WO2021114287A1 - 一种柔性电极及其制备方法 - Google Patents

一种柔性电极及其制备方法 Download PDF

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Publication number
WO2021114287A1
WO2021114287A1 PCT/CN2019/125389 CN2019125389W WO2021114287A1 WO 2021114287 A1 WO2021114287 A1 WO 2021114287A1 CN 2019125389 W CN2019125389 W CN 2019125389W WO 2021114287 A1 WO2021114287 A1 WO 2021114287A1
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Prior art keywords
layer
electrode
flexible
titanium dioxide
polydopamine
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English (en)
French (fr)
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吴天准
黄兆岭
曾齐
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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Priority to US17/618,198 priority Critical patent/US11970391B2/en
Priority to PCT/CN2019/125389 priority patent/WO2021114287A1/zh
Publication of WO2021114287A1 publication Critical patent/WO2021114287A1/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
    • B81C1/00134—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems comprising flexible or deformable structures
    • B81C1/00166—Electrodes
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00—Electrotherapy; Circuits therefor
    • A61N1/02—Details
    • A61N1/04—Electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B3/00—Devices comprising flexible or deformable elements, e.g. comprising elastic tongues or membranes
    • B81B3/0064—Constitution or structural means for improving or controlling the physical properties of a device
    • B81B3/0067—Mechanical properties
    • B81B3/0072—For controlling internal stress or strain in moving or flexible elements, e.g. stress compensating layers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B2201/00—Specific applications of microelectromechanical systems
    • B81B2201/06—Bio-MEMS
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B2203/00—Basic microelectromechanical structures
    • B81B2203/01—Suspended structures, i.e. structures allowing a movement
    • B81B2203/0145—Flexible holders
    • B81B2203/0172—Flexible holders not provided for in B81B2203/0154 - B81B2203/0163
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B2203/00—Basic microelectromechanical structures
    • B81B2203/04—Electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C2201/00—Manufacture or treatment of microstructural devices or systems
    • B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
    • B81C2201/0101—Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
    • B81C2201/0111—Bulk micromachining
    • B81C2201/0114—Electrochemical etching, anodic oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C2201/00—Manufacture or treatment of microstructural devices or systems
    • B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
    • B81C2201/0174—Manufacture or treatment of microstructural devices or systems in or on a substrate for making multi-layered devices, film deposition or growing
    • B81C2201/0183—Selective deposition
    • B81C2201/0185—Printing, e.g. microcontact printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C2201/00—Manufacture or treatment of microstructural devices or systems
    • B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
    • B81C2201/0174—Manufacture or treatment of microstructural devices or systems in or on a substrate for making multi-layered devices, film deposition or growing
    • B81C2201/0183—Selective deposition
    • B81C2201/0187—Controlled formation of micro- or nanostructures using a template positioned on a substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C2201/00—Manufacture or treatment of microstructural devices or systems
    • B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
    • B81C2201/0174—Manufacture or treatment of microstructural devices or systems in or on a substrate for making multi-layered devices, film deposition or growing
    • B81C2201/0191—Transfer of a layer from a carrier wafer to a device wafer
    • B81C2201/0194—Transfer of a layer from a carrier wafer to a device wafer the layer being structured

Definitions

  • the invention relates to the technical field of flexible electrode preparation, in particular to a flexible electrode and a preparation method thereof.
  • flexible electrodes processed and manufactured based on traditional MEMS (MEMS, Micro-Electro-Mechanical System) technology mainly include a flexible base layer and a metal electrode layer on it.
  • MEMS Micro-Electro-Mechanical System
  • the current gap between the surface metal layer and the flexible base layer in the flexible electrode The matching of Young's modulus is not high, and it is easy to cause the metal layer to fall off.
  • studies have shown that the polydopamine film can well deal with the problem of the Young's modulus mismatch between the metal layer and the flexible base layer, and enhance the adhesion between the two.
  • the preparation of polydopamine film is formed by self-assembly of its precursor solution (such as a mixture of dopamine hydrochloride and Tris buffer), but the self-assembly process is relatively long and usually takes more than 24 hours.
  • the use of strong oxidants or ultraviolet light can improve the film formation speed of polydopamine to a certain extent, for medical devices, strong oxidants are more toxic.
  • the accelerated film formation of ultraviolet light is environmentally friendly, but simple ultraviolet light does not Can not improve the film-forming speed of polydopamine (usually 30nm/6h).
  • platinum a metal with good biocompatibility
  • platinum ions are deposited on the polydopamine film to form platinum metal.
  • the layer usually takes more than 72 hours, and the preparation of the overall flexible electrode takes a long time.
  • the present invention provides a method for preparing a flexible electrode.
  • the speed of polydopamine film formation is greatly improved and the subsequent platinum ion
  • the speed of reduction to the platinum electrode layer solves the current problems that the polydopamine is difficult to form a film quickly and the platinum electrode layer is difficult to form quickly.
  • the present invention provides a method for preparing a flexible electrode, including the following steps:
  • a carrier board Provide a carrier board, and sequentially form a flexible base layer and an intermediate conductive layer on one side of the carrier board;
  • Electrode induction layer complementary to the electrode pattern
  • the intermediate conductive layer that is not covered by the electrode inducing layer, a mixture of nano titanium dioxide and a polydopamine precursor solution is dripped, the glass with a transparent conductive coating is used as the cathode, the intermediate conductive layer is the anode, and The transparent conductive layer and the intermediate conductive layer are disposed opposite to each other, and under the condition of ultraviolet light irradiation, an anodic oxidation method is used to form a titanium dioxide-polydopamine composite layer in the gap of the electrode induction layer;
  • the carrier plate is removed to obtain a flexible electrode.
  • the elastic template with electrode pattern is prepared by the following method: spin-coating photoresist on a hard substrate, and expose and develop a mask of a certain shape to obtain the positive film of the electrode pattern; The positive film is cast, and the film is uncovered after curing to obtain an elastic template with electrode patterns.
  • the acid used in the acid treatment includes at least one of hydrofluoric acid, nitric acid, and hydrochloric acid.
  • the applied pressure is 1.0-2.0N.
  • the precursor solution of polydopamine is a Tris solution of dopamine hydrochloride
  • the pH of the precursor solution is 6-9
  • the concentration of dopamine hydrochloride is 2-5 mg/mL.
  • the concentration of the nano titanium dioxide (TiO 2 ) in the mixed solution is 0.05-0.25 mg/mL.
  • the mass ratio of nano-titanium dioxide to dopamine hydrochloride is (0.025-0.05):1.
  • the voltage applied between the cathode and the anode is a direct current voltage of 1-5V.
  • the energy density of the ultraviolet light irradiation is 0.7-5 mW/cm 2 .
  • the distance between the cathode and the anode is 1-5 mm.
  • the ultraviolet light irradiation time is 3-15 minutes; the voltage application time between the cathode and the anode is 3-15 minutes.
  • the ultraviolet light irradiation time is 20-120 min; the voltage application time between the cathode and the anode is 20-120 min.
  • the electrophoretic deposition technology combined with ultraviolet light irradiation can make nano-TiO 2 produce electronic transitions, and improve the active oxygen in the mixed solution of TiO 2 and polydopamine precursor solution.
  • the quantity greatly increase the speed of dopamine oxidation and film formation, and finally quickly form a titanium dioxide-polydopamine composite layer;
  • nano-titanium dioxide can control the hydroxyl content in the platinum ion solution with the help of polydopamine itself.
  • the active group and the reduction effect of nano-TiO 2 in the titanium dioxide-polydopamine composite layer under illumination greatly increases the speed of platinum metal ion reduction to the platinum electrode layer, which is especially suitable for the production of large-area electrode layers; 3.
  • the titanium dioxide-polydopamine composite layer has a certain degree of adhesion, and can form chemical bonds with the platinum electrode layer and the intermediate conductive layer through its numerous molecular bonds to improve the adhesion between them, thereby enhancing the platinum to a certain extent.
  • An electrode inducing layer complementary to the electrode pattern can be quickly formed on the intermediate conductive layer by means of transfer, and the elastic template with the electrode pattern can be used multiple times.
  • the preparation method is simple and easy to operate, does not use expensive deposition equipment and toxic reagents, and the electrophoretic light deposition process used can greatly improve the formation efficiency of the titanium dioxide-polydopamine composite layer and the platinum electrode layer, which is environmentally friendly and efficient. , And reduce the manufacturing cost of flexible electrodes.
  • the second aspect of the present invention provides a flexible electrode, comprising: a flexible base layer and an intermediate conductive layer and an electrode induction layer sequentially arranged on the surface of the flexible base layer, and the gap between the electrode induction layer is provided with a titanium dioxide-polydopamine composite A platinum electrode layer is provided on the titanium dioxide-polydopamine composite layer.
  • the flexible electrode can be prepared by the preparation method described in the first aspect of the present invention.
  • the polydopamine is chelated with platinum atoms.
  • the material of the electrode induction layer is an insulating material. Specifically, it is the residual material after the reaction between the model glue and the acid.
  • the thickness of the flexible base layer is 2-6 ⁇ m.
