CN109752029B - Preparation method of paper-based capacitive flexible sensor - Google Patents
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Abstract
The invention discloses a preparation method of a paper-based capacitive flexible sensor, which comprises the following steps: processing a paper base to form a hydrophilic and hydrophobic pattern on the surface of the paper base; filling a conductive material into the hydrophilic area on the hydrophilic-hydrophobic pattern, enabling the conductive material to form a conductive layer on the surface of the paper base, and connecting an external lead at the edge of the conductive layer to form an external interface; packaging the paper base, the conducting layer and part of external leads by using a first packaging layer to form a single electrode plate; and attaching the surfaces, close to the conducting layer, of the two single-chip electrode plates in opposite directions to form a double-chip electrode plate, and packaging the surfaces of the double-chip electrode plates through a second packaging layer to obtain the capacitive flexible sensor. The preparation method provided by the invention has the advantages of simple manufacturing process, low Young modulus of the finished product, light weight, low cost, high flexibility, high sensitivity, good biocompatibility, wearability and the like.
Description
Technical Field
The invention belongs to the technical field of flexible sensors, and particularly relates to a preparation method of a paper-based capacitive flexible sensor.
Background
Wearable sensors have attracted extensive attention in academic and industrial fields due to their broad application prospects in the fields of personal health, human activity monitoring, artificial intelligent robots, and the like. Due to the properties of low modulus, light weight, strong flexibility, stretching and the like, the wearable sensor can be well attached to the skin or organs, can record micro physiological signals (such as pulse, heart rate, respiration and vocalization) to high-strength motion signals (such as muscle movement), and provides a new way for body-building information tracking, disease diagnosis and risk monitoring. Flexible sensors based on piezoelectric, piezoresistive, resistive and capacitive sensing principles have been developed. However, most of the methods rely on microelectronic manufacturing processes involving complex manufacturing processes such as ultraviolet irradiation, plasma treatment, thin film vacuum deposition, spin coating, photolithography, wet and dry etching, transfer printing, and the like. Although these methods have proven effective, the high cost of expensive equipment and materials limits their use. Through a simple manufacturing process, a novel flexible sensor with high sensitivity and high cost performance is still a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a preparation method of a paper-based capacitive flexible sensor with low cost and high sensitivity.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a paper-based capacitive flexible sensor comprises the following steps:
processing a paper base to form a hydrophilic and hydrophobic pattern on the surface of the paper base;
filling a conductive material into the hydrophilic area on the hydrophilic-hydrophobic pattern, enabling the conductive material to form a conductive layer on the surface of the paper base, and connecting an external lead at the edge of the conductive layer to form an external interface;
packaging the paper base, the conducting layer and part of external leads by using a first packaging layer to form a single electrode plate;
and attaching the surfaces, close to the conducting layer, of the two single-chip electrode plates in opposite directions to form a double-chip electrode plate, and packaging the surfaces of the double-chip electrode plates through a second packaging layer to obtain the capacitive flexible sensor.
Further, when the paper base is processed, the adopted processing method comprises one or more of a spin coating method, a laminating method, a photoetching method, a stamping method, a gravure printing method, a letterpress printing method, a wax printing method, an ink jet printing method, a screen printing method, a magnetron sputtering method, a thermal evaporation method, a printing and dyeing method, a chemical conversion film processing method, a folded paper template method, a tape transfer method, a physical vapor deposition method and a plasma etching method.
Further, the folded paper template method includes:
after a paper template is cut into folded hollow patterns, coating a barrier material on the paper template;
the method comprises the steps of putting a material capable of preparing the paper base into the middle of the folding paper template to form a sandwich structure, enabling the barrier material on the folding paper template to penetrate into the preparation material of the paper base after the barrier material contacts with the preparation material of the paper base, and further forming a hydrophilic and hydrophobic pattern on the prepared paper base.
Furthermore, the method for adding the conductive material to the hydrophilic area of the paper base is one or more of pipette dropping, a 3D printing method, a seal method and ink-jet printing.
