CN110608825A - Flexible pressure sensor based on polyimide substrate microstructure and preparation method thereof - Google Patents

Flexible pressure sensor based on polyimide substrate microstructure and preparation method thereof Download PDF

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Publication number
CN110608825A
CN110608825A CN201910861741.1A CN201910861741A CN110608825A CN 110608825 A CN110608825 A CN 110608825A CN 201910861741 A CN201910861741 A CN 201910861741A CN 110608825 A CN110608825 A CN 110608825A
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flexible
layer
pressure sensor
polyimide
piezoresistive material
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CN110608825B (en
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卢红亮
刘梦洋
张卫
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Fudan University
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Fudan University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01LMEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00Measuring force or stress, in general
    • G01L1/20Measuring 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
    • G01L1/22Measuring 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 using resistance strain gauges
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01LMEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L9/00Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means
    • G01L9/02Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means by making use of variations in ohmic resistance, e.g. of potentiometers, electric circuits therefor, e.g. bridges, amplifiers or signal conditioning
    • G01L9/04Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means by making use of variations in ohmic resistance, e.g. of potentiometers, electric circuits therefor, e.g. bridges, amplifiers or signal conditioning of resistance-strain gauges

Abstract

The invention discloses a flexible pressure sensor based on a polyimide substrate microstructure and a preparation method thereof. The flexible pressure sensor comprises a lower flexible substrate, a force-sensitive structure layer and an upper flexible packaging layer; the lower flexible substrate is a polyimide film, and the upper surface of the lower flexible substrate is provided with a raised microstructure array; the force-sensitive structure layer is tightly attached to the upper surface of the lower flexible substrate and comprises a lower electrode layer, a flexible piezoresistive material layer and an upper electrode layer from bottom to top, and the flexible piezoresistive material layer is a carbon-based nanoparticle/polymer piezoresistive material with piezoresistive characteristics; the upper flexible packaging layer is tightly attached to the upper surface of the force-sensitive structure layer to protect the sensor and prevent water. The flexible pressure sensor based on the polyimide substrate microstructure is prepared by adopting a micro-nano manufacturing technology from bottom to top, and has the advantages of high sensitivity, ultra-thin and ultra-light properties, simple process, easiness in array manufacturing and strong applicability.

Description

Flexible pressure sensor based on polyimide substrate microstructure and preparation method thereof
Technical Field
The invention belongs to the technical field of pressure measurement, and particularly relates to a flexible pressure sensor based on a polyimide substrate microstructure and a preparation method thereof.
Background
The skin plays a great role in human life, and a lot of work can be carried out with the help of the skin. However, for amputation and burn patients who have lost part of the skin sensing function, and high-risk and delicate mechanical arm work occasions, patients who have other health index signal monitoring need to feed back external signals and the health condition of the human body in real time, and therefore the flexible pressure sensor is generated and developed.
The flexible piezoresistive pressure sensor can easily convert compression, bending, torsion and other deformations into electric signals, and meanwhile, compared with piezoelectric and capacitive strain sensors, the piezoresistive pressure sensor is simple and convenient to test, small in interference signal and not inferior to human skin in the aspect of sensing external pressure.
In recent years, in order to pursue high tensile rate and high sensitivity of the flexible piezoresistive pressure sensor, a plurality of domestic and foreign research institutions mix carbon-based conductive particles and flexible polymers with each other to prepare a novel flexible piezoresistive material. Common flexible polymers such as Polyimide (PI), Polyurethane (PU), polyvinylidene fluoride (PVDF), styrene-based thermoplastic elastomer (SBS), Polydimethylsiloxane (PDMS), and the like, impart special properties such as stretchability, bendability, and transparency to the sensor; carbon-based conductive particles such as graphene, carbon nanotubes, graphite nanoplatelets, and the like impart electrical properties to the sensor. The polymer and the conductive particles are mixed with each other and matched with a special structure, so that the requirements of the pressure sensor can be easily met. However, most of the pressure sensors based on carbon-based conductive particle doped polymers have the disadvantages of large size, complex process and structure and poor applicability.
Disclosure of Invention
The invention aims to provide a flexible pressure sensor based on a polyimide substrate microstructure and a preparation method thereof. The flexible pressure sensor based on the polyimide substrate microstructure is prepared by adopting a micro-nano manufacturing technology from bottom to top, and has the advantages of high sensitivity, ultra-thin and ultra-light properties, simple process, easiness in array manufacturing and strong applicability. The technical scheme of the invention is specifically introduced as follows.