  • the thickness of the intermediate conductive layer is 10-30 nm.
  • the thickness of the titanium dioxide-polydopamine composite layer is 80-500 nm.
  • the thickness of the platinum electrode layer is 0.3-5 ⁇ m.
  • the flexible base layer and the platinum electrode layer are connected through an intermediate conductive layer and an adhesive titanium dioxide-polydopamine composite layer, and the titanium dioxide-polydopamine composite layer can pass through its own various
  • the molecular bonds form chemical bonds with the platinum electrode layer and the intermediate conductive layer, and under the action of non-covalent bonds, the adhesion between them is improved, thereby enhancing the adhesion between the platinum electrode layer and the flexible base layer to a certain extent. Bonding force; the resulting patterned platinum electrode layer has a small electrical impedance, which improves its safety in biological applications.
  • Figure 1 shows the surface morphology and the corresponding contact angle of the formed polydopamine film in the presence of nano-TiO 2 (a) and without nano-TiO 2 (b);
  • Figure 2 shows the surface morphology of platinum ion deposition on the polydopamine film with nano-TiO 2 (a) and without nano-TiO 2 (b) and the corresponding enlarged view; the right picture is the white solid picture on the left Magnification of the frame;
  • FIG. 3 is a structural design diagram of a metal electrode layer of a flexible electrode in an embodiment of the present invention.
  • FIG. 4 is a schematic diagram of the structure of a PDMS elastic template with an electrode structure in an embodiment of the present invention
  • Fig. 5 is a processing flow chart of a flexible electrode in an embodiment of the present invention.
  • FIG. 6 is a schematic diagram of a process of packaging the flexible electrode of FIG. 3 in an embodiment of the present invention.
  • FIG. 7 is a schematic diagram of the structure of the flexible electrode obtained after processing in FIG.
  • FIG. 8 is a surface morphology diagram of a titanium dioxide-polydopamine composite layer formed in an embodiment of the present invention, wherein (a) and (b) are different observation areas;
  • FIG. 9 is a surface topography diagram of a platinum electrode layer formed in an embodiment of the present invention, where (a) and (b) are different observation areas.
  • the embodiment of the present invention provides a method for preparing a flexible electrode, which includes the following steps:
  • a carrier board Provide a carrier board, and sequentially form a flexible base layer and an intermediate conductive layer on one side of the carrier board;
  • Electrode induction layer complementary to the electrode pattern
  • the intermediate conductive layer that is not covered by the electrode inducing layer, a mixture of nano titanium dioxide and a polydopamine precursor solution is dripped, the glass with a transparent conductive coating is used as the cathode, the intermediate conductive layer is the anode, and The transparent conductive layer and the intermediate conductive layer are disposed opposite to each other, and under the condition of ultraviolet light irradiation, an anodic oxidation method is used to form a titanium dioxide-polydopamine composite layer in the gap of the electrode induction layer;
  • the carrier plate is removed to obtain a flexible electrode.
  • the material of the carrying plate includes glass, silicon, plastic, metal or ceramic.
  • the bearing plate is mainly used as the bearing foundation for subsequent coatings, and needs to be removed after each coating is completed.
  • the flexible base layer may be formed by coating.
  • the material of the flexible base layer is a flexible insulating material, which can be selected from polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), One of polymethylmethacrylate (PMMA) and polyurethane (PUA).
  • PI polyimide
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PMMA polymethylmethacrylate
  • PDA polyurethane
  • the flexible base layer is polyimide, which has good bending resistance and insulation properties.
  • the material of the intermediate conductive layer includes but not limited to titanium, gold, silver, copper, palladium, niobium, tantalum and its alloys, titanium nitride (TixNy), iridium oxide (IrOx), indium tin oxide (ITO), One or more of aluminum-doped zinc oxide (AZO), fluorine-doped tin dioxide (FTO) and phosphorus-doped tin dioxide (PTO).
  • the form of the intermediate conductive layer includes: magnetron sputtering, chemical vapor deposition, electron beam evaporation, pulsed laser deposition, resistance evaporation, or spin coating.
  • the thickness of the flexible base layer is 2-6 ⁇ m.
  • the thickness of the intermediate conductive layer is 10-30 nm.
  • the thickness of the intermediate conductive layer is relatively thin, and it mainly plays a conductive role in the subsequent anodic oxidation and cathode reduction processes.
  • the elastic template with electrode pattern is prepared by the following method: spin-coating photoresist on a hard substrate, and expose and develop a mask of a certain shape to obtain the positive film of the electrode pattern; The positive film is cast, and the film is uncovered after curing to obtain an elastic template with electrode patterns.
  • the elastic template has an electrode pattern complementary to the positive membrane.
  • the elastic template is made of the same material as the model glue.
  • the material of the elastic template is selected from one or more of polydimethylsiloxane, polyethylene glycol diacrylate, polymethyl methacrylate, ethylene-vinyl acetate copolymer, polyurethane, and silica gel, but Not limited to this.
  • the model glue may be polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • the volume ratio of glue A to glue B in PDMS can be 1:10.
  • the model glue can be polyethylene glycol diacrylate (PEGDA), polymethyl methacrylate (PMMA), ethylene-vinyl acetate (EVA) copolymer, polyurethane (PUA) ), a kind of silica gel, but not limited to this, as long as it is a mold glue suitable for soft lithography.
  • the acid used in the acid treatment includes at least one of hydrofluoric acid, nitric acid, and hydrochloric acid.
  • the acid is a mixture of hydrochloric acid and nitric acid with a volume ratio of 3:1, or a mixture of hydrofluoric acid and nitric acid with a volume ratio of 3:1.
  • the applied pressure is 1.0-2.0N. This can better ensure that the polydopamine adhesion layer with electrode patterns is completely transferred to the surface of the thinner intermediate conductive layer, and it can also ensure that the carrier plate (for example, silicon wafer, glass substrate, etc.) is under pressure Will not deform and produce internal stress.
  • the carrier plate for example, silicon wafer, glass substrate, etc.
  • the precursor solution of polydopamine is a Tris solution of dopamine hydrochloride
  • the pH of the precursor solution is 6-9
  • the concentration of dopamine hydrochloride is 2-5 mg/mL.
  • the concentration of the nano titanium dioxide (TiO 2 ) in the mixed solution is 0.05-0.25 mg/mL.
  • the mass ratio of nano-titanium dioxide to dopamine hydrochloride is (0.025-0.05):1.
  • the material of the transparent conductive coating on the glass is indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), fluorine-doped tin dioxide (FTO), phosphorus-doped tin dioxide (PTO), titanium nitride At least one of (TixNy) and iridium oxide (IrOx), but not limited thereto.
  • the thickness of the titanium dioxide-polydopamine composite layer is 80-500 nm. Its thickness can be adjusted by the time of ultraviolet light irradiation and the time of applying power between the anode and cathode.
  • the droplets of the mixture of nano-titania and polydopamine precursor solution will quickly fill the gap of the electrode induction layer, and under the ultraviolet light irradiation of TiO 2, TiO 2 2
  • the combined action of the generated oxygen free radicals and ultraviolet light promotes the rapid oxidation of polydopamine precursors to form polydopamine, and the formation of a titanium dioxide-polydopamine composite layer.
  • the voltage applied between the cathode and the anode is a DC voltage of 1-5V.
  • the loading time of the voltage is 3-15 min.
  • the energy density of the ultraviolet light used is 0.7-5 mW/cm 2 , and the wavelength of the ultraviolet light used is 350-380 nm.
  • the ultraviolet light irradiation time is 3-15 min. The time of ultraviolet light irradiation can be equal to or different from the time of voltage application.
  • the distance between the cathode and the anode is 1-5 mm. If the distance is too large, the ultraviolet light reaching the electrode induction layer will lose more, and the cell line density between the cathode and the anode will be too small.
  • the ultraviolet light is irradiated on the surface of the cathode away from the transparent conductive coating. Because the cathode is transparent as a whole, ultraviolet light can pass through the cathode to reach the electrode induction layer.
  • the ultraviolet light can also be irradiated on the surface of the cathode away from the transparent conductive coating and the surface of the carrier plate away from the flexible base layer at the same time. That is, the ultraviolet light is applied to the upper and lower ends of the cathode and the anode after being arranged oppositely.
  • the thickness of the platinum electrode layer is 0.3-5 ⁇ m. Its thickness can be adjusted by the time of ultraviolet light irradiation and the time of applying power between the anode and cathode.
  • the droplets of the platinum ion solution flow, wetting the titanium dioxide-polydopamine composite layer and the electrode induction layer, and pass through the titanium dioxide-polydopamine composite layer and the electrode induction layer.
  • the dopamine composite layer is irradiated with ultraviolet light, the charge generated by the semiconductor material of titanium dioxide and the large number of phenolic hydroxyl and amine groups of polydopamine itself can promote the reduction of platinum metal ions faster, so that the titanium dioxide-polydopamine composite A patterned platinum electrode layer is formed on the layer.
  • the voltage applied between the cathode and the anode is a DC voltage of 1-5V.
  • the voltage loading time is 20-120 min.