Further, the pattern of the conducting layer formed on the paper base is a basic pattern of an ellipse, a circle, a rectangle, a star, a triangle, a pentagon, a hexagon, an arrow or a half moon, or is one or more of fractal curves of Bessel curves, Peano, Hilbert, Moore and Greek cross curves.
Further, the first packaging layer and the second packaging layer are both made of flexible materials, and the flexible materials comprise one or more of polyethylene naphthalate, polymethyl methacrylate, polyurethane acrylate, polydimethylsiloxane, polyacrylonitrile, polyethylene terephthalate, polyethylene, polypropylene, polyamide, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, polylactic acid, polyetherimide, polycarbonate, polyimide and polyvinyl chloride.
Further, the paper base is made of paper materials or/and biological materials containing microstructures, the paper materials of the paper base comprise one or more of facial tissue, nitrocellulose membranes, qualitative filter paper, chromatography paper, printing paper, absorbent paper, kraft paper, cellulose-carbon nanotube composite paper, fiber-silver ink composite paper and drawing paper, and the biological materials containing the microstructures of the paper base comprise one or more of PET membranes, nanofiber bases, cotton cloth, silk towels and natural rubber films.
Further, the conducting layer material comprises one or more of a metal material, a metal oxide, a liquid metal alloy, an inorganic semiconductor, an organic conducting polymer material and a carbon material; the carbon materials include but are not limited to graphene films, graphene walls, graphene nanoplatelets, graphene oxide, graphene, graphite, carbon black, carbon nanotubes, and carbon nanowires; the metal material comprises but is not limited to silver nanowires, platinum nanowires, gold nanowires, zinc oxide nanowires, silver nanoparticles, copper nanowires, monoatomic layer germanium alkene and biatomic layer germanium alkene; the metal oxides include, but are not limited to, indium tin oxide, fluorine tin oxide, aluminum zinc oxide; inorganic semiconductors include, without limitation, silicon, germanium, cadmium telluride; the liquid metal alloy includes, but is not limited to, gallium indium tin alloy; the organic conductive polymer material includes, but is not limited to, polythiophene, polyacetylene, polyaniline, and polypyrrole.
Furthermore, the external lead is a conducting wire or a conducting band made of pure metal or alloy of Cu, Au, Pt, Al, Ag, Ni, Pd and Ru.
Furthermore, the thickness of the paper base, the first packaging layer and the second packaging layer is 0.001-5mm, and the area is 0.1-100cm2The thickness of the conductive layer is 0.001-5mm, and the area is 0.1-100cm2And the diameter of the external lead is 0.1-5 mm.
The invention provides a preparation method of a paper-based capacitive flexible sensor, which is characterized in that a conductive material is filled in a hydrophilic area on a hydrophilic and hydrophobic pattern on the surface of a paper base, so that the conductive material forms a conductive layer with the same shape as the hydrophilic and hydrophobic pattern on the paper base, and the paper base, the conductive layer and part of external leads are packaged from two sides by a first packaging layer to form a single electrode plate; attaching the two single-chip electrode plates to one side, close to the conducting layer, of the single-chip electrode plates in an opposite direction to form a double-chip electrode plate, and then packaging the double-chip electrode plate through the surface of the second packaging layer to obtain the capacitive flexible sensor; therefore, the preparation method of the paper-based capacitive flexible sensor provided by the invention has the advantages of simple manufacturing process, low Young modulus of a finished product, light weight, low cost, high flexibility, high sensitivity, long service life, good biocompatibility, wearability and the like. The touch information acquisition device has good detection performance on the strain such as pressing, bending and stretching, and can well acquire touch information no matter instantaneous touch or continuous stressed extrusion. The device can be used for collecting various physiological signals such as respiratory signals, pulse signals, sound signals, body movement signals and the like in real time.
