CN112972888A - Nerve stimulation array system and preparation method thereof - Google Patents
Nerve stimulation array system and preparation method thereof Download PDFInfo
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- CN112972888A CN112972888A CN201911299958.4A CN201911299958A CN112972888A CN 112972888 A CN112972888 A CN 112972888A CN 201911299958 A CN201911299958 A CN 201911299958A CN 112972888 A CN112972888 A CN 112972888A
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Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/18—Applying electric currents by contact electrodes
- A61N1/32—Applying electric currents by contact electrodes alternating or intermittent currents
- A61N1/36—Applying electric currents by contact electrodes alternating or intermittent currents for stimulation
- A61N1/36046—Applying electric currents by contact electrodes alternating or intermittent currents for stimulation of the eye
-
- 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
- A61N1/05—Electrodes for implantation or insertion into the body, e.g. heart electrode
- A61N1/0526—Head electrodes
- A61N1/0543—Retinal electrodes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/18—Applying electric currents by contact electrodes
- A61N1/32—Applying electric currents by contact electrodes alternating or intermittent currents
- A61N1/36—Applying electric currents by contact electrodes alternating or intermittent currents for stimulation
- A61N1/3605—Implantable neurostimulators for stimulating central or peripheral nerve system
Abstract
The invention discloses a nerve stimulation array system which comprises a flexible substrate, a photoelectric response layer and an electrode layer, wherein the photoelectric response layer is embedded in the flexible substrate, the photoelectric response layer is formed by arranging photoelectric conversion material arrays, and the electrode layer is positioned on the photoelectric response layer. The nerve stimulation array system has the advantages of simple structure, low cost, good flexibility and good biocompatibility, can realize photoresponse electrical stimulation of spatial resolution, and can be used in the field of different in-vivo nerve electrical stimulation of eyes, brains and the like. The invention also provides a preparation method of the nerve stimulation array system.
Description
Technical Field
The invention relates to the technical field of biomedical engineering, in particular to a nerve stimulation array system and a preparation method thereof.
Background
The electrode-based nerve stimulation system is widely used for treating various diseases related to peripheral nerve and central nerve injury and the like, and has great potential in the aspect of treating diseases such as limb paralysis, depression, deafness, blindness and the like. In particular, in recent years, the artificial retina prosthesis system based on the high-density electrode array developed by the company of Second Sight Medical Products in the united states can effectively restore part of the visual ability of patients with advanced retinal degenerative diseases, and provides a feasible solution for such blindness-causing diseases which cannot be clinically treated in the past. However, such artificial retina prosthesis systems need to integrate a plurality of functional modules such as a visual signal acquisition module, a wireless signal transmission and reception module, an integrated chip control module, an electrode stimulation module, etc., and have high manufacturing cost, high integration difficulty and difficult implantation, thereby greatly limiting the popularization and application of such devices.
Disclosure of Invention
In view of this, the invention provides a novel nerve stimulation array system, which has photoelectric conversion materials and metal electrode layers arranged in an array manner, is simple in structure and low in manufacturing cost, can realize light response nerve stimulation with spatial resolution without integrating a complex signal acquisition module, a wireless signal transmission and reception module and an integrated chip control module, and can be used in different nerve stimulation fields such as visual stimulation and cerebral cortex stimulation.
Specifically, a first aspect of an embodiment of the present invention provides a neurostimulation array system, which includes: the photoelectric response layer is embedded into the flexible substrate, the photoelectric response layer is formed by arranging photoelectric conversion material arrays, and the electrode layer is located on the photoelectric response layer.
In the invention, the electrode of the electrode layer is positioned on the surface of the photoelectric conversion material of the photoelectric response layer. Obviously, the electrode layer is also arranged by the conductive material array.
Optionally, the thickness of the electrode layer is 50-300 nm.
Optionally, the flexible substrate has a thickness of 5-500 μm.
Wherein the thickness of the photoelectric response layer is less than or equal to the thickness of the flexible substrate. Preferably, the thickness of the photoresponsive layer is equal to the thickness of the flexible substrate, for example between 5 and 500 μm.
In one embodiment of the present invention, the flexible substrate has an array of holes, and the electro-optical response layer is filled in the holes of the array of holes; the holes are blind holes or through holes. The depth direction of the hole is parallel to the thickness direction of the flexible substrate. When the hole of the flexible substrate is a through hole penetrating through the thickness direction of the flexible substrate, the thickness of the photoelectric response layer is equal to that of the flexible substrate.
Further, the holes are circular, triangular, quadrilateral, polygonal or other irregular shapes. Accordingly, the cross section of the photoelectric conversion material of the photoelectric response layer is circular, triangular, quadrilateral, polygonal or other irregular shapes.
Preferably, the holes are circular, the diameter of the holes being between 100 μm and 2 mm.