  • the energy density of the ultraviolet light used is 0.7-5 mW/cm 2 , and the wavelength of the ultraviolet light used is 350-380 nm.
  • the ultraviolet light irradiation time is 20-120 min. The time of ultraviolet light irradiation can be equal to or different from the time of voltage application.
  • the distance between the cathode and the anode is 1-5 mm. If the distance is too large, the ultraviolet light reaching the electrode induction layer and the titanium dioxide-polydopamine composite layer will lose more, and the cell line density between the cathode and the anode will be too small.
  • the ultraviolet light is irradiated on the surface of the cathode away from the transparent conductive coating. Because the cathode is transparent as a whole, ultraviolet light can pass through the cathode to reach the electrode induction layer and the titanium dioxide-polydopamine composite layer.
  • the ultraviolet light may also be irradiated on the surface of the cathode facing away from the transparent conductive coating, and the carrier plate facing away from the One side of the flexible base layer. That is, the ultraviolet light is applied to the upper and lower ends of the cathode and the anode after being arranged oppositely.
  • the platinum electrode layer includes a plurality of stimulation electrode sites and a plurality of electrode connection points arranged oppositely, and each of the stimulation electrode sites and the electrode connection points are connected in a one-to-one correspondence with the electrode connection point by a wire.
  • the carrier plate before removing the carrier plate, it further includes: preparing an encapsulation layer on the platinum electrode layer and the electrode induction layer, and the stimulation electrode site and the electrode connection point of the platinum electrode layer are separated from the encapsulation layer Exposed.
  • the material of the encapsulation layer may be the same as or different from the material of the flexible base layer.
  • the material of the encapsulation layer is independently selected from one or more of polyimide, PDMS, silica gel, epoxy resin, polystyrene, and polybutylene terephthalate (PET) .
  • PET polybutylene terephthalate
  • the purpose of the encapsulation layer is to protect the platinum electrode layer as much as possible without affecting its use.
  • the forming method of the encapsulation layer includes injection molding, die casting or photolithography.
  • the preparation process of the encapsulation layer is as follows:
  • An encapsulation film is provided on the platinum electrode layer, the encapsulation film also covers the part of the electrode induction layer that is not covered by the platinum electrode layer;
  • the electrophoretic deposition technology combined with ultraviolet light irradiation can generate electronic transitions of nano-TiO 2 and improve the activity in the mixed solution of TiO 2 and polydopamine precursor solution.
  • the amount of oxygen greatly increases the speed of dopamine oxidation and film formation, and finally quickly forms a titanium dioxide-polydopamine composite layer;
  • nano-titanium dioxide can control the hydroxyl content in the platinum ion solution with the help of polydopamine itself.
  • the titanium dioxide-polydopamine composite layer has a certain degree of adhesion, and can form chemical bonds with the platinum electrode layer and the intermediate conductive layer through its many molecular bonds to improve the adhesion between them, and then to a certain extent.
  • the electrode inducing layer complementary to the electrode pattern can be quickly formed on the intermediate conductive layer by means of transfer, and the elastic template with the electrode pattern can be used multiple times use.
  • the preparation method is simple and easy to operate, does not use expensive deposition equipment and toxic reagents, and the electrophoretic light deposition process used can greatly improve the formation efficiency of the titanium dioxide-polydopamine composite layer and the platinum electrode layer, which is environmentally friendly and efficient. , And reduce the manufacturing cost of flexible electrodes.
  • the embodiment of the present invention also provides a flexible electrode, comprising: a flexible base layer and an intermediate conductive layer and an electrode induction layer sequentially arranged on the surface of the flexible base layer, and the gap between the electrode induction layer is provided with a titanium dioxide-polydopamine composite A platinum electrode layer is provided on the titanium dioxide-polydopamine composite layer.
  • the flexible electrode can be prepared by the preparation method described in the first aspect of the present invention.
  • the polydopamine is chelated with platinum atoms.
  • the material of the electrode induction layer is an insulating material. Specifically, it is the residual material after the reaction between the model glue and the acid.
  • the thickness of the intermediate conductive layer is 10-30 nm.
  • the thickness of the titanium dioxide-polydopamine composite layer is 80-500 nm.
  • the thickness of the platinum electrode layer is 0.3-5 ⁇ m.
  • the flexible electrode further includes an encapsulation layer, and the encapsulation layer covers a portion of the electrode induction layer that is not covered by the stimulation electrode site and the electrode connection point of the platinum electrode layer.
  • the flexible base layer and the platinum electrode layer are connected through an intermediate conductive layer and an adhesive titanium dioxide-polydopamine composite layer.
  • the titanium dioxide-polydopamine composite layer can pass through its own various The molecular bonds form chemical bonds with the platinum electrode layer and the intermediate conductive layer, and under the action of non-covalent bonds, the adhesion between them is improved, thereby enhancing the adhesion between the platinum electrode layer and the flexible base layer to a certain extent. Bonding force; the resulting patterned platinum electrode layer has a small electrical impedance, which improves its safety in biological applications.
  • the dopamine precursor solution is irradiated with ultraviolet light with a wavelength of 365nm under the same light intensity to complete the deposition of the polydopamine film.
  • the preparation process of the polydopamine (PDA) precursor solution containing nano-TiO 2 is as follows: dissolve dopamine hydrochloride (3-hydroxytyramine hydrochloride) in a 10 mM Tris buffer solution, adjust its pH value to 8.5 to form a polydopamine (PDA) precursor solution.
  • Figure 2 (a) is the surface morphology of the metal coating reduced by platinum ions on the surface of the TiO 2 -PDA composite film and the corresponding enlarged view
  • Figure 2 (b) shows the reduction of platinum ions on the surface of the pure PDA film. Surface topography and corresponding magnified image.
  • An embodiment of the present invention provides a method for preparing a flexible electrode. Please refer to FIG. 3 to FIG. 6 together, including the following steps:
  • a silicon wafer as the carrier board.
  • First use acetone, absolute ethanol and deionized water to clean the silicon wafer in sequence.
  • Second level 2500 revolutions, 40 seconds
  • spin-coating the solution of polyimide acid and form a wet film then bake at 100°C for 3 minutes to form the film, and then move to a vacuum dryer at 300°C for high-temperature baking
  • the polyimide acid was cyclized to form a 5 ⁇ m thick polyimide (PI) film, and the PI flexible base layer 10 was obtained.
  • PI polyimide
  • a plasma evaporation method is used to form a 10 nm thick Au conductive layer 20, which can subsequently be used as an electrode position for DC electrophoresis electroplating.
  • a layer of SU-8 photoresist was spin-coated on the cleaned silicon wafer, and after curing at 95°C for 30 minutes, a mask of a certain shape was used for exposure under 180mJ/cm 2 ultraviolet light energy, using SU- 8
  • the developer is subjected to development processing to clean the parts other than the mask to obtain the positive film of the electrode pattern;
  • the model glue used can be, for example, polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • the volume ratio of A glue to B glue in PDMS for pouring can be 1:10.
  • the curing process is carried out (for example, it can be baked in an oven at 80° C. for 3 hours).
  • the electrode pattern in the positive mold can be reliably transferred to the mold glue. Then peel off the cured model adhesive layer from the silicon wafer to obtain a PDMS elastic template with electrode structure (as shown in Figure 4).
  • the electrode template transfers the electrode pattern on the Au conductive layer 20 in step 2 by micro-contact printing (it is better to keep the surface of the Au conductive layer 20 wet before transfer), so that the Au conductive layer 20 is formed
  • the electrode induction layer 30 (as shown in FIG. 3).
  • the material of the electrode induction layer 30 is the residual material after the acid treatment of PDMS; the pressure applied during the micro-contact printing is 1.8N.
  • the transferred electrode induction layer 30 has a shape complementary to the electrode pattern. That is, the groove of the electrode induction layer 30 corresponds to the electrode to be formed.
  • the TiO 2 -PDA composite layer 40 is formed by direct current electrophoresis light deposition:
  • a mixture of nano-TiO 2 and polydopamine (PDA) precursor solution Dissolve dopamine hydrochloride (3-hydroxytyramine hydrochloride) in a 10mM Tris buffer solution, adjust its pH to 8.5 to form polydopamine Precursor solution, wherein the final concentration of dopamine hydrochloride in the precursor solution is 2mg/mL; then take an appropriate amount of nano-TiO 2 aqueous dispersion (mass concentration of 1.7 wt%) and add it to the above 100 mL of the above dopamine precursor In, stir evenly to obtain the mixed liquid.
  • PDA polydopamine
  • a DC voltage of 5V is applied between them; and under the condition of simultaneous ultraviolet light irradiation, the TiO 2 -PDA composite layer 40 is formed by electrodeposition in the gap of the electrode induction layer 30 by anodizing method. Then wash and dry with ultrapure water, and save it for the next step.
  • ultraviolet light is applied to the side of the ITO coated glass without the ITO coating so that the ultraviolet light reaches the mixed solution, and the energy density of the ultraviolet light used is 2mW/cm 2 ,
  • the time of ultraviolet light irradiation is 5 minutes; the time of applying a direct voltage between the anode and the cathode is 5 minutes, and the thickness of the formed TiO 2 -PDA composite layer 40 is 100 nm.