Drawings
FIG. 1 is a schematic flow chart of a method for manufacturing a paper-based capacitive flexible sensor according to an embodiment of the invention;
FIG. 2 is a schematic structural diagram of a paper-based capacitive flexible sensor fabricated in accordance with an exemplary embodiment of the present invention;
FIG. 3 is a graph of test results of a paper-based capacitive flexible sensor under different pressure effects provided by an embodiment of the invention;
fig. 4 is a pulse wave waveform diagram recorded when the paper-based capacitance type flexible sensor provided by the embodiment of the invention is placed at the radial artery of the wrist of a tester.
Detailed Description
In order to overcome the defects in the prior art, the invention provides a preparation method of a paper-based capacitive flexible sensor. In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be described in more detail below with reference to the accompanying drawings in the preferred embodiments of the present invention. The described embodiments are only some, but not all embodiments of the invention. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
As shown in fig. 1, a method for preparing a paper-based capacitive flexible sensor includes:
s100, processing the paper base to form a hydrophilic and hydrophobic pattern on the surface of the paper base;
s200, filling a conductive material into the hydrophilic area on the hydrophilic and hydrophobic pattern, so that the conductive material forms a conductive layer on the surface of the paper base, and connecting an external lead at the edge of the conductive layer to form an external interface;
s300, carrying out double-sided packaging on the paper base with the conducting layer and the external lead through the first packaging layer, and packaging the paper base, the conducting layer and part of the external lead in the first packaging layer to form a single electrode plate;
s400, attaching the surfaces, close to the conducting layer, of the two single-chip electrode plates in an opposite direction to form a double-chip electrode plate, and packaging the surface of the double-chip electrode plate through a second packaging layer to obtain the capacitive flexible sensor.
As shown in fig. 2, a paper-based capacitive flexible sensor prepared according to an embodiment of the present invention includes a first monolithic electrode plate 10 and a second monolithic electrode plate 20, where the first monolithic electrode plate 10 and the second monolithic electrode plate 20 include a paper base 30, a conductive layer 40 disposed on the paper base 30 and limited by a hydrophilic and hydrophobic structure on the paper base 30, an external lead 50 connected to the conductive layer 40 to form an external interface, and a first encapsulation layer 60 attached to the conductive layer 40 to encapsulate the paper base 30, the conductive layer 40, and a portion of the external lead 50; the second packaging layer (not shown) is disposed on the back surface of the first monolithic electrode plate 10 and the second monolithic electrode plate 20, and the first packaging layer 60 is used as the front surface of the first monolithic electrode plate 10 and the second monolithic electrode plate 20 to be attached together in an opposite manner.
The paper-based capacitive flexible sensor provided by the invention has the working principle that: when the sensor is compressed and bent by applying force to the sensor from the outside, the distance between the upper conducting layer and the lower conducting layer is changed, and the capacitance of the paper-based capacitance type flexible sensor is changed. The form change of the sensor under the current external force can be digitally represented through the change of the capacitance.
In a preferred embodiment, when the paper substrate is treated by the spin coating method, the lamination method, the photolithography method, the stamp method, the gravure printing method, the letterpress printing method, the wax printing method, the ink jet printing method, the screen printing method, the magnetron sputtering method, the thermal evaporation method, the textile printing method, the chemical conversion film treatment method, the folded paper template method, the tape transfer method, the physical vapor deposition method, and the plasma etching method, or a plurality of methods are used as the treatment method.
As a preferred embodiment, the folded paper template method includes:
after a paper template is cut into folded hollow patterns, coating a barrier material on the paper template;
the method comprises the steps of putting a material capable of preparing the paper base into the middle of a folding paper template to form a sandwich structure, enabling a barrier material on the folding paper template to penetrate into a preparation material of the paper base after the barrier material contacts with the preparation material of the paper base, and further forming a hydrophilic and hydrophobic pattern on the prepared paper base.
As a preferred embodiment, the method for adding the conductive material to the hydrophilic area of the paper base is one or more of pipette dropping, a 3D printing method, a stamping method and ink-jet printing.
