CN117305804A - Boron-doped diamond microelectrode and preparation method and electroencephalogram application thereof - Google Patents
Boron-doped diamond microelectrode and preparation method and electroencephalogram application thereof Download PDFInfo
- Publication number
- CN117305804A CN117305804A CN202210715354.9A CN202210715354A CN117305804A CN 117305804 A CN117305804 A CN 117305804A CN 202210715354 A CN202210715354 A CN 202210715354A CN 117305804 A CN117305804 A CN 117305804A
- Authority
- CN
- China
- Prior art keywords
- boron
- doped diamond
- substrate
- microelectrode
- reaction chamber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010432 diamond Substances 0.000 title claims abstract description 128
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 128
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052796 boron Inorganic materials 0.000 claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000011858 nanopowder Substances 0.000 claims abstract description 17
- 238000004050 hot filament vapor deposition Methods 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 32
- 229910052715 tantalum Inorganic materials 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000012159 carrier gas Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical group COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010899 nucleation Methods 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 53
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 51
- 210000004556 brain Anatomy 0.000 description 27
- 239000004205 dimethyl polysiloxane Substances 0.000 description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 8
- 210000004761 scalp Anatomy 0.000 description 8
- 210000001061 forehead Anatomy 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 239000002504 physiological saline solution Substances 0.000 description 5
- -1 Polydimethylsiloxane Polymers 0.000 description 4
- 210000005069 ears Anatomy 0.000 description 4
- 210000001595 mastoid Anatomy 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 210000003491 skin Anatomy 0.000 description 4
- 238000005234 chemical deposition Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 210000000434 stratum corneum Anatomy 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010009 beating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 210000003128 head Anatomy 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 208000003174 Brain Neoplasms Diseases 0.000 description 1
- 208000014644 Brain disease Diseases 0.000 description 1
- 208000019695 Migraine disease Diseases 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004397 blinking Effects 0.000 description 1
- 210000003710 cerebral cortex Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003759 clinical diagnosis Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 206010015037 epilepsy Diseases 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007917 intracranial administration Methods 0.000 description 1
- 239000010978 jasper Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 206010027599 migraine Diseases 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 210000002569 neuron Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 210000003625 skull Anatomy 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical 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 inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/271—Diamond only using hot filaments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/263—Bioelectric electrodes therefor characterised by the electrode materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
- A61B5/291—Bioelectric electrodes therefor specially adapted for particular uses for electroencephalography [EEG]
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical 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 inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/278—Diamond only doping or introduction of a secondary phase in the diamond
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical 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 method of coating
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
- A61B2562/02—Details of sensors specially adapted for in-vivo measurements
- A61B2562/0209—Special features of electrodes classified in A61B5/24, A61B5/25, A61B5/283, A61B5/291, A61B5/296, A61B5/053
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Biophysics (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Pathology (AREA)
- Biomedical Technology (AREA)
- Heart & Thoracic Surgery (AREA)
- Medical Informatics (AREA)
- Physics & Mathematics (AREA)
- Surgery (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
Abstract
The invention discloses a boron-doped diamond microelectrode and a preparation method and application thereof, wherein the preparation method comprises the following steps: and (3) ultrasonically cleaning and drying the substrate in the diamond micro-nano powder suspension to obtain a nucleated substrate, growing a boron-doped diamond film on the nucleated substrate by adopting an electronic auxiliary hot wire chemical vapor deposition method, and obtaining the boron-doped diamond microelectrode by adopting the electronic auxiliary hot wire chemical vapor deposition method, wherein the quality is better, the preparation is simple, and the process is mature. The boron-doped diamond microelectrode does not need to be added with conductive paste media to help signal acquisition. The boron-doped diamond film originally belongs to an intrinsic semiconductor, is not conductive, and changes the internal structure of atoms by introducing boron through substitutional doping, so that the boron-doped diamond film has good conductive performance.
Description
Technical Field
The invention belongs to the technical field of electroencephalogram (EEG) electrodes, and particularly relates to a Boron Doped Diamond (BDD) microelectrode, a preparation method and application thereof.
Background
Scalp electroencephalogram is a typical noninvasive brain wave measurement method, and records the electrophysiological activity of brain nerve cells on the surface of cerebral cortex or scalp. Hans Berger in 1924 recorded human electroencephalograms for the first time and Jasper in 1958 used EEG as the basis for clinical diagnosis and brain research. EEG as a noninvasive electroencephalogram monitoring means can detect brain diseases such as migraine, epilepsy, brain tumor and the like, and can assist diagnosis and research of functional diseases of a nervous system.