  • the platinum electrode layer 50 is formed by direct current electrophoresis light deposition:
  • the above-mentioned ITO-coated glass is used as the anode
  • the Au conductive layer 20 is the cathode
  • the distance between the cathode and the anode is controlled to be 1-2mm, and a DC voltage of 5V is applied between the anode and the cathode; and when the ultraviolet light is irradiated at the same time, the cathode is reduced in the TiO 2-
  • a platinum electrode layer 50 is formed on the PDA composite layer 40. Then wash and dry with ultrapure water, and save it for the next step.
  • ultraviolet light is applied to the side of the ITO coated glass without the ITO coating so that the ultraviolet light reaches the platinum ion solution, and the energy density of the ultraviolet light used is 2mW/cm 2
  • the time for ultraviolet light irradiation is 1 hour; the time for applying DC voltage between the cathode and anode is 1 hour, and the thickness of the formed platinum electrode layer 50 is 0.5 ⁇ m.
  • An encapsulation film 60' is provided on the platinum electrode layer 50, and the encapsulation film 60' also covers the portion of the electrode induction layer 30 that is not covered by the platinum electrode layer 50.
  • the material of the packaging film 60' can also be PI, and the setting process is as follows:
  • Two-level speed (first level: 300 revolutions, 15 seconds; second level: 3000 revolutions, 30 seconds) is used to coat the sacrificial material (specifically AZ4620 positive photoresist) on the aforementioned PI packaging film 60',
  • sacrificial material specifically AZ4620 positive photoresist
  • UV-expose the sacrificial layer Exposure amount is 40mJ/cm 2
  • post-baking at 120°C after exposure, and develop it with AZ300 developer after cooling to room temperature
  • a patterned sacrificial layer 70 is formed.
  • the patterned sacrificial layer 70 does not cover the stimulation electrode sites 51 and the electrode connection points 52 of the platinum electrode layer 50 (see FIG. 3).
  • etching parameters are set as follows: oxygen flow rate: 40 sccm, chamber pressure: 20-14 pa, power: 150 W, etching time: 10 min, 4 consecutive times.
  • FIG. 3 is a structural design diagram of the platinum electrode layer 50 of the flexible electrode in the embodiment of the present invention.
  • the platinum electrode layer 50 includes 10 stimulation electrode sites 51 and 10 electrode connection points 52 arranged oppositely, and each stimulation electrode site 51 and the electrode connection point 52 are connected in a one-to-one correspondence with the electrode connection point 52 via a wire 53.
  • the diameter of the stimulation electrode site 51 is 200 ⁇ m
  • the width of the wire 53 is 35 ⁇ m
  • the electrode connection point 52 is a 1*1mm square, which can be connected to a PCB board with a chip or connected to other instruments for testing. Wait.
  • FIG. 7 is a schematic diagram of the structure of a flexible electrode after packaging in an embodiment of the present invention.
  • the flexible electrode includes a flexible base layer 10 and an intermediate conductive layer 20 and an electrode induction layer 30 sequentially arranged on the surface of the flexible base layer 10.
  • the gap between the electrode induction layer 30 is provided with a titanium dioxide-polydopamine composite layer 40
  • a platinum electrode layer 50 is provided on the titanium dioxide-polydopamine composite layer 40.
  • the flexible electrode further includes an encapsulation layer 60 that covers the portion of the electrode induction layer 30 that is not covered by the stimulation electrode sites 51 and the electrode connection points 52 of the platinum electrode layer 50.
  • the electrode induction layer 30 and the platinum electrode layer 50 are both located in the accommodating space of the encapsulation layer 60, but the stimulation electrode site 51 and the electrode connection point 52 of the platinum electrode layer 50 are exposed from the encapsulation layer, and the platinum electrode layer 50 The wires of the electrode layer 50 are not exposed.