As a preferred embodiment, the pattern forming the conductive layer on the paper base is a basic pattern of an ellipse, a circle, a rectangle, a star, a triangle, a pentagon, a hexagon, an arrow, or a half moon, or is one or more of fractal curves of bezier curve, Peano, Hilbert, Moore, and greenk cross curve.
As a preferred embodiment, the first encapsulation layer and the second encapsulation layer are both made of flexible materials, and the flexible materials include one or more of polyethylene naphthalate, polymethyl methacrylate, polyurethane acrylate, polydimethylsiloxane, polyacrylonitrile, polyethylene terephthalate, polyethylene, polypropylene, polyamide, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, polylactic acid, polyetherimide, polycarbonate, polyimide, and polyvinyl chloride.
As a preferred embodiment, the paper base is made of a paper material or/and a biological material containing a microstructure, the paper material of the paper base comprises one or more of facial tissue, nitrocellulose membrane, qualitative filter paper, chromatography paper, printing paper, absorbent paper, kraft paper, cellulose-carbon nanotube composite paper, fiber-silver ink composite paper and drawing paper, and the biological material containing a microstructure of the paper base comprises one or more of a PET film, a nanofiber base, cotton cloth, silk towel and a natural rubber film.
As a preferred embodiment, the conductive layer material includes one or more of a metal material, a metal oxide, a liquid metal alloy, an inorganic semiconductor, an organic conductive polymer material, and a carbon material; carbon materials include, but are not limited to, graphene films, graphene walls, graphene nanoplatelets, graphene oxide, graphene, graphite, carbon black, carbon nanotubes, carbon nanowires; the metal material includes but is not limited to silver nanowires, platinum nanowires, gold nanowires, zinc oxide nanowires, silver nanoparticles, copper nanowires, monoatomic layer germanene, and diatomic layer germanene; metal oxides include, but are not limited to, indium tin oxide, fluorine tin oxide, aluminum zinc oxide; inorganic semiconductors include, without limitation, silicon, germanium, cadmium telluride; the liquid metal alloy includes, but is not limited to, gallium indium tin alloy; the organic conductive polymer material includes, but is not limited to, polythiophene, polyacetylene, polyaniline, and polypyrrole.
In a preferred embodiment, the external lead is a conductive wire or a conductive band made of a pure metal or an alloy of Cu, Au, Pt, Al, Ag, Ni, Pd, Ru.
In a preferred embodiment, the paper substrate, the first packaging layer and the second packaging layer have a thickness of 0.001-5mm and an area of 0.1-100cm2The thickness of the conductive layer is 0.001-5mm, and the area is 0.1-100cm2And the diameter of the external lead is 0.1-5 mm.
The sensor prepared by the preparation method of the paper-based capacitive flexible sensor provided by the embodiment comprises an upper monolithic conductive electrode and a lower monolithic conductive electrode, wherein the monolithic conductive electrode is composed of a conductive layer and an encapsulation layer, patterns of the conductive layer in the monolithic conductive electrode can be designed into different shapes according to needs, and meanwhile, the conductive layer is encapsulated by a first encapsulation layer and a second encapsulation layer which are prepared from flexible materials to form a single electrode plate, so that the two monolithic conductive electrodes form the capacitive flexible sensor, the sensor has high detection sensitivity which can reach 16kpa-1。
The following will specifically describe a method for manufacturing a paper-based capacitive flexible sensor according to the present invention by using specific embodiments.
Example 1:
(1) a paper template with channels is manufactured on the folded template paper by means of knife engraving, laser engraving or mechanical engraving, and the PDMS mixed solution (10:1) is uniformly coated on the paper template by a glass rod. Clamping a single-layer face tissue into a folding template, folding one face of the folding template, covering the folding template, standing for 1 minute, and taking out the internal face tissue after the PDMS solution completely soaks the face tissue and has no diffusion. And (3) putting the paper base on a heating plate at 60 ℃ to heat for 2 minutes, and taking out the paper base to obtain the facial tissue with the hydrophilic and hydrophobic pattern, wherein the pattern is a square electrode plate of 15X15 mm.
