WO2023017721A1 - Biosignal sensing electrode - Google Patents

Biosignal sensing electrode Download PDF

Info

Publication number
WO2023017721A1
WO2023017721A1 PCT/JP2022/028379 JP2022028379W WO2023017721A1 WO 2023017721 A1 WO2023017721 A1 WO 2023017721A1 JP 2022028379 W JP2022028379 W JP 2022028379W WO 2023017721 A1 WO2023017721 A1 WO 2023017721A1
Authority
WO
WIPO (PCT)
Prior art keywords
conductive film
mxene
particles
substrate
sensing electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/028379
Other languages
English (en)
French (fr)
Inventor
Brendan Boyce Murphy
Nicolette DRISCOLL
Flavia VITALE
Kosuke Sugiura
Mika FUJIWAKI
Takeshi TORITA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Murata Manufacturing Co Ltd
University of Pennsylvania Penn
Original Assignee
Murata Manufacturing Co Ltd
University of Pennsylvania Penn
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Murata Manufacturing Co Ltd, University of Pennsylvania Penn filed Critical Murata Manufacturing Co Ltd
Priority to CN202280054532.6A priority Critical patent/CN117769387A/zh
Priority to JP2024507991A priority patent/JP2024529086A/ja
Publication of WO2023017721A1 publication Critical patent/WO2023017721A1/en
Priority to US18/435,310 priority patent/US20240175841A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/263—Bioelectric electrodes therefor characterised by the electrode materials