  • FIG. 8 is a surface topography diagram of a TiO 2 -PDA composite layer formed by DC electrophoresis light deposition in an embodiment of the present invention
  • FIG. 9 is a surface topography diagram of a platinum electrode layer formed by DC electrophoresis light deposition in an embodiment of the present invention. It can be seen from Figure 8 that in the presence of nano-TiO 2 , using DC electrophoresis and ultraviolet light technology, a deep yellow TiO 2 -PDA composite layer can be quickly formed through the anode; it can be seen from Figure 9 that in the presence of TiO 2 -On the PDA composite layer, using DC electrophoresis and ultraviolet light technology, a black platinum electrode layer can be quickly formed.
  • the above-mentioned TiO 2 -PDA composite layer and the platinum electrode layer both form a coating in a predetermined groove structure, and the edge interface has a clear resolution.
  • the above results indicate that the flexible electrode preparation method provided by the present invention can quickly and orientedly prepare a TiO 2 -PDA composite layer and a platinum electrode layer with a regular structure.

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Abstract

一种柔性电极的制备方法，包括：在承载板上依次形成柔性基底层和中间导电层；将具有电极图案的弹性模用酸处理后，将电极图案转印到中间导电层上，形成电极诱导层；在未被电极诱导层覆盖的中间导电层上滴加纳米二氧化钛和聚多巴胺前驱体溶液的混合液，以中间导电层为阳极，在紫外光照射下，通过阳极氧化在电极诱导层的间隙形成二氧化钛-聚多巴胺复合层；在二氧化钛-聚多巴胺复合层和电极诱导层的表面滴加铂离子溶液，以中间导电层为阴极，在紫外光照射下，通过阴极还原在二氧化钛-聚多巴胺复合层上形成铂电极层；去除承载板。解决了当前聚多巴胺成膜慢，以及铂电极层形成慢的问题。还提供了一种柔性电极。

Description

一种柔性电极及其制备方法 技术领域
本发明涉及柔性电极制备技术领域，具体涉及一种柔性电极及其制备方法。
背景技术
目前基于传统MEMS(MEMS,Micro-Electro-Mechanical System)技术加工制造的柔性电极，主要包括柔性基底层及位于其上的金属电极层，但目前柔性电极中表面金属层与柔性基底层之间的杨氏模量的匹配性不高，容易造成金属层的脱落。基于此，有研究表明，聚多巴胺薄膜能够很好地处理金属层与柔性基底层的杨氏模量不匹配的问题，增强两者之间的粘附力。
通常，聚多巴胺薄膜制备是通过其前驱体溶液(如盐酸多巴胺与Tris缓冲液的混合)自组装形成，但该自组装过程较长，通常需要花费24小时以上。采用强氧化剂或采用紫外光照虽然在一定程度上可以提高聚多巴胺的成膜速度，但对于医用器件而沿，强氧化剂的毒性较大，而紫外光照加速成膜虽环保，但单纯的紫外光照并不能很好地提高聚多巴胺的成膜速度(通常30nm/6h)。
此外，对于医用柔性电极而言，在聚多巴胺薄膜沉积铂这种生物相容性较好的金属显得十分必要，但由于铂本身的功函数较高，在聚多巴胺薄膜上沉积铂离子形成铂金属层通常需要72小时以上，整体的柔性电极的制备花费时间较长。
因此，有必要提供一种快速制备柔性电极的环境友好型工艺。
发明内容
鉴于此，本发明提供了一种柔性电极的制备方法，通过纳米二氧化钛与聚多巴胺前驱体溶液在电泳和紫外光照相结合的条件下，极大地提高了聚多巴胺成膜的速度以及后续将铂离子还原成铂电极层的速度，解决了当前聚多巴胺难以快速成膜，以及铂电极层难以快速形成的问题。
第一方面，本发明提供了一种柔性电极的制备方法，包括以下步骤：
提供承载板，在所述承载板的一面依次形成柔性基底层和中间导电层；
制备具有电极图案的弹性模板，将所述弹性模板采用酸处理后，将其上的电极图案通过微接触印刷的方式转印到所述中间导电层的表面，以在所述中间导电层上形成与电极图案互补的电极诱导层；
在未被所述电极诱导层覆盖的所述中间导电层上滴加纳米二氧化钛和聚多巴胺前驱体溶液的混合液，以具有透明导电涂层的玻璃为阴极，所述中间导电层为阳极，并将所述透明导电层与所述中间导电层相对设置，在紫外光照射的情况下，采用阳极氧化方式在所述电极诱导层的间隙电沉积形成二氧化钛-聚多巴胺复合层；
在所述二氧化钛-聚多巴胺复合层和所述电极诱导层的表面滴加铂离子溶液，以所述具有透明导电涂层的玻璃为阳极，所述中间导电层为阴极，并将所述透明导电层朝向所述中间导电层，在紫外光照射的情况下，采用阴极还原的方式在所述二氧化钛-聚多巴胺复合层上形成铂电极层；
去除所述承载板，得到柔性电极。
其中，所述具有电极图案的弹性模板是通过以下方法制备：在硬质衬底上旋涂光刻胶，利用一定形状的掩膜版进行曝光、显影，得到电极图案的阳膜；用模型胶浇注所述阳膜，固化后揭膜，得到具有电极图案的弹性模板。
其中，所述酸处理时所用的酸包括氢氟酸、硝酸、盐酸中的至少一种。对所述弹性模板进行酸处理后，可便于在所述中间导电层上形成具有与电极图案互补的电极诱导层。
其中，在所述微接触印刷时，所施加的压力为1.0-2.0N。
其中，所述聚多巴胺的前驱体溶液为盐酸多巴胺的Tris溶液，所述前驱体溶液的pH为6-9，盐酸多巴胺的浓度为2-5mg/mL。
其中，所述纳米二氧化钛(TiO 2)在所述混合液中的浓度为0.05-0.25mg/mL。
可选地，所述混合液中，纳米二氧化钛与盐酸多巴胺的质量比为(0.025-0.05)：1。
其中，在所述阳极氧化和所述阴极还原过程中，阴极和阳极之间加载的电压为1-5V的直流电压。
其中，在所述阳极氧化和所述阴极还原过程中，所述紫外光照射的能量密度为0.7-5mW/cm 2。
其中，在所述阳极氧化和所述阴极还原的过程中，阴极和阳极之间的距离为1-5mm。
其中，在形成所述二氧化钛-聚多巴胺复合层的过程中，所述紫外光照射的时间为3-15min；阴极和阳极之间加载电压的时间为3-15min。
可选地，在形成所述铂电极层的过程中，所述紫外光照射的时间为20-120min；阴极和阳极之间加载电压的时间为20-120min。
本发明第一方面提供的柔性电极的制备方法中：1、通过电泳沉积技术结合紫外光照射，可使纳米TiO 2产生电子跃迁，提高TiO 2和聚多巴胺前驱体溶液的混合液中活性氧的数量，大大提高多巴胺氧化成膜的速度，最终快速形成二氧化钛-聚多巴胺复合层；2、通过电泳技术结合紫外光照射，可使纳米二氧化钛控制铂离子溶液中羟基含量，借助聚多巴胺自身的较多活性基团及二氧化钛-聚多巴胺复合层中纳米TiO 2在光照下产生的还原作用，大幅度地提高了铂金属离子还原成铂电极层的速度，尤其适合大面积电极层的制作；3、所述二氧化钛-聚多巴胺复合层具有一定的粘附性，并可通过其繁多的分子键与铂电极层、中间导电层形成化学键，提高它们之间的粘附力，进而在一定程度上增强了铂电极层与柔性基底层之间的结合力；4、通过转印的方式可快速在中间导电层上形成与电极图案互补的电极诱导层，且所述具有电极图案的弹性模板可多次利用。
总之，该制备方法简单易操作，没有采用使用昂贵的沉积仪器和毒性大的试剂，所采用的电泳光照沉积工艺可以极大地提高二氧化钛-聚多巴胺复合层和铂电极层的形成效率，绿色环保高效，并降低了柔性电极的制造成本。
本发明第二方面提供了一种柔性电极，包括：柔性基底层和依次设置在所述柔性基底层表面的中间导电层和电极诱导层，所述电极诱导层的间隙设有二氧化钛-聚多巴胺复合层，所述二氧化钛-聚多巴胺复合层上设有铂电极层。所述柔性电极可以采用如本发明第一方面所述的制备方法制得。
其中，所述二氧化钛-聚多巴胺复合层与所述铂电极层的界面处，所述聚多巴胺螯合有铂原子。
其中，所述电极诱导层的材质为绝缘材料。具体为模型胶与酸反应后的残留材料。
其中，所述柔性基底层的厚度为2-6μm。
其中，所述中间导电层的厚度为10-30nm。
其中，所述二氧化钛-聚多巴胺复合层的厚度为80-500nm。
