CN110063724A - Flexible biological electrode and preparation method thereof - Google Patents

Flexible biological electrode and preparation method thereof Download PDF

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Publication number
CN110063724A
CN110063724A CN201910343925.9A CN201910343925A CN110063724A CN 110063724 A CN110063724 A CN 110063724A CN 201910343925 A CN201910343925 A CN 201910343925A CN 110063724 A CN110063724 A CN 110063724A
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conductive substrates
nano material
dimensional electric
conductive
biological electrode
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CN110063724B (en
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冯雪
赵星蔚
梁紫微
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Tsinghua University
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Tsinghua University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00Measuring for diagnostic purposes; Identification of persons
    • A61B5/24Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00Measuring for diagnostic purposes; Identification of persons
    • A61B5/68Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient
    • A61B5/6801Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be attached to or worn on the body surface
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04Coating on selected surface areas, e.g. using masks
    • C23C16/042Coating on selected surface areas, e.g. using masks using masks
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02Electroplating of selected surface areas
    • C25D5/022Electroplating of selected surface areas using masking means
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B2562/00Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
    • A61B2562/12Manufacturing methods specially adapted for producing sensors for in-vivo measurements
    • A61B2562/125Manufacturing methods specially adapted for producing sensors for in-vivo measurements characterised by the manufacture of electrodes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B2562/00Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
    • A61B2562/14Coupling media or elements to improve sensor contact with skin or tissue
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B2562/00Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
    • A61B2562/16Details of sensor housings or probes; Details of structural supports for sensors
    • A61B2562/164Details of sensor housings or probes; Details of structural supports for sensors the sensor is mounted in or on a conformable substrate or carrier

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Abstract

The present invention provides a kind of flexible biological electrode and preparation method thereof.The flexible biological electrode includes: conductive substrates;One-dimensional electric nano material is formed in the conductive substrates surface in its axial mode substantially orthogonal with the surface of the conductive substrates, and the diameter of the one-dimensional electric nano material is 20~200nm, and length is 30~100 μm;Wherein at least there is polymer coating in the contact interface region of the conductive substrates and the one-dimensional electric nano material.Flexible biological electrode of the invention can be realized to be contacted with the effective of skin lines.Also, the noise of measurement will be with the raising of device and human body stickiness and significantly reduce.

Description

Flexible biological electrode and preparation method thereof
Technical field
The present invention relates to a kind of flexible biological electrodes and preparation method thereof, belong to body electrical signals monitoring and flexible electronic device Part technical field.
Background technique
Human skin surface there is a variety of electric signals relevant to physiological health situation, including brain electricity, electrocardio, eye electricity, Myoelectricity etc..The acquisition of the continuous real-time and precise of these electric signals the monitoring of cardiovascular disease, Athletess are monitored and Very important meaning is suffered to the research of cerebral nervous system.Traditionally, the acquisition of these electric signals is all based on heaviness Non-deformable rigid electronic device realize.But since skin histology of human body surface etc. is all very soft, tradition Modulus mismatch between electronic device and human skin tissue can not only cause sense of discomfort when long periods of wear, and because nothing Method and human body surface attach naturally, are easy to cause signal noise because of movement during wearing, cause to measurement accuracy Strong influence.
The appearance of flexible electronic technology breaches the non-deformable morphological feature of the intrinsic rigidity of conventional electronics, energy It is enough to be bent as rope, be stretched as rubber dramatically close to the mechanical characteristic of human skin tissue, sensitive paper It is equally bent, or even is deformed into any curved shape while without the damage of significant mechanics or other performance, be conducive to Device adapts to the variation of environment or is integrated with human-body biological, is bonded in the measurements with human body so as to improve conventional electronics The problems such as property is poor.But the surfaces of most of flexible electrodes for body electrical signals acquisition are all smooth, and human bodies Skin surface is but covered with many small folds and gully, and the presence of these micro-structures greatly restricts flexible electronic device With the complete fitting of human body surface, so being still remained the problem of contact impedance.
Citation [1] discloses a kind of body electrical signals monitoring electrode slice, including backing, conductive buckle, electrode chip And conducting resinl, the conductive buckle are buckled in the side of the backing, the electrode chip and conducting resinl and state backing positioned at described The other side, the electrode chip are electrically connected with the conductive buckle.The electrode slice further includes microneedle electrodes, the microneedle electrodes packet Netted gasket and the micropin that netted gasket side is set are included, the other side of the netted gasket passes through conducting resinl and electrode chip Electrical connection.The structure of the electrode slice is complex, and microneedle electrodes can still be pierced into skin, it is possible to cause skin injury.