Definitions

  • the present invention relates to a biosignal sensing electrode.
  • MXene has been attracting attention as a new material having conductivity.
  • MXene is a type of so-called two-dimensional material, and as will be described later, is a layered material in the form of one or plural layers.
  • MXene is in the form of particles (which can include powders, flakes, nanosheets, and the like) of such a layered material.
  • MXene exhibits high sensitivity when used as a biosignal sensing electrode such as an electroencephalographic sensor, a myoelectric sensor, or an electrocardiographic sensor in the form of a conductive film (dry film) (refer to Non Patent Literature 1).
  • Non Patent Literature 1 Nicolette Driscoll, et al., “Two-Dimensional Ti3C2MXene for High Resolution Neural Interfaces”, ACS Nano, 2018, Vol. 12, Issue 10, pp. 10419-10429
  • Non Patent Literature 2 Fanjie Xia, et al., “Ambient oxidation of Ti3C2MXene initialized by atomic defects”, Nanoscale, 2019, Vol. 11, Issue 48, pp. 23330-23337
  • Non Patent Literature 3 Chien-Wei Wu, et al., “Excellent oxidation resistant MXene aqueous ink for micro-supercapacitor application”, Energy Storage Materials, 2020, Vol. 25, pp.
  • Non Patent Literature 4 Varun Natu et al., “Edge Capping of 2D-MXene Sheets with Polyanionic Salts to Mitigate Oxidation in Aqueous Colloidal Suspensions”, Angewandte Chemie International Edition, 2019, Volume 58, Issue 36, pp. 12655-12660
  • Non Patent Literature 2 MXene is easily oxidized particularly in a solvent containing water. It has been known that MXene is oxidized over time in air (usually contains water and oxygen).
  • MXene when used as a biosignal sensing electrode in the form of a conductive film (dry film), MXene in the conductive film is oxidized over time due to contact with sweat, blood, or the like (usually contains water) derived from a living body or the like that may be a subject, or exposure to air, and as a result, the sensing capability of the conductive film deteriorates over time.
  • a conductive film dry film
  • Non Patent Literature 3 a method for mixing an aqueous dispersion of MXene particles with an aqueous solution of sodium ascorbate (refer to Non Patent Literature 3) and a method for adding a polyanion salt (specifically, a salt of polyphosphoric acid, polysilicic acid, or polyboric acid) to an aqueous colloidal suspension of MXene (refer to Non Patent Literature 4) have been proposed.
  • a polyanion salt specifically, a salt of polyphosphoric acid, polysilicic acid, or polyboric acid
  • these methods are methods for preventing oxidation of MXene in a case where the MXene particles form an aqueous dispersion/suspension, and do not directly deal with a case where the MXene particles form a conductive film (dry film).
  • a conductive film dry film
  • an additional step of separating the MXene particles from a liquid phase to form a film is required.
  • An object of the present invention is to provide a biosignal sensing electrode including a conductive film containing particles of MXene, in which deterioration of sensing capability over time is effectively reduced.
  • a biosignal sensing electrode including a substrate, and a conductive film which is located on the substrate and has a first face on a side of the substrate and a second face on a side opposite to the substrate, wherein the conductive film contains particles of a layered material containing one or plural layers, the one or plural layers containing a layer body represented by a formula below: M m X n wherein M is at least one metal of Group 3, 4, 5, 6, or 7, X is a carbon atom, a nitrogen atom, or a combination thereof, n is not less than 1 and not more than 4, and m is more than n but not more than 5, and a modifier or terminal T existing on a surface of the layer body, wherein T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom, and a hydrogen atom, and being oriented parallel to a surface of the substrate, wherein a protective
  • the polymer may penetrate into the conductive film.
  • the polymer may include at least one selected from the group consisting of polyvinyl alcohol, a polyisocyanate-crosslinked acrylic resin, an epoxy-crosslinked acrylic resin, and polyamide-imide.
  • the protective material may further cover an outer surrounding area of the second face of the conductive film.
  • the biosignal sensing electrode may further include a cover which is located on the second face of the conductive film, wherein a part of the second face is exposed from the cover.
  • the M m X n may be expressed by at least one selected from the group consisting of Ti 2 C, Ti 3 C 2 , Ti 3 (CN), (Cr 2 Ti)C 2 , (Mo 2 Ti)C 2 , (Mo 2 Ti 2 )C 3 , and (Mo 2.7 V 1.3 )C 3 .
  • a biosignal sensing electrode including a conductive film containing particles of a predetermined layered material (also referred to as “MXene” in the present specification)
  • Figs. 1(a) and 1(b) are diagrams for explaining a biosignal sensing electrode according to one embodiment of the present invention, in which Fig. 1(a) illustrates a schematic cross-sectional view of a biosignal sensing electrode, and Fig. 1(b) illustrates a schematic top view of Fig. 1(a).
  • Figs. 2(a) to 2(c) are diagrams for explaining a biosignal sensing electrode according to one embodiment of the present invention, in which Fig. 2(a) illustrates a schematic enlarged cross-sectional view of a region surrounded by an alternate long and short dash line in Fig. 1(a), Fig.
  • FIG. 2(b) illustrates a schematic cross-sectional view of MXene particles and a polymer (derived from a protective material) in a conductive film
  • Fig. 2(c) illustrates a schematic perspective view of MXene particles in a conductive film
  • Figs. 3(a) and 3(b) are schematic cross-sectional views illustrating MXene particles which are layered materials usable for a conductive film in one embodiment of the present invention, in which Fig. 3(a) illustrates single-layered MXene particles, and Fig. 3(b) illustrates multi-layered (exemplarily two-layered) MXene particles.
  • Fig. 4 is a schematic cross-sectional view illustrating one modification example of the biosignal sensing electrode of Fig.