In the invention, the flexible substrate is made of an insulating material, so that the diffusion of photoelectrons can be effectively inhibited, and the nerve stimulation array system realizes electric stimulation with resolution. The material of the flexible substrate may be a flexible insulating polymer, the choice of which depends on the end use and the desired effect of the use. For example, to ensure that a film substrate capable of effectively adhering to a curved surface structure can be formed, it is necessary to ensure that the flexible substrate material has good film formability and good mechanical properties under high curvature.
Optionally, the material of the flexible substrate includes one or more of polyimide, polydimethylsiloxane, polyethylene terephthalate, parylene and photoresist. The photoresist may be a positive or negative photoresist, and may specifically be, but not limited to, SU8 photoresist, AZ photoresist, and the like.
The material of the electrode layer is selected from at least one of platinum, gold, titanium, iridium, palladium, niobium, tantalum and alloys thereof, titanium nitride (TixNy), iridium oxide (IrOx), Indium Tin Oxide (ITO), aluminum-doped zinc oxide (AZO), fluorine-doped tin dioxide (FTO), and phosphorus-doped tin dioxide (PTO), but is not limited thereto.
In the invention, the photoelectric response layer has better photoelectric conversion efficiency and biocompatibility. Preferably, the photoelectric conversion material constituting the photoelectric response layer may be selected from at least one of the following substances having different photoelectric response mechanisms: the photovoltaic material, the photoinduced deformation material composite piezoelectric material and the up-conversion material composite photovoltaic material.
Wherein the photovoltaic material can absorb photon energy in a visible light region (400-800nm) and directly generate photoelectrons. The composite piezoelectric material of the photoinduced deformation material firstly depends on the photoinduced deformation material to generate deformation under the excitation of light rays in a visible light wave band (400-800nm), and then the deformation is transmitted to the piezoelectric material to generate a piezoelectric signal. The up-conversion material composite photovoltaic material absorbs photon energy in a near infrared region (780-2526nm) and emits photons with wavelengths in a visible light region (400-800nm), and then the photovoltaic material with response wavelength bands in the visible light region is excited to generate photoelectrons. When the photoelectric conversion material is an up-conversion material composite photovoltaic material, the obtained photoelectric response layer of the nerve stimulation system can respond to light in a near infrared region (808 and 2500nm) beyond a visible light region, so that the super-visual light perception capability is obtained.
Wherein the photovoltaic material is at least one of the following substances: monocrystalline silicon solar cell materials, thin-film solar cell materials represented by amorphous silicon, copper indium gallium selenide thin films and cadmium telluride thin films, dye-sensitized solar cell materials based on titanium dioxide and compounds thereof, perovskite solar cell materials based on perovskite type organic metal halides, and organic photovoltaic materials of polyacetylene, polythiophene, polyaniline, polypyrrole and derivatives and copolymers thereof. Examples of the perovskite-type organic metal halide include methylammonium lead iodide, methylammonium lead bromide, methylammonium lead chloride, and the like.
The photoinduced deformation material composite piezoelectric material is any one combination of the photoinduced deformation material and the piezoelectric material, wherein the photoinduced deformation material is at least one of the following materials: a photoisomerization material represented by azobenzene and a derivative thereof, spiropyran and a derivative thereof; a ferroelectric inorganic photoinduced deformation material represented by lead titanate, barium titanate, potassium niobate, lithium tantalate, bismuth layer-like perovskite structure ferroelectric, tungsten bronze type ferroelectric, bismuth ferrite, potassium dihydrogen phosphate, ammonium trinitrate sulfate, rosette, perovskite type organic metal halide ferroelectric; non-ferroelectric inorganic photo-deformation materials represented by strontium ruthenate, silicon, cadmium sulfide, gallium arsenide; wherein the piezoelectric material is at least one of the following materials: piezoelectric crystals represented by quartz crystals, lithium gallate, lithium germanate, titanium germanate, and lithium tantalate; piezoelectric ceramics represented by barium titanate, lead zirconate titanate, lead metaniobate, and lead barium lithium niobate; piezoelectric polymers represented by polyvinylidene fluoride ferroelectric polymers, odd-numbered nylons, polyacrylonitriles, vinylidene cyanide and copolymers thereof, polyureas, polyphenylcyanoethers, polyvinyl chloride, polyvinyl acetate, polypropylene, polytetrafluoroethylene. Among them, as the polyvinylidene fluoride-based ferroelectric polymer, poly (vinylidene fluoride-trifluoroethylene) [ P (VDF-TrFE) copolymer ], poly (vinylidene fluoride-chlorofluoroethylene) [ P (VDF-CFE) copolymer ], poly (vinylidene fluoride-chlorotrifluoroethylene) [ P (VDF-CTFE) copolymer ], poly (vinylidene fluoride-hexafluoropropylene) [ P (VDF-HFP) copolymer ], poly (vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) [ P (VDF-TrFE-CFE) terpolymer ], poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) [ P (VDF-TrFE-CTFE) terpolymer ], and poly (vinylidene fluoride-trifluoroethylene-hexafluoropropylene) [ P (VDF-TrFE-CTFE) terpolymer ] may be cited.