The traditional scalp brain electrode is an Ag-AgCl electrode coated with conductive paste, and is called a wet electrode, and the Ag-AgCl wet electrode has the advantages of low impedance, good stability, high signal to noise ratio and the like. However, the wet electrode has obvious disadvantages in that the experimental preparation process is complicated and time-consuming due to the need of applying the conductive paste. For example, the electrode has low spatial resolution, a tested person has uncomfortable feeling, and the conductive paste collected for a long time can be dried to influence the accuracy of signal collection, and the like, so that the wet electrode is inconvenient to use and difficult to popularize and develop.
Compared with a wet electrode using conductive adhesive, the scalp electroencephalogram electrode using the physiological saline as the electrolyte has obvious advantages, such as no pollution of the electrode, no phenomenon of colloid adhesion to hair, and the like. BDD brain electrical electrode has advantages of corrosion resistance, stability, low impedance and the like, and has few applications in brain electrical acquisition in skull. BDD, however, is among the hardest semiconductor materials, which makes it of limited application in brain or intra-cranial electroencephalogram acquisition.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a boron-doped diamond microelectrode.
Another object of the present invention is to provide a boron doped diamond microelectrode obtained by the above preparation method.
The aim of the invention is achieved by the following technical scheme.
The preparation method of the boron-doped diamond microelectrode comprises the following steps:
1) Ultrasonic treatment is carried out on a substrate in a diamond micro-nano powder suspension for 60-80 min, cleaning and drying are carried out, and a nucleated substrate is obtained, wherein the diamond micro-nano powder suspension is a mixture of diamond micro-nano powder and a solvent, the concentration of the diamond micro-nano powder in the diamond micro-nano powder suspension is 1-3 mg/mL, the substrate is tantalum wire or tantalum strip, the diameter of the tantalum wire is 0.2-0.6 mm, the width of the tantalum strip is 0.65-1.8 mm, and the length of the tantalum strip or tantalum wire is 40-50 mm;
in the step 1), the substrate is in a linear structure or a plane spiral shape, and the width of the plane spiral shape is 10-12 mm.
In the step 1), the thickness of the tantalum strip is 0.08-0.17 mm.
In the step 1), the solvent is a mixture of acetone and absolute ethyl alcohol, and the ratio of the acetone to the absolute ethyl alcohol in the solvent is 1 (1-1.2) in parts by volume.
In the step 1), the cleaning is: sequentially carrying out ultrasonic treatment on the mixture in absolute ethanol and ultrapure water for 5-8 min.
In the step 1), the drying is baking by a baking lamp.
In the step 1), the substrate is polished and cleaned before use, and the cleaning is sequentially carried out on ultrapure water, absolute ethanol and ultrapure water for at least 5min.
2) And growing a boron-doped diamond film on the nucleated substrate.
In the step 2), the thickness of the boron-doped diamond film is 15-17 mu m.
In the step 2), the boron-doped diamond film is composed of 96-97% of carbon, 1.3-1.7% of boron and the rest of oxygen in percentage by mass.
In the step 2), growing a boron doped diamond film on the nucleated substrate by adopting an electron assisted hot wire chemical vapor deposition method, wherein the electron assisted hot wire chemical vapor deposition method comprises the following steps: placing the nucleated substrate in a reaction chamber, continuously introducing hydrogen and methane into the reaction chamber, continuously inputting a boron source into the reaction chamber, applying bias voltage to the nucleated substrate, and simultaneously keeping the reaction chamber at 800-900 ℃ for 6-8 hours, wherein the current of the applied bias voltage power supply is 8-9A, and the voltage of the applied bias voltage power supply is 185-190V.
In the technical scheme, the flow ratio of the hydrogen to the methane introduced into the reaction chamber is 325 (6-8).
In the above technical scheme, the boron source is trimethyl borate, and is carried into the reaction chamber by carrier gas, and the specific method comprises the following steps: mixing a boron source and absolute ethyl alcohol to obtain mixed liquid, inputting carrier gas into the mixed liquid, bubbling and discharging the mixed liquid, and inputting the bubbled and discharged gas into the reaction chamber.
In the technical proposal, the ratio of the boron source and the absolute ethyl alcohol in the mixed liquid is 1 (3-3.2).
In the above technical solution, the hydrogen is divided into two parts: directly into the reaction chamber and as the carrier gas.
In the technical scheme, the flow ratio of the hydrogen directly introduced into the reaction chamber to the hydrogen used as the carrier gas is 300 (20-30).
In the technical scheme, the air pressure in the reaction chamber is 4.9-5.1 kPa.
The boron-doped diamond microelectrode obtained by the preparation method is provided.
The boron-doped diamond microelectrode is applied to electroencephalogram signal acquisition.