其中，所述铂电极层的厚度为0.3-5μm。
本发明第二方面提供的柔性电极中，通过中间导电层和粘附性的二氧化钛-聚多巴胺复合层来连接柔性基底层和铂电极层，所述二氧化钛-聚多巴胺复合层可通过其自身繁多的分子键与铂电极层、中间导电层形成化学键，并在非共价键等作用下，提高了它们之间的粘 附力，进而在一定程度上增强了铂电极层与柔性基底层之间的结合力；所得图案化的铂电极层的电阻抗较小，提高了其生物应用时的安全性。
本发明的优点将会在下面的说明书中部分阐明，一部分根据说明书是显而易见的，或者可以通过本发明实施例的实施而获知。
附图说明
图1为存在纳米TiO 2(a)和不存在纳米TiO 2(b)时，形成的聚多巴胺薄膜的表面形貌图和对应的接触角；
图2为存在纳米TiO 2(a)和不存在纳米TiO 2(b)的聚多巴胺薄膜上铂离子沉积的表面形貌图和对应的放大图；其中，右侧图为左侧图中白色实框处的放大；
图3为本发明实施例中柔性电极的金属电极层的结构设计图；
图4为本发明实施例中具有电极结构的PDMS弹性模板的结构示意图；
图5为本发明一实施例中柔性电极的加工流程图；
图6为本发明一实施例中对图3的柔性电极进行封装的过程示意图；
图7为经图6加工后所得柔性电极的结构示意图；
图8为本发明一实施例中形成的二氧化钛-聚多巴胺复合层的表面形貌图，其中，(a)、(b)为不同的观察区域；
图9为本发明一实施例中形成的铂电极层的表面形貌图，其中，(a)、(b)为不同的观察区域。
具体实施方式
以下所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明的保护范围。
本发明实施方式提供了一种柔性电极的制备方法，包括以下步骤：
提供承载板，在所述承载板的一面依次形成柔性基底层和中间导电层；
制备具有电极图案的弹性模板，将所述弹性模板采用酸处理后，将其上的电极图案通过微接触印刷的方式转印到所述中间导电层的表面，以在所述中间导电层上形成与电极图案互补的电极诱导层；
在未被所述电极诱导层覆盖的所述中间导电层上滴加纳米二氧化钛和聚多巴胺前驱体溶液的混合液，以具有透明导电涂层的玻璃为阴极，所述中间导电层为阳极，并将所述透明导电层与所述中间导电层相对设置，在紫外光照射的情况下，采用阳极氧化方式在所述电极诱导层的间隙电沉积形成二氧化钛-聚多巴胺复合层；
在所述二氧化钛-聚多巴胺复合层和所述电极诱导层的表面滴加铂离子溶液，以所述具有透明导电涂层的玻璃为阳极，所述中间导电层为阴极，并将所述透明导电层朝向所述中间导电层，在紫外光照射的情况下，采用阴极还原的方式在所述二氧化钛-聚多巴胺复合层上形成铂电极层；
去除所述承载板，得到柔性电极。
其中，所述承载板的材质包括玻璃、硅、塑料、金属或陶瓷。所述承载板主要作为后续各涂层的承载基础，在各涂层制作完成后需要除去。
其中，所述柔性基底层的形成方式可以为涂布。所述柔性基底层的材质为柔性绝缘材料，可以选自聚酰亚胺(Polyimide，PI)、聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚甲基丙烯酸甲酯(PMMA)和聚氨酯(PUA)中的一种。优选地，所述柔性基底层为聚酰亚胺，具有较好的耐弯折和绝缘性能。
其中，所述中间导电层的材质包括但不限于钛、金、银、铜、钯、铌、钽及其合金、氮化钛(TixNy)、氧化铱(IrOx)、氧化铟锡(ITO)、掺铝氧化锌(AZO)、掺氟二氧化锡(FTO)和掺磷二氧化锡(PTO)中的一种或多种。
可选地，所述中间导电层的形式方式包括：磁控溅射法、化学气相沉积法、电子束蒸发、脉冲激光沉积法、电阻蒸发法或旋涂法。
可选地，所述柔性基底层的厚度为2-6μm。
可选地，所述中间导电层的厚度为10-30nm。所述中间导电层的厚度较薄，其主要在后续阳极氧化、阴极还原过程中起导电作用。
其中，所述具有电极图案的弹性模板是通过以下方法制备：在硬质衬底上旋涂光刻胶，利用一定形状的掩膜版进行曝光、显影，得到电极图案的阳膜；用模型胶浇注所述阳膜，固化后揭膜，得到具有电极图案的弹性模板。其中，所述弹性模板具有与所述阳膜互补的电极图案。显然地，所述弹性模板与所述模型胶的材质相同。
所述弹性模板的材质选自聚二甲基硅氧烷、聚乙二醇二丙烯酸酯、聚甲基丙烯酸甲酯、乙烯-醋酸乙烯共聚物、聚氨酯、硅胶中的一种或多种，但不限于此。
可选地，所述模型胶可以是聚二甲基硅氧烷(PDMS)。其中，PDMS中A胶与B胶的体积比可以为1：10。当然，在本发明其他实施方式中，所述模型胶可以为聚乙二醇二丙烯酸酯(PEGDA)、聚甲基丙烯酸甲酯(PMMA)、乙烯-醋酸乙烯(EVA)共聚物、聚氨酯(PUA)、硅胶中的一种，但不限于此，只要是适用于软光刻法的模型胶即可。
其中，所述酸处理时所用的酸包括氢氟酸、硝酸、盐酸中的至少一种。对所述弹性模板进行酸处理后，可便于在所述中间导电层上形成与电极图案互补的电极诱导层。所述电极诱导层的形状与所述弹性模板的形状相同。可选地，所述酸为体积比3:1的盐酸和硝酸的混合，或者为体积比3:1的氢氟酸和硝酸的混合。
其中，在所述微接触印刷时，所施加的压力为1.0-2.0N。这样可以较好地保证具有电极图案的聚多巴胺粘附层完整地转印到厚度较薄的中间导电层表面，又能保证承载板(例如，硅晶圆，玻璃基底等)在压力的作用下不至于发生形变和产生内应力。
其中，所述聚多巴胺的前驱体溶液为盐酸多巴胺的Tris溶液，所述前驱体溶液的pH为6-9，盐酸多巴胺的浓度为2-5mg/mL。
其中，所述纳米二氧化钛(TiO 2)在所述混合液中的浓度为0.05-0.25mg/mL。
可选地，所述混合液中，纳米二氧化钛与盐酸多巴胺的质量比为(0.025-0.05)：1。
其中，玻璃上的所述透明导电涂层的材质为氧化铟锡(ITO)、掺铝氧化锌(AZO)、掺氟二氧化锡(FTO)、掺磷二氧化锡(PTO)、氮化钛(TixNy)和氧化铱(IrOx)中的至少一种，但不限于此。
可选地，所述二氧化钛-聚多巴胺复合层的厚度为80-500nm。其厚度可以通过紫外光照射的时间及阴阳极之间加载电源的时间来调节。在阴阳极之间加载有电流时，因电泳作用，纳米二氧化钛和聚多巴胺前驱体溶液的混合液的液滴会迅速填充在电极诱导层的间隙，并在有TiO 2的紫外光照射下，TiO 2产生的氧自由基及紫外光的共同作用促使了聚多巴胺前驱体快速氧化形成聚多巴胺，并形成了二氧化钛-聚多巴胺复合层。
可选地，所述阳极氧化过程中，阴极和阳极之间加载的电压为1-5V的直流电压。所述电压的加载时间为3-15min。
可选地，在形成所述二氧化钛-聚多巴胺复合层的过程中，所用紫外光的能量密度为0.7-5mW/cm 2，所用紫外光的波长在350-380nm。可选地，在形成所述二氧化钛-聚多巴胺复合层的过程中，所述紫外光照射的时间为3-15min。紫外光照射的时间可以与电压的加载时间相等，或不等。
其中，在所述阳极氧化过程中，阴极和阳极之间的距离为1-5mm。该距离若太大，会造成到达电极诱导层的紫外光损失较多，且阴极和阳极之间的电池线密度太小。
在本发明一实施方式中，在所述阳极氧化过程中，所述紫外光照射在所述阴极背离所述透明导电涂层的表面。因所述阴极整体透明，这样紫外光可以通过阴极而达到电极诱导层。当然，在本发明的其他实施方式中，所述紫外光也可以同时照射在所述阴极背离所述透明导电涂层的表面，及所述承载板背离所述柔性基底层的一面。即，紫外光加载在相对设置后的阴极和阳极的上下两端。
可选地，所述铂电极层的厚度为0.3-5μm。其厚度可以通过紫外光照射的时间及阴阳极之间加载电源的时间来调节。
在加载有电流时，因电泳在表界面的电润湿效应，所述铂离子溶液的液滴流动，润湿所述二氧化钛-聚多巴胺复合层和电极诱导层，并在经过所述二氧化钛-聚多巴胺复合层时，因紫外光照射二氧化钛这种半导体材料产生的电荷以及聚多巴胺自身大量的酚羟基和胺基基团能促使铂金属离子能够更快地还原，从而在所述二氧化钛-聚多巴胺复合层上形成图案化的铂电极层。
可选地，所述阴极还原过程中，阴极和阳极之间加载的电压为1-5V的直流电压。可选地，所述电压的加载时间为20-120min。
可选地，在形成所述铂电极层的过程中，所用紫外光的能量密度为0.7-5mW/cm 2，所用紫外光的波长在350-380nm。可选地，在形成所述铂电极层的过程中，所述紫外光照射的时间为20-120min。紫外光照射的时间可以与电压的加载时间相等，或不等。
其中，在所述阴极还原过程中，阴极和阳极之间的距离为1-5mm。该距离若太大，会造成到达电极诱导层和二氧化钛-聚多巴胺复合层的紫外光损失较多，且阴极和阳极之间的电池线密度会太小。
在本发明一实施方式中，在所述阴极还原过程中，所述紫外光照射在所述阴极背离所述透明导电涂层的表面。因所述阴极整体透明，这样紫外光可以通过阴极而达到电极诱导层和二氧化钛-聚多巴胺复合层。当然，在本发明的其他实施方式中，在所述阴极还原过程中时，所述紫外光也可以同时照射在所述阴极背离所述透明导电涂层的表面，及所述承载板背离所述柔性基底层的一面。即，紫外光加载在相对设置后的阴极和阳极的上下两端。
其中，所述铂电极层包括相对设置的多个刺激电极位点和多个电极连接点，每个所述刺激电极位点与电极连接点通过导线一一对应连接。
其中，在去除所述承载板之前还包括：在所述铂电极层上及所述电极诱导层上制备封装层，且所述铂电极层的刺激电极位点与电极连接点从所述封装层中露出。
所述封装层的材质可以与所述柔性基底层的材质相同或不同。可选地，所述封装层的材质独立地选自聚酰亚胺、PDMS、硅胶、环氧树脂、聚苯乙烯和聚对苯二甲酸丁二醇酯(PET)中的一种或多种。所述封装层的设置目的是为了尽量保护所述铂电极层，但又不影响其使用。