It includes that substrate and conduction are knitted that citation [2], which discloses a kind of textile electrode and electrocardiogram test instrument, the textile electrode, Object, the conductive fabric and the substrate secure bond, and it is formed with cavity between the conductive fabric and the substrate, it is described The flexible support of filling, is at least that honeycomb weave structure is woven to the conductive fabric of opposing regions with the substrate in cavity Object, the lair opening of the honeycomb structure are to deviate from the substrate, and fill out in the lair equipped with conducting resinl.The textile electrode Although the contact impedance between conductive fabric and skin can be reduced, due to the small fold of skin surface and gully, contact The problem of impedance, still remains.
Citation [1]: CN106551693A
Citation [2]: CN106551693A
Summary of the invention
Problems to be solved by the invention
Aiming at the problem that existing bioelectrode and skin contact impedance, it is an object of the present invention to provide a kind of flexibilities Bioelectrode, the problem of can effectively solve the problem that bioelectrode and skin contact impedance, and it will not be pierced into skin, skin will not be caused Damage.
Further, another object of the present invention is to provide a kind of preparation method of bioelectrode, this method is simply high Effect, raw material are easily obtained.
The solution to the problem
[1], a kind of flexible biological electrode comprising:
Conductive substrates;
One-dimensional electric nano material is formed in described in its axial mode substantially orthogonal with the surface of the conductive substrates The conductive substrates surface, the diameter of the one-dimensional electric nano material are 20~200nm, and length is 30~100 μm;Wherein
At least there is polymer coating in the contact interface region of the conductive substrates and the one-dimensional electric nano material.
[2], the flexible biological electrode according to [1], wherein all have polymerization in all surface of the conductive substrates Object coating.
[3], the flexible biological electrode according to [1] or [2], wherein the conductive substrates include:
Support film;And
It is formed in the conductive layer at least one surface of support film;
Preferably, metallic chromium layer is provided between the support film and conductive layer.
[4], the flexible biological electrode according to [3], wherein the conductive layer is metal conducting layer, and the metal is led Electric layer includes the combination of one or more of golden conductive layer, silver conductive layer, copper conductive layer;And/or
The material of the support film is polymer material, and the polymer material includes polyimides, poly- terephthaldehyde The combination of one or both of sour glycol ester.
[5], according to [1]-[4] described in any item flexible biological electrodes, wherein the one-dimensional electric nano material includes Nano wire and/or nanotube preferably include the combination of one or more of silver nanowires, nanowires of gold, carbon nanotube.
[6], according to [1]-[5] described in any item flexible biological electrodes, wherein the polymer coating is derived from organic Silicon compound, it is preferable that the organo-silicon compound include silicon rubber and/or siloxanes.
[7], a kind of preparation method of flexible biological electrode comprising following steps:
One-dimensional electric nano material is set to be formed in institute in its axial mode substantially orthogonal with the surface of the conductive substrates The conductive substrates surface is stated, the diameter of the one-dimensional electric nano material is 20~200nm, and length is 30~100 μm;
At least in the contact interface region coating polymer solution of the conductive substrates and the one-dimensional electric nano material, Polymer coating is formed after solidification.
[8], the preparation method according to [7], wherein
Made one-dimensional using the anodic oxidation aluminium formwork with through-hole using electrochemical deposition or the method for vapor deposition Electrical-conductive nanometer material is grown on the conductive substrates table in its axial mode substantially orthogonal with the surface of the conductive substrates Face.
[9], the preparation method according to [8], wherein the preparation method comprises the following steps:
Step 1 takes anodic oxidation aluminium formwork;
Step 2 is bonded the anodic oxidation aluminium formwork and the conductive substrates using binder;
Binder in step 3, the removing through-hole;
Step 4, using the method for electrochemical deposition or vapor deposition, so that the one-dimensional electric nano material is grown in institute It states in through-hole;
Step 5 at least polymerize with the contact interface region coating of the one-dimensional electric nano material in the conductive substrates Object solution forms polymer coating after solidification;
Step 6, the removal anodic oxidation aluminium formwork, obtain the flexible biological electrode.
[10], the preparation method according to [9], wherein between the step 3 and step 4, the preparation method is also Include the steps that growing one-dimensional electric nano material regionality;Specifically, the regional growth the following steps are included:
Step a deposits one layer of metallics on the surface far from the conductive substrates of anodic oxidation aluminium formwork;
Step b coats a layer photoresist on the surface of the metallics;
Step c is removed described in the part metallics and the part according to the assortment mode of the flexible biological electrode The photoresist on metallics surface;
Step d removes the remaining metallics and the residue after the completion of one-dimensional electric nano material growth The metallics surface the photoresist.