  • Fig. 5 is a schematic cross-sectional view illustrating another modification example of the biosignal sensing eleqctrode of Fig. 1.
  • Figs. 6(a) and 6(b) are diagrams for explaining a biosignal sensing electrode according to another embodiment of the present invention, in which Fig. 6(a) illustrates a schematic cross-sectional view of a biosignal sensing electrode, and Fig. 6(b) illustrates a schematic bottom view of Fig. 6(a).
  • a biosignal sensing electrode 20 of the present embodiment includes a substrate 11 and a conductive film 13 located on the substrate 11.
  • the conductive film 13 includes a first face 13a on the substrate 11 side and a second face 13b on the side opposite to the substrate 11.
  • the first face 13a and the second face 13b face each other, and may be, for example, faces parallel to each other.
  • the conductive film 13 further includes an edge 13c.
  • the edge 13c of the conductive film 13 is a surface (end face) connecting the first face 13a and the second face 13b.
  • a protective material 15 covers at least edge 13c of the conductive film 13.
  • the conductive film 13 may be connected with a lead 17 at any suitable portion thereof, but this is not essential if at least a surface 11a of the substrate 11 is conductive.
  • a length of the lead 17 is optional, and a pad (not shown) for connecting to another electric circuit element may be formed on the side of the lead 17 opposite to the conductive film 13 side.
  • the substrate 11 may or may not be conductive.
  • a size, a shape, and the like of the substrate 11 can vary depending on the application of the biosignal sensing electrode 20, and may be either flexible or rigid.
  • the substrate 11 may be formed of any suitable material, such as a polymer, metal, a semiconductor, ceramics, and the like.
  • the substrate 11 may be formed of one material or two or more materials.
  • the material may be a polymer, a semiconductor, ceramics, or the like having a metal layer on the surface 11a.
  • a flexible substrate made of a polymer such as polyimide is used as the substrate 11.
  • the conductive film 13 includes particles 10 of a predetermined layered material.
  • the predetermined layered material is MXene and is defined as:
  • a layered material (this can be understood as a layered compound, also represented as “M m X n T s ”, where s is any number and traditionally x is sometimes used instead of s) containing one or plural layers, the one or plural layers including a layer body (the layer body may have a crystal lattice in which each X is located in an octahedral array of M) represented by a formula below: M m X n (wherein M is at least one metal of Group 3, 4, 5, 6, or 7 and may contain at least one selected from the group consisting of so-called early transition metals such as Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and Mn, X is a carbon atom, a nitrogen atom, or a combination thereof, n is not less than
  • M is preferably at least one selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and Mn, and more preferably at least one selected from the group consisting of Ti, V, Cr, and Mo.
  • the M m X n is be expressed by at least one selected from the group consisting of Ti 2 C, Ti 3 C 2 , Ti 3 (CN), (Cr 2 Ti)C 2 , (Mo 2 Ti)C 2 , (Mo 2 Ti 2 )C 3 , and (Mo 2.7 V 1.3 )C 3 .
  • MXene particles (hereinafter, the particles are simply referred to as “MXene particles”) 10 can be synthesized by selectively etching (removing and optionally layer-separating) A atoms (and optionally a part of M atoms) from a MAX phase.
  • the MAX phase is represented by the following formula: M m AX n (wherein M, X, n, and m are as described above, and A is at least one element of Group 12, 13, 14, 15, or 16, is usually a Group A element, typically Group IIIA and Group IVA, more specifically, may include at least one selected from the group consisting of Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, S, and Cd, and is preferably Al), and has a crystal structure in which a layer formed of A atoms is located between two layers (each X may have a crystal lattice located within an octahedral array of M) represented by M m X n .
  • the MAX phase has a repeating unit in which one layer of X atoms is disposed between the layers of M atoms of n + 1 layers (these layers are also collectively referred to as “M m X n layer”), and a layer of A atoms (“A atom layer”) is disposed as a next layer of the (n + 1) th layer of M atoms; however, the present invention is not limited thereto.
  • the A atom layer (and optionally a part of the M atoms) is removed, and a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom, a hydrogen atom, and the like existing in an etching liquid (usually, but not limited to, an aqueous solution of a fluorine-containing acid is used) are modified on the exposed surface of the M m X n layer, thereby terminating the surface.
  • an etching liquid usually, but not limited to, an aqueous solution of a fluorine-containing acid is used
  • an etching treatment is performed with an acid such as HF, HCl, HBr, HI, sulfuric acid, phosphoric acid, or nitric acid using a fluororesin container.
  • an acid such as HF, HCl, HBr, HI, sulfuric acid, phosphoric acid, or nitric acid using a fluororesin container.
  • a method using a mixed solution of lithium fluoride and hydrochloric acid, a method using hydrofluoric acid, or the like may be used.
  • stirring is performed at a temperature of room temperature or higher and 40 degrees or lower for about not less than 5 hours and not more than 48 hours.
  • an operation of transferring a liquid after the etching treatment to, for example, a centrifuge tube, adding pure water thereto, stirring the mixture, separating a supernatant and a precipitate with a centrifugal separator, and discarding the supernatant may be repeated not less than 5 times and not more than 20 times.
  • the layer separation (delamination, separating multilayer MXene into single-layer MXene) of MXene may be promoted by any appropriate post-treatment (for example, ultrasonic treatment, handshaking, automatic shaker, or the like) as appropriate.
  • the delamination treatment can be performed for a predetermined time using a mechanical shaker, a vortex mixer, a homogenizer, an ultrasonic bath, or the like.
