WO2018113520A1 - Flexible pressure sensor and fabricating method thereof - Google Patents

Flexible pressure sensor and fabricating method thereof Download PDF

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Publication number
WO2018113520A1
WO2018113520A1 PCT/CN2017/114820 CN2017114820W WO2018113520A1 WO 2018113520 A1 WO2018113520 A1 WO 2018113520A1 CN 2017114820 W CN2017114820 W CN 2017114820W WO 2018113520 A1 WO2018113520 A1 WO 2018113520A1
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Prior art keywords
sensitive layer
flexible substrate
pressure sensor
flexible
electrode
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PCT/CN2017/114820
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French (fr)
Chinese (zh)
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张莹莹
蹇木强
夏凯伦
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清华大学
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Publication of WO2018113520A1 publication Critical patent/WO2018113520A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/01—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate comprising only passive thin-film or thick-film elements formed on a common insulating substrate
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00—Measuring force or stress, in general
    • G01L1/04—Measuring force or stress, in general by measuring elastic deformation of gauges, e.g. of springs
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/50—Piezoelectric or electrostrictive devices having a stacked or multilayer structure

Definitions

  • the invention relates to the field of pressure detection technology, and more particularly to a flexible pressure sensor and a preparation method thereof.
  • the pressure sensor is an electronic device that converts the pressure felt by the outside into a signal such as electricity, and is widely applied to wearable electronic devices.
  • pressure sensors need to meet high performance indicators such as high flexibility, high sensitivity, high stability, and low detection limit.
  • high performance indicators such as high flexibility, high sensitivity, high stability, and low detection limit.
  • conventional large-volume mechatronics are difficult to meet the requirements. Therefore, the development of high-performance flexible pressure sensors has become one of the important frontier topics in the field of flexible electronics.
  • the sensitive layer in the pressure sensor is generally made of metal film, metal nanowire, nano carbon material and conductive polymer material.
  • Nano carbon material is widely used due to its excellent flexibility, chemical stability and high conductivity.
  • researchers at Monash University in Australia deposited nano-thick gold foil on a microstructured substrate for use as a pressure sensor, but not for human-related physiological signals (Small 2015, 11, 1886-1891).
  • Zhang Wei a researcher at the Suzhou Institute of Nanotechnology and Nano-Bionics, Chinese Academy of Sciences, used carbon nanotube film as a sensitive layer of the sensor to obtain a flexible pressure sensor with a sensitivity of 1.8 kPa -1 ( ⁇ 0.3 kPa) and high stability (Adv.Mater). .2014,26,1336-1342).
  • the sensitivity of the sensor needs to be improved, and the bonding of the sensitive layer to the substrate requires annealing.
  • the present invention provides a flexible pressure sensor that overcomes the above problems or at least partially solves the above problems.
  • the flexible pressure sensor includes an upper flexible substrate and a lower flexible substrate disposed in parallel, a top sensitive layer adhered to the lower surface of the upper flexible substrate, and a lower sensitive layer conformally attached to the upper surface of the lower flexible substrate;
  • An upper electrode is disposed on the upper sensitive layer, a lower electrode is disposed on the lower sensitive layer, and the upper electrode and the lower electrode do not intersect each other, and the upper sensitive layer and the lower sensitive layer are formed a contact area;
  • the lower surface of the upper flexible substrate and the upper surface of the lower flexible substrate each comprise a plurality of multi-level protrusions.
  • the flexible surface containing the above-mentioned convex microstructure is in the specific flexible pressure sensor of the present invention, which greatly improves the surface roughness and makes the flexible pressure sensor have high sensitivity.
  • conformal means that when the sensitive layer is attached to the surface of the flexible substrate of the convex microstructure, the shape of the convex microstructure is not masked to maintain the original convex state.
  • Multiple in the present invention means two or more.
  • Multi-stage in the present invention means that the protrusions on the lower surface of the upper flexible substrate and the upper surface of the lower flexible substrate have a plurality of size levels.