[11], the preparation method according to [7]-[10], wherein the coating further includes, in the conductive substrates All surface is coated with the polymer solution.
[12], the preparation method according to [7]-[11], wherein the preparation method of the conductive substrates includes will be conductive The step of layer is connected with support film;Preferably, metallic chromium layer is also deposited between the conductive layer and support film.
The effect of invention
Flexible biological electrode of the invention can be realized to be contacted with the effective of skin lines.Also, the noise of measurement will It is significantly reduced with the raising of device and human body stickiness, and skin will not be pierced into, skin injury will not be caused.
The preparation method of bioelectrode of the invention is simple and efficient, and raw material is easily obtained, and is suitble to produce in enormous quantities.
Detailed description of the invention
Fig. 1 shows the overall structure diagram of the flexible biological electrode of the embodiment of the present invention.
Fig. 2 shows the preparation process of conductive substrates in the embodiment of the present invention.
Fig. 3 shows the process for combining conductive substrates and anodic oxidation aluminium formwork using photoresist in the embodiment of the present invention Schematic diagram.
Fig. 4, which is shown, to carry out upper surface patterning covering to anodic oxidation aluminium formwork in the embodiment of the present invention and carries out region The process schematic of the long silver nanowires of metaplasia.
Fig. 5 shows in the embodiment of the present invention and pours to silver nanowires bottom and flexible conducting substrate layer progress polymer Process schematic.
Description of symbols
1: one-dimensional electric nano material;2: conductive substrates;3: polymer coating.
Specific embodiment
It will be detailed below various exemplary embodiments, feature and aspect of the invention.Dedicated word " example herein Property " mean " being used as example, embodiment or illustrative ".Here as any embodiment illustrated by " exemplary " should not necessarily be construed as Preferred or advantageous over other embodiments.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below. It will be appreciated by those skilled in the art that without certain details, the present invention equally be can be implemented.In other example, Method well known to those skilled in the art, means, equipment and step are not described in detail, in order to highlight master of the invention Purport.
Such as without Special Statement, unit used in the present invention is SI units, and the number occurred in the present invention Value, numberical range should all be interpreted as containing the inevitable Systematic Errors of institute in industrial production.
Heretofore described " substantially " indicates that error is no more than 5% etc..
First embodiment
First embodiment of the invention provides a kind of flexible biological electrode comprising: conductive substrates 2;One-dimensional electric Nano material 1 is formed in described table of conductive substrates 2 in its axial mode substantially orthogonal with the surface of the conductive substrates 2 Face, the diameter of the one-dimensional electric nano material 1 are 20~200nm, and length is 30~100 μm;Wherein, at least in the conduction The contact interface region of substrate 2 and the one-dimensional electric nano material 1 has polymer coating 3.
Flexible biological electrode of the invention, which refers to, to bend under external force, folds the even processes such as stretcher strain In, still maintain the bioelectrode of normal function.The present invention is by being closely fixed on conductive base for one-dimensional electric nano material 1 On bottom 2, in the measurement process to human biological signal, one-dimensional electric nano material 1 is allowed to play its draw ratio Advantage, to realize that flexible biological electrode is contacted with the effective of skin lines.The present invention passes through setting polymer coating 3, thus It ensure that the connectivity robustness of one-dimensional electric nano material 1 Yu bottom conductive substrate 2, and significantly reduce device entirety Elasticity modulus, so that flexible biological electrode of the invention has more during carrying out human-body biological electrical measurement with skin attachement Good comfort, and it will not be pierced into skin, skin injury will not be caused.Specifically:
<conductive substrates>
Conductive substrates 2 of the invention are preferably flexible conducting substrate, and flexible conducting substrate is the conduction with mechanical flexibility Substrate.Specifically, flexible conducting substrate can be divided into two classes according to composition: one kind is that itself has single type conductive base flexible Bottom, such as smooth metal Electrospun;It is another kind of, it is to be formed on its surface answering for conductive layer using flexible material as support film Mould assembly flexible conducting substrate, the Typical Representative of this kind of flexible conducting substrates are exactly metal/high-molecular Material cladding type conductive base Bottom etc..
In the present invention, can select itself has single type electric conductor flexible as flexible conducting substrate.Certainly, exist Composite-type flexible conductive substrates can also be selected in the present invention, be specifically as follows metal/high-molecular Material cladding type conductive substrates Deng, it is preferable to use compound-type conducting substrate.
