CN118347611A - Method for constructing flexible pressure sensor by direct-writing printing micro-nano concave template bionic construction - Google Patents
Method for constructing flexible pressure sensor by direct-writing printing micro-nano concave template bionic construction Download PDFInfo
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Abstract
The invention provides a method for constructing a flexible pressure sensor by directly writing and printing micro-nano concave templates in a bionic mode, and relates to the field of pressure sensors, comprising the following steps of: s1, preparing a support material substrate; s2, preparing a viscoelastic fluid; s3, pre-curing; s4, setting printing parameters to print to obtain a template with a micro-nano concave structure; s5, modification treatment; s6, solidifying; s7, preparing a flexible electrode; s8, preparing the ultra-sensitive multi-layer multi-mode flexible pressure sensor. The invention prints the controllable micro-nano concave structure on the surface of the viscoelastic substrate by direct writing printing, thereby constructing the flexible electrode with the micro-nano convex structure, improving the performance of the sensor and realizing the preparation of the ultra-sensitive multi-layer multi-mode flexible pressure sensor.
Description
Technical Field
The invention relates to the field of pressure sensors, in particular to a method for constructing a flexible pressure sensor by directly writing and printing micro-nano concave template bionics.
Background
In recent years, the flexible pressure sensor plays an important role in the man-machine interface interaction fields of wearable equipment, life medical treatment, smart city, electronic skin, motion detection and the like by virtue of good mechanical flexibility and excellent pressure sensing performance. In order to meet the requirement of the flexible pressure sensor on ultra-sensitive pressure sensing such as accurate capture of pressure signals, multidimensional sensing response, rapid stable output and the like, systematic research is required in aspects such as material selection, structural design, processing technology and the like. The micro-nano structure flexible electrode determines the specific surface area, the deformable space, the deformation capacity and the like of a sensing area when being subjected to pressure, and has important influence on the pressure sensing performance of the flexible pressure sensor. The existing micro-nano structure processing method comprises the steps of copying, self-assembling a template, masking, etching and the like by means of a natural micro-nano bulge structure, however, the method has the defects of random shape and distribution of the micro-nano structure, high requirements on equipment precision and technological process and the like, the controllable construction of the flexible electrode of the micro-nano bulge structure is difficult to realize, and the preparation of an ultra-sensitive flexible pressure sensor is limited.
Direct-write printing has received much attention as a micro-nanostructure processing method. Compared with other micro-nano structure manufacturing methods, direct-writing printing is to disperse or dissolve functional materials (nano particles, polymers, liquid and the like) in a solvent to prepare ink, control a direct-writing printing needle to squeeze ink drops by using an automatic device, and break the ink drops to the surface of a substrate for deposition after the ink drops are contacted with the substrate, so that the required patterned micro-nano structure is formed. And the processes of mask, exposure etching and the like are not needed, so that the cost is saved and the pollution is reduced. Meanwhile, the method has the advantages of flexibility, rapidness, large-area preparation, strong environmental adaptability, adaptability to different base materials and the like.
Therefore, the controllable micro-nano concave structure is prepared by using the direct writing printing technology, and the flexible electrode with the micro-nano convex structure is constructed, so that the method has important significance for realizing the ultra-sensitive multi-layer multi-mode flexible pressure sensor.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a method for constructing a flexible pressure sensor by directly writing and printing a micro-nano concave template in a bionic way, and the prepared sensor is an ultra-sensitive multi-layer multi-mode flexible pressure sensor, wherein a controllable micro-nano concave structure can be printed on the surface of a viscoelastic substrate by directly writing and printing, so that a micro-nano convex structure flexible electrode is constructed, the performance of the sensor is improved, and the preparation of the ultra-sensitive multi-layer multi-mode flexible pressure sensor can be realized.