所述封装层的形成方式包括注塑、压铸或光刻。在本发明一实施方式中，所述封装层的制备过程如下：
b1、在所述铂电极层上设置封装膜，所述封装膜还覆盖所述电极诱导层上未被所述铂电极层覆盖的部分；
b2、在所述封装膜上涂布牺牲材料，对形成的牺牲层进行刻蚀，形成图案化的牺牲层；
b3、以图案化的牺牲层为掩膜版，对所述封装膜进行干法刻蚀，以使所述铂电极层暴露；
b4、剥离所述牺牲层，形成所述封装层。
本发明实施方式第一方面提供的柔性电极的制备方法中：1、通过电泳沉积技术结合紫外光照射，可使纳米TiO 2产生电子跃迁，提高TiO 2和聚多巴胺前驱体溶液的混合液中活性氧的数量，大大提高多巴胺氧化成膜的速度，最终快速形成二氧化钛-聚多巴胺复合层；2、通过电泳技术结合紫外光照射，可使纳米二氧化钛控制铂离子溶液中羟基含量，借助聚多巴胺自身的较多活性基团及二氧化钛-聚多巴胺复合层中纳米TiO 2在光照下产生的还原作用，大幅度地提高了铂金属离子还原成铂电极层的速度，尤其适合大面积电极层的制作；3、所述二氧化钛-聚多巴胺复合层具有一定的粘附性，并可通过其繁多的分子键与铂电极层、中间导电层形成化学键，提高它们之间的粘附力，进而在一定程度上增强了铂电极层与柔性基底层之间的结合力；4、通过转印的方式可快速在中间导电层上形成与电极图案互补的电极诱导层，且所述具有电极图案的弹性模板可多次利用。
总之，该制备方法简单易操作，没有采用使用昂贵的沉积仪器和毒性大的试剂，所采用的电泳光照沉积工艺可以极大地提高二氧化钛-聚多巴胺复合层和铂电极层的形成效率，绿色环保高效，并降低了柔性电极的制造成本。
本发明实施方式还提供了一种柔性电极，包括：柔性基底层和依次设置在所述柔性基底层表面的中间导电层和电极诱导层，所述电极诱导层的间隙设有二氧化钛-聚多巴胺复合 层，所述二氧化钛-聚多巴胺复合层上设有铂电极层。所述柔性电极可以采用如本发明第一方面所述的制备方法制得。
其中，所述二氧化钛-聚多巴胺复合层与所述铂电极层的界面处，聚多巴胺螯合有铂原子。
其中，所述电极诱导层的材质为绝缘材料。具体为模型胶与酸反应后的残留材料。
如上所述，所述中间导电层的厚度为10-30nm。所述二氧化钛-聚多巴胺复合层的厚度为80-500nm。所述铂电极层的厚度为0.3-5μm。
其中，所述柔性电极还包括封装层，所述封装层覆盖所述电极诱导层上未被所述铂电极层的刺激电极位点与电极连接点所覆盖的部分。
本发明第二方面提供的柔性电极中，通过中间导电层和粘附性的二氧化钛-聚多巴胺复合层来连接柔性基底层和铂电极层，所述二氧化钛-聚多巴胺复合层可通过其自身繁多的分子键与铂电极层、中间导电层形成化学键，并在非共价键等作用下，提高了它们之间的粘附力，进而在一定程度上增强了铂电极层与柔性基底层之间的结合力；所得图案化的铂电极层的电阻抗较小，提高了其生物应用时的安全性。
为了验证纳米TiO 2在二氧化钛-聚多巴胺复合层、铂电极层的快速形成过程中的作用，现设置以下验证实验。
取表面存在聚酰亚胺薄膜的完全相同的两个硅片(尺寸为1cm*1cm)，分别在硅片上涂覆含纳米TiO 2的聚多巴胺前驱体溶液，和不含纳米TiO 2的聚多巴胺前驱体溶液，并采用波长为365nm的紫外光在同等光照强度下进行照射，完成聚多巴胺膜的沉积。其中，含纳米TiO 2的聚多巴胺(PDA)前驱体溶液的配置过程如下：将盐酸多巴胺(3-羟基酪胺盐酸盐)溶解于10mM的Tris缓冲溶液，调节其pH值至8.5，形成聚多巴胺的前驱体溶液，其中，盐酸多巴胺在该前驱体溶液的最终浓度为2mg/mL；然后取适量的纳米TiO 2的水分散液(质量浓度为1.7wt％)，加入到上述100mL的上述多巴胺前驱液中，搅拌均匀得到混合液。
结果如图1所示，其中，图1中(a)为存在纳米TiO 2的情况下，紫外光照射1小时后形成的薄膜的表面形貌图和对应的表面接触角；图1中(b)为无纳米TiO 2的情况下，紫外光照射6小时后形成的薄膜的表面形貌图和对应的表面接触角。从图1中可以看出，在存在纳米TiO 2的情况下紫外光照射1小时后形成的薄膜与无纳米TiO 2的情况下紫外光照射6小时后形成的薄膜类似，两者的接触角接近，均为小角度的锐角，这说明都形成了亲水性的聚多 巴胺膜。但在存在纳米TiO 2时，聚多巴胺成膜的速度大大加快，可缩短至1小时内完成，与常规聚多巴胺成膜所需的24小时相比，大大提高了成膜效率。其中，(a)中形成的是TiO 2-PDA复合薄膜，纳米TiO 2颗粒均匀分布在PDA薄膜中；(b)中形成的是单纯的PDA薄膜。
然后，通过混合2.5mM的氯铂酸水溶液与5mM的甲酸水溶液形成铂离子溶液，将上述TiO 2-PDA复合薄膜和PDA薄膜分别放入上述铂离子溶液中，采用同等紫外光照射6小时，以进行铂离子的还原，结果如图2所示。其中，图2中(a)为铂离子在TiO 2-PDA复合薄膜表面还原金属涂层的表面形貌图和对应的放大图，图2中(b)表示铂离子在单纯PDA薄膜表面还原的表面形貌图和对应的放大图。
从图2中可以看出，在不存在纳米TiO 2时，即使在紫外光下照射6小时，也无法在PDA薄膜表面观察到铂金属层的形成；而在存在纳米TiO 2时，在紫外光下照射6小时，就能在TiO 2-PDA复合薄膜表面形成形貌规整的铂金属层。这与现有技术中沉积铂金属层需要72小时以上相比，将铂金属层的制备时间缩短了11倍，大大节约了制备时间。
基于上述验证试验的验证结果，下面以一个具体的例子来介绍本发明的内容。本发明一实施例提供了一种柔性电极的制备方法，请一并参阅图3-图6，包括以下步骤：
1、提供一硅片作为承载板，首先使用丙酮、无水乙醇以及去离子水依次清洁该硅片，在该硅片的一表面上采用两级速度(第一级：500转，10秒；第二级：2500转，40秒)旋涂聚酰亚胺酸的溶液，并形成湿膜；然后在100℃烘烤3分钟成膜，然后移到300℃的真空干燥器中进行高温烘烤30分钟，以使聚酰亚胺酸环化生成5μm厚的聚酰亚胺(PI)薄膜，即获得了PI柔性基底层10。
2、在步骤1中的5μm厚的PI柔性基底层10上，使用等离子体蒸镀的方法形成10nm厚度的Au导电层20，后续可将该导电层作为直流电泳电镀的一个电极位。
3、制备具有电极图案的弹性模板：
3.1另取一硅片作为硬质衬底，根据设计好的柔性电极的图形模板(如图3)，采用光刻法在其上制作电极图案的阳膜，具体包括以下步骤；
在清洗干净后的硅片上旋涂一层SU-8光刻胶，在95℃固化30分钟之后，利用一定形状的掩膜版在180mJ/cm 2的紫外光能量下进行曝光，使用SU-8显影液进行显影处理，清洗掉掩膜版以外的部分，得到电极图案的阳膜；
然后使用120℃的热板进行坚膜处理15分钟，以使残留的光刻胶中的溶剂全部挥发，进而使该阳膜更牢固地粘附在硅片表面，以便后续重复利用；
3.2往上述阳膜中浇注模型胶，经脱气泡、固化后揭膜，得到具有电极图案的弹性模板；所述弹性模板具有与所述阳膜互补的图案。所用模型胶例如可以是聚二甲基硅氧烷(PDMS)。其中，浇筑用PDMS中A胶与B胶的体积比可以为1：10。经脱泡机脱除气泡后，再进行固化处理(例如可以是在80℃的烘箱中烘烤3小时)。固化后，上述阳模中的电极图案能够可靠地转印到模型胶。然后从硅片上揭下固化后的模型胶层，即得到具有电极结构的PDMS弹性模板(如图4所示)。
4、配置氢氟酸(HF)和硝酸体积比为3:1的混合酸液，并将步骤3中制得的PDMS弹性模板沾上该混合酸液，之后并将沾有混合酸液的PDMS电极模板通过微接触印刷的方式使其上的电极图案转印到步骤2中的Au导电层20表面(转印前最好保持Au导电层20表面湿润)，这样在Au导电层20上形成了电极诱导层30(如图3所示)。其中，电极诱导层30的材质为PDMS经酸处理后的残留材料；在所述微接触印刷时，所施加的压力为1.8N。转印后的电极诱导层30具有与电极图案互补的形状。即，电极诱导层30的凹槽对应要形成的电极。
转印完成后，使用去离子水冲洗，并用氮气吹干，等待下一步使用。
5、通过直流电泳光照沉积形成TiO 2-PDA复合层40：
5.1配置纳米TiO 2和聚多巴胺(PDA)前驱体溶液的混合液：将盐酸多巴胺(3-羟基酪胺盐酸盐)溶解于10mM的Tris缓冲溶液，调节其pH值至8.5，形成聚多巴胺的前驱体溶液，其中，盐酸多巴胺在该前驱体溶液的最终浓度为2mg/mL；然后取适量的纳米TiO 2的水分散液(质量浓度为1.7wt％)，加入到上述100mL的上述多巴胺前驱液中，搅拌均匀得到所述混合液。
5.2取步骤4中带有依次层叠设置有PI柔性基底层10、Au导电层20、电极诱导层30的硅片，在未被电极诱导层30覆盖的Au导电层20上滴加上述混合液，以带ITO涂层的玻璃为阴极，Au导电层20为阳极，并将玻璃的ITO涂层与Au导电层20相对设置，控制阴极和阳极之间的距离为1-2mm，并在阴阳极之间加载5V的直流电压；并在同时进行紫外光照射的情况下，采用阳极氧化方式在电极诱导层30的间隙电沉积形成TiO 2-PDA复合层40。之后用超纯水进行清洗并烘干，留待下一步用。
其中，在该电沉积过程中，朝带ITO涂层的玻璃不具有ITO涂层的一面施加紫外光，以使紫外光到达所述混合液处，所用紫外光的能量密度为2mW/cm 2，紫外光照射的时间为 5min；阴阳极之间加载直流电压的时间为5min，所形成的TiO 2-PDA复合层40的厚度为100nm。
6、通过直流电泳光照沉积形成铂电极层50：
将80mL、2.5mM的氯铂酸水溶液与甲酸混合，加入去离子水，使混合后的溶液总体积为100mL，得到沉积铂电极层所需的铂离子溶液。