Compared with the prior art, the invention has the beneficial effects that:
1. the material for preparing the boron-doped diamond microelectrode is boron-doped diamond. The boron-doped diamond has good conductivity, excellent mechanical structure stability and no harm to human body, and can be well applied to electroencephalogram signal acquisition.
2. The boron-doped diamond microelectrode obtained by adopting the electron-assisted hot filament chemical vapor deposition method has the advantages of better quality, simple preparation and mature process.
3. The boron-doped diamond microelectrode does not need to be added with conductive paste media to help signal acquisition. When the boron-doped diamond microelectrode is used, the collected area is firstly gently wiped by using scrub cream, the stratum corneum is removed, then the boron-doped diamond microelectrode is fixed at a target position, and after a small amount of physiological saline is added, an electroencephalogram signal is opened for direct collection.
4. The boron-doped diamond film originally belongs to an intrinsic semiconductor, is not conductive, and changes the internal structure of atoms by introducing boron through substitutional doping, so that the boron-doped diamond film has good conductive performance.
5. The flexible boron-doped diamond microelectrode is prepared by using the planar spiral substrate, so that the boron-doped diamond microelectrode can be closely contacted with the scalp in the electroencephalogram signal acquisition to reduce the scalp resistance, and the boron-doped diamond microelectrode also has the advantages of reducing uncomfortable feeling and improving comfort.
6. The boron-doped diamond microelectrode prepared for the planar spiral substrate can be packaged by adopting PDMS, and the packaged boron-doped diamond microelectrode is positioned on one surface of a packaging carrier and is used for contacting with skin during testing, and the copper is used for conducting signals, so that the electrode is convenient to fix.
Drawings
FIG. 1 is a photograph of a boron doped diamond microelectrode obtained in example 1;
FIG. 2 is a photograph showing the diameter of the boron-doped diamond microelectrode prepared in example 1;
FIG. 3 shows the impedance (above the forehead brow) measured by the Ag/AgCl wet electrode (Fp 1) and the boron doped diamond microelectrode (F7) obtained in example 1 EEG acquisition procedure;
FIG. 4 is a waveform chart (blink) of the acquisition of an electrical brain signal of an Ag/AgCl wet electrode (Fp 1) and the boron doped diamond microelectrode (F7) obtained in example 1;
FIG. 5 is a waveform chart (biting) of the acquisition of an electroencephalogram signal of an Ag/AgCl wet electrode (Fp 1) and a boron-doped diamond microelectrode (F7) obtained in example 1;
FIG. 6 shows the impedance (occipital region) measured by the Ag/AgCl wet electrode (PZ) and boron doped diamond microelectrode (Oz) EEG signal acquisition procedure obtained in example 1;
FIG. 7 is an original waveform (open-eye) of an Ag/AgCl wet electrode (PZ) and boron-doped diamond microelectrode (Oz) brain electrical signal acquisition obtained in example 1;
FIG. 8 is a photograph of a boron doped diamond microelectrode obtained in example 2;
FIG. 9 is the impedance (above the forehead brow) measured by the Ag/AgCl wet electrode (Fp 1) and boron doped diamond microelectrode (F7) obtained in example 2 EEG acquisition procedure;
FIG. 10 is a waveform chart (blink) of the acquisition of an electrical brain signal of an Ag/AgCl wet electrode (Fp 1) and the boron doped diamond microelectrode (F7) obtained in example 2;
FIG. 11 is a waveform chart (biting) of the acquisition of an electroencephalogram signal of an Ag/AgCl wet electrode (Fp 1) and a boron-doped diamond microelectrode (F7) obtained in example 2;
FIG. 12 shows the impedance (occipital region) measured by the Ag/AgCl wet electrode (PZ) and boron doped diamond microelectrode (Oz) EEG signal acquisition procedure obtained in example 2;
FIG. 13 is a raw waveform (open-eye) of an acquisition of an electrical brain signal of an Ag/AgCl wet electrode (PZ) and a boron doped diamond microelectrode (Oz) obtained in example 2;
FIG. 14 is a photograph of a boron doped diamond microelectrode obtained in example 3;
FIG. 15 shows the impedance (above the forehead brow) measured by the Ag/AgCl wet electrode (Fp 1) and the boron doped diamond microelectrode (F7) obtained in example 3 EEG acquisition procedure;
FIG. 16 is a waveform chart (blink) of the acquisition of an electrical brain signal of an Ag/AgCl wet electrode (Fp 1) and the boron doped diamond microelectrode (F7) obtained in example 3;
FIG. 17 is a waveform chart (biting) of the acquisition of an electroencephalogram signal of an Ag/AgCl wet electrode (Fp 1) and a boron-doped diamond microelectrode (F7) obtained in example 3;