Specifically, conductive substrates 2 of the invention may include support film;And it is formed in the support film at least one The conductive layer on a surface.Wherein conductive layer is smooth metal conducting layer, such as: golden (Au) conductive layer, silver (Ag) conductive layer, copper (Cu) conductive layer etc., metal conducting layer can be deposited by electron beam evaporation or the modes such as magnetron sputtering deposit metal material On flexible support film.And the material for being used as support film can be polymer material, and such as: polyimides (PI), poly- pair Ethylene terephthalate (PET), polyvinyl alcohol (PVA), polycarbonate (PC) and silicone resin etc..
Further, when growing silver nanowire, because silver is close with the crystal constant of gold, the silver nanowires of growth There can be better adhesiveness with golden conductive layer.That is growth silver nanowires can use silver conductive layer or golden conductive layer, but Since the oxidisability of silver is good, it is preferable to use golden conductive layer not as good as gold.When conductive layer is golden conductive layer, in order to reinforce support film Interface binding power between when the material of support film (such as when using polyimides as) and conductive layer is thin in the support Metallic chromium layer is provided between film and conductive layer.When conductive layer is other conductive layers such as copper conductive layer, silver conductive layer, due to such Interface binding power between conductive layer and support film is stronger, no setting is required metallic chromium layer.
In the present invention, in order to preferably play the functions of conductive substrates 2, support film with a thickness of 3~20 μm, preferably It is 5~15 μm, more preferably 6~12 μm etc..Conductive layer with a thickness of 50~500nm, preferably 100~400nm, more preferably 150~300nm etc..The thickness of metallic chromium layer can be 3~20nm, preferably 5~15nm, more preferably 7~12nm.
<one-dimensional electric nano material>
One-dimensional electric nano material 1 of the invention is a kind of conductive material with high length-diameter ratio.Due to micro-nano-scale Effect, one-dimensional electric nano material 1 have great specific surface area, satisfactory electrical conductivity and mechanical property.The present invention is to understand The problem of the problem of certainly bioelectrode and skin gully contact, i.e. flexible biological electrode and skin contact impedance, hair of the invention Bright people's discovery forms one-dimensional electric nano material 1 in its axial mode substantially orthogonal with the surface of the conductive substrates 2 In the surface of conductive substrates 2, the electrode shape with class microvillus shape can be formed, so as to obtain with skin contact more Sufficient bioelectrode.
Specifically, it can use anodised aluminium (AAO) template with through-hole, it is heavy using electrochemical deposition or gas phase Long-pending method makes one-dimensional electric nano material 1, is grown in its axial mode substantially orthogonal with the surface of the conductive substrates The surface of conductive substrates 2.Wherein, electrochemical deposition refers to that electric current passes through negative ions in electrolyte solution under the action of an external electric field Migration and on the electrode the redox reaction of generation receiving and losing electrons and form the technology of coating.Vapor deposition is to utilize gas phase The physics of middle generation, chemical process form functional or decorative metal, nonmetallic or compound coat in workpiece surface Technology.The present invention utilizes the anodic oxidation aluminium formwork with through-hole, using electrochemical deposition or the method for vapor deposition, Ke Yisheng Grow one-dimensional electric nano material 1.
In the present invention, the diameter of the one-dimensional electric nano material 1 is 20~200nm, and length is 30~100 μm, long Diameter ratio (length-to-diameter) is 150~5000, preferably 300~4000, more preferably 500~2000, further preferably It is 600~1500, is still more preferably 700~1200 etc..Therefore, one-dimensional electric nano material 1 of the invention has suitable Draw ratio, so as to realize the contact to skin lines.Based on the size of one-dimensional electric nano material 1, can select flat Equal aperture is about 20~200nm, and the axial length of through-hole is about 30~100 μm of anodic oxidation aluminium formwork.
Specifically, one-dimensional electric nano material 1 is not particularly limited in the present invention, can be commonly used in the art one-dimensional lead Electric nano material 1.One-dimensional electric nano material 1 of the invention may include nano wire and/or nanotube, preferably include silver nanoparticle The combination of one or more of line, nanowires of gold, carbon nanotube.Wherein, silver nanowires can give full play to its major diameter The advantage of ratio realizes coming into full contact with for skin lines.
<polymer coating>
The present invention at least has in the contact interface region of the conductive substrates 2 and the one-dimensional electric nano material 1 poly- Close object coating 3.Polymer coating 3 can play the role of protecting conductive substrates 2 and 1 root of one-dimensional electric nano material, and Flexible biological electrode can also be made to have certain extending (stretching) property and better flexibility.In the present invention, polymer applies The thickness of layer 3 can be 1~15 μm, preferably 3~12 μm, and more preferable 5~10 μm.
