nanofilaments; and a counter-electrode comprising gold.
  • the detector was further tested in solutions having different concentrations of peroxide and the response was measured using chronoamperometry. The results are shown in the graph of FIG. 26. It will be appreciated that the response of the detector was linear with changes in peroxide concentration. This detector may also be used for measuring glucose concentration (using glucose oxidase).
  • a detector was used for measuring oxygen levels produced by algae and bacteria in their culture environment. The results are shown in the graph of FIG. 27. It will be appreciated that while the measured current remained at zero (0 A) when the detector is used in a solution having no cells, the measured current varied with varying voltage when used in a solution having algae and bacteria producing oxygen.
  • the detector had a working electrode comprising silver nanofilaments; a reference electrode comprising 14 000748
  • silver nanofilaments and a counter-electrode comprising silver nanofilaments coated with platinum.
  • FIG. 28 therein illustrated is the current response measured using different sweep speeds in a solution having benzoquinone. It will be appreciated that the current response is varying as the voltage is varied, thereby showing that the reduction and oxidation reactions are detected.
  • FIG. 29 therein illustrated are microscope images according to one example showing deposit of silver nanofilaments at transparencies of 91 %, 86%, 82%, 44% and 30%.
  • FIG. 30 illustrates the surface area versus changing transparencies for two trials. It will be appreciated that the surface area remained consistent for transparencies at equal or above 80%.
  • FIG. 31 shows a microscope image according to one example of deposit of silver nanofilaments having been coated with platinum. It will be appreciated that porousness of the nanofilaments is maintained even after being coated with platinum.
  • FIG. 32 illustrates a graph showing transparency over a range of wavelengths of the electrode having silver nanofilaments having been coated with platinum.
  • FIG. 33 therein illustrated is a side elevation view of an eye patch or contact lens that may be used for measuring a property the surface of the eye.
  • the contact lens includes a substrate 100 on which is formed a multi-electrode detector 400. 14 000748

Abstract

La présente invention concerne un électrode comprenant une pluralité d'éléments de nanomatériau qui définissent une pluralité de pores. L'électrode permet le passage d'au moins 60 % d'une lumière ayant une longueur d'onde comprise entre environ 390 nm et environ 1200 nm. L'électrode peut être utilisée pour mesurer la capacité, la résistance, l'inductance, les propriétés électrochimiques et/ou les propriétés photoélectriques d'un élément à analyser. L'invention concerne également un procédé de fabrication de l'électrode, le procédé comprenant la formation, sur un substrat, d'un motif conducteur comprenant une pluralité d'éléments de nanomatériau conducteur et, éventuellement, la fonctionnalisation d'une première sous-région du motif conducteur avec un matériau sensible à au moins un premier type d'analyte. Le motif conducteur peut comprendre une pluralité de pores, et l'électrode formée permet le passage d'au moins 60 % d'une lumière ayant une longueur d'onde comprise entre environ 390 nm et environ 1200 nm. En outre, l'invention concerne un détecteur comprenant une électrode de travail, une contre-électrode et une électrode de référence, chaque électrode ayant une pluralité de nanomatériaux définissant une pluralité de pores.
PCT/CA2014/000748 2013-10-17 2014-10-17 Électrodes, détecteurs, leurs utilisations et leurs procédés de fabrication WO2015054775A1 (fr)