  • the supernatant and the precipitate are separated by a centrifugal separator, and the recovered supernatant can be obtained as a dispersion of MXene particles in a monolayer form.
  • MXene may contain a relatively small amount of remaining A atoms, for example, 10% by mass or less with respect to the original A atoms.
  • the residual amount of A atoms may be preferably 8% by mass or less, and more preferably 6% by mass or less. However, even if the residual amount of A atoms exceeds 10% by mass, there may be no problem depending on the application and use conditions of the conductive film (and the biosignal sensing electrode including the conductive film).
  • the MXene particles 10 synthesized in this manner may be particles of a layered material (as examples of the MXene particles 10, the MXene particles 10a in one layer are illustrated in Fig. 3(a), and the MXene particles 10b in two layers are illustrated in Fig. 3(b), but the present invention is not limited to these examples) including one or plural MXene layers 7a and 7b.
  • the MXene layers 7a and 7b have layer bodies (M m X n layers) 1a and 1b represented by M m X n , and modifier or terminals T 3a, 5a, 3b, and 5b existing on the surfaces (more specifically, at least one of two surfaces facing each other in each layer) of the layer bodies 1a and 1b. Therefore, the MXene layers 7a and 7b are also represented as “M m X n T s ”, and s is an optional number.
  • the MXene particles 10 may be one in which such MXene layers are individually separated and exist in one layer (the single-layer structure illustrated in Fig.
  • MXene particles 10 may be particles (which may also be referred to as powders or flakes) as an aggregate formed of the single-layer MXene particles 10a and/or the multilayer MXene particles 10b.
  • multilayer MXene particles two adjacent MXene layers (for example, 7a and 7b) do not necessarily have to be completely separated from each other, and may be partially in contact with each other.
  • each layer of MXene (which corresponds to the MXene layers 7a and 7b) is, for example, not less than 0.8 nm and not more than 5 nm, and particularly not less than 0.8 nm and not more than 3 nm (which may mainly vary depending on the number of M atom layers included in each layer), and the maximum dimension (which may correspond to the “in-plane dimension” of the particle) in a plane parallel to the layer (two-dimensional sheet plane) is, for example, not less than 0.1 ⁇ m, particularly not less than 1 ⁇ m, for example, not more than 200 ⁇ m, and particularly not more than 40 ⁇ m.
  • an interlayer distance is, for example, not less than 0.8 nm and not more than 10 nm, particularly not less than 0.8 nm and not more than 5 nm, and more particularly about 1 nm
  • the maximum dimension (which may correspond to the “in-plane dimension” of the particles) in a plane (two-dimensional sheet plane) perpendicular to the lamination direction is, for example, not less than 0.1 ⁇ m, particularly not less than 1 ⁇ m, for example, not more than 100 ⁇ m, and particularly not more than 20 ⁇ m.
  • the total number of layers in the MXene particles may be 1 or not less than 2, but is, for example, not less than 1 and not more than 20, and the thickness in the lamination direction (which may correspond to the “thickness” of the particles) is, for example, not less than 0.8 nm and not more than 20 nm.
  • the MXene particles When the MXene particles are laminate (multilayer MXene) particles, the MXene particles may have a small number of layers.
  • the term “the number of layers is small” means that, for example, the number of stacked layers of MXene is six or less.
  • the thickness of the multilayer MXene having a small number of layers in the lamination direction may be less than 10 nm.
  • the “multilayer MXene having a small number of layers” is also referred to as a “few-layer MXene”.
  • the MXene particles may be particles (also referred to as nanosheets) in which most of the MXene particles are formed of single-layer MXene and/or few-layer MXene.
  • the single-layer MXene and the few-layer MXene may be collectively referred to as “single-layer/few-layer MXene”.
  • these dimensions described above may be obtained as a number average dimension (for example, a number average of at least 40) based on a photograph of a scanning electron microscope (SEM), a transmission electron microscope (TEM), or an atomic force microscope (AFM) or a distance in a real space calculated from a position on a reciprocal lattice space of a (002) plane measured by an X-ray diffraction (XRD) method.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • AFM atomic force microscope
  • XRD X-ray diffraction
  • the layer of MXene particles 10 is oriented parallel to the surface 11a of the substrate 11.
  • the fact that the layer of MXene particles 10 is oriented parallel to the surface 11a of the substrate 11 means that most of the MXene particles 10, for example, not less than 80%, particularly not less than 90%, of the entire MXene particles 10 form an angle within ⁇ 10° with respect to the surface 11a of the substrate 11 in the two-dimensional plane (sheet plane) of the layer of MXene particles 10.
  • the surface 11a of the substrate 11 is a face in contact with the first face 13a of the conductive film 13.
  • the conductive film 13 in which the layers of the MXene particles 10 are oriented in parallel to the surface 11a of the substrate 11 may be manufactured by any appropriate method. Although the present embodiment is not limited, for example, by preparing a slurry in which the MXene particles synthesized as described above are dispersed and/or suspended in an appropriate solvent, spraying the slurry onto the surface 11a of the substrate 11, and drying and removing the solvent (at least partially, preferably substantially entirely), the conductive film 13 can be formed on the substrate 11. The drying can occur naturally while being supplied onto the substrate 11 and/or be performed subsequently. By such spraying and drying, the MXene particles 10 are deposited in a state where the layer of the MXene particles 10 is oriented in parallel to the surface 11a of the substrate 11. The conductive film 13 thus obtained can be binderless.
