CN113460950A - Flexible wearable cardiac electrode for cardiovascular disease monitoring and preparation method thereof - Google Patents

Flexible wearable cardiac electrode for cardiovascular disease monitoring and preparation method thereof Download PDF

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CN113460950A
CN113460950A CN202110750535.0A CN202110750535A CN113460950A CN 113460950 A CN113460950 A CN 113460950A CN 202110750535 A CN202110750535 A CN 202110750535A CN 113460950 A CN113460950 A CN 113460950A
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electrode
pdms
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quartz glass
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CN113460950B (en
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王明浩
樊晔
郭帮帮
程瑜华
王高峰
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Hangzhou Dianzi University
Hangzhou Dianzi University Wenzhou Research Institute Co Ltd
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Hangzhou Dianzi University Wenzhou Research Institute Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81BMICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B7/00Microstructural systems; Auxiliary parts of microstructural devices or systems
    • B81B7/02Microstructural systems; Auxiliary parts of microstructural devices or systems containing distinct electrical or optical devices of particular relevance for their function, e.g. microelectro-mechanical systems [MEMS]
    • 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
    • A61B5/25Bioelectric electrodes therefor
    • A61B5/251Means for maintaining electrode contact with the body
    • A61B5/256Wearable electrodes, e.g. having straps or bands
    • 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
    • A61B5/25Bioelectric electrodes therefor
    • A61B5/263Bioelectric electrodes therefor characterised by the electrode materials
    • A61B5/268Bioelectric electrodes therefor characterised by the electrode materials containing conductive polymers, e.g. PEDOT:PSS polymers
    • 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
    • A61B5/25Bioelectric electrodes therefor
    • A61B5/279Bioelectric electrodes therefor specially adapted for particular uses
    • A61B5/28Bioelectric electrodes therefor specially adapted for particular uses for electrocardiography [ECG]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00015Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
    • B81C1/00134Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems comprising flexible or deformable structures
    • B81C1/00166Electrodes
    • 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 invention discloses a flexible wearable cardiac electrode for cardiovascular disease monitoring and a preparation method thereof. Currently, standard commercial Ag/AgCl electrodes for ECG signal detection maintain good electrical conductivity between the electrode and the skin primarily through conductive glue. However, such conductive pastes may become dry over time, resulting in changes in electrode-tissue interface impedance and a dramatic decrease in signal quality. The invention intends to adopt PDMS and SU-8 with low Young's modulus and high biocompatibility as the substrate of the dry electrode, and improve the wearing comfort by conformal attachment and stimulation reduction. On the other hand, in order to improve the stability of signals, the hollow microneedle array is adopted to pierce the stratum corneum of the skin, and the interfacial impedance between the electrode and the tissue is reduced by combining electrochemical modification and electrolyte slow release, so that the quality and the stability of ECG signals are improved.

Description

Flexible wearable cardiac electrode for cardiovascular disease monitoring and preparation method thereof
Technical Field
The invention belongs to the technical field of MEMS sensors, and particularly relates to a flexible wearable cardiac electrode for cardiovascular disease monitoring and a preparation method thereof, wherein the chip realizes the preparation and integration of an Electrocardiogram (ECG) electrode on an SU-8 substrate and a PDMS substrate through MEMS micromachining and micro-assembly technologies.
Background
Today, despite the miniaturization and wireless transmission of wearable flexible ECG sensors, the use of everyday ECG recording systems is still limited by the discomfort and inconvenience of wet electrodes to the patient, which puts new demands on ECG electrodes with high performance and good biocompatibility. Standard commercial Ag/AgCl electrodes for ECG signal detection maintain good electrical conductivity between the electrode and the skin, mainly by conductive glue. However, such conductive pastes may become dry over time, resulting in changes in electrode-tissue interface impedance and a dramatic decrease in signal quality. In addition, such conductive adhesives can also irritate the skin of the patient, causing excessive discomfort to the patient. Furthermore, sweat is another factor that causes the wet electrode signal to deteriorate. These above problems make conventional Ag/AgCl electrodes unsuitable for routine and repeated ECG recording in cardiovascular disease monitoring. Therefore, there is a need to develop a wearable flexible ECG dry electrode capable of realizing 24-hour uninterrupted electrocardiographic monitoring, which can meet the requirements for high signal-to-noise ratio and high stability ECG signal acquisition in cardiovascular disease monitoring.