(2) And (3) sucking the silver nanowire solution by using a 100ul liquid-moving gun, dropwise adding the silver nanowire solution to the hydrophilic area of the facial tissue, and naturally drying to obtain the silver nanowire conducting layer on the facial tissue.
(3) And leading in a lead at the edge position of the circuit, and dropwise adding silver paste to connect the conductive layer with the tail end of the lead.
(4) And packaging the facial tissue with the silver nanowire conducting layer and the external lead on two sides through the PU film, so that the facial tissue, the silver nanowire conducting layer and part of the external lead are packaged in the PU film to form the single-sheet electrode plate.
(5) And (3) oppositely laminating one surfaces, close to the conducting layer, of the two flexible single-sheet conducting electrode plates obtained in the steps (1) to (4) to form a double-sheet electrode plate, and integrally packaging the double-sheet electrode plate through two PU films to obtain the capacitive flexible sensor.
Example 2
Referring to embodiment 1, the difference between the manufacturing method of the paper-based capacitive flexible sensor provided in this embodiment and embodiment 1 is that in step (1), an ink-jet printing method is used to perform paper-based surface modification, and the specific steps are replaced as follows: inputting the reverse mould of the pattern edited conductive layer pattern into a computer, and carrying out ink-jet printing of oily waterproof ink on napkin paper by a Canon iP2780 ink-jet printer to obtain the printing paper base with hydrophilic and hydrophobic patterns.
Example 3
Referring to example 1, the present example provides a paper-based capacitive type flexible sensor manufacturing method, which is different from example 1 in that the channel pattern on the paper template in step (1) is changed from a square shape of 15X15mm to an "F" shape with a size of 15X15mm and a line width of 500 μm.
Example 4
Referring to example 1, the difference between the manufacturing method of the paper-based capacitive flexible sensor provided in this embodiment and example 1 is that the conductive layer material used in step (2) is a carbon nanotube solution.
Example 5
Referring to embodiment 1, the difference between the method for manufacturing a paper-based capacitive flexible sensor provided in this embodiment and embodiment 1 is that the encapsulation material used in step (4) and step (5) is a PDMS film.
Example 6
The paper-based capacitive flexible sensor prepared by the method of embodiment 1 is attached to the radial artery of the wrist of a tested person, the L CR meter is used for reading the capacitive signal of the sensor, and the waveform record is shown in FIG. 4.
Referring to FIG. 3, the paper-based capacitive type flexible sensor prepared by the embodiment of the invention shows bilinear change under different pressures, and the sensitivity of the flexible sensor can reach 7.492kPa in the pressure range of 0-1kPa-1The sensitivity of the flexible sensor can reach 0.896kPa in the pressure range of 1-2.5Ka-1The method can meet the requirement of measuring physiological signals of human bodies, such as the measurement of micro signal pulse waves. The paper-based capacitive flexible sensor has the characteristics of high sensitivity, good wearability and good stability.
Referring to fig. 4, the paper-based capacitive flexible sensor prepared by the embodiment of the invention has clear and accurate pulse wave waveform, contains characteristic peaks of standard pulse waves, and shows that the paper-based capacitive flexible sensor has higher sensitivity and can detect slightly-changed physiological signals. The method has the advantages of high sensitivity, high signal-to-noise ratio, high repeatability, low hysteresis, low error and the like.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (8)
1. A preparation method of a paper-based capacitive flexible sensor is characterized by comprising the following steps:
(1) processing the paper base by a folding paper template method to form a hydrophilic and hydrophobic pattern on the surface of the paper base; the folding paper template method is characterized in that after a paper template is cut into folded hollow patterns, a barrier material is coated on the paper template, a material capable of preparing a paper base is placed in the middle of the folding paper template to form a sandwich structure, after the barrier material on the folding paper template contacts the preparation material of the paper base, the barrier material permeates the preparation material of the paper base, and then hydrophilic and hydrophobic patterns are formed on the prepared paper base;
(2) filling a conductive material into the hydrophilic region on the hydrophilic-hydrophobic pattern, enabling the conductive material to form a conductive layer on the surface of the paper base, connecting an external lead at the edge of the conductive layer to form an external interface, and packaging the paper base, the conductive layer and part of the external lead by using a first packaging layer to form a single-chip electrode plate;
(3) and attaching the surfaces, close to the conducting layer, of the two single-chip electrode plates in opposite directions to form a double-chip electrode plate, and packaging the surfaces of the double-chip electrode plates through a second packaging layer to obtain the capacitive flexible sensor.