  • the surface contains a plurality of protrusions having a height of a micron order, and the surface of the micron-sized protrusions further includes a plurality of protrusions having a height of a nanometer order.
  • the multistage projections have an average length of 50 to 100 ⁇ m, an average height of 1-10 ⁇ m, more preferably an average length of 50 to 70 ⁇ m, and an average height of 2 to 5 ⁇ m.
  • the flexible pressure sensor prepared by the flexible surface containing the multi-stage protrusion has high sensitivity at low pressure.
  • the projections are prepared by using a plant blade having a surface area of 1 to 30 cm 2 or a sandpaper having a grit size of 0.5 to 20 ⁇ m.
  • the protrusions are prepared by using a plant blade having a surface area of 2 to 10 cm 2 or a sandpaper having a grit size of 1 to 5 ⁇ m.
  • the plant leaves are more preferably green leaves.
  • the upper and lower flexible substrates in the present invention may be made of a flexible material commonly used in the art, such as one or more of polydimethylsiloxane, polyethylene terephthalate or polyimide.
  • the upper and lower flexible substrate materials may be different or the same.
  • the upper and lower flexible substrates of the present invention are preferably made of polydimethylsiloxane.
  • the upper flexible substrate and the lower flexible substrate have the same thickness of 30 to 3000 ⁇ m, preferably 100 to 500 ⁇ m, more preferably 200 to 300 ⁇ m, and most preferably 250 ⁇ m.
  • the convex microstructure of the upper and lower flexible substrate surface of the present invention can be obtained by using an impression, and the specific steps are as follows:
  • the precursor solution of the flexible substrate is dropped on the surface of the device which produces the convex microstructure, and is dropped on the surface of the plant leaf or the sandpaper having a sand particle size of 0.5 to 20 ⁇ m, and the stamp is solidified.
  • the roughness of the surface of the flexible substrate is increased.
  • the temperature is usually 20 to 150 ° C, and the time is 10 min to 24 h, preferably, the temperature. It is 70-80 ° C and the time is 2 h ⁇ 3 h.
  • the upper and lower sensitive layers in the present invention may be a graphene film or a carbon nanotube/graphene composite film.
  • the upper and lower sensitive layers of the present invention may be a film formed of the same substance or a film formed of different substances.
  • the upper and lower sensitive layers are the same substance, preferably both graphene film or carbon nanotube/graphene composite film.
  • the sensitive layer of the present invention is a graphene film or a carbon nanotube/graphene composite film
  • the graphene may be a single layer or a plurality of layers.
  • the obtained flexible pressure sensor can also have higher sensitivity at lower pressure. More preferably, the carbon nanotube arrays in the upper sensitive layer and the carbon nanotube array in the lower sensitive layer are parallel or perpendicular to each other. Most preferably, the array of carbon nanotubes in the array of carbon nanotubes and the lower layer of the upper sensitive layer are perpendicular to each other. At this point, the resulting flexible pressure sensor has a sensitivity of at least 19.8 kPa -1 in a pressure range of less than 0.3 kPa.
  • the obtained flexible pressure sensor can have higher sensitivity at a lower pressure, and the obtained flexible pressure sensor has a pressure range of less than 0.3 kPa, and the sensor has at least 40 kPa -1 . Sensitivity.
  • the thickness of the upper sensitive layer and the lower sensitive layer in the present invention may be the same or different, and preferably the thickness of both is the same, both being 0.34 to 100 nm, preferably, when the sensitive layer is a carbon nanotube/graphene composite In the case of a film, the thickness is preferably from 30 to 50 nm; when the sensitive layer is a graphene film, the thickness is preferably from 0.34 to 10 nm. In the present invention, a sensitive layer having a width of 0.1 to 10 cm can also be used.
  • the upper and lower sensitive layers of the present invention are each completely conformally attached to the upper and lower flexible substrate surfaces, the width of which corresponds to the width of the flexible substrate.