Yuki Yamamoto et al, Osaka Familion university, Japan, in the paper "Efficient Skin Temperature Sensor and Stable Gel-Less Sticky ECG Sensor for a Wearable Flexible Healthcare Patch" proposes an adhesive ECG Sensor based on Carbon Nanotube (CNT) and Polyethoxyethyleneimine (PEIE) doped PDMS composite. In the composite material, CNT mainly improves the conductive property of the ECG electrode, and PEIE mainly improves the adhesion property of the ECG electrode and the skin. Although the quality of the recorded ECG signal can be improved by controlling the concentration of CNTs and PEIEs in the composite material, the performance of such ECG electrodes can still be affected by sweat and movement conditions. An ECG sensor based on SU-8 micro-needle Array is proposed in the paper "contamination of Parylene-Coated micro Electrode for week ECG Device" by Affraiz Tariq Satti et al at the university of Jiaquan in Korea, and the Electrode-tissue interface impedance is reduced by puncturing the skin stratum corneum, so that the exercise electrocardiographic monitoring and the long-term electrocardiographic monitoring are realized. However, the biocompatibility of such stainless steel-based SU-8 microneedle arrays has not been verified, and thus has not been suitable for application to the human body.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to form a hollow SU-8 micro-needle array on the surface of SU-8 by using an MEMS micro-processing technology, form a contact electrode point consisting of metal and conductive polymer on the surface of the SU-8 micro-needle by sputtering and electroplating, and realize the preparation of the ECG electrode with low contact impedance by combining physical puncture, electrochemical modification and electrolyte release.
The invention relates to a flexible wearable heart electrode for cardiovascular disease monitoring, which comprises an electrode part, a flexible substrate and a metal bonding pad. The electrode portion comprises SU-8 microneedles and a support layer. The SU-8 micro-needle and the supporting layer are made of SU-8 or PI. The supporting layer is provided with an electrode position; a plurality of SU-8 micro-needles in a conical shape are arranged on the electrode position. The SU-8 micro-needle is provided with a fluid pore canal which penetrates through the SU-8 micro-needle and the supporting layer. And a metal pad is arranged on the supporting layer. A metal layer is deposited on the support layer. The metal layer covers each SU-8 micro-needle, and a wire connecting the electrode site and the metal pad is formed on the support layer. The surface of each SU-8 microneedle is provided with a conductive polymer. The supporting layer is attached to the PDMS flexible substrate. The PDMS flexible substrate is provided with a fluid chamber therein. Electrolyte is stored in the fluid chamber and is communicated with the fluid pore channel on the SU-8 micro needle.
Preferably, the SU-8 microneedle is obtained by back-exposure on a support layer. The support layer and the PDMS flexible substrate are bonded together by thermal pressure after plasma treatment of the surfaces. Electroplating a layer of conductive polymer on the surface of the SU-8 micro-needle through electrochemical deposition; the conductive polymer is made of PEDOT PSS.
Preferably, the electrode is circular with the diameter of 0.5-2 cm; the SU-8 micro-needle is conical, the diameter of the bottom of the SU-8 micro-needle is 100-500 microns, and the height of the SU-8 micro-needle is 50-700 microns. The diameter of the fluid pore in the SU-8 microneedle is 10-100 microns. The thickness of the support layer is 5-100 microns, and the thickness of the PDMS flexible substrate is 0.1-2 mm.
Preferably, during use, the protruding SU-8 microneedles penetrate through the stratum corneum into the dermis, reducing the electrode-skin interface impedance through physical puncture. And the fluid chamber in the PDMS flexible substrate releases electrolyte to the skin through the fluid pore channel on the SU-8 micro-needle, so that the conducting polymer on the SU-8 micro-needle conducts electricity through ions and holes, and the interface impedance of the electrode and the skin is reduced.
Preferably, the conductive polymer is PEDOT: PSS, and is electroplated on the SU-8 micro-needle in an electrochemical deposition mode.
Preferably, the material of the supporting layer is SU-8; the support layer and the PDMS flexible substrate are bonded together through hot pressing after plasma treatment is carried out on the surfaces.
