CN114739504B - Flexible hydrophone based on graphene-hydrogel and manufacturing method thereof - Google Patents
Flexible hydrophone based on graphene-hydrogel and manufacturing method thereof Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 89
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 60
- 229920001721 polyimide Polymers 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 14
- 239000010931 gold Substances 0.000 claims description 14
- 229910052737 gold Inorganic materials 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 239000002985 plastic film Substances 0.000 claims description 8
- 229920006255 plastic film Polymers 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000002356 single layer Substances 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 238000005240 physical vapour deposition Methods 0.000 claims description 7
- 239000012945 sealing adhesive Substances 0.000 claims description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims 2
- 239000010439 graphite Substances 0.000 claims 2
- 238000003756 stirring Methods 0.000 claims 2
- 238000001514 detection method Methods 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 238000004891 communication Methods 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 12
- 239000004926 polymethyl methacrylate Substances 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000005530 etching Methods 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000010146 3D printing Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical class [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01H—MEASUREMENT OF MECHANICAL VIBRATIONS OR ULTRASONIC, SONIC OR INFRASONIC WAVES
- G01H11/00—Measuring mechanical vibrations or ultrasonic, sonic or infrasonic waves by detecting changes in electric or magnetic properties
- G01H11/06—Measuring mechanical vibrations or ultrasonic, sonic or infrasonic waves by detecting changes in electric or magnetic properties by electric means
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A90/00—Technologies having an indirect contribution to adaptation to climate change
- Y02A90/30—Assessment of water resources
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Transducers For Ultrasonic Waves (AREA)
Abstract
The invention discloses a graphene-hydrogel hydrophone and a manufacturing method thereof, which belong to the technical field of underwater acoustic sensor manufacturing, and the hydrophone has the characteristics of flexibility, small volume, high sensitivity detection capability for low-frequency acoustic waves and the like, can be used for constructing a next-generation underwater sonar detection system, and is expected to exert application value in military and civil fields such as future petroleum exploration, marine communication, positioning, navigation, target detection and the like; comprises a polyimide film electrode (1), a hydrogel film (2), a graphene film (3) and SiO-containing film 2 Is a Si substrate (4).
Description
Technical Field
The invention relates to the field of underwater acoustic signal detection, in particular to a graphene-hydrogel flexible hydrophone and a manufacturing method thereof.
Background
Underwater acoustic sensor technology is an important means of underwater information acquisition. Materials commonly used in the current preparation of underwater acoustic sensors are piezoelectric ceramics, PVDF piezoelectric films and optical fibers. According to the current requirements of the hydrophone on wide frequency band, high sensitivity, flexibility and miniaturization in the underwater sound field, the invention provides a hydrophone design scheme based on graphene-hydrogel by utilizing the unique electronic structure of graphene and the characteristic that hydrogel is easy to form an electric double layer, and the hydrophone has the technical potential of flexibility, small volume and high sensitivity. The single-layer graphene has a series of advantages such as field effect phenomenon, large specific surface area, high mobility, high sensitivity, flexibility, miniaturization and integration due to the unique nano structure and electronic structure, so that the single-layer graphene can be used for preparing a high-performance miniature sensor; meanwhile, due to the characteristics of low underwater acoustic impedance, the graphene is easy to realize impedance matching with fluid media such as water and the like, so that the graphene is suitable for being used as a underwater acoustic sensor.
The graphene-hydrogel acoustic sensor is different from the existing piezoelectric acoustic sensor and fiber bragg grating acoustic sensor in sensing principle, has the characteristics of flexibility, miniaturization, integration and the like, can be used for constructing a next-generation underwater sonar detection system, and is expected to play an application value in military and civil fields such as future petroleum exploration, marine communication, positioning, navigation, target detection and the like.
Disclosure of Invention
The invention aims to overcome the defects of the conventional piezoelectric and optical fiber hydrophone and provides a graphene-hydrogel hydrophone and a manufacturing method thereof, wherein the graphene-hydrogel hydrophone has good low-frequency underwater sound wave detectability and higher detection sensitivity.
In order to solve the technical problems, the invention provides the following technical scheme: a graphene-hydrogel hydrophone comprises a metal top electrode, a hydrogel film with a three-dimensional microstructure, a single-layer or double-layer graphene film, a nano silicon dioxide dielectric layer and a gate electrode.