FIG. 18 shows the impedance (occipital region) measured by the Ag/AgCl wet electrode (PZ) and boron doped diamond microelectrode (Oz) EEG signal acquisition procedure obtained in example 3;
FIG. 19 is a raw waveform (open-eye) of an acquisition of an electrical brain signal of an Ag/AgCl wet electrode (PZ) and a boron doped diamond microelectrode (Oz) obtained in example 3;
FIG. 20 is a photograph of a boron doped diamond microelectrode obtained in example 4;
FIG. 21 is a photograph (after encapsulation) of the boron-doped diamond microelectrode obtained in example 4;
FIG. 22 shows the impedance (above the forehead brow) measured by the Ag/AgCl wet electrode (Fp 1) and the boron doped diamond microelectrode (F7) obtained in example 4 EEG acquisition procedure;
FIG. 23 is a waveform chart (blink) of the acquisition of an electrical brain signal of an Ag/AgCl wet electrode (Fp 1) and the boron doped diamond microelectrode (F7) obtained in example 4;
FIG. 24 is a waveform chart (biting) of the acquisition of an electrical brain signal of an Ag/AgCl wet electrode (Fp 1) and a boron doped diamond microelectrode (F7) obtained in example 4;
FIG. 25 is the impedance (posterior occipital region) measured by the Ag/AgCl wet electrode (PZ) and boron doped diamond microelectrode (Oz) EEG signal acquisition procedure obtained in example 4;
FIG. 26 is a raw waveform (open-eye) of an Ag/AgCl wet electrode (PZ) and boron-doped diamond microelectrode (Oz) brain electrical signal acquisition obtained in example 4;
fig. 27 is a photograph of a mold of the boron doped diamond microelectrode packaging tool obtained in example 4.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
Electron assisted hot wire chemical deposition apparatus (HFCVD): the Shenyang scientific instruments Co., ltd (volume of the reaction chamber 120L);
an electroencephalogram amplifier: neuroscan, australia, greal model.
The plane spiral shape is 2-3 circles.
Polishing: sequentially polishing the surface of the substrate by using sand paper with the roughness of 70 meshes ((212 mu m) and 220 meshes (68 mu m), removing surface impurities, polishing scratches with the same direction on the surface, and flatly attaching the polished substrate to a plane.
Example 1
The preparation method of the boron-doped diamond microelectrode comprises the following steps:
1) Preparing a substrate in a straight line shape: the substrate is tantalum wire with the diameter of 0.6mm and the length of 40mm.
Sequentially polishing a substrate, sequentially carrying out ultrasonic treatment on the substrate in ultrapure water, absolute ethyl alcohol and ultrapure water for 10min, sequentially carrying out ultrasonic treatment on the substrate in a diamond micro-nano powder suspension for 60min so as to enable particles of the diamond micro-nano powder to sufficiently nucleate on the surface of the substrate, sequentially carrying out ultrasonic treatment on the substrate in the absolute ethyl alcohol and the ultrapure water for 5min, and sequentially carrying out baking by a baking lamp (250W) for 10min to obtain a nucleated substrate, wherein the diamond micro-nano powder suspension is a mixture of diamond micro-nano powder (manufactured by Shanghai Allatin technology Co., ltd.) and a solvent, the concentration of the diamond micro-nano powder in the diamond micro-nano powder suspension is 1mg/mL, the solvent is a mixture of acetone and absolute ethyl alcohol, and the ratio of the acetone to the absolute ethyl alcohol in the solvent is 1:1 in terms of volume parts;
2) Growing a boron-doped diamond film on the nucleated substrate by adopting an electron-assisted hot filament chemical vapor deposition method, wherein the electron-assisted hot filament chemical vapor deposition method comprises the following steps of: placing the nucleated substrate on a sample stage in a reaction chamber of an electronic auxiliary hot wire chemical deposition device, enabling the nucleated substrate to be attached to a table top of the sample stage, continuously introducing hydrogen and methane (purity is 99.999%) into the reaction chamber, wherein the flow ratio of the introduced hydrogen to the methane is 325:6. continuously inputting a boron source into the reaction chamber, applying bias voltage to the nucleated substrate, simultaneously keeping the reaction chamber at 900 ℃ for 6 hours through a filament in the reaction chamber, closing the electronic auxiliary hot filament chemical deposition equipment, and naturally cooling to room temperature to obtain the boron-doped diamond microelectrode, wherein the current of the applied bias voltage source is 8A, the voltage of the applied bias voltage source is 185V, and the applied bias voltage source is a direct current source (the bias voltage is the bias voltage between the filament and a sample stage, the sample stage is the anode, and the filament is the cathode), as shown in fig. 1 and 2. The flow rate of methane was 6mL/min. The gas pressure in the reaction chamber was 5kPa.