Preferably, the material of the supporting layer is PI; the support layer and the PDMS flexible substrate are adhered together through silicon glue.
Under the condition that the supporting layer is made of SU-8, the preparation method of the flexible wearable cardiac electrode for cardiovascular disease monitoring comprises the following specific steps:
1) PMMA was spin-coated on a quartz glass plate and cured to a sacrificial layer by heating.
2) And (3) spin-coating SU-8 photoresist on the sacrificial layer and carrying out photoetching patterning to form an SU-8 supporting layer.
3) And depositing a layer of metal on the SU-8 supporting layer and patterning to form an opaque metal mask.
4) And spin-coating a layer of SU-8 photoresist on the SU-8 support layer on which the metal is deposited again, and carrying out back exposure from the back of the quartz glass sheet.
5) And depositing a layer of metal on the SU-8 supporting layer and carrying out photoetching and patterning to form an SU-8 micro-needle, a lead and a metal pad structure.
6) And adhering a layer of water-soluble adhesive tape on the front surface of the quartz glass sheet, and releasing the electrode part from the quartz glass sheet by using the water-soluble adhesive tape.
7) And spin-coating a layer of SU-8 photoresist on the other unused quartz glass sheet, and carrying out photoetching patterning to form the inverse mode structure of PDMS.
8) And depositing a layer of parylene C on the surface of the inverse mold structure to be used as a release agent of PDMS.
9) And spin-coating a layer of PDMS precursor on the front surface of the quartz glass, and heating and curing to form a fluid chamber structure.
10) And releasing the cured PDMS flexible substrate from the inverted mould structure, and bonding the substrate with the opening facing upwards to another unused quartz glass sheet.
11) Respectively treating the surfaces of the PDMS flexible substrate and the SU-8 supporting layer by oxygen plasma, then bonding the PDMS flexible substrate and the SU-8 supporting layer together, and pressurizing and heating to realize bonding.
12) And (3) the bonded flexible wearable core electrode is taken off from the quartz glass sheet, and then the bonded flexible wearable core electrode is put into the ionized water to dissolve the water-soluble adhesive tape to realize release.
Under the condition that the supporting layer is made of PI, the preparation method of the flexible wearable cardiac electrode for cardiovascular disease monitoring comprises the following specific steps:
1) PMMA was spin-coated on a quartz glass plate and cured to a sacrificial layer by heating.
2) And spin-coating PI photoresist on the sacrificial layer and carrying out photoetching patterning to form a PI supporting layer.
3) And depositing a layer of metal on the PI supporting layer and patterning to form an opaque metal mask.
4) And spin-coating a layer of SU-8 photoresist on the PI supporting layer on which the metal is deposited again, and carrying out back exposure from the back of the quartz glass sheet.
5) And depositing a layer of metal on the PI supporting layer and carrying out photoetching and patterning to form SU-8 micro-needle, lead and metal pad structures.
6) And adhering a layer of water-soluble adhesive tape on the front surface of the quartz glass sheet, and releasing the electrode part from the quartz glass sheet by using the water-soluble adhesive tape.
7) And spin-coating a layer of SU-8 photoresist on the other unused quartz glass sheet, and carrying out photoetching patterning to form the inverse mode structure of PDMS.
8) And depositing a layer of parylene C on the surface of the inverse mold structure to be used as a release agent of PDMS.
9) And spin-coating a layer of PDMS precursor on the front surface of the quartz glass, and heating and curing to form a fluid chamber structure.
10) And releasing the cured PDMS flexible substrate from the inverted mould structure, and bonding the substrate with the opening facing upwards to another unused quartz glass sheet.
11) Coating a layer of silica gel on the upper surface of the PDMS flexible substrate, and then adhering the PI supporting layer on the PDMS flexible substrate;
12) and (3) the bonded flexible wearable core electrode is taken off from the quartz glass sheet, and then the bonded flexible wearable core electrode is put into the ionized water to dissolve the water-soluble adhesive tape to realize release.
The invention has the beneficial effects that:
1. the invention realizes the preparation of the hollow SU-8 micro-needle structure by using the back exposure process of SU-8 or PI, and the ECG electrode can puncture the stratum corneum and release electrolyte through the SU-8 micro-needle, thereby reducing the contact impedance of the ECG electrode and the skin.