Preferably, preparation and the preferably effect of performance polymer coating 3 for convenience, it is all in the conductive substrates 2 Surface all has polymer coating 3.I.e. as shown in Figure 1, conductive substrates 2 to be wrapped in the inside of polymer coating.At this point, whole From the point of view of, the close one-dimensional electric nano material 1 of polymer coating 3 with far from one-dimensional electric nano material 1 while it Between maximum distance (thickness containing conductive substrates 2) be 30~500 μm.
The polymer coating 3 can be obtained by using polymer solution is cured.In the present invention, described " solidification " It refers to that binder, liquid polymer solution etc. is made to become solid form from the use form of liquid.For cured means, Such as solution in binder, liquid polymer solution can be removed using the forms such as dry.It is some preferred in the present invention In embodiment, removal solution can carry out under heating conditions.In the scope of " solidification " of the invention, allow cured product Inside is at least partially formed network structure.Such network structure can be formed by way of condensation forms covalent bond, It is also possible to be formed via the form of the non-covalent bonds such as intermolecular force.For polymer coating 3, after hardening It can have certain elasticity, so that flexible biological electrode of the invention be made to be further equipped with flexibility.
In the present invention, the polymer coating 3 is derived from organo-silicon compound, those are usually passed through oxygen, sulphur, nitrogen etc. The compound for making organic group be connected with silicon atom is also as organo-silicon compound.Preferably, the organo-silicon compound include Silicon rubber and/or siloxanes.
In the present invention, used silicon rubber is organic silicon rubber.Organic silicon rubber is containing Si-C key and at least One organic group is the compound being directly connected with silicon atom.Used siloxanes is organosiloxane.Organosiloxane is The polymer of the composition backbone structure of key containing Si-O-Si.Silicon rubber and/or siloxanes can under weak stress deformation it is significant, stress It can be promptly restored to after relaxation close to original state and size.
For example, silicon rubber for example can be platinum catalysis silicon rubber, such as: ecoflex0020, ecoflex0030 etc.. Siloxanes for example can be dimethyl silicone polymer (PDMS) etc..
The present invention is by setting polymer coating 3, to ensure that one-dimensional electric nano material 1 and bottom conductive substrate 2 Connectivity robustness, and significantly reduce the elasticity modulus of device entirety so that flexible biological electrode of the invention with Skin attachement carries out having better comfort during human-body biological electrical measurement.
Second embodiment
Second embodiment of the present invention provides a kind of preparation of the flexible biological electrode of first embodiment of the invention Method, specifically includes the following steps:
Make one-dimensional electric nano material, institute is formed in its axial mode substantially orthogonal with the surface of the conductive substrates The conductive substrates surface is stated, the diameter of the one-dimensional electric nano material is 20~200nm, and length is 30~100 μm;
At least in the contact interface region coating polymer solution of the conductive substrates and the one-dimensional electric nano material, Polymer coating is formed after solidification.
Typically, the present invention utilizes the anodic oxidation aluminium formwork with through-hole, using electrochemical deposition or vapor deposition Method, make one-dimensional electric nano material, be grown in and led in its axial mode substantially orthogonal with the surface of the conductive substrates The electric substrate surface.
Specifically, the preparation method comprises the following steps:
Step 1 takes anodic oxidation aluminium formwork;
Step 2 is bonded the anodic oxidation aluminium formwork and the conductive substrates using binder;
Binder in step 3, the removing through-hole;
Step 4, using the method for electrochemical deposition or vapor deposition, be grown in one-dimensional electric nano material described logical Kong Zhong;
Step 5 at least polymerize with the contact interface region coating of the one-dimensional electric nano material in the conductive substrates Object solution forms polymer coating after solidification;
Step 6, the removal anodic oxidation aluminium formwork, obtain the flexible biological electrode.
The main chemical compositions of anodic oxidation aluminium formwork are aluminum oxide (Al2O3).It can be sent out when using aluminium as anode Raw redox reaction, to form one layer of film being made of aluminium oxide, as anodic oxidation aluminium formwork on aluminium electrode surface. Since anodic oxidation aluminium formwork has through-hole, the growth of one-dimensional electric nano material can be made in the through hole.
The present invention, can be in this hair during carrying out the growth of one-dimensional electric nano material using anodic oxidation aluminium formwork A layer binder is coated in bright conductive substrates.The binder can be fluid organic material, in order to prepare it is convenient, it is preferable to use Photoresist is to realize the function of bonding.When using photoresist as binder, thick glue can be used, thin glue also can be used, It is preferable to use thick glue, such as: thick glue 4620, thick glue SU8 etc..