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CN106290498A (zh) * 2016-08-08 2017-01-04 青岛科技大学 基于PEDOT‑rGO‑Ni(OH)2复合纳米材料的无酶葡萄糖传感器电极的制备方法
CN106324057A (zh) * 2016-08-01 2017-01-11 红河学院 一种免疫传感器对黄曲霉毒素的检测方法
CN107231745A (zh) * 2017-06-08 2017-10-03 鹤山市中富兴业电路有限公司 一种用于医疗检测所用的pcb板及其制作方法
CN107661752A (zh) * 2017-09-13 2018-02-06 中山大学 一种氧化石墨烯/普鲁士蓝纳米颗粒复合材料固相微萃取探针及其制备方法和应用
CN108752627A (zh) * 2018-06-20 2018-11-06 安徽江淮汽车集团股份有限公司 一种新型抗菌剂的制备方法
CN108760857A (zh) * 2018-06-01 2018-11-06 徐州医科大学 一种纳米金修饰的二氧化钛纳米纤维酶电极及其制备方法和应用
CN109270136A (zh) * 2018-11-20 2019-01-25 中国科学院大学 一种抗hct干扰的葡萄糖传感器
CN109270141A (zh) * 2018-11-21 2019-01-25 鲁东大学 基于氧化石墨烯-多壁碳纳米管-金纳米棒复合材料的电化学传感器的制备方法
CN109490390A (zh) * 2018-11-21 2019-03-19 鲁东大学 氧化石墨烯-多壁碳纳米管-Au@Pt NPs无酶葡萄糖电化学传感器的制备方法
CN109613090A (zh) * 2018-11-14 2019-04-12 衡阳师范学院 海胆型普鲁士蓝-钯核壳结构负载氮掺杂石墨烯纳米复合材料及其制备得到的电极与应用
WO2020234338A1 (fr) * 2019-05-20 2020-11-26 Albert-Ludwig-Universität Freiburg Capteur portable jetable destiné à une surveillance continue de la biochimie de l'haleine
CN112666235A (zh) * 2021-01-19 2021-04-16 郑州轻工业大学 基于PtNi双金属的两电极集成无酶葡萄糖传感器及制备方法

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CN105651846A (zh) * 2015-12-29 2016-06-08 东莞市青麦田数码科技有限公司 基于智能手机的胆固醇检测装置
CN106324057A (zh) * 2016-08-01 2017-01-11 红河学院 一种免疫传感器对黄曲霉毒素的检测方法
CN106324057B (zh) * 2016-08-01 2018-09-14 红河学院 一种免疫传感器对黄曲霉毒素的检测方法
CN106290498B (zh) * 2016-08-08 2019-11-05 青岛科技大学 基于PEDOT-rGO-Ni(OH)2复合纳米材料的无酶葡萄糖传感器电极的制备方法
CN106290498A (zh) * 2016-08-08 2017-01-04 青岛科技大学 基于PEDOT‑rGO‑Ni(OH)2复合纳米材料的无酶葡萄糖传感器电极的制备方法
CN107231745A (zh) * 2017-06-08 2017-10-03 鹤山市中富兴业电路有限公司 一种用于医疗检测所用的pcb板及其制作方法
CN107661752A (zh) * 2017-09-13 2018-02-06 中山大学 一种氧化石墨烯/普鲁士蓝纳米颗粒复合材料固相微萃取探针及其制备方法和应用
CN108760857A (zh) * 2018-06-01 2018-11-06 徐州医科大学 一种纳米金修饰的二氧化钛纳米纤维酶电极及其制备方法和应用
CN108752627A (zh) * 2018-06-20 2018-11-06 安徽江淮汽车集团股份有限公司 一种新型抗菌剂的制备方法
CN109613090A (zh) * 2018-11-14 2019-04-12 衡阳师范学院 海胆型普鲁士蓝-钯核壳结构负载氮掺杂石墨烯纳米复合材料及其制备得到的电极与应用
CN109613090B (zh) * 2018-11-14 2020-10-09 衡阳师范学院 海胆型普鲁士蓝-钯核壳结构负载氮掺杂石墨烯纳米复合材料及其制备得到的电极与应用
CN109270136A (zh) * 2018-11-20 2019-01-25 中国科学院大学 一种抗hct干扰的葡萄糖传感器
CN109270141A (zh) * 2018-11-21 2019-01-25 鲁东大学 基于氧化石墨烯-多壁碳纳米管-金纳米棒复合材料的电化学传感器的制备方法
CN109490390A (zh) * 2018-11-21 2019-03-19 鲁东大学 氧化石墨烯-多壁碳纳米管-Au@Pt NPs无酶葡萄糖电化学传感器的制备方法
CN109270141B (zh) * 2018-11-21 2020-11-10 鲁东大学 基于氧化石墨烯-多壁碳纳米管-金纳米棒复合材料的电化学传感器的制备方法
WO2020234338A1 (fr) * 2019-05-20 2020-11-26 Albert-Ludwig-Universität Freiburg Capteur portable jetable destiné à une surveillance continue de la biochimie de l'haleine
CN112666235A (zh) * 2021-01-19 2021-04-16 郑州轻工业大学 基于PtNi双金属的两电极集成无酶葡萄糖传感器及制备方法
CN112666235B (zh) * 2021-01-19 2023-03-10 郑州轻工业大学 基于PtNi双金属的两电极集成无酶葡萄糖传感器及制备方法

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