The invention specifically provides a graphene-hydrogel hydrophone, which sequentially comprises a polyimide film metal electrode (1) and a hydrogelGlue film (2), graphene film (3), siO-containing film 2 A Si substrate (4);
and metal electrodes are arranged at two ends of the surface of one side of the graphene film (3) adjacent to the hydrogel film (2).
Further, in the above technical scheme, the hydrogel film (2) and the graphene film (3) are contacted through the three-dimensional microstructure of hydrogel in the hydrogel film (2).
Further, in the technical scheme, the hydrogel film (2) contains salt solutions with different ion concentrations, and the graphene film (3) has a single-layer or double-layer graphene structure.
Further, in the above technical scheme, the salt solution is selected from aqueous solution or mixed solution of sodium chloride, aluminum chloride, potassium chloride, sodium sulfate or potassium sulfate.
Further, in the above technical scheme, the hydrogel film (2) is made of a single polymer of monomers such as acrylamide, acrylic acid, hydroxyethyl methacrylate or hydroxyethyl acrylate or a copolymer of a plurality of monomers.
Further, in the above technical solution, the metal electrode is made of gold, molybdenum, palladium, titanium, or the like.
Further, in the technical proposal, the thickness of the polyimide film is 5-50 mu m, the thickness of the metal gold is 2-20 mu m, the thickness of the hydrogel film (2) is 0.5-3mm, the thickness of the graphene film (3) is 0.5-5nm, and the polyimide film contains SiO 2 The thickness of the Si substrate (4) is 0.1-0.5mm; the thickness of the metal electrode arranged at the two ends of the surface of the graphene film (3) is 5-10 mu m.
Further, in the technical scheme, a conical protruding structure is arranged on one side, facing the graphene film (3), of the hydrogel film (2), and the protruding height is 0.2-1mm.
The invention provides a manufacturing method of the graphene-hydrogel hydrophone, which comprises the following steps:
step one: preparing a polyimide film electrode (1) containing a metal layer by a physical vapor deposition method, and taking the polyimide film electrode as a top electrode material;
step two: preparing a hydrogel film (2) with a three-dimensional microstructure;
step three: preparing a graphene film (3) by adopting a chemical vapor deposition method, and step four: transferring the graphene film (3) onto a Si substrate by a graphene transfer film technology;
step five: will contain SiO 2 A gold electrode is physically deposited at two ends of the upper surface of the graphene film on the Si substrate (4) to serve as a gate electrode;
and the three-dimensional microstructure of the hydrogel film (2) is attached to the surface of the graphene film (3); and then, attaching one side of the polyimide film metal electrode with metal to the surface of the hydrogel film, and packaging the graphene-hydrogel hydrophone by using a plastic film and a sealing adhesive tape.
Further, in the above technical solution, the packaging is performed by using a plastic film and a sealing tape.
Further, in the above technical solution, the method for manufacturing the graphene-hydrogel hydrophone specifically includes the following steps:
step one: and (3) preparing a metal top electrode. Taking a polyimide film as a matrix material, and depositing gold on the surface of the polyimide film by physical vapor deposition to serve as a top electrode material;
step two: preparation of a three-dimensional microstructured hydrogel film. The 3D printing technology is utilized to print a mould with an inverted cone structure, acrylamide is taken as a monomer, N, N-methylene bisacrylamide is taken as a cross-linking agent, ammonium persulfate is taken as an initiator, and tetramethyl ethylenediamine is taken as an accelerator, so that the hydrogel film with different flexibilities is prepared.
Step three: and (3) preparing a graphene film. Preparing a single-layer or double-layer graphene film by adopting a chemical vapor deposition method, taking a copper sheet as a substrate, decomposing methane and hydrogen in a high-temperature furnace to grow the graphene film on the surface of the copper sheet, and regulating the gas flow and the gas pressure in the pipe; controlling the growth temperature and the growth time; and adjusting the proportions of different gas components, and finally preparing and obtaining the graphene film.