The invention provides a flexible pressure sensor based on a polyimide substrate microstructure, which is integrally of a film structure and comprises a lower-layer flexible substrate, a force-sensitive structure layer and an upper-layer flexible packaging layer, wherein the lower-layer flexible substrate, the force-sensitive structure layer and the upper-layer flexible packaging layer are tightly attached from bottom to top; the lower-layer flexible substrate is a polyimide film, and the upper surface of the polyimide film is provided with a raised microstructure array; the force-sensitive structure layer comprises a lower electrode layer, a flexible piezoresistive material layer and an upper electrode layer from bottom to top, the flexible piezoresistive material layer is made of one or more carbon-based nanoparticles doped with a polymer piezoresistive material, and the flexible piezoresistive material layer is prepared by spin-coating and solidifying a carbon-based nanoparticle/polymer mixed solution.
Further, the microstructure array is prepared by photoetching and plasma etching processes, the distance between the microstructures is 10 ~ 500 mu m, and the cross section of each microstructure is rectangular, trapezoidal or dome-shaped.
Furthermore, the lower electrode layer is a metal film made of conductive metal, is manufactured on the upper surface of the lower flexible substrate in a patterning mode through a sputtering or evaporation technology and is tightly attached to the lower flexible substrate, and the thickness of the lower electrode layer is 100 n ~ 1000 nm.
Further, the carbon-based nanoparticles in the flexible piezoresistive material layer are graphene, carbon nanotubes or graphite nanosheets, and the polymer is polyimide PI, polyurethane PU, polyvinylidene fluoride PVDF, styrene thermoplastic elastomer SBS or polydimethylsiloxane PDMS. Under the action of pressure, the contact area of the flexible piezoresistive material layer and the lower flexible substrate microstructure can generate a stress concentration phenomenon, so that the deformation of the flexible piezoresistive material layer can be increased, and the sensitivity of the pressure sensor is further improved.
Furthermore, the upper electrode layer is a metal film made of conductive metal and is manufactured on the upper surface of the flexible piezoresistive material layer in a patterning mode through a sputtering or evaporation technology, the thickness of the upper electrode layer is 100 ~ 1000 nm, the upper electrode layer is tightly attached to the flexible piezoresistive material layer, a force sensitive unit is formed at the position, corresponding to the upper electrode layer and the lower electrode layer, and is used for measuring the resistance value and the change of the resistance value between the upper surface and the lower surface of the carbon-based nanoparticle/polymer piezoresistive layer, and the size of contact pressure can be detected according to the resistance value and the change of the resistance value.
The upper flexible packaging layer is prepared on the force-sensitive structure layer through processes of pouring, spin coating, curing or evaporation and the like, is made of flexible polymer, is made of Polyimide (PI) or Parylene (Parylene) and has the thickness of 1 ~ 20 mu m, serves as a force transmission layer of the force-sensitive structure layer and is used for protecting a sensor and preventing water.
The invention also provides a preparation method of the flexible pressure sensor, which comprises the following specific steps:
(1) spin-coating a polyimide solution on a silicon wafer, and curing to obtain a polyimide film;
(2) spin-coating photoresist on the upper surface of the polyimide film, and forming a photoresist microstructure array after a photoetching process; taking the photoresist microstructure array as a mask, carrying out plasma etching processing on the upper surface of the polyimide film by using a plasma etching process, wherein the etching gas uses O2And SF6After etching, removing photoresist on the surface of the polyimide by using a photoresist removing solution, and cleaning the polyimide by using acetone to prepare a lower-layer flexible substrate of the pressure sensor;
(3) manufacturing a patterned metal electrode on the upper surface of the lower layer flexible substrate by a sputtering or evaporation technology to form a lower electrode layer of the pressure sensor;
(4) uniformly mixing one or more carbon-based nanoparticles and a polymer in an organic solvent, spin-coating a carbon-based nanoparticle/polymer solution on a lower-layer flexible substrate, and heating and curing to form a flexible piezoresistive material layer;
(5) manufacturing a patterned metal electrode on the upper surface of the flexible piezoresistive material layer by a sputtering or evaporation technology to form an upper electrode layer of the pressure sensor;
(6) and preparing an upper flexible packaging layer on the force-sensitive structure layer by using a flexible polymer through pouring, spin coating curing or evaporation coating process.