When using photoresist as binder, the present invention can when photoresist is uncured by anodic oxidation aluminium formwork with Conductive substrates compress, and can be bonded together both after solidification, and utilize the method for plasma etching (RIE) by anodic oxidation aluminum dipping form Photoresist in plate hole etches away carries out subsequent electrochemical deposition or vapor deposition again, so that one-dimensional electric nano material is grown In the through hole.
Further, between above-mentioned steps 3 and step 4, the preparation method further includes making one-dimensional electric nano material The step of regionality growth.Specifically can according to the assortment mode of one-dimensional electric nano material, by carry out patterning covering or Person patterns photoetching treatment, and the regional growth of one-dimensional electric nano material may be implemented.
Specifically, the regional growth the following steps are included:
Step a deposits one layer of metallics on the surface far from the conductive substrates of anodic oxidation aluminium formwork;
Step b coats one layer of photoresist on the surface of the metallics;
Step c removes the part metallics and the part according to the assortment mode of the one-dimensional electric nano material The photoresist on metallics surface;
Step d removes the remaining metallics and the residue after the completion of one-dimensional electric nano material growth The metallics surface the photoresist.
Negative photoresist and positive photoresist two can be divided to according to the chemical reaction mechanism of photoresist and development principle for photoresist Class.Form insoluble material after illumination is negative photoresist;Conversely, be to certain solvents it is insoluble, become solvable after illumination Substance is positive photoresist.It can the figure needed for metallics surface etch by photoresist making coatings using this performance Shape, one-dimensional electric nano material can carry out regional growth according to the figure.
In the present invention, the photoresist for carrying out photoetching is not particularly limited, as long as demand of the invention may be implemented i.e. It can.In general, thin glue preferably can be used in the photoresist for carrying out photoetching, and such as: AZ5214 etc..
In addition, in the present invention, being not particularly limited to the assortment mode of the one-dimensional electric nano material, it can be and appoint The assortment mode of meaning.
Specifically, it can be deposited first with electron beam evaporation, in anodic oxidation aluminium formwork far from the conductive substrates Surface deposits one layer of metallics.Electron beam evaporation is one kind of vacuum vapor plating, is to utilize electron beam under vacuum conditions Heating evaporation material is directly carried out, make to evaporate material gasification and is transported to substrate, the method for forming film is condensed in substrate.
The thickness of this layer obtained after being deposited by electron beam evaporation the metallics can be 0.5~3 μm, preferably may be used To be 1~2 μm.Then a layer photoresist is coated on the surface of metallics.Then utilize the method for photoetching by part metals object The photoresist of matter and the part metals material surface etches away, thus realize patterning etching, it is required so as to obtain having The model of assortment mode.At this time in the surface far from the conductive substrates of anodic oxidation aluminium formwork, metallics and photoresist The part etched away will exposed portion through-hole, and where through-hole is still closed to metallics.
Preferably, metallics can be metallic copper, gold, titanium etc., in order to reduce cost, it is preferable to use metallic copper.
In growth of one-dimensional electrical-conductive nanometer material, using above-mentioned model as working electrode, platinum electrode is used as to electrode in electricity It solves and carries out direct current electrochemical deposition in liquid.Due to the place covered by copper and photoresist, electrolyte be cannot be introduced into, so will not sink Product nanowire structure.The ground for only exposing through-hole can grow nano wire just now.One-dimensional electric nano material can basis as a result, Required assortment mode carries out compartmentalization growth.
In addition, the present invention is not particularly limited the concrete composition of electrolyte, as long as being able to satisfy requirement of the invention. For example: when carrying out direct current chemical deposition silver nanowire, the salting liquid of silver is added in the electrolytic solution, such as: AgNO3 Deng to realize the growth of silver nanowire.
It is in the present invention, described to coat the combination one or more of can be dipping, spin coating, spray, pour, By coating, polymer solution can be made uniformly at least to be covered on the conductive substrates and the one-dimensional electric nano material Contact interface region.
Preferably, the coating further includes being coated with the polymer solution in all surface of the conductive substrates.
Before being coated, need to remove the photoetching of remaining metallics He the remaining metallics surface Glue.Such as: it can be removed by the way of wet etching.For example: can use copper etching liquid and acetone removes respectively Remove remaining metallics and the remaining metallics photomask surface glue.At this point, anodic oxidation aluminium formwork and conductive base About 5~10 μm of gap is had between bottom, can in this gap coated polymer solution, then polymer solution is consolidated Change, polymer coating can be obtained.In order to facilitate preparation, and the performance of obtained flexible biological electrode is more excellent, preferably adopts With the mode poured, the polymer solution is coated in all surface of the conductive substrates.