  • the upper and lower sensitive layers of the present invention can be prepared by methods conventional in the art.
  • the sensitive layer is a carbon nanotube/graphene film
  • it can be obtained by chemical vapor deposition.
  • the steps of the chemical vapor deposition method of the present invention are as follows:
  • the carbon nanotube film extracted from the carbon nanotube array is spun on the surface of the copper foil or the nickel foil, and graphene is grown on the surface thereof.
  • the carbon source has an inlet rate of 1 to 50 mL/min, and the graphene growth time is 5 to 120 min.
  • the growth temperature is 900 to 1060 °C.
  • the intake rate is 15 to 30 mL/min
  • the graphene growth time is 30 to 60 min
  • the growth temperature is 1000 to 1050 °C.
  • Methane is preferably used as the carbon source.
  • the sensitive layer is a carbon nanotube film
  • it can be directly extracted from the vertical array of carbon nanotubes.
  • the sensitive layer is a graphene film
  • it can be obtained by chemical vapor deposition. Specific steps are as follows:
  • the graphene is grown on the surface of the copper foil or the nickel foil, the carbon source has an inlet rate of 1 to 50 mL/min, the graphene growth time is 5 to 120 min, and the growth temperature is 900 to 1060 °C.
  • the inlet rate is 5-15 mL/min
  • the growth time of graphene is 60-90 min
  • the growth temperature is 1000 ⁇ 1050 ° C.
  • the upper and lower electrodes of the present invention may be respectively disposed at the middle or the side of the upper and lower sensitive layers under the premise of not intersecting.
  • the upper electrode of the present invention is disposed at a side of the upper sensitive layer
  • the lower electrode is disposed at a side of the lower sensitive layer, wherein the upper and lower electrodes do not intersect, and more preferably, the upper electrode is disposed at an edge of the upper sensitive layer
  • the lower electrode is disposed at an edge of the lower sensitive layer away from the side of the upper electrode.
  • the upper and lower electrodes are preferably one.
  • the upper flexible substrate and the lower flexible substrate are generally disposed face to face such that the upper sensitive layer and the lower sensitive layer are contacted by the convex microstructure to achieve conduction.
  • the upper and lower electrodes of the present invention may be made of the same material of the same thickness or may be made of different materials of different thicknesses, and the electrode layer of the same thickness is preferably used in the present invention.
  • the upper and lower electrodes can be made of a conductive nonwoven fabric having a thickness of 0.25 to 3 mm, a carbonized textile of 0.25 to 3 mm, a copper foil having a thickness of 1 to 500 ⁇ m, or a copper wire having a diameter of 10 to 1000 ⁇ m.
  • a copper foil having a thickness of 25 to 50 ⁇ m and a width of 1 to 2 mm or a copper wire having a diameter of 50 to 150 ⁇ m is preferably used.
  • the copper wire is more preferably 100 ⁇ m.
  • the electrodes can be placed on the edges of the sensitive layer using methods commonly found in the art, typically bonded to the edges of the sensitive layer using a conductive silver paste.