2. The invention realizes SU-8 micro-needle surface modification by electrochemical deposition, and can realize electric conduction between the ECG electrode and the skin through holes and ions by conductive polymer modification, thereby reducing the contact impedance of the ECG electrode and the skin.
3. The invention uses PDMS as the supporting material of the ECG electrode, and can improve the conformal attachment and biocompatibility of the ECG electrode by reducing the Young modulus, thereby improving the contact stability of the ECG electrode and the skin.
Drawings
FIG. 1 is a schematic diagram of the overall structure of an ECG electrode according to the present invention;
FIG. 2 is a schematic structural diagram of an ECG electrode part and a PDMS flexible substrate according to the present invention;
FIG. 3 is a diagram showing the effect of the surface modification of the conductive polymer on the ECG electrode part according to the present invention;
FIG. 4 is a flow chart of a process for manufacturing an ECG electrode according to the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example 1
As shown in fig. 1, a flexible wearable cardiac electrode for cardiovascular disease monitoring comprises an electrode part 1, a PDMS flexible substrate 2 and a metal pad 3 which together form a cardiac electrode structure.
As shown in fig. 2, the electrode portion 1 is composed of hollow SU-8 microneedles 1-1 and a bottom SU-8 support layer 1-2. Three electrode positions are arranged on the SU-8 supporting layer 1-2; a plurality of conical SU-8 micro-needles 1-1 are uniformly distributed on each electrode position. Each SU-8 micro-needle 1-1 is provided with a fluid pore canal which penetrates through the SU-8 micro-needle 1-1 and the SU-8 supporting layer 1-2.
Three metal pads 3 are arranged on the SU-8 support layer 1-2. A metallic layer is deposited on SU-8 support layer 1-2. The metal layer covers each SU-8 microneedle 1-1 and forms a plurality of wires on the SU-8 support layer 1-2. The metal layers of the SU-8 micro-needles 1-1 on the three electrode positions are electrically connected with the three metal pads 3 through corresponding wires respectively to form a conductive path.
As shown in FIG. 3, the surface of each SU-8 microneedle 1-1 is plated with a layer of conductive polymer (specifically PEDOT: PSS) by means of electrochemical deposition. PSS is a conductive polymer with pseudocapacitance characteristics, and has hole conductivity and ion conductivity in the presence of an electrolyte.
The SU-8 supporting layer 1-2 is attached to the PDMS flexible substrate 2. The PDMS flexible substrate 2 is composed of a hollow fluid chamber 2-1 and a peripheral PDMS support layer 2-2. The PDMS flexible substrate 2 is provided with a plurality of fluid chambers 2-1 corresponding to the number of the electrode bits. The SU-8 supporting layer 1-2 and the PDMS flexible substrate 2 are bonded together by hot pressing after plasma treatment is carried out on the surfaces. The fluid chambers 2-1 are aligned with corresponding electrode sites and communicate with respective fluid channels on the corresponding electrode section 1. The electrolyte stored in the fluid chamber 2-1 can be released through the fluid pore of the SU-8 microneedle 1-1. Furthermore, only one fluid chamber 2-1 may be provided; and the fluid chamber 2-1 is connected to all three electrode sites.
The fluid chamber 2-1 is filled with an electrolyte. In the use process of the flexible wearable cardiac electrode, electrolyte can seep out through a fluid pore channel on the SU-8 micro-needle 1-1; when the environment required by electrocardio signal acquisition is provided, conductive adhesive does not need to be coated, and a large-area wet area is not generated, so that the electrocardio signal acquisition process is more comfortable.
The flexible wearable cardiac electrode for cardiovascular disease monitoring comprises the following specific preparation steps:
1) PMMA was spin-coated on a quartz glass plate and cured by heating at 110 ℃ for 5 minutes, 150 ℃ for 5 minutes and 180 ℃ for 10 minutes. This process forms the sacrificial layer of the ECG electrode.