Compared with the prior art, the invention has the beneficial effects that:
1. the flexible pressure sensor based on the polyimide substrate microstructure manufacturing technology can measure the contact pressure;
2. the whole sensor pressure sensor is of a film structure, and all parts are made of flexible materials, so that the sensor pressure sensor is more convenient to arrange on the surface of a curved surface;
3. the polyimide substrate microstructure of the sensor can increase the strain of the flexible piezoresistive material layer when stressed, and has the advantage of high pressure sensitivity;
4. the sensor is prepared by a micro-nano manufacturing technology from bottom to top, and has the advantages of ultrathin property, ultralight property, high precision, strong applicability and easiness in realizing array manufacturing.
Drawings
Fig. 1 is a schematic structural diagram of a pressure sensor according to the present invention.
FIG. 2 is a scanning electron microscope characterization view of a polyimide-based bottom surface dome-shaped microstructure array according to the present invention.
Fig. 3 is a cross-sectional view of a pressure sensor of the present invention.
FIG. 4 is a schematic view of the force-sensitive structure layer of the present invention deformed under a force.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
The invention provides a flexible pressure sensor based on a polyimide substrate microstructure, wherein the whole pressure sensor is of a film structure, and the whole body is made of a flexible material. As shown in fig. 1, the pressure sensor includes a lower flexible substrate 1, a force-sensitive structure layer 2 and an upper flexible encapsulation layer 3, which are tightly attached to each other. The force-sensitive structural layer 2 comprises a lower electrode layer 201, a flexible piezoresistive material layer 202 and an upper electrode layer 203. The sensor has the advantages of simple structure and easy array manufacturing. The preparation process specifically comprises the following steps:
(1) the polyimide solution is spin-coated on a silicon wafer, and the curing temperature and the curing time are respectively 120 ℃ for 30 min, 180 ℃ for 30 min and 250 ℃ for 30 min. The thickness of the cured polyimide film can be adjusted according to the concentration of the polyimide solution and the spin-coating rotating speed;
(2) and spin-coating photoresist on the upper surface of the polyimide film, and forming a photoresist microstructure array after a photoetching process. Taking the photoresist microstructure array as a mask, carrying out plasma etching processing on the upper surface of the polyimide film by using a plasma etching process, wherein the etching gas uses O2And SF6The etching power does not exceed 100W. The height and the appearance of the photoresist microstructure can be adjusted according to the parameters of the photoetching process, and the etching depth and the appearance can be adjusted according to the etching parameters. After etching is finished, photoresist on the surface of the polyimide is removed by using a photoresist removing solution, and the photoresist is cleaned by using acetone to prepare a lower-layer flexible substrate 1 of the pressure sensor; the upper surface of the flexible polyimide substrate is provided with a microstructure array, and fig. 2 is a scanning electron microscope characterization diagram of the polyimide substrate bottom surface dome-shaped microstructure array. As shown in fig. 3, the microstructure array on the lower flexible substrate 1 is closely attached to the force-sensitive structure layer 2, and under the action of pressure, a stress concentration phenomenon is generated in a contact region between the microstructure array and the force-sensitive structure layer 2, so as to increase the deformation of the flexible piezoresistive material layer 202.
(3) Manufacturing a patterned metal electrode on the upper surface of the lower flexible substrate 1 by a sputtering or evaporation technology, and tightly attaching the patterned metal electrode to the lower flexible substrate 1 to form a lower electrode layer 201 of the pressure sensor, wherein the thickness of the electrode is 100 ~ 1000 nm;
(4) uniformly mixing graphene, carbon nanotubes or graphite nanosheets and Polyurethane (PU), styrene thermoplastic elastomer (SBS) or Polydimethylsiloxane (PDMS) in toluene, spin-coating a carbon-based nanoparticle/polymer solution on a lower layer flexible substrate 1, heating and curing to form a flexible piezoresistive material layer 202, wherein the thickness of the flexible piezoresistive material layer 202 can be adjusted according to the concentration of the mixed solution and the spin-coating rotation speed, and the resistivity of the flexible piezoresistive material layer can be adjusted according to the doping proportion of carbon-based conductive particles;
(5) patterning silver, chromium/gold metal electrodes by sputtering or evaporation technology to form an upper electrode layer 203 of the pressure sensor on the upper surface of the flexible piezoresistive material layer 202, wherein the thickness of the electrodes is 100 ~ 1000 nm;
(6) the flexible packaging layer 3 is prepared on the force-sensitive structure layer by Polyimide (PI) or Parylene (Parylene) through casting, spin coating curing or evaporation and other processes, is used as a force transmission layer of the force-sensitive structure layer and is used for protecting a sensor and preventing water, and the thickness of the flexible packaging layer 3 is 1 ~ 20 mu m.