  • the flexible pressure sensor of the present invention preferably:
  • the flexible substrate on the polydimethylsiloxane and the flexible substrate under the polydimethylsiloxane are disposed in a relatively parallel arrangement, and the sensitive layer on the carbon nanotube/graphene composite film conformally adhered to the lower surface of the upper flexible substrate And a carbon nanotube/graphene composite film lower sensitive layer adhered to the upper surface of the lower flexible substrate; an upper electrode and a lower electrode respectively disposed on the upper sensitive layer and the lower sensitive layer, the upper electrode And the lower electrode do not cross each other, a contactable region is formed between the upper sensitive layer and the lower sensitive layer; the lower surface of the upper flexible surface and the upper surface of the lower flexible substrate each have a plurality of levels a protrusion; the upper flexible substrate and the lower flexible substrate each having a thickness of 200 to 300 ⁇ m; wherein the carbon nanotubes in the upper sensitive layer and the array of carbon nanotubes in the lower sensitive layer are parallel or perpendicular to each other; The upper sensitive layer and the lower sensitive layer each have a thickness of 30 to 50
  • the flexible pressure sensor of the present invention is preferably:
  • the invention comprises a flexible substrate on a polydimethylsiloxane and a flexible substrate under a polydimethylsiloxane disposed in parallel, and a sensitive layer adhered to the graphene film attached to the lower surface of the upper flexible substrate and conformally attached thereto a lower graphene film under the upper flexible substrate; an upper electrode and a lower electrode respectively disposed on the upper sensitive layer and the lower sensitive layer, wherein the upper electrode and the lower electrode do not cross each other Forming a contactable region between the sensitive layer and the lower sensitive layer; the lower surface of the upper flexible surface and the upper surface of the lower flexible substrate each comprise a plurality of multi-level protrusions; the upper flexible substrate and the The thickness of the flexible substrate is 200-300 ⁇ m; the thickness of the upper sensitive layer and the lower sensitive layer are both 0.34-10 nm.
  • the flexible pressure sensor has a sensitivity of at least 40 kPa -1 in a pressure range of less than 0.3 kPa.
  • the flexible pressure sensor of the present invention maintains good stability after 30,000 cycles under a pressure of 100 Pa or more. More preferably, the sensor maintains good stability after 35,000 cycles at a constant pressure of 150 Pa.
  • the flexible pressure sensor of the present invention may further comprise an encapsulating layer, which may be made of materials commonly used in the art.
  • the encapsulating layer is one or more of polydimethylsiloxane, polypropylene, polyethylene, epoxy resin. Made.
  • the encapsulating layer is preferably made of polydimethylsiloxane.
  • a method of preparing a flexible pressure sensor comprising:
  • the precursor solutions of the upper flexible substrate and the lower flexible substrate are dropped on the surface of the device containing the protrusions, and the stamps are solidified to obtain an upper flexible substrate containing the protrusions, respectively.
  • a lower flexible substrate comprising the protrusion; wherein the temperature during the stamping process is 20 to 150 ° C, and the time is 10 min to 24 h;
  • step 2) transferring the upper sensitive layer and the lower sensitive layer to the lower surface of the upper flexible substrate containing the protrusions in step 1) and the upper surface of the lower flexible substrate containing the protrusions,
  • the upper electrode and the lower electrode are respectively disposed on the sensitive layer and the lower sensitive layer;
  • step 2) The upper flexible substrate and the lower flexible substrate in step 2) are disposed in parallel so that the upper sensitive layer and the lower sensitive layer form a contactable region.
  • the device is a plant blade or a sandpaper having a sand particle size of 0.5-20 ⁇ m, that is, the precursor solution of the upper flexible substrate and the lower flexible substrate is respectively added to the plant blade or the sand particle size is 0.5-20 ⁇ m.
  • the stamp is cured to obtain an upper flexible substrate containing the protrusions and a lower flexible substrate containing the protrusions, respectively.
  • the upper sensitive layer and the lower sensitive layer are contacted by the protrusions, and when a certain pressure is applied, the contact area of the upper sensitive layer and the lower sensitive layer is increased, so that the current is increased, and the pressure is detected.
  • an encapsulating material is further included, and the specific step is to package the above device using the encapsulating material.
  • the upper flexible substrate and the lower flexible substrate are preferably the same, the microstructure is preferably the same, the upper sensitive layer and the lower sensitive layer are preferably the same, and the upper electrode is the same as the lower electrode, that is, in the preparation process, the micro-preparation can be prepared first.
  • the upper flexible substrate of the structure and the upper sensitive layer containing the upper electrode are combined to form a sensing unit, and the lower flexible substrate containing the microstructure and the lower sensitive layer containing the lower electrode are prepared by the same method as described above. They are combined into another sensing unit, and then the two sensing units are placed as needed, such that the upper flexible substrate and the lower flexible substrate are disposed in parallel with each other such that contact is formed between the upper sensitive layer and the lower sensitive layer. region.