2) And (3) spin-coating a layer of SU-8(GM1060) photoresist with the thickness of 10 microns on the PMMA sacrificial layer, standing for 5 minutes, and then carrying out pre-baking at the temperature of 65 ℃ for 3 minutes and 95 ℃ for 30 minutes. After the pre-baking is finished, exposure is carried out, and the exposure dose is 400mJ/cm2. Then, postbaking was carried out at 65 ℃ for 5 minutes and 95 ℃ for 20 minutes. After standing for 10 minutes, the mixture was put into PGMEA (propylene glycol methyl ether acetate) and developed for 4.5 minutes. After the development is finished, hard baking is carried out; the hard-baking temperature is 135 ℃, and the hard-baking time is 2 hours. This process forms the SU-8 support layer 1-2 of the ECG electrode.
3) And a layer of metal Cr and a layer of metal Au are sequentially deposited on the SU-8 supporting layer, wherein the thicknesses of the metal Cr and the metal Au are respectively 20 nanometers and 200 nanometers. And then spin-coating positive photoresist with the thickness of 5 microns on the SU-8 supporting layer and carrying out photoetching patterning to form a photoresist mask of the metal layer. And then, respectively patterning the metal Au and the metal Cr by adopting a wet etching technology. This process forms a back exposure mask of hollow SU-8 microneedles.
4) In depositing goldAnd spin-coating a layer of SU-8(GM1060) photoresist with the thickness of 50 microns on the SU-8 supporting layer, standing for 15 minutes, and then carrying out pre-baking at the temperature of 65 ℃ for 15 minutes and 95 ℃ for 60 minutes. After the pre-baking is finished, back exposure is carried out, and the exposure dose is 650mJ/cm2. Then, post-baking was carried out at 65 ℃ for 10 minutes and at 95 ℃ for 30 minutes. After standing for 10 minutes, the mixture was put into PGMEA and developed for 4 minutes. After the development, hard baking was carried out at 135 ℃ for 2 hours. This process forms SU-8 microneedles 1-1 with hollow micropores.
5) A layer of metal Cr and a layer of metal Au are deposited on the SU-8 supporting layer 1-2 with the SU-8 micro-needle in sequence, and the thicknesses of the metal Cr and the metal Au are 20 nanometers and 200 nanometers respectively. Then, a positive resist with a thickness of 5 μm was spin-coated on the metal layer and patterned by photolithography to form a resist mask for the metal layer. And then, respectively patterning the metal Au and the metal Cr by adopting a wet etching technology. This process forms the electrode portion 1, lead and pad structure of the ECG electrode.
6) A water-soluble adhesive tape is stuck on the front surface of the quartz glass sheet, and the electrode part 1 of the ECG electrode is released from the quartz glass sheet by the water-soluble adhesive tape.
7) And another quartz glass sheet is taken, a layer of SU-8(GM1060) photoresist with the thickness of 50 microns is coated on the quartz glass sheet in a spin mode, standing is carried out for 15 minutes, and then pre-baking is carried out, wherein the pre-baking temperature is 65 ℃ for 15 minutes, and the pre-baking temperature is 95 ℃ for 60 minutes. After the pre-baking is finished, back exposure is carried out, and the exposure dose is 650mJ/cm2. Then, post-baking was carried out at 65 ℃ for 10 minutes and at 95 ℃ for 30 minutes. After standing for 10 minutes, the mixture was put into PGMEA and developed for 4 minutes. After the development was completed, hard baking was carried out at 135 ℃ for 2 hours. This process formed the SU-8 inverse of the PDMS of the fluid chamber.
8) A5 micron thick layer of parylene C was deposited on the surface of the SU-8 inverse mold using a chemical vapor deposition system as a release agent for PDMS.
9) A layer of PDMS precursor 500 microns thick was spin-coated on the front side of a quartz glass plate (i.e., SU-8 reverse mold) and cured by heating in an oven at 60 ℃ for 4 hours. This process forms the PDMS flexible substrate 2 structure with the fluid chamber 2-1.
10) And releasing the cured PDMS flexible substrate 2 from the SU-8 reverse mold, passivating the surface of the DMS flexible substrate 2 by using oxygen plasma, and finally bonding the DMS flexible substrate to another unused quartz glass sheet in a mode that the opening of the fluid chamber 2-1 faces upwards.