The working principle of the invention is as follows:
as shown in fig. 4, the flexible piezoresistive material layer 202 is a carbon-based nanoparticle/polymer composite material, and the resistance between the lower electrode layer 201 and the upper electrode layer 203, i.e. the resistance of the flexible piezoresistive material layer 202, depends on the conductive network formed by the conductive carbon-based nanoparticles in the flexible piezoresistive material layer 202. In the absence of external pressure, the flexible piezoresistive material layer 202 has a resistance R0. When the flexible piezoresistive material layer 202 is subjected to external contact pressure F, the upper flexible packaging layer 3 transmits pressure to the flexible piezoresistive material layer 202, and the flexible piezoresistive material layer 202 is compressed and deformed under the action of the pressure, so that the distance between carbon-based conductive particles in the flexible piezoresistive material layer 202 is reduced and the contact area is increased due to the deformation, the contact resistance between the carbon-based conductive particles is reduced, the number of conductive paths is increased, and finally the resistance of the flexible piezoresistive material layer 202 is reduced to R1. Resistance change amount R0-R1The magnitude and the contact pressure F are positively correlated. Furthermore, according to the change of the resistance value, the external contact pressure can be reflected.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. A flexible pressure sensor based on a polyimide substrate microstructure is characterized in that: the whole body is of a thin film structure and comprises a lower flexible substrate, a force-sensitive structure layer and an upper flexible packaging layer which are tightly attached from bottom to top; the lower-layer flexible substrate is a polyimide film, and the upper surface of the polyimide film is provided with a raised microstructure array; the force-sensitive structure layer comprises a lower electrode layer, a flexible piezoresistive material layer and an upper electrode layer from bottom to top, the flexible piezoresistive material layer is made of one or more carbon-based nanoparticles doped with a polymer piezoresistive material, and the flexible piezoresistive material layer is prepared by spin-coating and solidifying a carbon-based nanoparticle/polymer mixed solution.
2. The flexible pressure sensor of claim 1, wherein the array of microstructures is fabricated by photolithography and plasma etching, the spacing between the microstructures is 10 ~ 500 μm, and the microstructures have a rectangular, trapezoidal, or dome-shaped cross-section.
3. The flexible pressure sensor of claim 1, wherein the lower electrode layer is made of a conductive metal and is patterned on the upper surface of the lower flexible substrate by a sputtering or evaporation technique, and the lower electrode layer has a thickness of 100 ~ 1000 nm.
4. The flexible pressure sensor of claim 1, wherein: the carbon-based nanoparticles in the flexible piezoresistive material layer are graphene, carbon nanotubes or graphite nanosheets; the polymer is polyimide PI, polyurethane PU, polyvinylidene fluoride PVDF, styrene thermoplastic elastomer SBS or polydimethylsiloxane PDMS.
5. The flexible pressure sensor of claim 1 wherein the upper electrode layer is a conductive metal patterned on the upper surface of the flexible piezoresistive material layer by a sputtering or evaporation technique, and has a thickness of 100 ~ 1000 nm.
6. The flexible pressure sensor of claim 1, wherein the upper flexible packaging layer is made of flexible polymer and is formed on the force-sensitive structure layer by casting, spin-on curing or evaporation, and the thickness of the upper flexible packaging layer is 1 ~ 20 μm.
7. A method for preparing a flexible pressure sensor according to claim 1 ~ 6, comprising the following steps:
(1) spin-coating a polyimide solution on a silicon wafer, and curing to obtain a polyimide film;
(2) spin-coating photoresist on the upper surface of the polyimide film, and forming a photoresist microstructure array after a photoetching process; taking the photoresist microstructure array as a mask, carrying out plasma etching processing on the upper surface of the polyimide film by using a plasma etching process, wherein the etching gas uses O2And SF6After etching, removing photoresist on the surface of the polyimide by using a photoresist removing solution, and cleaning the polyimide by using acetone to prepare a lower-layer flexible substrate of the pressure sensor;
(3) manufacturing a patterned metal electrode on the upper surface of the lower layer flexible substrate by a sputtering or evaporation technology to form a lower electrode layer of the pressure sensor;
(4) uniformly mixing one or more carbon-based nanoparticles and a polymer in an organic solvent, spin-coating a carbon-based nanoparticle/polymer solution on a lower-layer flexible substrate, and heating and curing to form a flexible piezoresistive material layer;
(5) manufacturing a patterned metal electrode on the upper surface of the flexible piezoresistive material layer by a sputtering or evaporation technology to form an upper electrode layer of the pressure sensor;
(6) and preparing an upper flexible packaging layer on the force-sensitive structure layer by using a flexible polymer through pouring, spin coating curing or evaporation coating process.
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