Step four: and transferring the graphene film. Firstly, spin-coating a layer of PMMA solution on the surface of a copper foil growing with a graphene film, and then placing the copper sheet into ammonium persulfate etching solution until the copper sheet is in a straight stateUntil the copper foil is completely etched; placing graphene with PMMA film on a substrate containing SiO 2 And (3) dissolving the PMMA protective layer on the Si sheet substrate by using acetone to obtain the graphene film transferred to the Si sheet.
Step five: graphene-hydrogel hydrophone assembly. And physically depositing gold electrodes at two ends of a graphene film on the Si sheet, attaching a conical three-dimensional microstructure of the hydrogel film to the graphene, attaching a polyimide film electrode to the surface of the hydrogel film, and packaging the graphene-hydrogel hydrophone by using a plastic film and a sealing adhesive tape.
The invention has the beneficial effects that: the graphene-hydrogel hydrophone has the advantages of flexibility, small volume, high low-frequency sound wave detection sensitivity and the like, and is suitable for being used as a underwater acoustic sensor due to the characteristics of low underwater acoustic impedance of graphene and hydrogel, easiness in realizing impedance matching with fluid media such as water and the like.
Drawings
FIG. 1 is a schematic structural diagram of a graphene-hydrogel hydrophone of the present invention;
description of the drawings: 1. polyimide film electrodes; 2. a hydrogel film; 3. a graphene film; 4. containing SiO 2 Is a Si substrate of (C).
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
A graphene-hydrogel hydrophone comprises a polyimide film electrode 1, gold is deposited on the polyimide film electrode 1 through a physical vapor deposition method, a hydrogel film 2 contains a three-dimensional conical microstructure, a graphene film 3 is prepared through a chemical vapor deposition method, and a Si substrate 4 contains 200 nm-later SiO 2 A layer.
A manufacturing method of a graphene-hydrogel hydrophone comprises the following steps:
step one: taking a polyimide film as a matrix material, and depositing gold on the surface of the polyimide film by physical vapor deposition to serve as a top electrode material;
step two: acrylamide is used as a monomer, N, N-methylene bisacrylamide is used as a cross-linking agent, ammonium persulfate is used as an initiator, tetramethyl ethylenediamine is used as an accelerator, and hydrogel films with different flexibilities are prepared by changing the dosage of the cross-linking agent;
step three: the copper sheet is taken as a substrate, and the gas flow and the gas pressure in the pipe are regulated; controlling the growth temperature and the growth time; adjusting the proportions of different gas components to prepare and obtain a graphene film;
step four: spin-coating a layer of PMMA solution on the surface of the copper foil growing with the graphene film, and then placing the copper sheet into ammonium persulfate etching solution until the copper foil is completely etched; placing graphene with PMMA film on a substrate containing SiO 2 After that, acetone is used for dissolving the PMMA protective layer on the Si sheet substrate to obtain a graphene film transferred on the Si sheet;
step five: and physically depositing gold electrodes at two ends of the upper surface of the graphene film on the Si sheet, attaching the conical three-dimensional microstructure of the hydrogel film to graphene, attaching a polyimide film electrode to the surface of the hydrogel film, and packaging the graphene-hydrogel hydrophone by using a plastic film and a sealing adhesive tape.
In specific implementation, taking the first embodiment and the second embodiment as examples:
example 1
Fig. 1 is a schematic structural diagram of a graphene-hydrogel hydrophone, and the structure mainly comprises a polyimide film electrode 1, a hydrogel film 2, a graphene film 3 and a hydrogel film containing SiO 2 Is a silicon substrate 4 of (c).
The graphene-hydrogel hydrophone can be used for detecting underwater low-frequency sound waves, and the main technical index is that the frequency range of the detected underwater sound waves is 10 Hz-2000 Hz. The preparation method comprises the following steps:
step one: cutting a polyimide film into a size of 10mm multiplied by 10mm, and depositing a 50nm gold layer on the surface of the polyimide film by physical vapor deposition;
step two: according to the three-dimensional microstructure form of the hydrogel film 2, a conical bulge structure is arranged on one side of the hydrogel film 2 facing the graphene film 3, and the bulge height is 0.2-1mm; the mold for curing the hydrogel was printed using 3D printing techniques. 1.564g of acrylamide monomer is added into 10mL of deionized water, 0.056g of N, N-methylene bisacrylamide is added as a cross-linking agent, 0.003g of ammonium persulfate is added as an initiator, 10 mu L of tetramethyl ethylenediamine is added as an accelerator, the solution is stirred until the solution is uniform and transparent, the solution is poured into a mold, a glass cover plate is covered, and the solution is cured for 1.5 hours at 50 ℃ to obtain a hydrogel film, and then the hydrogel film is placed into a 1M concentration NaCl salt solution for 24 hours.