11) Respectively treating the surfaces of the electrode part 1 formed by the PDMS flexible substrate 2 and the SU-8 by using oxygen plasma, then pasting a PDMS supporting layer of the PDMS flexible substrate 2 and an SU-8 supporting layer of the electrode part 1 together, and bonding by pressurizing and heating to form the flexible wearable core electrode for cardiovascular disease monitoring.
12) And (3) the bonded flexible wearable core electrode is taken off from the quartz glass sheet, and then the bonded flexible wearable core electrode is put into the ionized water to dissolve the water-soluble adhesive tape to realize release.
Example 2
A flexible wearable cardiac electrode for cardiovascular disease monitoring, the present embodiment differing from embodiment 1 in that: SU-8 support layer 1-2 was replaced with a PI support layer.
The specific preparation steps of the flexible wearable cardiac electrode for cardiovascular disease monitoring are as follows:
1) PMMA was spin-coated on a quartz glass plate and cured by heating at 110 ℃ for 5 minutes, 150 ℃ for 5 minutes and 180 ℃ for 10 minutes. This process forms the sacrificial layer of the ECG electrode.
2) And (3) spinning a layer of Polyimide (PI) photoresist with the thickness of 10 microns on the PMMA sacrificial layer, standing for 5 minutes, and then performing prebaking at the temperature of 80 ℃ for 10 minutes, 120 ℃ for 30 minutes, 150 ℃ for 10 minutes, 180 ℃ for 10 minutes and 220 ℃ for 40 minutes. This process forms the PI support layer of the ECG electrode.
3) And a layer of metal Cr and a layer of metal Au are sequentially deposited on the PI supporting layer, wherein the thicknesses of the metal Cr and the metal Au are respectively 20 nanometers and 200 nanometers. And then spin-coating positive photoresist with the thickness of 5 microns on the PI supporting layer and carrying out photoetching patterning to form a photoresist mask of a metal layer. And then, respectively patterning the metal Au and the metal Cr by adopting a wet etching technology. The process forms a back exposure mask of the SU-8 micro-needle hollow micropore structure.
4) Spinning on a PI supporting layer after metal depositionCoating a layer of SU-8(GM1060) photoresist with the thickness of 50 microns, standing for 15 minutes, and then carrying out prebaking at 65 ℃ for 15 minutes and 95 ℃ for 60 minutes. After the pre-baking is finished, back exposure is carried out, and the exposure dose is 650mJ/cm2. Then, post-baking was carried out at 65 ℃ for 10 minutes and at 95 ℃ for 30 minutes. After standing for 10 minutes, the mixture was put into PGMEA and developed for 4 minutes. After the development, hard baking was carried out at 135 ℃ for 2 hours. The process forms SU-8 micro needle structure with hollow micro-hole.
5) And placing a stainless steel hard mask prepared by laser cutting on the PI supporting layer with SU-8 microneedles, and then sequentially depositing a layer of metal Cr and a layer of metal Au, wherein the thicknesses of the metal Cr and the metal Au are respectively 20 nanometers and 200 nanometers. The metal Au and the metal Cr were then patterned after the stainless steel hard mask was removed from the substrate. This process forms the electrode portion, lead and pad structure of the ECG electrode.
6) And sticking a layer of water-soluble adhesive tape on the front surface of the quartz glass sheet, and releasing the electrode part from the quartz glass sheet by using the water-soluble adhesive tape.
7) And another quartz glass sheet is taken, a layer of SU-8(GM1060) photoresist with the thickness of 50 microns is coated on the quartz glass sheet in a spin mode, standing is carried out for 15 minutes, and then pre-baking is carried out, wherein the pre-baking temperature is 65 ℃ for 15 minutes, and the pre-baking temperature is 95 ℃ for 60 minutes. After the pre-baking is finished, back exposure is carried out, and the exposure dose is 650mJ/cm2. Then, post-baking was carried out at 65 ℃ for 10 minutes and at 95 ℃ for 30 minutes. After standing for 10 minutes, the mixture was put into PGMEA and developed for 4 minutes. After the development was completed, hard baking was carried out at 135 ℃ for 2 hours. This process formed the SU-8 inverse of the PDMS of the fluid chamber.
8) A5 micron thick layer of parylene C was deposited on the surface of the SU-8 inverse mold using a chemical vapor deposition system as a release agent for PDMS.