  • the spraying and drying may be appropriately repeated until a desired film thickness is obtained.
  • a combination of spraying and drying may be repeated a plurality of times.
  • a relatively thick film for example, a thickness of 0.5 ⁇ m or more
  • the number of sprays (and optionally drying) performed until a desired film thickness is obtained can be reduced.
  • the thickness of the conductive film 13 is not particularly limited, but may be, for example, not less than 200 nm and not more than 20 ⁇ m. When the thickness of the conductive film 13 is 200 nm or more, continuity of the film is maintained, and sensing can be stably performed. When the thickness of the conductive film 13 is 20 ⁇ m or less, the flexibility of the substrate is not impaired, and stress concentration due to bending is small, so that sensing can be stably performed. Preferably, the thickness of the conductive film 13 may be not less than 500 nm but/or not more than 10 ⁇ m.
  • the protective material 15 further covers the outer surrounding area of the second face 13b of the conductive film 13, but this is not essential to the present invention.
  • the outer surrounding area of the second face 13b may be any region on the second face 13b adjacent to the edge 13c. In the illustrated aspect, the outer surrounding area is a region of the second face 13b excluding the sensing region A, but is not limited thereto.
  • these functional groups of the polymer 16 can bond to the MXene particles 10, and more particularly form hydrogen bonds with the modifier or terminal T (T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom, and a hydrogen atom) of the MXene particles 10
  • T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom, and a hydrogen atom
  • the acceptor of the functional group can form a hydrogen bond to a hydrogen donor of the modifier/terminal T
  • the hydrogen donor of the functional group can form a hydrogen bond to the acceptor of the modifier/terminal T.
  • the oxidation of the MXene particles 10 can be effectively suppressed (preferably prevented) by allowing the layer of the MXene particles 10 oriented in parallel to the surface 11a of the substrate 11 in the conductive film 13, covering at least the edge 13c of the conductive film 13 with the protective material 15 containing the polymer 16 having the functional group, and bonding (hydrogen bonding to modifier/terminal T) the functional group of the polymer 16 to the MXene particles 10 at least at the edge 13c.
  • the protective material 15 may be understood as protection of the MXene particles 10 from oxidation.
  • the present invention is not bound by any theory, it is considered that a component that is derived from air as a surrounding environment, a living body that can be a subject, or the like and that leads to oxidation of the MXene particles 10 (water, water vapor, oxygen, and the like) is likely to enter from the edge 13c of the conductive film 13 through the edge of the layer of the MXene particles 10, and oxidation can be started from the edge of the layer of the MXene particles 10.
  • the polymer 16 is strongly bonded (hydrogen-bonded) to the MXene particles 10, so that the component such as water, water vapor, oxygen, and the like can be effectively prevented from accessing the edge 13c of the conductive film 13.
  • the polymer 16 having a functional group capable of forming a hydrogen bond as described above can penetrate into the conductive film 13. More specifically, the polymer 16 can enter between the MXene particles 10 of the conductive film 13, and the functional group of the polymer 16 can be bonded (hydrogen-bonded to modifier/terminal T) to the MXene particles 10 inside the conductive film 13, thereby more effectively suppressing the oxidation of the MXene particles 10. (Note that a portion of the protective material 15 that does not penetrate the conductive film 13 may also be referred to as a protective film.)
  • the penetration of the polymer 16 into the interior of the conductive film 13 may be one or more depths of the MXene particles 10. Since the protective material 15 covers the edge 13c, a penetration depth dt in the thickness direction from the edge 13c may be equal to or more than the thickness of the MXene particles 10. When the protective material 15 further covers the outer surrounding area of the second face 13b, the penetration depth dp in the in-plane direction from the second face 13b may be equal to or larger than the in-plane dimension of the MXene particle 10.
  • the MXene particles 10 have both a modifier/terminal T (at least one of a hydroxyl group and a hydrogen atom) that can be a hydrogen donor and a modifier/terminal T (at least one selected from the group consisting of a fluorine atom, a chlorine atom, and an oxygen atom) that can be a hydrogen acceptor.
  • a modifier/terminal T at least one selected from the group consisting of a fluorine atom, a chlorine atom, and an oxygen atom
  • the polymer 16 may be at least one selected from the group consisting of polyvinyl alcohol, a polyisocyanate-crosslinked acrylic resin, an epoxy-crosslinked acrylic resin, and polyamide-imide. As illustrated in Table 2, these polymers have a functional group capable of being bonded (hydrogen-bonded to modifier/terminal T) to the MXene particles, a high bonding force is obtained with respect to the MXene particles, the MXene particles can be firmly bound to each other, and the polymers are hardly peeled off from the conductive film 13.
  • the polymers available in the present embodiment are not limited thereto.
  • a method for covering a predetermined region (at least the edge 13c and if necessary, the outer surrounding area of the second face 13a) of the conductive film 13 with the protective material 15 is not particularly limited.
  • coating, bar coater, screen printing, and the like can be appropriately used.
  • the lead 17 may be formed at any suitable timing as long as it is ultimately connected with the conductive film 13.
  • the lead 17 may be provided on the substrate 11 before the conductive film 13 is formed, and when the substrate 11 has a metal layer on the surface 11a, the lead wire may be integrally formed with the metal layer.