Step three: the copper sheet is used as a substrate, a single-layer graphene film is prepared by using a chemical vapor deposition method, and the specific growth parameters are as follows: vacuum degree in furnace 2Torr, growth temperature 1000 deg.C, H 2 Flow rate 143sccm, CH 4 The flow rate was 71.5sccm, the Ar flow rate was 191.82sccm, and the growth time was 20 minutes.
Step four: spin-coating a PMMA solution with a mass fraction of 4.0wt.% on the surface of a graphene film growing on the surface of a copper foil, wherein the rotating speed is set at 3000 rpm; then placing the copper sheet into ammonium persulfate etching solution with the concentration of 0.1g/mL until the copper foil is completely etched; placing graphene with PMMA film on a substrate containing SiO 2 Placing the Si sheet substrate on a vacuum oven, vacuumizing and treating at 100 ℃ for 24 hours; then, acetone is used for dissolving the PMMA protective layer, and a graphene film transferred on the Si sheet is obtained;
step five: and physically depositing 50nm thick gold electrodes at two ends of the graphene film, attaching a conical three-dimensional microstructure of the hydrogel film to the graphene, attaching a polyimide film electrode to the surface of the hydrogel film, and packaging the graphene-hydrogel hydrophone by using a plastic film and a sealing adhesive tape.
Example 2
A graphene-hydrogel hydrophone for detecting underwater sound waves has the structure same as that of the embodiment 1, and the main technical index is that the frequency range of the underwater sound waves is 20 Hz-3000 Hz. The preparation method comprises the following steps:
step one: cutting a polyimide film into a size of 10mm multiplied by 10mm, and depositing a 50nm gold layer on the surface of the polyimide film by physical vapor deposition;
step two: the mold for curing the hydrogel is printed using 3D printing techniques according to the three-dimensional microstructure form of the hydrogel film 2. 1.564g of acrylamide monomer is added into 10mL of deionized water, 0.340g of N, N-methylene bisacrylamide is added as a cross-linking agent, 0.003g of ammonium persulfate is added as an initiator, 10 mu L of tetramethyl ethylenediamine is added as an accelerator, the solution is stirred until the solution is uniform and transparent, the solution is poured into a mold, a glass cover plate is covered, the solution is cured for 1.5 hours at 50 ℃ to obtain a hydrogel film, and the hydrogel film is placed into a LiCl salt solution with 5M concentration for 24 hours.
Step three: the copper sheet is used as a substrate, a single-layer graphene film is prepared by using a chemical vapor deposition method, and the specific growth parameters are as follows: first, adjust H 2 The flow rate was such that the pressure in the furnace was 2Torr. The specific growth parameters are as follows: vacuum degree in furnace 2Torr, growth temperature 1000 deg.C, H 2 Flow 320sccm, CH 4 The flow is 71.5sccm, the growth time is 10min, the temperature is slowly reduced, and Ar gas is introduced in the later stage of the temperature reduction.
Step four: spin-coating a layer of PMMA solution with the mass fraction of 4.0wt.% on the surface of the copper foil growing with the graphene film, wherein the rotating speed is set at 3000 rpm; then placing the copper sheet into ammonium persulfate etching solution with the concentration of 0.1g/mL until the copper foil is completely etched; placing graphene with PMMA film on a substrate containing SiO 2 Placing the Si sheet substrate on a vacuum oven, vacuumizing and treating at 100 ℃ for 24 hours; then, acetone is used for dissolving the PMMA protective layer, and a graphene film transferred on the Si sheet is obtained;
step five: and physically depositing 50nm thick gold electrodes at two ends of the graphene film, attaching a conical three-dimensional microstructure of the hydrogel film to the graphene, attaching a polyimide film electrode to the surface of the hydrogel film, and packaging the graphene-hydrogel hydrophone by using a plastic film and a sealing adhesive tape.