在TiO 2-PDA复合层40和电极诱导层30的表面滴加该铂离子溶液，此时以上述带ITO涂层的玻璃为阳极，Au导电层20为阴极，并将玻璃的ITO涂层朝向Au导电层20，控制阴极和阳极之间的距离为1-2mm，并在阴阳极之间加载5V的直流电压；并在同时进行紫外光照射的情况下，采用阴极还原的方式在TiO 2-PDA复合层40上形成铂电极层50。之后用超纯水进行清洗并烘干，留待下一步用。
其中，在该电沉积过程中，朝带ITO涂层的玻璃不具有ITO涂层的一面施加紫外光，以使紫外光到达所述铂离子溶液处，所用紫外光的能量密度为2mW/cm 2，紫外光照射的时间为1小时；阴阳极之间加载直流电压的时间为1小时，所形成的铂电极层50的厚度为0.5μm。
7、制作柔性电极的封装层60：
b1、在铂电极层50上设置封装膜60’，该封装膜60’还覆盖电极诱导层30上未被铂电极层50覆盖的部分。该封装膜60’的材质也可以为PI，其设置过程如下：
先将带铂电极层50的承载板在120℃下加热5分钟以去除水蒸气，然后通过匀胶机在其表面旋涂聚酰亚胺酸的溶液，形成5μm厚的湿膜；然后在100℃烘烤3分钟，将软化3min后的样品放入烘箱后，先从室温(约25℃)快速加热至40℃，然后以3℃/min的速率升温至300℃，高温烘烤30分钟后，以使聚酰亚胺酸环化生成PI，自然冷却至室温。
b2、在上述PI封装膜60’上采用两级速度(第一级：300转，15秒；第二级：3000转，30秒)涂布牺牲材料(具体为AZ4620正性光刻胶)，以构建约3μm厚的牺牲层；对形成的牺牲层进行紫外曝光(曝光量为40mJ/cm 2)，并在曝光后进行120℃的后烘处理，待冷至室温后用AZ300显影液进行显影，形成图案化的牺牲层70。其中，图案化的牺牲层70未覆盖铂电极层50的刺激电极位点51与电极连接点52(参见图3)。
b3、以图案化的牺牲层70为掩膜版，对上述PI封装膜60’进行等离子(RIE)刻蚀，以使被覆盖的铂电极层50的刺激电极位点51与电极连接点52暴露出来，而不暴露导线等其他部分，形成封装层60。其中刻蚀参数设置为：氧气流量：40sccm，室压：20-14pa，功率：150W，刻蚀时间：10min，连续4次。
b4、将上述RIE蚀刻后的样品浸泡在丙酮中，以将残留的牺牲材料(AZ4620正性光刻胶)完全溶解在丙酮中，然后用去离子水清洗表面，氮气干燥，得到具有封装层60的柔性电极。
8、去除与PI柔性基底层10连接的承载硅片，完成整个柔性电极的制作。最终所得的柔性电极产品如图6所示。
图3为本发明实施例中柔性电极的铂电极层50的结构设计图。所述铂电极层50包括相对设置的10个刺激电极位点51和10个电极连接点52，每个刺激电极位点51与电极连接点52通过导线53一一对应连接。图3中刺激电极位点51的直径为200μm，导线53的宽度为35μm，电极连接点52为1*1毫米的正方形，其后期可与带芯片的PCB板进行连接，或者连接其他仪器进行测试等。
图7为本发明实施例中封装后的柔性电极的结构示意图。请一并参阅图3，该柔性电极包括柔性基底层10和依次设置在柔性基底层10表面的中间导电层20和电极诱导30层，电极诱导层30的间隙设有二氧化钛-聚多巴胺复合层40，二氧化钛-聚多巴胺复合层40上设有铂电极层50。
该柔性电极还包括封装层60，封装层60覆盖电极诱导层30上未被铂电极层50的刺激电极位点51与电极连接点52所覆盖的部分。也就是说，电极诱导层30、铂电极层50均位于封装层60的容置空间内，但铂电极层50的刺激电极位点51与电极连接点52从所述封装层中露出，而铂电极层50的导线未露出。
图8为本发明实施例中采用直流电泳光照沉积形成的TiO 2-PDA复合层的表面形貌图；图9为本发明一实施例中直流电泳光照沉积形成铂电极层的表面形貌图。从图8中可以看出，在纳米TiO 2存在下，采用直流电泳加紫外光照技术，通过阳极可以快速形成呈深黄色的TiO 2-PDA复合层；从图9中可以看出，在TiO 2-PDA复合层上，采用直流电泳加紫外光照技术，可以快速形成呈黑色的铂电极层。而且，上述TiO 2-PDA复合层和铂电极层均是在预定的凹槽结构中形成涂层，且其边缘界面具有清晰的分辨率。以上结果表明，本发明提供的柔性电极制备方法，可以快速且有导向地制得结构规则的TiO 2-PDA复合层和铂电极层。
以上所述实施例仅表达了本发明的示例性实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (18)

  1. 一种柔性电极的制备方法，其特征在于，包括以下步骤：
    提供承载板，在所述承载板的一面依次形成柔性基底层和中间导电层；
    制备具有电极图案的弹性模板，将所述弹性模板采用酸处理后，将其上的电极图案通过微接触印刷的方式转印到所述中间导电层的表面，以在所述中间导电层上形成与电极图案互补的电极诱导层；
    在未被所述电极诱导层覆盖的所述中间导电层上滴加纳米二氧化钛和聚多巴胺前驱体溶液的混合液，以具有透明导电涂层的玻璃为阴极，所述中间导电层为阳极，并将所述透明导电层与所述中间导电层相对设置，在紫外光照射的情况下，采用阳极氧化方式在所述电极诱导层的间隙电沉积形成二氧化钛-聚多巴胺复合层；
    在所述二氧化钛-聚多巴胺复合层和所述电极诱导层的表面滴加铂离子溶液，以所述具有透明导电涂层的玻璃为阳极，所述中间导电层为阴极，并将所述透明导电层朝向所述中间导电层，在紫外光照射的情况下，采用阴极还原的方式在所述二氧化钛-聚多巴胺复合层上形成铂电极层；
    去除所述承载板，得到柔性电极。
  2. 如权利要求1所述的柔性电极的制备方法，其特征在于，所述具有电极图案的弹性模板是通过以下方法制备：
    在硬质衬底上旋涂光刻胶，利用一定形状的掩膜版进行曝光、显影，得到电极图案的阳膜；
    用模型胶浇注所述阳膜，固化后揭膜，得到具有电极图案的弹性模板。
  3. 如权利要求1所述的柔性电极的制备方法，其特征在于，在所述微接触印刷时，所施加的压力为1.0-2.0N。
  4. 如权利要求1所述的柔性电极的制备方法，其特征在于，所述酸处理时所用的酸包括氢氟酸、硝酸、盐酸中的至少一种。
  5. 如权利要求1所述的柔性电极的制备方法，其特征在于，所述聚多巴胺的前驱体溶液为盐酸多巴胺的Tris溶液，所述前驱体溶液的pH为6-9，盐酸多巴胺的浓度为2-5mg/mL；所述纳米二氧化钛在所述混合液中的浓度为0.05-0.25mg/mL。
  6. 如权利要求1所述的柔性电极的制备方法，其特征在于，在所述阳极氧化和所述阴极还原过程中，阴极和阳极之间加载的电压为1-5V的直流电压。
  7. 如权利要求6所述的柔性电极的制备方法，其特征在于，在所述阳极氧化和所述阴极还原的过程中，阴极和阳极之间的距离为1-5mm。
  8. 如权利要求1所述的柔性电极的制备方法，其特征在于，在所述阳极氧化和所述阴极还原过程中，所述紫外光照射的能量密度为0.7-5mW/cm 2。
  9. 如权利要求7所述的柔性电极的制备方法，其特征在于，在形成所述二氧化钛-聚多巴胺复合层的过程中，所述紫外光照射的时间为3-15min；阴极和阳极之间加载电压的时间为3-15min。
  10. 如权利要求7所述的柔性电极的制备方法，其特征在于，在形成所述铂电极层的过程中，所述紫外光照射的时间为20-120min；阴极和阳极之间加载电压的时间为20-120min。
  11. 如权利要求7所述的柔性电极的制备方法，其特征在于，所述二氧化钛-聚多巴胺复合层的厚度为80-500nm。
  12. 一种柔性电极，其特征在于，包括：柔性基底层和依次设置在所述柔性基底层表面的中间导电层和电极诱导层，所述电极诱导层的间隙设有二氧化钛-聚多巴胺复合层，所述二氧化钛-聚多巴胺复合层上设有铂电极层。
  13. 如权利要求12所述的柔性电极，其特征在于，所述中间导电层的厚度为10-30nm。
  14. 如权利要求12所述的柔性电极，其特征在于，所述二氧化钛-聚多巴胺复合层的厚度为80-500nm。
  15. 如权利要求12所述的柔性电极，其特征在于，铂电极层的厚度为0.3-5μm。
  16. 如权利要求12所述的柔性电极，其特征在于，所述柔性基底层的厚度为2-6μm。
  17. 如权利要求12-16任一项所述的柔性电极，其特征在于，所述铂电极层包括相对设置的多个刺激电极位点和多个电极连接点，每个所述刺激电极位点与电极连接点通过导线一一对应连接。
  18. 如权利要求17所述的柔性电极，其特征在于，所述柔性电极还包括封装层，所述封装层覆盖所述电极诱导层上未被所述铂电极层的刺激电极位点与电极连接点所覆盖的部分。
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CN106950267A (zh) * 2017-02-24 2017-07-14 首都师范大学 一种柔性电极制备方法及柔性电极
CN107610817A (zh) * 2017-09-17 2018-01-19 赵兵 一种层层自组装银纳米线柔性导电薄膜
CN108693225A (zh) * 2018-02-13 2018-10-23 首都师范大学 一种可拉伸柔性传感器及其制备方法与应用
CN109215848A (zh) * 2018-07-31 2019-01-15 华南师范大学 一种高结合力透明导电电极的制备方法
CN109802013A (zh) * 2019-01-25 2019-05-24 香港理工大学 嵌入式金属网柔性透明电极及其制备方法

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