  • the lead 17 may be connected to a region (for example, by soldering) of the conductive film 13 that is not covered with the protective material 15 after a predetermined region of the conductive film 13 is covered with the protective material 15.
  • a sensing region A (and optionally one or more other regions, for example a region B (not shown) for connecting the lead 17) of the conductive film 13 is not covered with the protective material 15 and is exposed from the protective material 15.
  • the sensing region A is a region intended and/or designed to detect a biological signal.
  • the sensing region A may have various modes as long as it is exposed from the protective material 15 and can detect a biological signal.
  • the sensing region A may be in direct or indirect contact with a living body or biological tissue that may be a subject, and may be capable of directly or indirectly detecting a biological signal from the subject.
  • a living body can be understood as a subject in a broad sense, and a biological tissue can be understood as a subject in a narrow sense.
  • the biological tissue may form a part of a living body (for example, a human body), but may be separated from the living body.
  • the biological tissue (measurement target) as the subject that emits the biological signal can be skin such as a human body, and can be blood vessels, muscles, brains, other organs, and the like under the skin.
  • the measurement target is a biological tissue (for example, skin) exposed to the outside
  • the sensing region A may be brought into contact with the biological tissue of the measurement target (directly or indirectly as described later) to directly detect (measure) the biological signal from the biological tissue of the measurement target.
  • the measurement target is a biological tissue under another biological tissue (for example, skin) exposed to the outside
  • the sensing region A may be brought into contact with the above another biological tissue (for example, skin) (directly or indirectly as described later) to indirectly detect (measure) the biological signal from the biological tissue of the measurement target.
  • the sensing region A may be exposed (exposed) to the external atmosphere of the biosignal sensing electrode 20.
  • the sensing region A can be brought into direct contact with the living body or the biological tissue.
  • the sensing region A may be covered with any appropriate other laminate (not shown).
  • the sensing region A can be indirectly brought into contact with the living body or the biological tissue via the other laminate.
  • the other laminate may be, for example, a conductive material layer, a gel or a film permeable to ions, or the like.
  • the ion-permeable film may be a porous membrane.
  • the porous membrane may be a membrane having a large number of fine pores and capable of selectively transmitting ions and molecules having a size smaller than a pore diameter.
  • Such other laminates are not particularly limited and may be formed of organic materials, inorganic materials, or mixtures thereof. Polymers such as hydrophilic polymers as the organic materials, and ceramics as the inorganic materials, or a combination thereof can be exemplified.
  • the thickness of the other laminates may be, for example, not less than 0.1 ⁇ m and not more than 300 ⁇ m.
  • the porous membrane may have, for example, an average pore diameter of not less than 1 nm and not more than 1 ⁇ m.
  • the porous membrane may be, for example, an aggregated particulate porous membrane, a network porous membrane, a fibrous porous membrane, a porous membrane having a plurality of isolated and/or communicating pipe holes, a porous membrane having a honeycomb structure, or the like, depending on the pore shape.
  • An area of the sensing region A is not particularly limited, but may be, for example, not less than 0.5 mm 2 and not more than 750 mm 2 .
  • the area of the sensing region A is 0.5 mm 2 or more, (direct or indirect) contact with a living body or a biological tissue (for example, skin) that can be a subject is improved, and stable biological signal sensing can be performed.
  • the area of the sensing region A is 750 mm 2 or less, it is possible to minimize the influence of motion artifacts due to the motion of the subject (for example, body motion) and to perform stable biological signal sensing.
  • the area of the sensing region A may be not less than 2 mm 2 and/or not more than 500 mm 2 .
  • the sensing region A may be brought into direct or indirect contact with a living body or a biological tissue at least when sensing a biological signal.
  • the sensing region A (and another laminate when present) may be covered with a peelable protective seal (not shown), and the protective seal may be peeled off when the biosignal sensing electrode 20 senses the biological signal, and the sensing region A may be brought into direct or indirect contact with the living body or the biological tissue (via the other laminate).
  • the biosignal sensing electrode 20 of the present embodiment by using the conductive film 13 containing the MXene particles 10, it is possible to effectively suppress oxidation of the MXene particles 10 in the conductive film 13 as described above while achieving relatively high conductivity (eventually, relatively low impedance), and thereby, it is possible to effectively reduce deterioration of the sensing capability over time.
  • the sensing capability can be interface impedance between the conductive film 13 and the living body or the biological tissue (for example, skin of a human body) in the sensing region A, and can be typically impedance of the conductive film measured by a three-electrode method.
  • a temporal change in the impedance of the conductive film 13 can be effectively reduced, and high stability can be obtained.
  • biosignal sensing electrode according to one embodiment of the present invention has been described in detail above, the biosignal sensing electrode according to the above embodiment can be variously modified.
  • biosignal sensing electrodes 21 and 23 may further include a cover 19.