The boron source is trimethyl borate, and is carried into the reaction chamber by carrier gas, and the specific method comprises the following steps: mixing a boron source and absolute ethyl alcohol to obtain a mixed liquid, wherein the ratio of the boron source to the absolute ethyl alcohol in the mixed liquid is 1:3, inputting a carrier gas into the mixed liquid, then bubbling and discharging the carrier gas from the mixed liquid, and inputting the bubbling and discharging gas into a reaction chamber. Wherein, divide hydrogen into two parts: the flow rate of the hydrogen directly introduced into the reaction chamber and the flow rate of the hydrogen used as the carrier gas are 300mL/min, and the flow rate ratio of the hydrogen directly introduced into the reaction chamber and the hydrogen used as the carrier gas is 300:25.
The thickness of the boron doped diamond film was tested to be 16 μm. The boron-doped diamond film consists of 96.19% of carbon, 1.3% of boron and 2.51% of oxygen in percentage by mass.
Example 2
A method for preparing a boron-doped diamond microelectrode is substantially the same as in example 1, except that the substrate is used. The substrate used in this example was a linear tantalum bar having a width of 1.8mm and a length of 40mm, and the thickness of the tantalum bar was 0.16mm.
The tantalum strip obtaining method in the embodiment comprises the following steps: tantalum wire with the length of 40mm and the diameter of 0.6mm is selected, and is pressed into tantalum strips with the width of 1.8mm by a manual pair roller machine.
The photograph of the boron doped diamond microelectrode obtained in this example is shown in FIG. 8.
Example 3
A method for preparing a boron-doped diamond microelectrode is substantially the same as in example 1, except that the substrate is used. The substrate used in this example was a linear tantalum bar with a width of 0.65mm and a length of 50mm, and the thickness of the tantalum bar was 0.09mm.
The tantalum strip obtaining method in the embodiment comprises the following steps: tantalum wire with the length of 50mm and the diameter of 0.2mm is selected, and is pressed into tantalum strips with the width of 0.65mm by a manual pair roller machine.
The photograph of the boron doped diamond microelectrode obtained in this example is shown in FIG. 14.
Example 4
A method for preparing a boron-doped diamond microelectrode is substantially the same as in example 1, except that the substrate is used. The substrate adopted in this embodiment is: the width of the tantalum strip is 0.65mm, the length of the tantalum strip is 50mm, and the width of the plane spiral is 10mm.
The tantalum strip obtaining method in the embodiment comprises the following steps: selecting tantalum wires with the length of 50mm and the diameter of 0.2mm, firstly winding the tantalum wires into a plane spiral shape, and then manually pressing the tantalum wires into tantalum strips with the width of 0.65mm and the thickness of 0.09mm by a pair of rollers.
The photograph of the boron doped diamond microelectrode obtained in this example is shown in FIG. 20.
The boron-doped diamond microelectrode obtained in the embodiment is packaged by the following method:
(1) preparing a Polydimethylsiloxane (PDMS) mold: the polydimethylsiloxane mould is provided with a cylindrical groove with the diameter of 15mm and the height of 6mm, the top surface of the groove is open, a convex structure is formed at the bottom of the groove, a blind hole is formed at the bottom of the groove, the bottom end of a copper column with the diameter of 1mm is inserted into the blind hole, and the copper column is contacted with the convex structure after the copper column is inserted, as shown in fig. 27.
(2) Uniformly mixing PDMS prepolymer with a mass ratio of 10:1 and a curing agent (Dow Corning PDMS polydimethylsiloxane, model number 184), pouring into a groove of a polydimethylsiloxane mould, standing for 20min under a baking lamp (250W) for curing, and obtaining a packaging carrier in the groove, wherein the existence of a convex structure enables the bottom surface of the packaging carrier to form a planar spiral groove capable of embedding the boron-doped diamond microelectrode;
(3) and taking out the packaging carrier from the groove, embedding the boron-doped diamond microelectrode in the planar spiral groove and contacting with the copper column, and conducting signals by utilizing the copper column to complete packaging. The photograph after encapsulation is shown in fig. 21.
The boron doped diamond microelectrode is used on one side for contacting with skin.
Example 5
Electroencephalogram signal acquisition test (forehead eyebrow): 3 conventional Ag/AgCl wet electrodes (produced by beijing electronic technology corporation), scrub paste (produced by Weaver and Company), conductive paste (produced by Compumedics USA Inc), syringe, medical tape, and electroencephalogram amplifier were prepared.