Application example
According to Q/710J 66-2017 (1 Hz-2000 Hz vector hydrophone calibration standard), the hydrophone prepared in example 1 is detected, and signals in the frequency range of 10 Hz-2000 Hz can be detected, and the sound pressure sensitivity is > -170dB.
The above is a preferred embodiment of the present invention, and a person skilled in the art can also make alterations and modifications to the above embodiment, therefore, the present invention is not limited to the above specific embodiment, and any obvious improvements, substitutions or modifications made by the person skilled in the art on the basis of the present invention are all within the scope of the present invention.
Claims (7)
1. A graphene-hydrogel hydrophone, characterized in that: the electrode sequentially comprises a polyimide film metal electrode (1), a hydrogel film (2), a graphene film (3), a Si substrate (4) containing SiO, wherein the polyimide film metal electrode (1) is used as a top electrode material;
the two ends of the surface of the side, adjacent to the hydrogel film (2), of the graphene film (3) are provided with metal electrodes;
the hydrogel film (2) and the graphene film (3) are contacted through the three-dimensional microstructure of the hydrogel in the hydrogel film (2);
a conical bulge structure is arranged on one side of the hydrogel film (2) facing the graphene film (3);
the preparation method of the hydrogel film (2) comprises the steps of adding 1.564g of acrylamide monomer into 10mL of deionized water, adding 0.056g of N, N-methylene bisacrylamide as a cross-linking agent, adding 0.003g of ammonium persulfate as an initiator, adding 10 mu L of tetramethyl ethylenediamine as an accelerator, stirring until the solution is uniform and transparent, pouring into a mold, covering a glass cover plate, curing at 50 ℃ for 1.5h to obtain the hydrogel film, and then placing the hydrogel film into a 1M NaCl salt solution for 24h.
2. The graphene-hydrogel hydrophone according to claim 1, wherein the hydrogel film (2) contains salt solutions with different ion concentrations, and the graphene film (3) has a single-layer or double-layer graphene structure.
3. The graphene-hydrogel hydrophone of claim 2, wherein the salt solution is selected from the group consisting of aqueous solutions or mixed solutions of sodium chloride, aluminum chloride, potassium chloride, sodium sulfate, or potassium sulfate.
4. The graphene-hydrogel hydrophone according to claim 1, wherein the hydrogel film (2) is made of a single polymer of acrylamide, acrylic acid, hydroxyethyl methacrylate or hydroxyethyl acrylate monomers or a copolymer of a plurality of monomers.
5. The graphene-hydrogel hydrophone of claim 1, wherein the metal electrode is gold, molybdenum, palladium, or titanium.
6. The method for manufacturing a graphene-hydrogel hydrophone according to claim 1, wherein: the method comprises the following steps:
step one: preparing a polyimide film metal electrode (1) containing a metal layer by a physical vapor deposition method, and taking the polyimide film metal electrode as a top electrode material;
step two: preparing a hydrogel film (2) with a three-dimensional microstructure; the preparation method of the hydrogel film (2) comprises the steps of adding 1.564g of acrylamide monomer into 10mL of deionized water, adding 0.056g of N, N-methylene bisacrylamide as a cross-linking agent, adding 0.003g of ammonium persulfate as an initiator, adding 10 mu L of tetramethyl ethylenediamine as an accelerator, stirring until the solution is uniform and transparent, pouring into a mold, covering a glass cover plate, curing at 50 ℃ for 1.5 hours to obtain the hydrogel film, and then placing the hydrogel film into a 1M NaCl salt solution for 24 hours;
step three: preparing a graphene film (3) by adopting a chemical vapor deposition method;
step four: transferring the graphene film (3) onto a Si substrate by a graphite transfer film technology;
step five: physically depositing gold electrodes at two ends of the upper surface of a graphite film on a Si substrate (4) containing SiO as gate electrodes;
and the three-dimensional microstructure of the hydrogel film (2) is attached to the surface of the graphene film (3); and then, attaching one side of the polyimide film metal electrode with metal to the surface of the hydrogel film, and packaging the graphene-hydrogel hydrophone by using a plastic film and a sealing adhesive tape.
7. The method of manufacturing a graphite-hydrogel hydrophone as recited in claim 6, wherein: the packaging is carried out by adopting a plastic film and a sealing adhesive tape.
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