Specifically, the invention provides a method for constructing a flexible pressure sensor by directly writing and printing a micro-nano concave template in a bionic mode, which comprises the following steps:
s1, preparing a support material substrate: cutting, cleaning and drying the support material to prepare a support material substrate;
S2, preparing a viscoelastic fluid mixture: mixing the prepolymer with a curing agent to obtain a viscoelastic fluid mixture;
S3, pre-curing: spin coating a viscoelastic fluid mixture on a support material substrate and pre-curing to obtain a viscoelastic substrate;
S4, setting printing parameters to print: placing the pre-cured viscoelastic substrate in the step S3 on an operation base of a dispensing machine, filling nanoparticle ink into a needle cylinder matched with the dispensing machine and connecting the nanoparticle ink with the dispensing machine, adjusting the distance between a needle head and the viscoelastic substrate and the distance between ink drop matrixes during ink discharge, curing a printed sample, and then physically flushing the cured sample to obtain a micro-nano concave structure template;
s5, modification treatment: performing grafting modification on the micro-nano concave structure template obtained in the step S4 by adopting air plasma, and performing silanization treatment on the surface by utilizing a vapor deposition method;
s6, curing: pouring the viscoelastic fluid mixture configured in the step S2 on the micro-nano concave structure template processed in the step S5, and stripping after solidification to obtain a micro-nano convex structure substrate;
s7, preparing a flexible electrode by utilizing the micro-nano bulge structure substrate obtained in the step S6;
S8, preparing an ultrasensitive multi-layer multi-mode flexible pressure sensor: and stacking the two flexible electrodes with the micro-nano bulge structures face to face, so that the micro-nano bulge structures of the flexible electrodes with the same structure are opposite to the gaps of the bulge structures of the other flexible electrode to form an interlocking structure, and thus the ultra-sensitive multi-layer multi-mode flexible pressure sensor is obtained.
Preferably, the support material in step S1 is one of polyethylene terephthalate, polyimide, silicon wafer, glass or metal plate.
Preferably, the prepolymer in step S2 has viscoelasticity, and the prepolymer is one of polydimethylsiloxane, epoxy resin, thermoplastic polyurethane or natural rubber.
Preferably, the pre-curing method in step S3 includes thermal curing and photo-curing.
Preferably, in step S4, nanoparticle ink is adopted, direct writing printing is performed on the surface of the viscoelastic substrate, a recess occurs in the surface area of the viscoelastic substrate contacted by the ink droplet, and the nanoparticles in the ink droplet form dynamic extrusion assembly along with volatilization of the solvent in the recess area, so that a spherical micro-nano structure is formed by deposition and embedded in the surface of the substrate; and after the viscoelastic substrate is solidified, removing the deposited spherical micro-nano structure by a physical flushing mode, and forming a micro-nano concave structure on the surface of the film.
Preferably, the curing method in step S6 includes thermal curing and photo curing.
Preferably, the flexible electrode is prepared in step S7 by using a flexible substrate material to replicate and then depositing a conductive material on the surface of the flexible substrate material to realize a flexible electrode with a micro-nano convex structure, and the flexible electrode with the micro-nano convex structure is directly obtained by compositing the conductive material and the flexible substrate material and then replicating.
Preferably, the flexible pressure sensor in step S8 comprises a capacitive pressure sensor, a piezoresistive pressure sensor or a piezoelectric pressure sensor.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention utilizes direct writing printing to print nanoparticle ink on the surface of a viscoelastic substrate to prepare a micro-nano concave structure template, controls printing conditions by controlling the pre-curing degree of the viscoelastic substrate, regulates and controls the shape, the size and the spacing of the micro-nano concave structure, and obtains a corresponding micro-nano convex structure flexible substrate by duplicating the micro-nano concave structure, and combines conductive materials to construct the micro-nano convex structure flexible electrode with excellent mechanical and electrical properties. According to the working principle of the flexible pressure sensor, flexible electrodes with micro-nano bulge structures are stacked to prepare the flexible pressure sensor, so that ultra-sensitive pressure sensing performance is realized.