Wherein the up-conversion material composite photoelectric material is a composite material formed by up-conversion nanometer and at least one of the following materials: polyacetylene, polythiophene, polyaniline, polypyrrole and derivatives and copolymers thereof. Wherein the up-conversion nanoparticles comprise a host material, a sensitizer and an activator, wherein the host material is NaYF4Or NaGdF4The sensitizer is Yb, and the activator is Er, Tm or Ho. Specifically, the up-conversion fluorescent material comprises NaYF4:Yb3+,Er3+、YF3:Yb3+,Er3+、NaYF4:Yb3+,Tm3+、YF3:Yb3+,Tm3+、NaYF4:Yb3+,Ho3+And YF3:Yb3+,Ho3+At least one of (1).
The nerve stimulation array system provided by the first aspect of the invention comprises a flexible substrate, a photoelectric response layer which is arranged on the flexible substrate and is composed of photoelectric conversion materials arranged in an array manner, and an array electrode layer arranged on the photoelectric response layer, and complex signal acquisition modules, wireless signal transmission and reception modules, integrated chip control modules and other multifunctional modules are not required to be integrated, wherein the photoelectric response layer can directly generate photoelectrons with spatial resolution under light stimulation for stimulating nerves, and the nerve electrical stimulation with the spatial resolution can be realized through the array electrode layer. The nerve stimulation array system has the advantages of simple structure, low cost, good flexibility, high photoelectric conversion efficiency and good biocompatibility, can realize photoresponse electric stimulation of spatial resolution, and can be used in different nerve electric stimulation fields of eyes, brains and the like.
In a second aspect, an embodiment of the present invention provides a method for preparing a neurostimulation array system, which includes the following steps:
providing a hard substrate, and preparing a flexible substrate on the hard substrate;
preparing a hole array on the flexible substrate, and filling a photoelectric conversion material into holes of the hole array to form a photoelectric response layer embedded in the flexible substrate;
forming an electrode layer on the photoelectric conversion material of the photoelectric response layer;
removing the hard substrate to obtain a nerve stimulation array system; the photoelectric response layer is formed by arranging photoelectric conversion material arrays.
In one embodiment of the present invention, preparing an array of wells on the flexible substrate specifically comprises: coating photoresist on the flexible substrate, and photoetching to form a patterned photoresist layer; forming a metal film on the patterned photoresist layer, removing the photoresist and forming a patterned metal mask layer; the flexible substrate is etched to form a flexible substrate having an array of apertures. The patterned photoresist layer may be formed by exposing and developing the coated photoresist. The metal mask layer is made of aluminum, gold, silver and platinum. Preferably aluminum. Aluminum is used as a metal mask layer, so that the aluminum can be removed easily at the later stage.
Further, after forming an electrode layer on the photoelectric conversion material of the photoelectric response layer, the method further includes: and removing the patterned metal mask layer.
The hard substrate is made of glass, metal, silicon or ceramic.
Wherein the flexible substrate may be formed by a coating method or a casting method of a flexible material.
Wherein the array of holes is formed by at least one of photolithography, plasma dry etching, and machining.
Wherein, the filling mode of the photoelectric conversion material comprises one or more of physical embedding, coating, casting and in-situ growth.
The preparation method of the nerve stimulation array system provided by the second aspect of the invention is simple and easy to operate, can quickly prepare the nerve stimulation array system with high integration level and simple structure, and greatly reduces the manufacturing cost of the current nerve stimulation system.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
FIG. 1 is a schematic cross-sectional view of a neurostimulation array system according to example 1 of the present invention;
FIG. 2 is a top view (a) and a bottom view (b) of the neurostimulation array system of FIG. 1;
FIG. 3 is a schematic structural diagram of a neurostimulation array system in embodiment 3 of the invention;
FIG. 4 is a schematic structural diagram of a neurostimulation array system in example 4 of the present invention;
fig. 5 is a schematic structural diagram of a neurostimulation array system in embodiment 5 of the invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
A nerve stimulation array system is structurally shown in fig. 1, and comprises a flexible substrate 10, a photoelectric response layer 20 embedded in the flexible substrate 10, and an electrode layer 30 covering the surface of the photoelectric response layer 20, wherein the photoelectric response layer 20 is formed by arranging photoelectric conversion material arrays.
In the present embodiment, as shown in fig. 2, the flexible substrate 10 has a hole array formed by 9 circular through holes with a diameter of 2mm, and the photoelectric response layer 20 is filled in the holes of the hole array; the thickness of the photoelectric response layer 20 is 200 μm, and the material thereof is copper indium gallium selenide thin-film solar cell material. The thickness of the flexible substrate 10 is 200 μm, and the material thereof is Polydimethylsiloxane (PDMS); the electrode layer 30 is 300nm thick and made of Indium Tin Oxide (ITO).