  • the cover 19 is located on the second face 13b of the conductive film 13, in which the sensing region A (and another laminate when present) is exposed from the cover 19.
  • the sensing region A (and another laminate when present) which is a part of the second face 13b may be exposed from the protective material 15, and more specifically, the protective material 15 may cover the outer surrounding area of the second face 13b and exist between the conductive film 13 and the cover 19.
  • the protective material 15 may serve a function of adhering the cover 19 to the conductive film 13 and a function of adhering the cover 19 to the substrate 11.
  • the polymer derived from the protective material 15 can penetrate into the conductive film 13.
  • the entire second face 13b is exposed from the protective material 15, and the sensing region A (and another laminate when present) which is a part of the second face 13b is exposed from the cover 19.
  • the protective material 15 does not cover the outer surrounding area of the second face 13b, and may not exist between the conductive film 13 and the cover 19.
  • the protective material 15 may serve a function of adhering the cover 19 to the substrate 11.
  • the polymer derived from the protective material 15 can penetrate into the conductive film 13.
  • the adhering function may use a hydrogen bond, but is not limited thereto.
  • a size, a shape, and the like of the cover 19 can vary depending on the application of the biosignal sensing electrodes 21 and 23, and may be either flexible or rigid.
  • the cover 19 may be formed of any suitable material, such as a polymer, metal, a semiconductor, ceramics, and the like.
  • the cover 19 may be formed of one material or two or more materials.
  • a biosignal sensing electrode 25 of another embodiment includes a substrate 11 and a conductive film 13 disposed on the substrate 11, a sensing region A (and another laminate when present) which is a part of a second face 13b may be exposed from a protective material 15, and more specifically, the protective material 15 may cover an edge 13c of the conductive film 13 and an outer surrounding area of the second face 13b. Furthermore, in the illustrated aspect, the cover 19 may be adhered to the edge 13c of the conductive film 13 and the outer surrounding area of the second face 13b via the protective material 15.
  • the substrate 11 may be conductive, and may be connected to or integrally molded with a conductive terminal portion 12.
  • the substrate 11 and the terminal portion 12 may be formed of metal.
  • the cover 19 is not essential, and the cover 19 may not be provided.
  • Biosignal sensing electrode samples having different polymers of the protective material were produced, and the stability of sensing capability thereof was evaluated. In addition, a cross section of the conductive film of each sample was analyzed.
  • a slurry in which the MXene particles were dispersed in water at a concentration of 10 mg/mL was prepared.
  • the slurry prepared above was spray-coated on a gold-deposited slide glass (on a gold-deposited surface), and dried in a vacuum oven (350 mm Torr) at 70°C overnight to form a conductive film of MXene particles on the gold-deposited slide glass.
  • a protective material-containing liquid (described later) was adhered to the edge of the conductive film and a predetermined region on the upper surface of the conductive film (a region excluding the sensing region A and the region B for connecting the lead) by screen printing.
  • a corresponding polymer film (an opening corresponding to the sensing region A and an opening corresponding to the region B for connecting the lead ) was disposed on the predetermined region, and dried in an oven at 70°C for 5 hours.
  • a lead (for evaluation) including a lead wire was soldered to the conductive film in the region B.
  • the soldered portion was coated with Kapton tape to seal the region B from the ambient atmosphere.
  • a protective material-containing liquid As a protective material-containing liquid (a liquid material containing a raw material of a protective material), a liquid material in which each polymer shown in Table 3 was dispersed in a solvent (for example, water in a case of polyvinyl alcohol) was used in Examples 1 to 4 and Comparative Examples 1 to 4. biosignal sensing electrode samples having different polymers of protective materials were produced under the same conditions as in Examples 1 to 4 and Comparative Examples 1 to 4 except that different protective material-containing liquids were used.
  • a solvent for example, water in a case of polyvinyl alcohol
  • the impedance measurement was performed using a potentiostat manufactured by AUTOLAB under the condition of 10 Hz by a three-electrode method using a sample as a working electrode (more specifically, a conductive film on a gold-deposited film is used as a working electrode via a lead wire), platinum as a counter electrode, and a silver/silver chloride electrode as a reference electrode (what is measured by this is the impedance between the reference electrode and the working electrode).
  • the measured values before immersion, after immersion for 12 hours, and after immersion for 24 hours are also shown in Table 3.
  • Examples 1 to 4 Polymer: polyvinyl alcohol, polyisocyanate-crosslinked acrylic resin, epoxy-crosslinked acrylic resin, polyamide-imide
  • a temporal change in the measured value of impedance was almost observed even after immersion for 24 hours, and high stability was exhibited.
  • Comparative Examples 1 to 4 Polymer: polyethylene, polypropylene, fluorine-based resin, ethylene-vinyl acetate copolymer resin
  • the temporal change in the measured value of impedance was observed after immersion for 12 hours, and the stability was poor.
  • the biosignal sensing electrode of the present invention can be used for any appropriate application, and can be used in a state where a sensing region of the conductive film is brought into direct or indirect contact with a living body or a biological tissue (for example, skin of a human body) that can be a subject in order to sense a biological signal, but is not limited thereto.
  • a biological tissue for example, skin of a human body