Further, for the preparation method of conductive substrates, the present invention is not particularly limited, and can be used commonly used in the art Preparation method be prepared.Specifically: the preparation method of the conductive substrates includes that conductive layer is connected with support film The step of connecing.Such as: conductive material can be deposited using electron beam evaporation on the surface of support film, to form conductive layer.
Preferably, metallic chromium layer is additionally provided between the conductive layer and support film.It is i.e. heavy on the surface of support film Before the conductive material of product, electron beam evaporation deposited metal layers of chrome is utilized.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is It can be with conventional products that are commercially available.
Embodiment
1, the preparation of conductive substrates
Conductive substrates are mainly by the golden conductive layer of commercial style polyimides (PI) film and upper layer flexible in the present embodiment Composition.The commercial style Kapton with a thickness of 8 μm.
Fig. 2 show the preparation process of conductive substrates.As shown in Fig. 2, the specific preparation step of conductive substrates are as follows: prepare one The clean sheet glass of block, and above with one strata dimethyl siloxane (PDMS) of the revolving speed spin coating of 300r/min, and heat 100 Degree keeps 30min to be solidified.After cured, the flexible conducting substrate layer prepared is lain flat on into dimethyl silicone polymer On.Then on the surface of polyimides using the metallic chromium layer of electron beam evaporation deposition 10nm thickness, later again in metallic chromium layer The metal layer gold of upper deposition 200nm thickness is as conductive layer.
2, the bonding of conductive substrates and anodised aluminium (AAO) template
Fig. 3 show the adhesion process of conductive substrates and anodic oxidation aluminium formwork.Specific steps are as follows: above-mentioned ready With one layer of AZ4620 photoresist of the speed spin coating of 3000r/min in conductive substrates, with i.e. by the sun of a piece of through-hole with perforation Pole alumina formwork thin slice (80~100nm of average pore size, with a thickness of 80 microns) slightly presses and is affixed on uncured AZ4620 light It on photoresist, and places and heats 110 degree of holdings solidification in 90 seconds in heating plate, thus complete conductive substrates and anodic oxidation aluminium formwork Bonding ((a) shown in) in Fig. 3.Above-mentioned overall structure is placed in progress plasma etching (RIE) in reactive ion etching machine. Anodic oxidation aluminium formwork has the AZ4620 photoresist in the part of through-hole clean by complete etching at this time, and is oxidized anodically aluminium The part that template covers still is able to retain (shown in (b) in Fig. 3).
3, the patterning on anodic oxidation aluminium formwork surface covers and the compartmentalization of silver nanowires is grown
The patterning that Fig. 4 show anodic oxidation aluminium formwork surface covers and the compartmentalization growth course of silver nanowires. Specific steps are as follows: deposited using electron beam evaporation, the surface of the separate conductive substrates of above-mentioned anodic oxidation aluminium formwork is deposited one The metallic copper of 1.5 μ m-thick of layer.Immediately at one layer of AZ5214 photoresist of the surface spin coating of metallic copper (in Fig. 4 shown in (a)).Pass through light It carves, part metals copper and the part metals copper surface A Z5214 photoresist is etched away, realize that the patterning of copper etches (in Fig. 4 (b) shown in).At this time in the surface far from the conductive substrates of anodic oxidation aluminium formwork, metallic copper and AZ5214 photoresist The part etched away will exposed portion through-hole, and metallic copper where through-hole be still it is closed, obtain model.
Using the model as working electrode, platinum electrode is used as and carries out direct current electrochemical deposition in the electrolytic solution to electrode.Electricity Liquid is solved by the AgNO of 20g/L3With the H of 20g/L3BO3Aqueous solution composition, add HNO3PH value is adjusted to 2, for growing silver Nanowire.Impressed DC voltage is 0.2V, sedimentation time 40min.Due to the place covered by copper, electrolyte be cannot be introduced into, So silver nanowire will not be deposited.The ground for only exposing through-hole can grow silver nanowire just now.Thus, it is possible to according to silver nanoparticle The assortment mode of line carries out the deposition of compartmentalization (shown in (c) in Fig. 4).
4, coated polymer solution
Fig. 5 show the process for preparing coated polymer solution.Using wet etching, distinguished using copper etching liquid and acetone Remove remaining metallic copper and the AZ5214 photoresist of the remaining copper surface (shown in (a) in Fig. 5).At this point, will One about 10 microns of gap can be reserved between anodic oxidation aluminium formwork and conductive substrates.It, will by pouring PDMS solution After flexible substrates and nano wire root are fully wrapped around, and it is heating and curing (shown in (b) in Fig. 5).Then by product obtained It is sequentially placed into the NaOH solution for being put into 10% mass fraction and 4mol/L and carries out the corrosion of anodic oxidation aluminium formwork (in Fig. 5 (c) shown in).After anodic oxidation aluminium formwork removal is clean, flexible biological electrode is removed from glass sheet surface, can be obtained To product shown in FIG. 1 (shown in (d) in Fig. 5).