The preparation method of the nerve stimulation array system comprises the following steps:
1) surface treatment of hard substrates
Taking a monocrystalline silicon wafer as a hard substrate, and cleaning the surface of the monocrystalline silicon wafer to remove organic and inorganic impurities on the surface. The specific cleaning steps are as follows: ultrasonic cleaning in acetone, absolute ethyl alcohol and ultrapure water in sequence, drying by nitrogen and then drying in an oven; and then, carrying out oxygen plasma treatment on the dried silicon wafer to make the surface hydrophilic.
2) Preparation of Flexible substrates
Uniformly spin-coating a layer of Polydimethylsiloxane (PDMS) pre-polymerization liquid on the surface of a monocrystalline silicon piece by using a spin-coating instrument, and heating at 80 ℃ for 30min to solidify the PDMS pre-polymerization liquid to obtain a PDMS film with the thickness of 200 mu m, namely the flexible substrate. Then, coating SU-8 photoresist with the thickness of 20 μm on the surface of the PDMS film in a spin coating manner, and patterning the photoresist by photoetching to obtain a patterned photoresist layer; forming an Al film with the thickness of 50nm on the surface of the PDMS film through magnetron sputtering, and dissolving the photoresist by using SU-8 developing solution to form an Al patterned metal mask layer on the surface of the PDMS film; and finally, carrying out plasma etching on the PDMS film which is not covered by the Al mask layer to form a PDMS flexible substrate with the thickness of 200 μm and 9 circular hole arrays with the diameter of 2 mm.
3) Preparation of photoelectric response layer
Embedding a cylindrical copper indium gallium selenide thin-film solar cell material with the thickness of 200 mu m and the diameter of 2mm into the circular hole of the PDMS flexible substrate; and filling PDMS pre-polymerization liquid in the gap, and heating at 80 ℃ for 30min to solidify the PDMS pre-polymerization liquid, so that the CIGS thin-film solar cell material and the PDMS flexible substrate form an integrated structure.
4) Preparation of metal electrode layer
Under the mask action of the Al mask layer, an Indium Tin Oxide (ITO) electrode layer with the thickness of 300nm is deposited on the surface of the PDMS flexible substrate compounded with the photoelectric response layer by a magnetron sputtering coating method, and the metal electrode layer is positioned on the photoelectric conversion material of the photoelectric response layer. Then, an Al mask layer as a mask is dissolved by using NaOH solution, and the single crystal silicon wafer is removed, thereby finally obtaining the neurostimulation array system shown in fig. 1.
The nerve stimulation array system of the embodiment 1 of the invention is provided with 9 electrodes, wherein a single electrode is a sunlight simulation illumination system (100 mW/cm) with an emission waveband of visible light region (400-800nm)2) The output voltage generated under the excitation of the optical nerve stimulation device is more than 5V, the output current is more than 10mA, and the optical nerve stimulation device can stimulate visual ganglion cells to show excitability.
Example 2
A nerve stimulation array system is structurally shown in figures 1-2 and comprises a flexible substrate 10, a photoelectric response layer 20 embedded in the flexible substrate 10 and an electrode layer 30 covering the surface of the photoelectric response layer 20, wherein the photoelectric response layer 20 is formed by arranging photoelectric conversion material arrays.
In the present embodiment, the flexible substrate 10 has a hole array formed by 9 circular through holes having a diameter of 200 μm, and the photo-responsive layer 20 is filled in the holes of the hole array; the thickness of the photoelectric response layer 20 is 5 μm, and the material thereof is a titanium dioxide nano array with photovoltaic characteristics. The thickness of the flexible substrate 10 is 5 μm, and the material thereof is polyimide; the electrode layer 30 is 50nm thick and made of Au.
The preparation method of the nerve stimulation array system comprises the following steps:
1) surface treatment of hard substrates
Taking a polycrystalline silicon wafer as a hard substrate, and cleaning the surface of the substrate to remove organic and inorganic impurities on the surface. The specific cleaning steps are as follows: ultrasonic cleaning in acetone, absolute ethyl alcohol and ultrapure water in sequence, drying by nitrogen and then drying in an oven; and then, carrying out oxygen plasma treatment on the dried silicon wafer to make the surface hydrophilic.
2) Preparation of a Flexible polymeric substrate layer
Uniformly spin-coating a polyimide acid solution on the surface of a polycrystalline silicon wafer by using a spin coater to form a wet film, heating at 100 ℃ for 3min, and then heating in a 300 ℃ oven for 0.5h to cyclize the polyimide acid to generate polyimide with the thickness of 5 microns, thus obtaining the flexible substrate. Then, coating SU-8 photoresist with the thickness of 20 mu m on the surface of the polyimide layer in a spinning mode, and patterning the polyimide layer through photoetching to obtain a patterned photoresist layer; forming an Al film with the thickness of 50nm on the surface of the polyimide layer by magnetron sputtering, and forming an Al patterned metal mask layer on the surface of the polyimide layer after dissolving the photoresist; and finally, performing plasma etching on the polyimide which is not covered by the Al mask layer to form a polyimide flexible substrate layer with the thickness of 5 microns and 9 circular hole arrays with the diameters of 200 microns.