9) A 500 micron thick PDMS precursor was spin-coated on the front side of the quartz glass plate (i.e., on the SU-8 inverse mold) and cured by heating in an oven at 60 ℃ for 4 hours. This process forms the PDMS flexible substrate 2 structure with the fluid chamber 2-1.
10) The cured PDMS flexible substrate 2 was released from the SU-8 flip-mold and subsequently bonded to another piece of unused quartz glass with the fluid chamber 2-1 open upward.
11) Coating a layer of silica gel on the upper surface of the PDMS flexible substrate 2, then pasting the electrode part 1 on the PDMS flexible substrate 2 with the PI supporting layer facing downwards, and standing at normal temperature for 24 hours for curing.
12) And (3) the adhered flexible wearable core electrode is taken off from the quartz glass sheet, and then the flexible wearable core electrode is put into the ionized water to dissolve the water-soluble adhesive tape to realize release.

Claims (9)

1. A flexible wearable cardiac electrode for cardiovascular disease monitoring, characterized by: the flexible circuit board comprises an electrode part (1), a flexible substrate and a metal bonding pad (3); the electrode part (1) comprises SU-8 micro-needles (1-1) and a supporting layer (1-2); the SU-8 microneedle (1-1) and the support layer (1-2) are made of SU-8 or PI; an electrode position is arranged on the supporting layer (1-2); a plurality of SU-8 micro-needles (1-1) in a conical shape are arranged on the electrode position; a fluid pore passage which penetrates through the SU-8 microneedle (1-1) and the supporting layer (1-2) is arranged on the SU-8 microneedle (1-1); a metal pad (3) is arranged on the supporting layer (1-2); a metal layer is deposited on the support layer (1-2); the metal layer covers each SU-8 micro-needle (1-1), and a lead for connecting the electrode position and the metal pad (3) is formed on the support layer (1-2); the surface of each SU-8 micro-needle (1-1) is provided with a conductive polymer; the support layer (1-2) is attached to the PDMS flexible substrate (2); a fluid chamber (2-1) is arranged in the PDMS flexible substrate (2); electrolyte is stored in the fluid chamber (2-1) and is communicated with the fluid pore channel on the SU-8 micro-needle.
2. A flexible wearable cardiac electrode for cardiovascular disease monitoring according to claim 1 wherein: the SU-8 micro-needle is obtained by back exposure on the support layer (1-2); the support layer and the PDMS flexible substrate (2) are bonded together by hot pressing after plasma treatment is carried out on the surfaces; electroplating a layer of conductive polymer on the surface of the SU-8 micro-needle through electrochemical deposition; the conductive polymer is made of PEDOT PSS.
3. A flexible wearable cardiac electrode for cardiovascular disease monitoring according to claim 1 wherein: the electrode is in a circular shape with the diameter of 0.5-2 cm; the SU-8 micro-needle (1-1) is conical, the diameter of the bottom of the SU-8 micro-needle is 100-500 microns, and the height of the SU-8 micro-needle is 50-700 microns; the diameter of the fluid pore in the SU-8 micro-needle is 10-100 micrometers; the thickness of the support layer is 5-100 microns, and the thickness of the PDMS flexible substrate is 0.1-2 mm.
4. A flexible wearable cardiac electrode for cardiovascular disease monitoring according to claim 1 wherein: during use, the raised SU-8 microneedles penetrate through the stratum corneum into the dermis, and reduce the electrode-skin interface impedance through physical puncture; and the fluid chamber in the PDMS flexible substrate releases electrolyte to the skin through the fluid pore channel on the SU-8 micro-needle, so that the conducting polymer on the SU-8 micro-needle conducts electricity through ions and holes, and the interface impedance of the electrode and the skin is reduced.
5. A flexible wearable cardiac electrode for cardiovascular disease monitoring according to claim 1 wherein: the conductive polymer is made of PEDOT: PSS and is electroplated on the SU-8 micro-needle (1-1) in an electrochemical deposition mode.
6. A flexible wearable cardiac electrode for cardiovascular disease monitoring according to claim 1 wherein: the supporting layer (1-2) is made of SU-8; the support layer (1-2) and the PDMS flexible substrate (2) are bonded together by hot pressing after plasma treatment is carried out on the surfaces.