The method is characterized in that the frosting paste is used for slightly wiping the mastoid at the back of the ears of a tested person to remove the stratum corneum, so that a better contact effect between the electrode and the scalp is achieved, the needle cylinder is used for respectively beating 0.3mL of conductive paste on the two Ag/AgCl wet electrodes, and the conductive paste is fixed at the mastoid at the back of the ears of the tested person by using a medical adhesive tape. One of the two Ag/AgCl wet electrodes is used as a reference electrode, and the other is used as a grounding electrode. Two adjacent areas are selected above the forehead and the upper part of the forehead of the tested person along the horizontal direction: wiping the first area and the second area by using scrub paste, applying 0.3mL of conductive paste on the third Ag/AgCl wet electrode, and fixing the third Ag/AgCl wet electrode on the area of the tested person by using a medical adhesive tape to serve as a working electrode; one of the boron-doped diamond microelectrodes obtained in examples 1 to 4 (referred to as BDD microelectrode in the following, the boron-doped diamond microelectrode after encapsulation in example 4) is placed in the second area of the tested person, the boron-doped diamond microelectrode is fixed by a medical adhesive tape to be used as a working electrode, 0.6mL of physiological saline water drops are sucked by an injector to be arranged between the boron-doped diamond microelectrode and the skin (the boron-doped diamond is used as a semiconductor electrode, the physiological saline is added to increase the conductivity of the boron-doped diamond microelectrode, and the boron-doped diamond microelectrode has higher stability in electroencephalogram acquisition), and finally the boron-doped diamond microelectrode is sleeved on a head net.
The brain amplifier Curry8 signal acquisition software is started, the impedance of the third Ag/AgCl wet electrode and the boron doped diamond microelectrode obtained in the embodiment 1 are 13.4KΩ and 12.8KΩ respectively, as shown in FIG. 3, the waveform of Fp1 is the signal of the Ag/AgCl wet electrode, and the waveform of F7 is the signal of the BDD microelectrode. The impedances of the third Ag/AgCl wet electrode and the boron-doped diamond microelectrode obtained in example 2 were 13.1KΩ and 9.6KΩ, respectively, as shown in FIG. 9; the impedances of the third Ag/AgCl wet electrode and the boron-doped diamond microelectrode obtained in example 3 were 14.8KΩ and 9.3KΩ, respectively, as shown in FIG. 15; the impedances of the fourth Ag/AgCl wet electrode and the boron-doped diamond microelectrode obtained in example 4 were 17.4KΩ and 4.8KΩ, respectively, as shown in FIG. 22.
After the waveform is stabilized, the signal is recorded, the tested person is required to blink three times within 10 seconds, a peak value appears in the brain electrical signal when blinking is performed each time, when the peak values appearing in the three blinks are the same, waveforms collected by the third Ag/AgCl wet electrode and the boron-doped diamond microelectrode brain electrical signal obtained in the embodiment 1 are shown in fig. 4, waveforms collected by the third Ag/AgCl wet electrode and the boron-doped diamond microelectrode brain electrical signal obtained in the embodiment 2 are shown in fig. 10, waveforms collected by the third Ag/AgCl wet electrode and the boron-doped diamond microelectrode brain electrical signal obtained in the embodiment 3 are shown in fig. 16, waveforms collected by the fourth Ag/AgCl wet electrode and the boron-doped diamond microelectrode brain electrical signal obtained in the embodiment 4 are shown in fig. 23, and signal connection is proved to be successful.
In the acquisition of the biting signals, a tested person is required to bite three times within 10 seconds, each biting lasts for 1-2 seconds, a high-frequency high-amplitude waveform appears through waveforms during each biting, waveforms acquired by the third Ag/AgCl wet electrode and the boron-doped diamond microelectrode electroencephalogram obtained in the embodiment 1 are shown in fig. 5, waveforms acquired by the third Ag/AgCl wet electrode and the boron-doped diamond microelectrode electroencephalogram obtained in the embodiment 2 are shown in fig. 11, waveforms acquired by the third Ag/AgCl wet electrode and the boron-doped diamond microelectrode electroencephalogram obtained in the embodiment 3 are shown in fig. 17, waveforms acquired by the third Ag/AgCl wet electrode and the boron-doped diamond microelectrode electroencephalogram obtained in the embodiment 4 are shown in fig. 24, and signal connection is proved to be successful.
Example 6
Electroencephalogram signal acquisition test (posterior occipital region): 3 conventional Ag/AgCl wet electrodes (produced by beijing electronic technology corporation), scrub paste (produced by Weaver and Company), conductive paste (produced by Compumedics USA Inc), syringe, medical tape, and electroencephalogram amplifier were prepared.