3) Preparation of photoelectric response layer
Selectively growing a titanium dioxide nanowire array with the thickness of 5 micrometers on the surface of a bare silicon wafer in a circular hole of a polyimide flexible substrate layer by a hydrothermal method, and controlling the thickness of the formed titanium dioxide nanowire array by controlling the addition amount and the reaction time of a reaction precursor (tetrabutyl titanate).
4) Preparation of metal electrode layer
And under the mask action of the Al mask layer, depositing an Au metal electrode layer with the thickness of 50nm on the surface of the polyimide flexible substrate compounded with the photoelectric response layer by a magnetron sputtering coating method. And then dissolving the Al mask layer, and removing the monocrystalline silicon wafer to finally obtain the nerve stimulation array system shown in figure 1.
The nerve stimulation array system of the embodiment 2 of the invention is provided with 9 electrodes, wherein a single electrode is a sunlight simulation illumination system (100 mW/cm) with an emission waveband of visible light region (400-800nm)2) Is more than 500mV and outputThe current is more than 100 muA, and the visual ganglion cells can be stimulated to show excitability.
Example 3
A nerve stimulation array system is shown in fig. 3, and comprises a flexible substrate 10, a photoelectric response layer 20 embedded in the flexible substrate 10, and an electrode layer 30 covering the surface of the photoelectric response layer 20, wherein the photoelectric response layer 20 is formed by arranging photoelectric conversion material arrays.
In the present embodiment, the flexible substrate 10 has a hole array formed by 9 square through holes with a side of 500 μm, and the photoelectric response layer 20 is filled in the through holes of the hole array, but the through holes are not filled; the thickness of the photoelectric response layer 20 is 9.8 μm, and the material is a perovskite type light absorption substance with photoelectric response characteristic, such as methotrexate-lead-iodine. The thickness of the flexible substrate 10 is 10 μm, and the material thereof is parylene; the electrode layer 30 is 300nm thick and made of Au.
The preparation method of the nerve stimulation array system comprises the following steps:
1) surface treatment of hard substrates
Taking a glass sheet as a hard substrate, and cleaning the surface of the glass sheet to remove organic and inorganic impurities on the surface. The specific cleaning steps are as follows: ultrasonic cleaning in acetone, absolute ethyl alcohol and ultrapure water in sequence, drying by nitrogen and then drying in an oven; and then carrying out oxygen plasma treatment on the dried glass sheet to make the surface of the glass sheet hydrophilic.
2) Preparation of a Flexible polymeric substrate layer
And uniformly spin-coating a layer of parylene solution on the surface of the glass sheet by using a spin coater, and regulating the rotating speed to obtain a parylene film with the thickness of 10 mu m, so as to obtain the flexible substrate. Then, coating SU-8 photoresist with the thickness of 20 mu m on the surface of the parylene layer in a spinning mode, and carrying out photoetching and patterning on the surface of the parylene layer to obtain a patterned photoresist layer; forming an Al film with the thickness of 50nm on the surface of the parylene film through magnetron sputtering, and forming an Al patterned metal mask layer on the surface of the parylene film after dissolving the photoresist; and finally, carrying out plasma etching on the parylene which is not covered by the Al mask layer to form a parylene flexible substrate with the thickness of 10 microns and 9 square through hole arrays with the side length of 500 microns.
3) Preparation of photoelectric response layer
Selectively growing a methotrexate-plumbum-iodine layer with the thickness of 9.8 mu m on the surface of a bare glass sheet in a round hole of a parylene flexible substrate layer by a one-step solution method, and controlling the thickness of the formed methotrexate-plumbum-iodine layer by controlling the addition amount of reaction precursors (lead iodide and iodomethylamine).
4) Preparation of metal electrode layer
And under the mask action of the Al mask layer, depositing an Au metal electrode layer with the thickness of 300nm on the surface of the film compounded with the photoelectric response layer by a magnetron sputtering coating method. Then, the Al mask layer used as a mask is dissolved, and the monocrystalline silicon wafer is removed, and finally the nerve stimulation array system shown in figure 1 is obtained.
The single electrode of the nerve stimulation array system in embodiment 3 of the invention is a sunlight simulation illumination system (100 mW/cm) with an emission waveband of visible light region (400-800nm)2) The output voltage generated by the stimulation is more than 5V, the output current is more than 500 muA, and the visual ganglion cells can be stimulated to show excitability.