(2) The microstructure on the surface of the sensor electrode can rapidly react to micro pressure, shows good sensing performance in a wider pressure range, and has good application prospects in the aspects of motion tracking, health detection and the like.
Drawings
FIGS. 1a and 1b are schematic flow diagrams of a method for constructing an ultrasensitive multilayer multimode flexible pressure sensor by using a direct-writing printing micro-nano concave template in a bionic mode; wherein, FIG. 1a is a schematic flow chart, and FIG. 1b is a specific schematic diagram of the preparation method;
FIG. 2 is a schematic diagram of deposition behavior of direct-write nanoparticle ink droplets on the surface of a viscoelastic substrate and a schematic diagram of morphology regulation of micro-nano recessed structures;
FIG. 3 is a schematic diagram of a microstructure array of different morphologies;
FIG. 4 is a schematic diagram of a flexible pressure sensor sensing mechanism;
Fig. 5a to 5l are optical microscope diagrams of micro-nano concave structures obtained by setting different printing pitches and different needle diameters and three-dimensional morphology diagrams obtained by scanning by a step-by-step machine, wherein fig. 5a, 5b, 5c, 5g, 5h and 5i are respectively optical microscope diagrams, and fig. 5d, 5e, 5f, 5j, 5k and 5l are corresponding three-dimensional morphology diagrams;
FIGS. 6a to 6l are respectively three-dimensional topography diagrams of the micro-nano raised structures obtained by scanning the optical microscope images and the step-by-step instrument of the micro-nano raised structures corresponding to FIGS. 5a to 5 l;
FIGS. 7 a-7 f are graphs of flexible pressure sensor performance studies, wherein FIGS. 7a, 7b, and 7c are graphs of different spacing sensors responding under 1g (a), 5g (b), and 10g (c) weight loading/unloading conditions; FIG. 7d is a response recovery time of the sensor; FIG. 7e shows the relative resistance change of a micro-nanostructure sensor to applied pressure; FIG. 7f is a durability and stability study of the sensor;
Fig. 8 is an application study of the flexible pressure sensor, wherein a, b, c, d is the respiration monitoring, acoustic vibration, pulse vibration, and wrist bending test, respectively.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
Specifically, the invention provides a method for constructing a flexible pressure sensor by directly writing and printing a micro-nano concave template in a bionic mode, which comprises the following steps:
s1, preparing a support material substrate: cutting, cleaning and drying the support material to prepare the support material substrate.
S2, preparing a viscoelastic fluid mixture: the prepolymer is mixed with a curative to obtain a viscoelastic fluid mixture. The prepolymer in step S2 has viscoelasticity and includes polydimethylsiloxane, epoxy resin, thermoplastic polyurethane and natural rubber.
S3, pre-curing: the viscoelastic fluid mixture is spin coated on a support material substrate and pre-cured to provide a viscoelastic substrate. The pre-curing means in this step includes thermal curing and photo-curing.
S4, setting printing parameters to print: and (3) placing the pre-cured viscoelastic substrate in the step (S3) on an operation base of a dispensing machine, filling nanoparticle ink into a needle cylinder matched with the dispensing machine and connecting the nanoparticle ink with the dispensing machine, adjusting the distance between a needle head and the viscoelastic substrate and the distance between ink drop lattices during ink discharging, curing a printed sample, and then physically flushing the cured sample to obtain the micro-nano concave structure template. In the step, nanoparticle ink is adopted to directly write and print on the surface of a viscoelastic substrate, recessing can occur in the surface area of the viscoelastic substrate contacted by ink drops, and nanoparticles in the ink drops can form dynamic extrusion assembly along with volatilization of a solvent in the recessing area, so that spherical micro-nano structures are formed by deposition and embedded on the surface of the substrate. And after the viscoelastic substrate is solidified, removing the deposited spherical micro-nano structure by a physical flushing mode, and forming a micro-nano concave structure on the surface of the film.
S5, modification treatment: and (3) carrying out grafting modification on the micro-nano concave structure template obtained in the step (S4) by adopting air plasma, and carrying out silanization treatment on the surface by utilizing a vapor deposition method.
S6, curing: and (3) pouring the viscoelastic fluid mixture configured in the step (S2) on the micro-nano concave structure template processed in the step (S5), and stripping after curing to obtain the micro-nano convex structure substrate. The curing mode comprises heat curing and photo-curing.
S7, preparing the flexible electrode by utilizing the micro-nano convex structure substrate obtained in the step S6. The method for preparing the flexible electrode comprises the steps of using a flexible substrate material to copy, then depositing a conductive material on the surface of the flexible substrate material to realize the flexible electrode with the micro-nano bulge structure, and directly obtaining the flexible electrode with the micro-nano bulge structure by compounding the conductive material and the flexible substrate material and then copying.
S8, preparing an ultrasensitive multi-layer multi-mode flexible pressure sensor: and stacking the two flexible electrodes with the micro-nano bulge structures face to face, so that the micro-nano bulge structures of the flexible electrodes with the same structure are opposite to the gaps of the bulge structures of the other flexible electrode, and the adjacent two flexible electrodes form an interlocking structure, thereby obtaining the ultra-sensitive multi-layer multi-mode flexible pressure sensor. The prepared flexible pressure sensor comprises capacitive pressure, piezoresistance and piezoelectric type.
Detailed description of the preferred embodiments
The embodiment provides a method for constructing a flexible pressure sensor by directly writing and printing micro-nano concave templates in a bionic mode, as shown in fig. 1a and 1b, nanoparticle ink is directly written and printed on the surface of a viscoelastic substrate, the shape, the distance and the size of a micro-nano concave structure are regulated and controlled, and particularly, the method can be seen in fig. 2. And the corresponding micro-nano bulge structure flexible substrate is obtained through the micro-nano concave structure replication, and the micro-nano bulge structure flexible electrode with excellent mechanical and electrical properties is constructed by combining a conductive material, as shown in figure 3. According to the working principle of the flexible pressure sensor, flexible electrodes with micro-nano bulge structures are stacked to prepare the flexible pressure sensor, so that ultra-sensitive pressure sensing performance is realized. The pressure applied on the sensor can cause the deformation of the micro-nano raised structure on the surface of the flexible electrode, so that the contact area of the two electrodes and the width of the actual channel are induced to change rapidly, the contact resistance of the conductive layer is changed, and the sensor detects the micro pressure, as shown in fig. 4. The method has the advantages of large area, flexibility, mass preparation, low cost, environment friendliness and the like.
Second embodiment
The embodiment provides a method for constructing a flexible pressure sensor by directly writing and printing micro-nano concave templates in a bionic mode, which comprises the following steps:
s1, preparing a support material substrate: cutting, cleaning and drying the support material to prepare the support material substrate.
S2, preparing a viscoelastic fluid mixture: the prepolymer is mixed with a curative to obtain a viscoelastic fluid mixture.
S3, pre-curing: and spin-coating the viscoelastic fluid mixture on the support material substrate and performing pre-curing to obtain the pre-cured viscoelastic substrate.
In this example, polyethylene terephthalate (PET) was cut into pieces of 3cm by 3cm and placed in an ethanol solution for ultrasonic cleaning, and after cleaning, placed in an oven at 60℃for baking. Weighing a Polydimethylsiloxane (PDMS) precursor and a curing agent in a beaker, wherein the mass ratio of the precursor to the curing agent is 10:1, stirring uniformly, and vacuumizing to remove bubbles. Spin-coating the prepared PDMS on the surface of PET, wherein the spin-coating thickness is 200 mu m, and placing the PET in a vacuum drying oven for pre-curing at 70 ℃ for 5min to obtain the viscoelastic substrate.
S4, setting printing parameters to print: placing the pre-cured viscoelastic substrate on an operation base of a dispenser, filling nanoparticle ink into a needle cylinder matched with the dispenser and connecting the nanoparticle ink with the dispenser, and adjusting the distance between a needle head and the viscoelastic substrate during ink discharge, wherein the distance is adjusted according to requirements. The pitch of the dot array is set as required, and preferably can be set between 100 and 300 μm, and the needle diameter is preferably set between 100 and 200 μm. And solidifying the printed sample, and then physically flushing the solidified sample to obtain the micro-nano concave structure template. In the preparation process, nanoparticle ink is adopted to directly write and print on the surface of a viscoelastic substrate, recessing can occur in the surface area of the viscoelastic substrate contacted by ink drops, and nanoparticles in the ink drops can form dynamic extrusion assembly along with volatilization of a solvent in the recessing area, so that spherical micro-nano structures are formed by deposition and embedded on the surface of the substrate. And after the viscoelastic substrate is solidified, removing the deposited spherical micro-nano structure by a physical flushing mode, and forming a micro-nano concave structure on the surface of the film.
S5, modification treatment: and carrying out grafting modification on the micro-nano concave structure template by adopting air plasma, and carrying out silanization treatment on the surface by utilizing a vapor deposition method.
S6, curing: and (3) pouring the viscoelastic fluid mixture configured in the step (S2) on the micro-nano concave structure template processed in the step (S5), and stripping after curing to obtain the micro-nano convex structure substrate.
S7, preparing a flexible electrode, wherein the specific process is as follows: and (3) after the flexible substrate material is subjected to replica, depositing a conductive material on the surface of the flexible substrate material to realize the flexible electrode with the micro-nano bulge structure, and directly obtaining the flexible electrode with the micro-nano bulge structure by compounding the conductive material and the flexible substrate material and then performing replica.
S8, preparing an ultrasensitive multi-layer multi-mode flexible pressure sensor: and stacking the two flexible electrodes with the micro-nano bulge structures face to face, so that the micro-nano bulge structures of the flexible electrodes with the same structure are opposite to the gaps of the bulge structures of the other flexible electrode to form an interlocking structure, and thus the ultra-sensitive multi-layer multi-mode flexible pressure sensor is obtained.
FIGS. 5a to 5l are three-dimensional topography of micro-nano recessed structures obtained by optical microscopy images and step-by-step scanning of micro-nano recessed structures with different printing pitches (three groups of a:300 μm, b:200 μm, c:100 μm) and different needle diameters (three groups of g:100 μm, h:150 μm, i:200 μm) were set in example 2. Fig. 6a to 6l are respectively optical microscope images of the micro-nano raised structures corresponding to fig. 5a to 5l and three-dimensional topography of the micro-nano raised structures obtained by scanning with a step-by-step instrument. FIGS. 7 a-7 f are flexible pressure sensor performance studies, wherein FIGS. 7a, 7b, and 7c are responses of different spacing sensors under 1g (a), 5g (b), and 10g (c) weight loading/unloading conditions; FIG. 7d is a response recovery time of the sensor; FIG. 7e shows the relative resistance change of a micro-nanostructure sensor to applied pressure; fig. 7f is a durability and stability study of the sensor. Fig. 8 is an application study of the flexible pressure sensor, wherein a), b), c), d) are breath monitoring, acoustic vibration, pulse vibration, and wrist bending test, respectively.
The above examples are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (8)
1. A method for constructing a flexible pressure sensor by directly writing and printing micro-nano concave templates in a bionic mode is characterized by comprising the following steps of: which comprises the following steps:
s1, preparing a support material substrate: cutting, cleaning and drying the support material to prepare a support material substrate;
S2, preparing a viscoelastic fluid mixture: mixing the prepolymer with a curing agent to obtain a viscoelastic fluid mixture;
S3, pre-curing: spin coating a viscoelastic fluid mixture on a support material substrate and pre-curing to obtain a viscoelastic substrate;
S4, setting printing parameters to print: placing the pre-cured viscoelastic substrate in the step S3 on an operation base of a dispensing machine, filling nanoparticle ink into a needle cylinder matched with the dispensing machine and connecting the nanoparticle ink with the dispensing machine, adjusting the distance between a needle head and the viscoelastic substrate and the distance between ink drop matrixes during ink discharge, curing a printed sample, and then physically flushing the cured sample to obtain a micro-nano concave structure template;
s5, modification treatment: performing grafting modification on the micro-nano concave structure template obtained in the step S4 by adopting air plasma, and performing silanization treatment on the surface by utilizing a vapor deposition method;
s6, curing: pouring the viscoelastic fluid mixture configured in the step S2 on the micro-nano concave structure template processed in the step S5, and stripping after solidification to obtain a micro-nano convex structure substrate;
s7, preparing a flexible electrode by utilizing the micro-nano bulge structure substrate obtained in the step S6;
S8, preparing an ultrasensitive multi-layer multi-mode flexible pressure sensor: and stacking the two flexible electrodes with the micro-nano bulge structures face to face, so that the micro-nano bulge structures of the flexible electrodes with the same structure are opposite to the gaps of the bulge structures of the other flexible electrode to form an interlocking structure, and thus the ultra-sensitive multi-layer multi-mode flexible pressure sensor is obtained.
2. The method for constructing the flexible pressure sensor by using the direct-writing printing micro-nano concave template in a bionic mode, which is characterized by comprising the following steps of: in the step S1, the supporting material is one of polyethylene terephthalate, polyimide, silicon wafer, glass or metal plate.
3. The method for constructing the flexible pressure sensor by using the direct-writing printing micro-nano concave template in a bionic mode, which is characterized by comprising the following steps of: in the step S2, the prepolymer has viscoelasticity, and is one of polydimethylsiloxane, epoxy resin, thermoplastic polyurethane or natural rubber.
4. The method for constructing the flexible pressure sensor by using the direct-writing printing micro-nano concave template in a bionic mode, which is characterized by comprising the following steps of: the pre-curing method in step S3 includes thermal curing and photo-curing.
5. The method for constructing the flexible pressure sensor by using the direct-writing printing micro-nano concave template in a bionic mode, which is characterized by comprising the following steps of: in the step S4, nanoparticle ink is adopted to directly write and print on the surface of the viscoelastic substrate, the surface area of the viscoelastic substrate contacted by ink drops is recessed, the nanoparticles in the ink drops form dynamic extrusion assembly along with the volatilization of a solvent in the recessed area, so that spherical micro-nano structures are formed by deposition and embedded on the surface of the substrate; and after the viscoelastic substrate is solidified, removing the deposited spherical micro-nano structure by a physical flushing mode, and forming a micro-nano concave structure on the surface of the film.
6. The method for constructing the flexible pressure sensor by using the direct-writing printing micro-nano concave template in a bionic mode, which is characterized by comprising the following steps of: the curing method in step S6 includes thermal curing and photo curing.
7. The method for constructing the flexible pressure sensor by using the direct-writing printing micro-nano concave template in a bionic mode, which is characterized by comprising the following steps of: the flexible electrode is prepared in the step S7 by using a flexible substrate material to copy and then depositing a conductive material on the surface of the flexible substrate material to realize the flexible electrode with the micro-nano bulge structure, and the flexible electrode with the micro-nano bulge structure is directly obtained by compounding the conductive material and the flexible substrate material and then copying.
8. The method for constructing the flexible pressure sensor by using the direct-writing printing micro-nano concave template in a bionic mode, which is characterized by comprising the following steps of: the flexible pressure sensor in step S8 comprises a capacitive pressure sensor, a piezoresistive pressure sensor or a piezoelectric pressure sensor.
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| CN202410307198.1A CN118347611A (en) | 2024-03-18 | 2024-03-18 | Method for constructing flexible pressure sensor by direct-writing printing micro-nano concave template bionic construction |
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| CN202410307198.1A CN118347611A (en) | 2024-03-18 | 2024-03-18 | Method for constructing flexible pressure sensor by direct-writing printing micro-nano concave template bionic construction |
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