  • a flexible pressure sensor is also provided for use in preparing a monitor for detecting minute mechanical forces, acoustic vibrations, and/or pulses.
  • the flexible pressure sensor of the present invention has a high sensitivity and a low detection limit.
  • the sensor has a sensitivity of at least 12.7 kPa -1 , preferably a sensitivity of 19.8 kPa -1 , more preferably 40.7, when the pressure is less than 0.3 kPa. Sensitivity of kPa -1 .
  • the flexible pressure sensor of the present invention can detect a pressure of not more than 0.6 Pa.
  • the flexible pressure sensor of the invention can be used for detecting small mechanical forces such as bending force and torsion force because of its good sensitivity and stability, and can be used for detecting small pressure caused by sound vibration, and can also be attached to the pulse of the human body. It is used to detect the pressure of the human body pulse on the blood vessel wall and realize the detection of the human body pulse.
  • the flexible pressure sensor proposed by the present application comprises a flexible substrate containing a specific multi-stage convex microstructure by an impression, which greatly increases the surface roughness and greatly improves the sensitivity of the sensor; the invention uses high conductivity and high Specific surface area of graphene film or carbon nanotube/graphite As a sensitive layer, the ene film can achieve conformal contact with a flexible substrate with a convex microstructure, improve the sensitivity and stability of the pressure sensor, and realize the detection of small pressure, which can be used for micro mechanical force and sound vibration. Pulse monitoring.
  • FIG. 1 is a schematic structural view of a flexible pressure sensor in accordance with a preferred embodiment of the present invention
  • Example 2 is a scanning electron micrograph of a flexible substrate having a convex microstructure in Example 1 according to the present invention
  • FIG. 3 is an optical micrograph (a), a scanning electron micrograph (b), and an atomic force microscope photograph (c, d) of a multi-stage convex structure in a flexible substrate having a convex microstructure according to Embodiment 1 of the present invention;
  • FIG. 4 is a scanning electron micrograph, a transmission electron micrograph, and a Raman characterization diagram of a carbon nanotube/graphene film of a sensitive layer material of a flexible pressure sensor according to Embodiment 1 of the present invention
  • FIG. 5 is a graph showing transmittance and conductivity of a carbon nanotube/graphene film of a sensitive layer material in a flexible pressure sensor according to Embodiment 1 of the present invention
  • FIG. 6 is a scanning electron micrograph of a carbon nanotube/graphene film of a sensitive layer material and a flexible substrate containing the microstructure in a flexible pressure sensor according to Embodiment 1 of the present invention
  • Figure 7 is a graph showing the relationship between sensitivity and pressure of a flexible pressure sensor according to Embodiment 1 of the present invention.
  • Embodiment 8 is a low detection limit test chart of a flexible pressure sensor according to Embodiment 1 of the present invention.
  • Embodiment 9 is a long-term stability test chart of a flexible pressure sensor according to Embodiment 1 of the present invention.
  • Figure 10 is a test diagram of a flexible pressure sensor for micro mechanical force detection according to Embodiment 2 of the present invention.
  • Figure 11 is a monitoring diagram of a flexible pressure sensor for sound vibration and pulse according to Embodiment 2 of the present invention.
  • Figure 12 is a graph showing the relationship between sensitivity and pressure of a flexible pressure sensor according to Embodiment 3 of the present invention.
  • Figure 13 is a graph showing the relationship between sensitivity and pressure of a flexible pressure sensor according to Embodiment 4 of the present invention.
  • Figure 14 is a scanning electron micrograph of a sensitive layer of graphene in a flexible substrate containing a microstructure according to Embodiment 5 of the present invention.
  • Figure 15 is a graph showing the sensitivity versus pressure of a flexible pressure sensor in accordance with Example 5 of the present invention.