Example 4
A nerve stimulation array system capable of being simply integrated is shown in fig. 4 and comprises a flexible substrate 10, a photoelectric response layer 20 embedded in the flexible substrate 10 and an electrode layer 30 covering the surface of the photoelectric response layer 20, wherein the photoelectric response layer 20 is formed by arranging photoelectric conversion material arrays.
In the present embodiment, the flexible substrate 10 has a hole array formed by 9 circular through holes having a diameter of 500 μm, and the photo-responsive layer 20 is filled in the through holes of the hole array, but the through holes are not filled; the thickness of the photoelectric response layer 20 is 190 μm, and the material thereof is organic photovoltaic material poly (3-n-hexylthiophene). The thickness of the flexible substrate 10 is 200 μm, and the material thereof is polydimethylsiloxane; the electrode layer 30 is 50nm thick and made of Pt.
The preparation method of the nerve stimulation array system comprises the following steps:
1) surface treatment of hard substrates
Taking a monocrystalline silicon wafer as a hard substrate, and cleaning the surface of the monocrystalline silicon wafer to remove organic and inorganic impurities on the surface. The specific cleaning steps are as follows: ultrasonic cleaning in acetone, absolute ethyl alcohol and ultrapure water in sequence, drying by nitrogen and then drying in an oven; and then, carrying out oxygen plasma treatment on the dried silicon wafer to make the surface hydrophilic.
2) Preparation of Flexible substrates
Uniformly spin-coating a layer of Polydimethylsiloxane (PDMS) pre-polymerization liquid on the surface of a monocrystalline silicon piece by using a spin-coating instrument, and heating at 80 ℃ for 30min to solidify the PDMS pre-polymerization liquid to obtain a PDMS film with the thickness of 200 mu m, namely the flexible substrate. Then, coating SU-8 photoresist with the thickness of 20 μm on the surface of the PDMS film in a spin coating manner, and patterning the photoresist by photoetching to obtain a patterned photoresist layer; forming an Al film with the thickness of 50nm on the surface of the PDMS film through magnetron sputtering, and dissolving the photoresist to form an Al patterned metal mask layer on the surface of the PDMS film; and finally, carrying out plasma etching on the PDMS film which is not covered by the Al mask layer to form a PDMS flexible substrate with the thickness of 200 μm and 9 circular hole arrays with the diameter of 500 μm.
3) Preparation of photoelectric response layer
Poly (3-n-hexylthiophene) with the thickness of 190 mu m is formed on the surface of an exposed silicon wafer in the round hole of the PDMS flexible substrate by a tape casting film forming method, and the thickness of the formed poly (3-n-hexylthiophene) layer is controlled by controlling the volume and concentration of a poly (3-n-hexylthiophene) solution used for tape casting film formation.
4) Preparation of metal electrode layer
Under the action of the mask of the Al mask layer, a Pt metal electrode layer with the thickness of 50nm is deposited on the surface of the PDMS flexible substrate compounded with the photoelectric response layer by a magnetron sputtering coating method, and the metal electrode layer is positioned on the photoelectric conversion material of the photoelectric response layer. Then, the Al mask layer as a mask is removed, and the monocrystalline silicon wafer is removed, and finally, the neurostimulation array system shown in fig. 1 is obtained.
The nerve stimulation array system of the embodiment 4 has 9 electrodes, wherein a single electrode is a sunlight simulation illumination system (100 mW/cm) with an emission waveband of visible light region (400-800nm)2) The output voltage generated by the stimulation is more than 200mV, the output current is more than 100 muA, and the stimulation can stimulate the visual ganglion cells to show excitability.
Example 5
As shown in fig. 5, the neurostimulation array system comprises a flexible substrate 10, a photoelectric response layer 20 embedded in the flexible substrate 10, and an electrode layer 30 covering the surface of the photoelectric response layer 20, wherein the photoelectric response layer 20 is formed by arranging photoelectric conversion material arrays.
In the present embodiment, the flexible substrate 10 has a hole array formed by 9 circular blind holes with a diameter of 200 μm, and the photoelectric response layer 20 is filled in the blind holes of the hole array; the thickness of the photoelectric response layer 20 is 18 μm, and the material is poly (vinylidene fluoride-trifluoroethylene) which is prepared by compounding azobenzene derivative with the photo-induced deformation characteristic and has the piezoelectric effect. The thickness of the flexible substrate 10 is 20 μm, and the material thereof is polyethylene terephthalate (PET); the electrode layer 30 is 50nm thick and made of Pt.
The preparation method of the nerve stimulation array system comprises the following steps:
1) surface treatment of hard substrates
Taking a monocrystalline silicon wafer as a hard substrate, and cleaning the surface of the monocrystalline silicon wafer to remove organic and inorganic impurities on the surface. The specific cleaning steps are as follows: ultrasonic cleaning in acetone, absolute ethyl alcohol and ultrapure water in sequence, drying by nitrogen and then drying in an oven; and then, carrying out oxygen plasma treatment on the dried silicon wafer to make the surface hydrophilic.