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Pathology (AREA)
  • Physics & Mathematics (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Engineering & Computer Science (AREA)
  • Biophysics (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Medical Informatics (AREA)
  • Surgery (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
  • Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
  • Laminated Bodies (AREA)
PCT/JP2022/028379 2021-08-11 2022-07-21 Biosignal sensing electrode Ceased WO2023017721A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202280054532.6A CN117769387A (zh) 2021-08-11 2022-07-21 生物信号传感电极
JP2024507991A JP2024529086A (ja) 2021-08-11 2022-07-21 生体信号センシング電極
US18/435,310 US20240175841A1 (en) 2021-08-11 2024-02-07 Biosignal sensing electrode

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202163231850P 2021-08-11 2021-08-11
US63/231,850 2021-08-11

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US18/435,310 Continuation US20240175841A1 (en) 2021-08-11 2024-02-07 Biosignal sensing electrode

Publications (1)

Publication Number Publication Date
WO2023017721A1 true WO2023017721A1 (en) 2023-02-16

Family

ID=85200441

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/028379 Ceased WO2023017721A1 (en) 2021-08-11 2022-07-21 Biosignal sensing electrode

Country Status (4)

Country Link
US (1) US20240175841A1 (https=)
JP (1) JP2024529086A (https=)
CN (1) CN117769387A (https=)
WO (1) WO2023017721A1 (https=)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119119786B (zh) * 2024-11-08 2025-02-14 西安热工研究院有限公司 一种抗高温水蒸汽氧化的涂层浆料、涂层及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019055784A1 (en) * 2017-09-15 2019-03-21 The Trustees Of The University Of Pennsylvania IMPLANTABLE DEVICES USING 2D METALLIC CARBIDES AND NITRIDES (MXENES)
CN110631743A (zh) * 2019-09-30 2019-12-31 北京航空航天大学 压阻式传感器及其制备方法
WO2021072320A1 (en) * 2019-10-11 2021-04-15 The Trustees Of The University Of Pennsylvania Rapid manufacturing of absorbent substrates for soft, conformable sensors and conductors

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7683323B2 (en) * 2007-03-20 2010-03-23 The Trustees Of Columbia University In The City Of New York Organic field effect transistor systems and methods
US11406299B2 (en) * 2019-02-22 2022-08-09 International Business Machines Corporation Biosensors with programmable sensing cavities

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019055784A1 (en) * 2017-09-15 2019-03-21 The Trustees Of The University Of Pennsylvania IMPLANTABLE DEVICES USING 2D METALLIC CARBIDES AND NITRIDES (MXENES)
CN110631743A (zh) * 2019-09-30 2019-12-31 北京航空航天大学 压阻式传感器及其制备方法
WO2021072320A1 (en) * 2019-10-11 2021-04-15 The Trustees Of The University Of Pennsylvania Rapid manufacturing of absorbent substrates for soft, conformable sensors and conductors

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SALEH ABDULELAH, WUSTONI SHOFARUL, BIHAR ELOISE, EL-DEMELLAWI JEHAD K, ZHANG YIZHOU, HAMA ADEL, DRUET VICTOR, YUDHANTO ARIEF, LUBI: "Inkjet-printed Ti3C2Tx MXene electrodes for multimodal cutaneous biosensing", JOURNAL OF PHYSICS: MATERIALS, vol. 3, no. 4, 1 October 2020 (2020-10-01), pages 044004, XP093035155, DOI: 10.1088/2515-7639/abb361 *

Also Published As

Publication number Publication date
CN117769387A (zh) 2024-03-26
US20240175841A1 (en) 2024-05-30
JP2024529086A (ja) 2024-08-01

Similar Documents

Publication Publication Date Title
US20230242407A1 (en) Conductive two-dimensional particle and method for producing same, conductive film, conductive composite material, and conductive paste
RU2548604C2 (ru) Пьезоэлектрический и/или пироэлектрический композиционный твердый материал, способ его получения и применение такого материала
US20240175841A1 (en) Biosignal sensing electrode
US20150183189A1 (en) Graphene Hydrogel, Graphene Hydrogel Nanocomposite Materials, and Preparation Method Thereof
US20230165500A1 (en) Biosignal sensing electrode
Panwar et al. Enhanced sensing performance of carboxyl graphene–ionic liquid attached ionic polymer–metal nanocomposite based polymer strain sensors
US12516195B2 (en) Electrode and method for producing the same
US20230233127A1 (en) Biosignal sensing electrode
JP7670178B2 (ja) 複合材料および複合材料構造体の製造方法
JP2024533946A (ja) 電極およびその製造方法
WO2023106153A1 (ja) 導電性膜、電極、および導電性膜の製造方法
US12046389B2 (en) Conductive film and method for producing same
US20250388740A1 (en) Two-dimensional particle-containing composition and production method for two-dimensional particle-containing composition
Dorovskikh et al. Bimetallic Pt, Ir-containing coatings formed by MOCVD for medical applications
CN120641044A (zh) 电极和电极的制造方法
EP4388561A1 (en) Two-dimensional particles, conductive film, conductive paste and method for producing two-dimensional particles
JP7786571B2 (ja) 膜および電極
WO2022107784A1 (ja) 生体用電極
WO2024262455A1 (ja) 電極
US20250072807A1 (en) Electrode and method for manufacturing electrode
US20240327227A1 (en) Two-dimensional particle, conductive film, conductive paste, and composite material
US20260001769A1 (en) Two-dimensional particle, and electroconductive film and method for producing same
US20250066208A1 (en) Conductive two-dimensional particle and method for producing same, conductive film, conductive paste, and conductive composite material
Kataky et al. Graphene oxide nanocapsules within silanized hydrogels suitable for electrochemical pseudocapacitors

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22855785

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202280054532.6

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2024507991

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22855785

Country of ref document: EP

Kind code of ref document: A1