2. The preparation method of the paper-based capacitive flexible sensor according to claim 1, wherein the method for adding the conductive material to the hydrophilic region of the paper base is one or more of pipette dropping, a 3D printing method, a stamping method and ink-jet printing.
3. The method for preparing the paper-based capacitive flexible sensor according to claim 1, wherein the pattern of the conductive layer formed on the paper base is a basic pattern of an ellipse, a circle, a rectangle, a star, a triangle, a pentagon, a hexagon, an arrow or a half moon, or is one or more of fractal curves of Bessel curves, Peano, Hilbert, Moore and Greek cross curves.
4. The method for preparing the paper-based capacitive flexible sensor according to claim 1, wherein the first packaging layer and the second packaging layer are both made of flexible materials, and the flexible materials comprise one or more of polyethylene naphthalate, polymethyl methacrylate, polyurethane acrylate, polydimethylsiloxane, polyacrylonitrile, polyethylene terephthalate, polyethylene, polypropylene, polyamide, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, polylactic acid, polyetherimide, polycarbonate, polyimide and polyvinyl chloride.
5. The method for preparing the paper-based capacitive flexible sensor according to claim 1, wherein the paper-based material is prepared from one or more of facial tissue, nitrocellulose membrane, qualitative filter paper, chromatography paper, printing paper, absorbent paper, kraft paper, cellulose-carbon nanotube composite paper, fiber-silver ink composite paper and drawing paper, and/or a biological material containing a microstructure, and the biological material containing the microstructure of the paper-based material comprises one or more of a PET (polyethylene terephthalate) film, a nanofiber base, cotton cloth, a silk towel and a natural rubber film.
6. The method for preparing the paper-based capacitive flexible sensor according to claim 1, wherein the conductive layer material comprises one or more of a metal material, a metal oxide, a liquid metal alloy, an inorganic semiconductor, an organic conductive polymer material and a carbon material; the carbon materials include but are not limited to graphene films, graphene walls, graphene nanoplatelets, graphene oxide, graphene, graphite, carbon black, carbon nanotubes, and carbon nanowires; the metal material comprises but is not limited to silver nanowires, platinum nanowires, gold nanowires, zinc oxide nanowires, silver nanoparticles, copper nanowires, monoatomic layer germanium alkene and biatomic layer germanium alkene; the metal oxides include, but are not limited to, indium tin oxide, fluorine tin oxide, aluminum zinc oxide; inorganic semiconductors include, without limitation, silicon, germanium, cadmium telluride; the liquid metal alloy includes, but is not limited to, gallium indium tin alloy; the organic conductive polymer material includes, but is not limited to, polythiophene, polyacetylene, polyaniline, and polypyrrole.
7. The method for preparing a paper-based capacitive type flexible sensor as claimed in claim 1, wherein the external lead is a conductive wire or band made of pure metal or alloy of Cu, Au, Pt, Al, Ag, Ni, Pd, Ru.
8. The method for preparing the paper-based capacitive flexible sensor according to claim 1, wherein the thickness of the paper base, the first packaging layer and the second packaging layer is 0.001-5mm, and the area is 0.1-100cm2The thickness of the conductive layer is 0.001-5mm, and the area is 0.1-100cm2And the diameter of the external lead is 0.1-5 mm.
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