2) Preparation of Flexible substrates
And uniformly spin-coating PET on the surface of the monocrystalline silicon wafer by using a spin coater, and regulating the rotating speed to obtain a PET film with the thickness of 20 mu m, namely the flexible substrate. Then, coating SU-8 photoresist with the thickness of 20 mu m on the surface of the PET layer in a spinning mode, and carrying out photoetching and patterning on the PET layer to obtain a patterned photoresist layer; forming an Al film with the thickness of 50nm on the surface of the PDMS film through magnetron sputtering, and dissolving the photoresist to form an Al patterned metal mask layer on the surface of the PDMS film; and finally, carrying out plasma etching on the PDMS film which is not covered by the Al mask layer to form the PET flexible substrate with the thickness of 18 microns and the hole array of 9 round blind holes with the diameter of 200 microns.
3) Preparation of photoelectric response layer
And (3) dropwise coating a precursor solution containing the vinylidene fluoride-trifluoroethylene copolymer and the 4- (10-bromodecyloxy) -4' -octyloxyazobenzene with the total mass concentration of 10mg/mL and the mass ratio of 4:1 into arrayed round holes of the PET flexible substrate, completely drying at room temperature, and finally obtaining a photoelectric response layer (the thickness is 18 microns) with the thickness slightly smaller than that of the flexible polymer substrate layer by controlling the number of dropwise coating.
4) Preparation of metal electrode layer
Depositing a Pt metal electrode layer with the thickness of 50nm on the surface of the film compounded with the photoelectric response layer by a magnetron sputtering coating method, wherein the metal electrode layer is positioned on the photoelectric conversion material of the photoelectric response layer. Then, the Al mask layer as a mask is dissolved, and finally, the neurostimulation array system shown in fig. 1 is obtained.
The neurostimulation array system of this example 5 had 9 electrodes, with the individual electrodes being visible light (100 mW/cm) at wavelengths of 405, 532 and 650nm, respectively2) The output voltage generated by the stimulation is more than 20mV, the output current is more than 100 muA, and the stimulation can stimulate the visual ganglion cells to show excitability.
Example 6
A nerve stimulation array system is shown in fig. 1 and comprises a flexible substrate 10, a photoelectric response layer 20 embedded in the flexible substrate 10 and an electrode layer 30 covering the surface of the photoelectric response layer 20, wherein the photoelectric response layer 20 is formed by arranging photoelectric conversion material arrays.
In the present embodiment, the flexible substrate 10 has a hole array formed by 9 circular through holes having a diameter of 200 μm, and the photo-responsive layer 20 is filled in the holes of the hole array; the thickness of the photoelectric response layer 20 is 20 μm, and the material is strontium ruthenate with photoinduced deformation characteristic and poly (vinylidene fluoride-trifluoroethylene) with piezoelectric effect. The thickness of the flexible substrate 10 is 20 μm, and the material thereof is polyethylene terephthalate (PET); the electrode layer 30 is 50nm thick and made of Pt.
The neurostimulation array system is prepared by a method similar to that of example 5, except that: in the step 3), a precursor solution containing the vinylidene fluoride-trifluoroethylene copolymer with the mass concentration of 10mg/mL and the strontium ruthenate nano particles with the mass concentration of 0.1mg/mL is dropwise coated in arrayed round holes of a PET flexible substrate, the PET flexible substrate is thoroughly dried at room temperature, and the photoelectric response layer with the thickness (20 mu m) consistent with that of the flexible polymer substrate layer is finally obtained by controlling the dropping coating times.
The neurostimulation array system of this example 6 was used for visible light (100 mW/cm) with wavelengths of 532 nm and 650nm, respectively2) The output voltage generated by the stimulation is more than 50mV, the output current is more than 200 muA, and the stimulation can stimulate the visual ganglion cells to show excitability.
Example 7
A nerve stimulation array system is shown in fig. 1 and comprises a flexible substrate 10, a photoelectric response layer 20 embedded in the flexible substrate 10 and an electrode layer 30 covering the surface of the photoelectric response layer 20, wherein the photoelectric response layer 20 is formed by arranging photoelectric conversion material arrays.
In the present embodiment, the flexible substrate 10 has a hole array formed by 9 circular through holes having a diameter of 200 μm, and the photo-responsive layer 20 is filled in the holes of the hole array; the thickness of the photoelectric response layer 20 is 20 μm, and the material is the up-conversion nano-particle NaYF4:Yb3+,Er3+The composite organic photovoltaic material is poly (3-n-hexylthiophene). The thickness of the flexible substrate 10 is 20 μm, and the material thereof is polyethylene terephthalate (PET); the electrode layer 30 is 50nm thick and made of Pt.