The method is characterized in that the frosting paste is used for slightly wiping the mastoid at the back of the ears of a tested person to remove the stratum corneum, so that a better contact effect between the electrode and the scalp is achieved, the needle cylinder is used for respectively beating 0.3mL of conductive paste on the two Ag/AgCl wet electrodes, and the conductive paste is fixed at the mastoid at the back of the ears of the tested person by using a medical adhesive tape. One of the two Ag/AgCl wet electrodes is used as a reference electrode, and the other is used as a grounding electrode. The occipital area of the brain of the tested person is selected from two adjacent areas along the horizontal direction: wiping the first area and the second area by using scrub paste, applying 0.3mL of conductive paste on the third Ag/AgCl wet electrode, and fixing the third Ag/AgCl wet electrode on the area of the tested person by using a medical adhesive tape to serve as a working electrode; one of the boron-doped diamond microelectrodes obtained in examples 1 to 4 was placed in a second region of the subject, the sample was fixed with a medical adhesive tape as a working electrode, 0.6mL of physiological saline was sucked by an injector between the boron-doped diamond microelectrode and the skin, and finally the sample was covered with a head net.
The brain amplifier Curry8 signal acquisition software was started, and the impedances of the third Ag/AgCl wet electrode and the boron doped diamond microelectrode obtained in example 1 were 13.1kΩ and 12.1kΩ, respectively, as shown in fig. 6. The impedances of the third Ag/AgCl wet electrode and the boron-doped diamond microelectrode obtained in example 2 were 12.9KΩ and 11.5KΩ, respectively, as shown in FIG. 12; the impedances of the third Ag/AgCl wet electrode and the boron-doped diamond microelectrode obtained in example 3 were 12.5KΩ and 9.2KΩ, respectively, as shown in FIG. 18; the impedances of the third Ag/AgCl wet electrode and the boron-doped diamond microelectrode obtained in example 4 were 12.0KΩ and 6.4KΩ, respectively, as shown in FIG. 25.
After the waveform is stable, the signal is recorded, the tested person is required to open and close eyes within 10s, the eyes are closed for the first 5s, the eyes are opened for the second 5s, and the original waveform is observed, so that the alpha rhythm characteristic can be obviously seen. The original waveforms of the boron-doped diamond microelectrode and the Ag/AgCl wet electrode electroencephalogram signal acquired in the embodiment 1 are shown in fig. 7, the frequency is low when the eyes are closed for the first 5s, the amplitude is large, the frequency is high when the eyes are opened for the second 5s, and the amplitude is small. The original waveforms of the acquisition of the brain electrical signals of the boron doped diamond microelectrode and the Ag/AgCl wet electrode obtained in the example 2 are shown in FIG. 13. The original waveforms of the acquisition of the brain electrical signals of the boron doped diamond microelectrode and the Ag/AgCl wet electrode obtained in example 3 are shown in FIG. 19. The original waveforms of the acquisition of the brain electrical signals of the boron doped diamond microelectrode and the Ag/AgCl wet electrode obtained in the example 4 are shown in FIG. 26.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (10)
1. The preparation method of the boron-doped diamond microelectrode is characterized by comprising the following steps of:
1) Ultrasonic treatment is carried out on a substrate in a diamond micro-nano powder suspension for 60-80 min, cleaning and drying are carried out, and a nucleated substrate is obtained, wherein the diamond micro-nano powder suspension is a mixture of diamond micro-nano powder and a solvent, the concentration of the diamond micro-nano powder in the diamond micro-nano powder suspension is 1-3 mg/mL, the substrate is tantalum wire or tantalum strip, the diameter of the tantalum wire is 0.2-0.6 mm, the width of the tantalum strip is 0.65-1.8 mm, and the length of the tantalum strip or tantalum wire is 40-50 mm;
2) And growing a boron-doped diamond film on the nucleated substrate.
2. The method according to claim 1, wherein in the step 1), the substrate is in a straight line structure or a planar spiral shape, and the width of the planar spiral shape is 10 to 12mm;
the thickness of the tantalum strip is 0.08-0.17 mm.
3. The preparation method according to claim 1, wherein in the step 1), the solvent is a mixture of acetone and absolute ethanol, and the ratio of the acetone to the absolute ethanol in the solvent is 1 (1-1.2) in parts by volume;
in the step 1), the cleaning is: sequentially carrying out ultrasonic treatment on the mixture in absolute ethyl alcohol and ultrapure water for 5-8 min;
in the step 1), the drying is baking by a baking lamp;
in the step 1), the substrate is polished and cleaned before use, and the cleaning is sequentially carried out on ultrapure water, absolute ethanol and ultrapure water for at least 5min.
4. The method according to claim 1, wherein in the step 2), the thickness of the boron doped diamond film is 15 to 17 μm.
5. The production method according to claim 1 or 4, wherein in the step 2), the boron-doped diamond film is composed of 96 to 97% carbon, 1.3 to 1.7% boron and the remaining oxygen in mass%.