Flexible biological electrode of the invention can be used for skin surface, to detect telecommunications relevant to physiological health situation etc. Number.Flexible biological electrode of the invention can be realized to be contacted with the effective of skin lines.Also, flexible biological electrode of the invention Measurement noise will be with the raising of device and human body stickiness and significantly reduce, and skin will not be pierced into, skin will not be caused Skin damage.Therefore, the monitoring of cardiovascular disease, Athletess can be monitored with the acquisition of real-time and precise and to brain mind Through systematic research etc..
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle Within the scope of.

Claims (12)

1. a kind of flexible biological electrode characterized by comprising
Conductive substrates;
One-dimensional electric nano material is formed in the conduction in its axial mode substantially orthogonal with the surface of the conductive substrates The substrate surface, the diameter of the one-dimensional electric nano material are 20~200nm, and length is 30~100 μm;Wherein
At least there is polymer coating in the contact interface region of the conductive substrates and the one-dimensional electric nano material.
2. flexible biological electrode according to claim 1, which is characterized in that have in all surface of the conductive substrates There is polymer coating.
3. flexible biological electrode according to claim 1 or 2, which is characterized in that the conductive substrates include:
Support film;And
It is formed in the conductive layer at least one surface of support film;
Preferably, metallic chromium layer is provided between the support film and conductive layer.
4. flexible biological electrode according to claim 3, which is characterized in that the conductive layer is metal conducting layer, described Metal conducting layer includes the combination of one or more of golden conductive layer, silver conductive layer, copper conductive layer;And/or
The material of the support film is polymer material, and the polymer material includes polyimides, poly terephthalic acid second The combination of one or both of diol ester.
5. flexible biological electrode according to claim 1-4, which is characterized in that the one-dimensional electric nano material Including nano wire and/or nanotube, one or more of silver nanowires, nanowires of gold, carbon nanotube are preferably included Combination.
6. flexible biological electrode according to claim 1-5, which is characterized in that the polymer coating is derived from Organo-silicon compound, it is preferable that the organo-silicon compound include silicon rubber and/or siloxanes.
7. a kind of preparation method of flexible biological electrode, which comprises the following steps:
One-dimensional electric nano material is set to be formed in described lead in its axial mode substantially orthogonal with the surface of the conductive substrates The electric substrate surface, the diameter of the one-dimensional electric nano material are 20~200nm, and length is 30~100 μm;
At least in the contact interface region coating polymer solution of the conductive substrates and the one-dimensional electric nano material, solidification After form polymer coating.
8. preparation method according to claim 7, which is characterized in that
One-dimensional electric is made using electrochemical deposition or the method for vapor deposition using the anodic oxidation aluminium formwork with through-hole Nano material is grown on the conductive substrates surface in its axial mode substantially orthogonal with the surface of the conductive substrates.
9. preparation method according to claim 8, which is characterized in that the preparation method comprises the following steps:
Step 1 takes anodic oxidation aluminium formwork;
Step 2 is bonded the anodic oxidation aluminium formwork and the conductive substrates using binder;
Binder in step 3, the removing through-hole;
Step 4, using the method for electrochemical deposition or vapor deposition, be grown in the one-dimensional electric nano material described logical Kong Zhong;
It is step 5, at least molten in the contact interface region coating polymer of the conductive substrates and the one-dimensional electric nano material Liquid forms polymer coating after solidification;
Step 6, the removal anodic oxidation aluminium formwork, obtain the flexible biological electrode.
10. preparation method according to claim 9, which is characterized in that further include making between the step 3 and step 4 The step of one-dimensional electric nano material regionality is grown;Specifically, the regional growth the following steps are included:
Step a deposits one layer of metallics on the surface far from the conductive substrates of anodic oxidation aluminium formwork;
Step b coats a layer photoresist on the surface of the metallics;
Step c removes metal described in the part metallics and the part according to the assortment mode of the flexible biological electrode The photoresist of material surface;
Step d removes the remaining metallics and the remaining institute after the completion of one-dimensional electric nano material growth State the photoresist on metallics surface.
11. according to the described in any item preparation methods of claim 7-10, which is characterized in that the coating further includes, described The all surface of conductive substrates is coated with the polymer solution.
12. according to the described in any item preparation methods of claim 7-11, which is characterized in that the preparation method of the conductive substrates Include the steps that for conductive layer being connected with support film;Preferably, gold is also deposited between the conductive layer and support film Belong to layers of chrome.
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