The preparation method of the nerve stimulation array system comprises the following steps:
1) surface treatment of hard substrates
Taking a monocrystalline silicon wafer as a hard substrate, and cleaning the surface of the monocrystalline silicon wafer to remove organic and inorganic impurities on the surface. The specific cleaning steps are as follows: ultrasonic cleaning in acetone, absolute ethyl alcohol and ultrapure water in sequence, drying by nitrogen and then drying in an oven; and then, carrying out oxygen plasma treatment on the dried silicon wafer to make the surface hydrophilic.
2) Preparation of Flexible substrates
And uniformly spin-coating PET on the surface of the monocrystalline silicon wafer by using a spin coater, and regulating the rotating speed to obtain a PET film with the thickness of 20 mu m, namely the flexible substrate. Then, coating SU-8 photoresist with the thickness of 20 mu m on the surface of the PET layer in a spinning mode, and carrying out photoetching and patterning on the PET layer to obtain a patterned photoresist layer; forming an Al film with the thickness of 50nm on the surface of the PDMS film through magnetron sputtering, and dissolving the photoresist to form an Al patterned metal mask layer on the surface of the PDMS film; and finally, carrying out plasma etching on the PDMS film which is not covered by the Al mask layer to form the PET flexible substrate with the thickness of 20 microns and the hole array of 9 round holes with the diameter of 200 microns.
3) Preparation of photoelectric response layer
Adding up-conversion nano particles NaYF with the mass concentration of 10mg/mL4:Yb3+,Er3+Adding poly (3-n-hexylthiophene) solution (the main material is NaYF4, the sensitizer is Yb, and the activator is Er) into arrayed round holes coated on the PET flexible substrate, completely drying at room temperature, and finally obtaining the photoelectric response layer with the thickness (20 mu m) consistent with that of the flexible polymer substrate layer by controlling the dripping and coating times.
4) Preparation of metal electrode layer
Depositing a Pt metal electrode layer with the thickness of 50nm on the surface of the film compounded with the photoelectric response layer by a magnetron sputtering coating method, wherein the metal electrode layer is positioned on the photoelectric conversion material of the photoelectric response layer. Then, the Al mask layer as a mask is dissolved, and finally, the neurostimulation array system shown in fig. 1 is obtained.
The emission wavelengths of the single electrodes of the neurostimulation array system of the embodiment 7 are respectively 808nm, 1200nm and 2500nm near-infrared lamps (100 mW/cm)2) The output voltage generated by the stimulation is more than 200mV, the output current is more than 100 muA, and the stimulation can stimulate the visual ganglion cells to show excitability.
The above-mentioned embodiments only express exemplary embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. A neurostimulation array system, which is characterized by comprising a flexible substrate, a photoelectric response layer and an electrode layer; the photoelectric response layer is embedded in the flexible substrate, the photoelectric response layer is formed by arranging photoelectric conversion material arrays, and the electrode layer is located on the photoelectric response layer.
2. The neurostimulation array system of claim 1, wherein the thickness of the electro-optic responsive layer is less than or equal to the thickness of the flexible substrate.
3. The neurostimulation array system according to claim 2, wherein the thickness of the electro-optical response layer is 5-500 μm, and the thickness of the flexible object substrate is 5-500 μm.
4. The neurostimulation array system according to claim 1, wherein the flexible substrate is provided with an array of holes, and the photoelectric response layer is filled in the holes of the array of holes; the holes are through holes or blind holes.
5. The neurostimulation array system of claim 1, wherein the holes are circular, triangular, quadrilateral, polygonal, or irregular in shape.
6. The neurostimulation array system according to claim 1, wherein the thickness of the electrode layer is 50-300 nm.
7. The neurostimulation array system according to claim 1, wherein the photoelectric conversion material is at least one of photovoltaic material, photo-deformable material composite piezoelectric material and up-conversion material composite photoelectric material.
8. The neurostimulation array system of claim 1, wherein the electrode layer is made of a material selected from at least one of platinum, gold, titanium, iridium, palladium, niobium, tantalum and alloys thereof, titanium nitride, iridium oxide, indium tin oxide, aluminum-doped zinc oxide, fluorine-doped tin dioxide and phosphorus-doped tin dioxide.
9. A method of making a neurostimulation array system, comprising the steps of:
providing a hard substrate, and preparing a flexible substrate on the hard substrate;
preparing a hole array on the flexible substrate, and filling a photoelectric conversion material into holes of the hole array to form a photoelectric response layer embedded in the flexible substrate; the photoelectric response layer is formed by arranging a photoelectric conversion material array;
forming an electrode layer on the photoelectric conversion material of the photoelectric response layer;
and removing the hard substrate to obtain the nerve stimulation array system.
10. The method of claim 9, wherein the flexible substrate is formed by a coating method, a casting method, or a casting method.
11. The method of manufacturing of claim 9, wherein the array of holes is formed by at least one of photolithography, plasma dry etching, and machining.
12. The production method according to claim 9, wherein the filling manner of the photoelectric conversion material includes one or more of physical embedding, coating, casting, and in-situ growth.
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