6. The method of claim 1, wherein in step 2), an electron assisted hot wire chemical vapor deposition method is used to grow a boron doped diamond film on the post-nucleation substrate, the electron assisted hot wire chemical vapor deposition method comprising the steps of: placing the nucleated substrate in a reaction chamber, continuously introducing hydrogen and methane into the reaction chamber, continuously inputting a boron source into the reaction chamber, applying bias voltage to the nucleated substrate, and simultaneously keeping the reaction chamber at 800-900 ℃ for 6-8 hours, wherein the current of the applied bias voltage power supply is 8-9A, and the voltage of the applied bias voltage power supply is 185-190V.
7. The preparation method according to claim 6, wherein the flow ratio of hydrogen to methane is 325 (6-8);
the boron source is trimethyl borate, and is carried into the reaction chamber by carrier gas, and the specific method comprises the following steps: mixing a boron source and absolute ethyl alcohol to obtain a mixed liquid, inputting a carrier gas into the mixed liquid, then bubbling and discharging the mixed liquid, inputting the bubbled and discharged gas into the reaction chamber, wherein the ratio of the boron source to the absolute ethyl alcohol in the mixed liquid is 1 (3-3.2);
dividing the hydrogen into two parts: the flow ratio of the hydrogen directly introduced into the reaction chamber to the hydrogen used as the carrier gas is 300 (20-30).
8. The method according to claim 1, wherein the gas pressure in the reaction chamber is 4.9 to 5.1kPa.
9. A boron doped diamond microelectrode obtainable by the process of any one of claims 1 to 8.
10. The use of the boron doped diamond microelectrode of claim 9 in electroencephalogram acquisition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210715354.9A CN117305804A (en) | 2022-06-22 | 2022-06-22 | Boron-doped diamond microelectrode and preparation method and electroencephalogram application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210715354.9A CN117305804A (en) | 2022-06-22 | 2022-06-22 | Boron-doped diamond microelectrode and preparation method and electroencephalogram application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117305804A true CN117305804A (en) | 2023-12-29 |
Family
ID=89279935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210715354.9A Pending CN117305804A (en) | 2022-06-22 | 2022-06-22 | Boron-doped diamond microelectrode and preparation method and electroencephalogram application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117305804A (en) |
-
2022
- 2022-06-22 CN CN202210715354.9A patent/CN117305804A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huch et al. | Transcutaneous measurement of blood Po2 (tcPo2)—method and application in perinatal medicine | |
| Gross et al. | Recording of spontaneous activity with photoetched microelectrode surfaces from mouse spinal neurons in culture | |
| US8406841B2 (en) | Dry electrode for biomedical signal measuring sensor | |
| CN107690307A (en) | The dry electrode and application method sensed for biopotential and Skin Resistance | |
| CN104688223A (en) | Bioelectrical signal sensor and acquisition device | |
| JP2003520094A (en) | Medical electrode | |
| CN114728539A (en) | Rapid manufacturing of absorbent substrates for soft conformal sensors and conductors | |
| CN112450938B (en) | Hydrogel electrode for long-term electroencephalogram acquisition and preparation method thereof | |
| CN108309291B (en) | Flexible contact brain electrode and preparation method thereof | |
| CN113261978B (en) | Self-supporting graphene wall electrode and preparation method and application thereof | |
| CN105232035A (en) | Bioelectric signal sensor | |
| CN117305804A (en) | Boron-doped diamond microelectrode and preparation method and electroencephalogram application thereof | |
| CN2882531Y (en) | Intracranial skin electrode | |
| Nguyen et al. | Electrode-Skin contact impedance: In vivo measurements on an ovine model | |
| Ku et al. | Electro-deposited nanoporous platinum electrode for EEG monitoring | |
| Shen et al. | A gelatin-based hydrogel electrode with high moisturizing ability for wearable EEG recording | |
| CN106236087A (en) | A kind of glue-free biopotential electrode and electrode auxiliary device | |
| Shi et al. | Claw-shaped flexible and low-impedance conductive polymer electrodes for EEG recordings: Anemone dry electrode | |
| CN208910252U (en) | A kind of flexible contact electrode for encephalograms | |
| CN114190947A (en) | Non-invasive electroencephalogram sensor based on flexible substrate and preparation method thereof | |
| CN111990994B (en) | EEG flexible dry electrode and preparation method and application thereof | |
| CN116509404A (en) | Graphene EEG electrode based on titanium dioxide nanotube array and preparation method thereof | |
| Jiang et al. | Comparing auditory brainstem responses evoked by click and sweep-tone in normal-hearing adults | |
| CN116889408A (en) | Implantable brain electricity/neurotransmitter double-response graphene microelectrode array sensor | |
| Lozano et al. | Microspike array electrode with flexible backing for biosignal monitoring |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |