CN112816111B - Flexible touch sensor and manufacturing method thereof - Google Patents
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- CN112816111B CN112816111B CN202011559268.0A CN202011559268A CN112816111B CN 112816111 B CN112816111 B CN 112816111B CN 202011559268 A CN202011559268 A CN 202011559268A CN 112816111 B CN112816111 B CN 112816111B
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- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/20—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress
Abstract
The invention provides a flexible touch sensor and a manufacturing method thereof, wherein the method comprises the following steps: s1, preparing flexible metal aerogel based on metal nanowires such as silver, copper and gold, and cutting the metal aerogel into a size to be determined; s2, placing the metal aerogel monomer obtained in the step S1 on the surface of a substrate with a bonding pad structure and a signal circuit designed on the surface after aligning, and heating and sintering to form a sensing passage; s3, carrying out precision machining and surface treatment on the sensing channel obtained in the step S2, immersing the sensing channel in a liquid organic polymer monomer, fully standing, filling, and obtaining a touch sensing unit or array through heating and curing; a flexible tactile sensor with high flexibility and high sensitivity is formed. Compared with the traditional single flexible touch sensor with the carbon material and the metal particles as the conductive substrate, the flexible touch sensor prepared by the invention has stronger conductive performance and higher sensitivity due to the adoption of the metal aerogel as the conductive substrate and the formation of the sensing array.
Description
Technical Field
The invention relates to the technical field of flexible electronic skin, in particular to a flexible touch sensor and a manufacturing method thereof.
Background
Aiming at the research of robots, the electronic technology is utilized to simulate various human perceptions, which is the key for realizing the development of human-computer seamless connection, artificial intelligence and bionic robots, while along with the development of the technical field of robots towards autonomous manual direction, an advanced touch sensor is crucial for realizing the safe interaction between the robots and the environment thereof, and the flexible electronic skin with high flexibility and high sensitivity is the technical guarantee for realizing the whole-course perception of the contact of the robots, enhancing the service capacity of human-computer interaction and the operation safety, thereby having important research significance and application value. However, although research work of flexible electronic skin touch sensing has been greatly progressed in recent years, electronic skin which can be attached to a complex three-dimensional static/dynamic surface and accurately finish measurement tasks in different strain states is quite rare, so that it is required to develop a flexible touch sensor with the characteristics of high flexibility, high sensitivity, high reliability and the like, and technical support is provided for intelligent and accurate operation of robots.
The three-dimensional porous network structure formed by self-assembly of the metal aerogel and the metal nanowires has excellent stability, conductivity and higher sensitivity, when the external stress and strain are changed, the overlapping degree between the internal metal nanowires is changed, the conductivity of the metal aerogel can be changed, the response speed is high, but the aerogel is low in strength, and the metal aerogel is often compounded with a flexible substrate material to prepare a flexible touch sensor for application.
The flexible substrate material needs to have good adhesion and stretchability, and is usually obtained by heating and curing an organic polymer solution such as Polydimethylsiloxane (PDMS), polyimide (PI) and the like. The high-molecular polymers with different elastic moduli can be obtained by using different solution proportions and curing temperatures, and are widely applied to flexible substrate materials in flexible sensors due to good flexibility and stability. The flexible substrate material and the metal aerogel are compounded, so that the overall strength of the flexible sensor can be improved.
The flexible touch sensor is usually combined with a substrate with a conductive path, so that the sensitivity and the identification range of the flexible touch sensor can be enhanced by forming an array, and the technical requirements of intelligent operation of a robot can be met.
The prior art CN202010052115.0 provides a method for preparing a pure metal aerogel and a flexible composite material, the method for preparing the pure metal aerogel comprises the following steps: adding the active material matrix into a solvent, and mixing to obtain a three-dimensional growth active agent; the method comprises the steps of (1) mixing a required metal precursor and a surfactant into a solvent, adding a three-dimensional growth active agent, uniformly mixing, and placing into a closed reaction mold for reaction; and heating the mold to obtain a metal gel structure with the same shape as the mold and containing the solvent, taking out the metal gel structure, cleaning to remove residual solvent, free nanowire monomers and active agent, and drying to finally obtain the pure metal aerogel with the three-dimensional structure. The technical scheme is the same group of patent applications, and the metal aerogel used in the patent is the method described in the technical scheme, so the preparation of the metal aerogel is not described in detail so as to avoid conflict.
Disclosure of Invention
According to the flexible touch sensor and the manufacturing method thereof, the metal aerogel is used as an active conductive material, and is compounded with a flexible base material on a substrate to form a sensor array, so that the flexible touch sensor with high flexibility and high sensitivity is obtained.
In this regard, the invention adopts the following technical scheme:
a flexible touch sensor and a manufacturing method thereof are characterized by comprising the following steps:
s1, preparing flexible metal aerogel based on metal nanowires such as silver, copper and gold, and cutting the metal aerogel into a size to be determined;
s2, placing the metal aerogel monomer obtained in the step S1 on the surface of a substrate with a bonding pad structure and a signal circuit designed on the surface after aligning, and heating and sintering to form a sensing passage;
and S3, carrying out precision machining and surface treatment on the sensing channel obtained in the step S2, immersing the sensing channel into a liquid organic polymer monomer, fully standing, filling, and heating and curing to obtain the touch sensing unit or array.
As a further improvement of the invention, in the step S1, the metal aerogel is formed by self-assembling metal nanowires of silver, copper, gold and the like, the inside of the metal aerogel is of a three-dimensional porous structure, the pore diameter between the metal nanowires is 40nm-30 mu m, and the conductivity of the metal aerogel is 2000-300000S/m. By adopting the technical scheme, the metal aerogel has good stability, higher conductivity and quick response capability, and when the metal aerogel is subjected to external stress strain change, the overlapping degree between the metal nanowires in the metal aerogel changes, so that the resistance of the metal aerogel is reduced, and the conductivity is increased. The metal aerogel is of a three-dimensional porous structure, organic polymer solution can be filled and dispersed in the metal aerogel, and the flexible touch sensor unit with better flexibility and higher strength is obtained after the metal aerogel is integrally solidified.
As a further improvement of the present invention, in step S1, the metal aerogel is cut to be sized, and the thickness of the metal aerogel can be controlled to 0.01-2mm by compression. By adopting the technical scheme, the conductive active substance of the flexible touch sensor with thinner thickness can be obtained, the compression effect can reduce the space between the metal nanowires in the metal aerogel, enhance the conductive capability of the aerogel, ensure the good responsiveness and sensitivity of the metal aerogel and meet the mounting requirement of the electronic skin on the surface of the bionic robot.
As a further improvement of the invention, in step S2, the surface of the bonding pad is provided with a conductive adhesive, which can be low-temperature soft solder, nano silver paste, silver paste and the like; and in the heating sintering process, the temperature is 50-120 ℃, the heating time is 20-80min, and the aerogel is connected with a signal line through a bonding pad to transmit a touch signal or response. By adopting the technical scheme, the metal aerogel and the bonding pad can be connected together, and the bonding pad is connected with the signal line of the lower substrate to form a conductive path, so that the transmission of the touch signal and the response signal is realized.
As a further improvement of the present invention, in step S2, the substrate may be a rigid, flexible printed circuit board or a metal, ceramic, polymer or other substrate, and may be integrated with a signal buffer module or a processing module, a wireless signal transmission module, or the like. By adopting the technical scheme, different matrix materials can provide more application scenes for the flexible touch sensor prepared by the invention. The signal buffer module, the processing module and the wireless signal transmission module are designed and integrated on the substrate base body, when the metal aerogel receives external signals, the metal aerogel can be converted into electric signals, the electric signals are transmitted to the substrate through the bonding pad structure, and the signal processing module on the substrate can perform calculation processing or directly transmit sensing signals in a wired or wireless mode.
As a further improvement of the present invention, in step S3, precision machining may be performed by laser, photolithography, machining, etc., cutting the aerogel into discrete sensing units to form a sensing array, or machining a continuous transparent grid structure with different hole shapes such as circular, diamond, hexagonal, etc. By adopting the technical scheme, the aerogel is cut into discrete sensing units, a multifunctional sensing array can be formed, the sensitivity and the identification range of the aerogel can be improved through array design, and the sensing function of stress direction can be realized; the metal aerogel is processed into a continuous transparent grid structure with different hole shapes such as a circle, a diamond, a hexagon and the like, a specific pattern is formed under the condition of keeping circuit connection, and the flexible touch sensor can be applied to the specific transparent sensor field.
As a further improvement of the present invention, in step S3, the surface treatment of the flexible tactile sensor unit includes surface spraying, surface sensitization, surface coupling, and the like. By adopting the technical scheme, the surface of the metal aerogel can be modified, and the contact effect of the metal aerogel and the organic polymer solution is enhanced.
As a further improvement of the present invention, in step S3, the organic high molecular monomer includes an insulating material such as Polydimethylsiloxane (PDMS), polyimide (PI), and silica gel, or a conductive high molecular polymer such as poly 3, 4-ethylenedioxythiophene (PEDOT), polyaniline (PANI), and sodium polyacrylate (PANa). According to the technical scheme, the metal aerogel can be compounded by using the Polydimethylsiloxane (PDMS), polyimide (PI), silica gel and other insulating materials, so that the integral strength of the flexible touch sensor unit is improved. Conductive high molecular polymers such as poly 3, 4-ethylenedioxythiophene (PEDOT), polyaniline (PANI), sodium polyacrylate (PANa) and the like are used, so that the conductive capability and flexibility of the flexible touch sensor can be enhanced.
As a further improvement of the invention, in the step S3, the standing time is 5-60min, the curing temperature is 50-300 ℃ and the curing time is 10-100min. By adopting the technical scheme, the standing process can fully disperse the organic polymer solution in the metal aerogel, and the organic polymer solution can be solidified into a solid structure with certain flexibility and compressive strength by heating and solidifying.
The invention further provides a flexible touch sensor which is prepared by the manufacturing method.
Compared with the prior art, the invention has the beneficial effects that:
first, the flexible touch sensor obtained by the technical scheme of the invention has higher conductivity and sensitivity. The metal aerogel is self-assembled by metal nano silver wires, has a three-dimensional network structure inside, and can be filled with organic polymer solution. When the metal aerogel is subjected to external stress, the overlapping degree between the internal metal nanowires is increased, so that the metal aerogel has better conductivity and excellent sensitivity, and the metal aerogel is used as an active substance for the flexible touch sensor, so that the flexible touch sensor has higher conductivity and sensitivity.
Secondly, the flexible touch sensor obtained by the technical scheme of the invention has higher flexibility and stability. The surface modification effect is achieved by carrying out surface treatment on the metal aerogel, so that the contact effect of the metal aerogel and the organic polymer solution is enhanced. After the metal aerogel and the organic polymer solution are mixed and cured, the overall strength and stability of the flexible touch sensor unit can be improved.
Thirdly, the flexible touch sensor is characterized in that the metal aerogel is connected with the substrate with the signal circuit through the bonding pad structure, and then the metal aerogel is processed into an array structure or a continuous transparent network structure through precision processing. The substrate with the signal line can perform preliminary processing on the signal received by the sensor or transmit the signal out in a wired and wireless mode; the flexible touch sensor with the array structure can realize the detection of stress in different directions, and has excellent sensitivity and identification range; the flexible touch sensor with the continuous transparent network structure can be applied to the specific transparent sensor field by cutting aerogel into different hole structures and forming specific patterns under the condition of keeping circuit connection.
Drawings
Fig. 1 is a schematic diagram of the structure of the flexible tactile sensor unit employed in embodiments 1 and 2 of the present invention.
Fig. 2 is a schematic diagram of a flexible touch sensor array used in embodiments 1 and 2 of the present invention.
Fig. 3 is a schematic diagram of a network structure of a flexible touch transparent sensor used in embodiment 3 of the present invention.
In the figure, 1 is a flexible substrate covered outside metal aerogel, 2 is metal aerogel, 3 is a bonding pad, 4 is a printed circuit board, 5 is a surface adhesive on the surface of the bonding pad, 6 is a sensing unit, 7 is a signal lead-out circuit of a single sensing unit, and 8 is a flexible touch transparent sensor network structure.
Detailed Description
The preferred embodiments of the present invention and the accompanying drawings will be described in further detail below, but the present invention is not limited thereto.
Example 1
Referring to fig. 1, a method for preparing a nano silver wire aerogel composite polydimethylsiloxane flexible tactile array sensor specifically comprises the following steps:
(1) The nano silver wire aerogel is prepared by a liquid-phase induced reduction reaction and supercritical drying method, and is cut by using a low-voltage electronic beam, and is compressed in the thickness direction, so that the nano silver wire aerogel 2 with the thickness of 1mm is obtained.
(2) The compressed nano silver wire aerogel is aligned and placed on a bonding pad 3 of a rigid printed circuit board 4, a signal circuit is integrated on the circuit board, and a silver adhesive 5 is adhered on the bonding pad 3. And then placing the composite structure in a constant temperature heating furnace, wherein the temperature is 60 ℃, the heating time is 30min, and connecting the nano silver wire aerogel with the bonding pad to form the sensing unit.
(3) The sensing units are subjected to laser processing, and the nano silver wire aerogel is cut into a structure shown in fig. 2, so that a plurality of sensing units 6 are combined into an array structure.
(4) And (3) carrying out surface sensitization treatment on the cut sensing units, immersing the sensing units into a polydimethylsiloxane solution, standing for 15min, fully dispersing the polydimethylsiloxane into the nano silver wire aerogel, and carrying out heating solidification, wherein the heating temperature is 80 ℃ and the heating time is 40min.
In this example, the nano silver wire aerogel has excellent conductivity of 10000S/m, extremely low density of about 4mg/cm 3 The inside is formed by self-assembly of nano silver wires, has a three-dimensional network porous structure, and when the outside stress changes, the overlapping degree between the nano silver wires is increased, so that the aerogel conductivity is improved, and the sensing effect is achieved. By forming the array structure, the sensitivity and recognition of the flexible sensor can be enhancedOther ranges; through solidification and compounding with the polydimethylsiloxane, the maximum bearable stress of the flexible touch sensor is not lower than 1MPa, the maximum recoverable strain is greater than 50%, the minimum strain fatigue failure frequency of the flexible touch sensor is greater than 5000 times in the recoverable strain range, the flexible touch sensor also has excellent sensitivity, the minimum detectable contact force is 0.5N, and the response time is 100ms.
Example 2
Referring to fig. 1, a method for preparing a nano copper wire aerogel composite polyimide flexible touch array sensor specifically comprises the following steps:
(1) The nano copper wire aerogel is prepared by a liquid-phase induced reduction reaction and freeze drying method, and is cut by using a low-voltage electronic beam, and is compressed in the thickness direction to obtain the nano copper wire aerogel with the thickness of 1.5 mm.
(2) The compressed nano copper wire aerogel is aligned and placed on the bonding pad 3 of the ceramic plate 4, and the low-temperature soft solder 5 is adhered to the bonding pad 3. And then placing the composite structure in a constant temperature heating furnace, wherein the temperature is 100 ℃, the heating time is 20min, and connecting the nano copper wire aerogel with the bonding pad to form the sensing unit.
(3) The sensing cells were machined and the nano copper wire aerogel was cut into the structure shown in fig. 2 so that a plurality of sensing cells 6 were combined into an array structure.
(4) And (3) carrying out surface coupling treatment on the cut sensing units, immersing the sensing units in polyimide solution, standing for 30min to enable the polyimide solution to be fully dispersed into the nano copper wire aerogel, heating and solidifying, firstly, heating to 100 ℃, keeping the temperature for 0.5h, then heating to 150 ℃, keeping the temperature for 40min, continuously heating to 260 ℃, heating for 0.5h, and keeping the heating process at 100 ℃/h. And heating to obtain the nano silver wire aerogel composite polyimide flexible touch array sensor.
In this example, unlike example 1, polyimide and nano copper aerogel are used to compound, and the cured polyimide has stronger tensile strength than polydimethylsiloxane, which can reach more than 50Mpa, and has more stable mechanical properties, simple preparation method and good processability.
Example 3
A preparation method of a nano silver wire aerogel composite polydimethylsiloxane flexible touch transparent sensor specifically comprises the following steps:
(1) The nano silver wire aerogel is prepared by a liquid-phase induced reduction reaction and supercritical drying method, and is cut by using a low-voltage electronic beam, and is compressed in the thickness direction, so that the nano silver wire aerogel 2 with the thickness of 0.1mm is obtained.
(2) The compressed nano silver wire aerogel is placed on a polymer matrix 8 with conductive adhesive on the surface, then the sensing unit is subjected to laser processing, the nano silver wire aerogel is cut into a continuous transparent network structure as shown in fig. 3 through the laser processing, and the width of the nano silver wire aerogel on the matrix is about 30 mu m.
(3) And (3) carrying out surface sensitization treatment on the cut sensing circuit, immersing the sensing circuit into a polydimethylsiloxane solution, standing for 10min, fully dispersing the polydimethylsiloxane into the nano silver wire aerogel, and carrying out heating solidification, wherein the heating temperature is 60 ℃ and the heating time is 60min.
In this embodiment, unlike embodiment 1, the aerogel is cut into a continuous transparent network structure with a hexagonal cavity shape by means of a laser processing technology, and the width of the nano silver wire aerogel is controlled to be small enough, so that the overall transparent property of the sensor can be realized to a certain extent while the signal path is maintained, and the method can be applied to the field of certain flexible touch transparent sensors.
Comparative example 1
A preparation method of a graphene composite porous sponge material flexible touch sensor comprises the following specific steps:
(1) 0.6g of conductive active material (carbon black, graphene=2:1) was dissolved in 15ml of naphtha to form a suspension, and the suspension was subjected to ultrasonic treatment for 20min to uniformly disperse the conductive active material.
(2) Cutting the porous sponge by a low-voltage electron beam to obtain porous sponge blocks with the size of 5 multiplied by 1.5mm, cleaning by ethanol, and drying at a constant temperature of 40 ℃ for 2 hours in a constant temperature drying oven.
(3) Immersing the dried porous sponge square block into the uniformly dispersed conductive active substance suspension, and continuously extruding the sponge square block to enable the conductive active substance to be uniformly dispersed into the internal gaps of the sponge square block, wherein the dispersing time is 10min.
(4) The sponge block was removed from the solution and dried in a constant temperature oven at 75deg.C for 15min. And (5) coating a layer of silver paste on two sides of the sponge block after the sponge block is taken out, and compositing the silver paste with copper foil to form the conductive electrode.
In the embodiment, graphene and conductive carbon black are compounded to serve as conductive active substances, and the conductive active substances are dispersed into a porous sponge to prepare the flexible touch sensor. The preparation process is complex, the processing is difficult, the production cost is high, the deformation degree of the porous sponge under the condition of being stressed is high, and the compressive strength is low.
Comparative example 2
A preparation method of a carbon nano tube composite polydimethylsiloxane flexible touch sensor specifically comprises the following steps:
(1) 1.0g of multi-wall carbon nano tube is taken as conductive filling particles, 2.0g of polymethylphenylsiloxane is taken as a modification material to be dissolved in 15ml of chloroform, and the dispersion mother liquor which is uniformly dispersed is obtained after ultrasonic treatment for 1.5 hours.
(2) Adding 10g of polydimethylsiloxane into the dispersion mother solution, performing ultrasonic dispersion for 20min, and volatilizing the solvent to obtain the carbon nano tube/PDMS prepolymer.
(3) Adding 1g of carbon nano tube cross-linking agent into the carbon nano tube/PDMS prepolymer, fully stirring, putting into a vacuum box to remove bubbles, heating to 75 ℃, and curing for 60min.
(4) Cutting the solidified carbon nano tube/PDMS material into cuboid small blocks with the length of 4 multiplied by 1mm by a low-voltage electron beam, smearing uniform low-temperature soldering paste on two ends of the material, and sintering at the temperature of 75 ℃ for 60min to form the electrode.
In the embodiment, the multi-wall carbon nano tube is compounded with PDMS to obtain the carbon nano tube compounded polydimethylsiloxane flexible touch sensor. Under the action of external force, the gaps among the carbon nanotubes are changed, and the resistivity is changed, so that the sensing effect is achieved. However, compared with the nano silver wire aerogel used in the present invention, the carbon nano tube preparation process is complex, and aggregation easily occurs when dispersed in a dispersing agent, and the uniformity in PDMS solution is poor.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (2)
1. A method for manufacturing a flexible touch sensor is characterized in that,
(1) Preparing nano copper wire aerogel by a liquid-phase induced reduction reaction and freeze drying method, cutting the nano copper wire aerogel by using a low-voltage electronic beam, and compressing the nano copper wire aerogel in the thickness direction to obtain the nano copper wire aerogel with the thickness of 1.5 mm;
(2) Aligning and placing the compressed nano copper wire aerogel on a bonding pad of a ceramic plate, wherein the bonding pad is bonded with low-temperature soft solder; then placing the composite structure in a constant temperature heating furnace, wherein the temperature is 100 ℃, the heating time is 20min, and connecting the nano copper wire aerogel with the bonding pad to form a sensing unit;
(3) Machining the sensing units, and cutting the nano copper wire aerogel to enable a plurality of sensing units to be combined into an array structure;
(4) And (3) carrying out surface coupling treatment on the cut sensing unit, immersing the sensing unit into polyimide solution, standing for 30min to enable the polyimide solution to be fully dispersed into the nano copper wire aerogel, heating and solidifying, firstly, heating to 100 ℃, keeping the constant temperature for 0.5h, then heating to 150 ℃, keeping the temperature for 40min, continuously heating to 260 ℃, heating for 0.5h, keeping the temperature rising process at 100 ℃/h, and heating to obtain the nano silver wire aerogel composite polyimide flexible touch array sensor.
2. A flexible tactile sensor, characterized by: is prepared by the preparation method of claim 1.
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| CN113858742A (en) * | 2021-09-30 | 2021-12-31 | 南京恒电先进微波技术研究院有限公司 | Flexible electromagnetic shielding film and preparation method thereof |
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| CN102910625B (en) * | 2012-11-14 | 2015-07-01 | 北京理工大学 | Graphene oxide aerogel, preparation method and application |
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