7. A flexible wearable cardiac electrode for cardiovascular disease monitoring according to claim 1 wherein: the supporting layer (1-2) is made of PI; the support layer (1-2) and the PDMS flexible substrate (2) are adhered together through silica gel.
8. A method of making a flexible wearable cardiac electrode for cardiovascular disease monitoring as claimed in claim 1, wherein: the supporting layer is made of SU-8; the preparation method specifically comprises the following steps:
1) spin-coating PMMA on a quartz glass sheet and heating and curing the PMMA into a sacrificial layer;
2) spin-coating SU-8 photoresist on the sacrificial layer and performing photoetching patterning to form an SU-8 supporting layer;
3) depositing a layer of metal on the SU-8 supporting layer and patterning to form an opaque metal mask;
4) spin-coating a layer of SU-8 photoresist on the SU-8 supporting layer on which the metal is deposited again, and performing back exposure from the back of the quartz glass sheet;
5) depositing a layer of metal on the SU-8 supporting layer and carrying out photoetching and patterning to form an SU-8 micro-needle, a lead and a metal pad structure;
6) sticking a layer of water-soluble adhesive tape on the front surface of the quartz glass sheet, and releasing the electrode part from the quartz glass sheet by using the water-soluble adhesive tape;
7) spin-coating a layer of SU-8 photoresist on the other unused quartz glass sheet, and performing photoetching patterning to form a PDMS reverse mold structure;
8) depositing a layer of parylene C on the surface of the inverse mold structure to be used as a release agent of PDMS;
9) spin-coating a layer of PDMS precursor on the front surface of the quartz glass, and heating and curing to form a fluid chamber (2-1) structure;
10) releasing the cured PDMS flexible substrate (2) from the inverted mould structure, and bonding the substrate to another unused quartz glass sheet with an opening facing upwards;
11) respectively treating the surfaces of the PDMS flexible substrate (2) and the SU-8 supporting layer by using oxygen plasma, then bonding the PDMS flexible substrate (2) and the SU-8 supporting layer together, and realizing bonding by pressurizing and heating;
12) and (3) the bonded flexible wearable core electrode is taken off from the quartz glass sheet, and then the bonded flexible wearable core electrode is put into the ionized water to dissolve the water-soluble adhesive tape to realize release.
9. A method of making a flexible wearable cardiac electrode for cardiovascular disease monitoring as claimed in claim 1, wherein: the supporting layer is made of PI; the preparation method specifically comprises the following steps:
1) spin-coating PMMA on a quartz glass sheet and heating and curing the PMMA into a sacrificial layer;
2) spin-coating PI photoresist on the sacrificial layer and carrying out photoetching patterning to form a PI supporting layer;
3) depositing a layer of metal on the PI supporting layer and patterning to form a lighttight metal mask;
4) spin-coating a layer of SU-8 photoresist on the PI supporting layer on which the metal is deposited again, and performing back exposure from the back of the quartz glass sheet;
5) depositing a layer of metal on the PI supporting layer and carrying out photoetching and patterning to form SU-8 micro-needle, lead and metal pad structures;
6) sticking a layer of water-soluble adhesive tape on the front surface of the quartz glass sheet, and releasing the electrode part from the quartz glass sheet by using the water-soluble adhesive tape;
7) spin-coating a layer of SU-8 photoresist on the other unused quartz glass sheet, and performing photoetching patterning to form a PDMS reverse mold structure;
8) depositing a layer of parylene C on the surface of the inverse mold structure to be used as a release agent of PDMS;
9) spin-coating a layer of PDMS precursor on the front surface of the quartz glass, and heating and curing to form a fluid chamber (2-1) structure;
10) releasing the cured PDMS flexible substrate (2) from the inverted mould structure, and bonding the substrate to another unused quartz glass sheet with an opening facing upwards;
11) coating a layer of silica gel on the upper surface of the PDMS flexible substrate (2), and then adhering a PI supporting layer on the PDMS flexible substrate (2);
12) and (3) the bonded flexible wearable core electrode is taken off from the quartz glass sheet, and then the bonded flexible wearable core electrode is put into the ionized water to dissolve the water-soluble adhesive tape to realize release.
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