  • the present embodiment provides a flexible pressure sensor comprising an upper flexible substrate and a lower flexible substrate disposed in parallel, a top sensitive layer conformally attached to the lower surface of the upper flexible substrate, and a conformal adhesion to the upper surface of the lower flexible substrate a lower sensitive layer; an upper electrode is disposed on the upper sensitive layer, a lower electrode is disposed on the lower sensitive layer, and the upper electrode and the lower electrode are respectively disposed at a side of the upper sensitive layer and the lower portion The edge of the sensitive layer, the upper electrode and the lower electrode do not cross each other; a contactable region is formed between the upper sensitive layer and the lower sensitive layer.
  • the encapsulation layer 4 is contained outside the upper flexible substrate and the lower flexible substrate, as shown in FIG.
  • the upper flexible substrate and the lower flexible substrate are the same, both are polydimethylsiloxane films containing the convex microstructure of the fresh green radish leaves, as shown in the flexible substrate layer 1 in FIG. 1, the upper sensitive layer and the lower sensitive layer are the same, both For the carbon nanotube/graphene film, see the sensitive layer 2 in FIG. 1, wherein the direction of the carbon nanotubes in the upper sensitive layer and the lower sensitive layer is kept perpendicular, and the upper electrode is the same as the lower electrode, and both have a thickness of 25 ⁇ m and a width of 1 mm.
  • Made of copper foil see electrode 3 in Figure 1.
  • the embodiment also provides a preparation method of the above flexible pressure sensor, and the specific steps are as follows:
  • Step 1 the precursor of the polydimethylsiloxane and the curing agent are uniformly mixed in a ratio of 10:1, and sprayed on the surface of the fresh green leaves of the washed and dried;
  • Step 2 After the surface of the blade is substantially flat, the polydimethylsiloxane is cured in an oven at 70 ° C for 3 hours, and the curing is completed, and the polydimethylsiloxane film is removed to obtain a microstructured substrate.
  • the thickness of the flexible substrate is 250 ⁇ m;
  • Step 3 The carbon nanotube film is directly extracted from the vertical carbon nanotube array, and has a width of 2 cm.
  • the surface of the carbon nanotube film is placed on the surface of the copper foil, and ethanol is added dropwise. When the ethanol is volatilized, the carbon nanotube film is firmly bonded to the surface of the copper foil;
  • Step 4 Place the carbon nanotube film/copper foil in a quartz tube and grow graphene at 1050 ° C.
  • the carbon source is methane, the inlet rate is 15 mL/min, and the growth time is 30 min;
  • Step 5 etching the copper foil substrate in a liquid phase to obtain a carbon nanotube/graphene film having a thickness of 30 nm;
  • Step 6 Transfer the carbon nanotube/graphene film to the flexible substrate
  • Step 7 Prepare an electrode at the edge of the sensitive layer.
  • the electrode 3 is a copper foil having a thickness of 25 ⁇ m and a width of 1 mm.
  • the electrode is bonded to the edge of the sensitive layer 2 by a conductive silver paste.
  • Step 8 Place two flexible substrates covered with the sensitive layer and the electrodes face to face, the two electrodes do not contact, and the direction of the carbon nanotubes in the two sensitive layers remains vertical;
  • Step 9 The encapsulating material polydimethylsiloxane encapsulates the device.
  • a scanning electron micrograph of a polydimethylsiloxane flexible substrate containing raised microstructures of green leaves is shown in Figure 2.
  • the surface of the flexible substrate has a plurality of protrusions, and has micron-level and nano-scale protrusions, wherein the nano-scale protrusions have micro-scale convex surfaces, and the multi-level protrusions have an average length of 50-70 ⁇ m, and the average height is 2-5 ⁇ m, see Figure 3.
  • the sensitive layer in the present embodiment is obtained by combining carbon nanotubes and graphene. As shown in FIG. 4, the carbon nanotubes are fused with graphene, and the graphene is mainly a small layer structure. As shown in FIG. 5 and FIG.
  • the composite film has high conductivity, flexibility and transparency, and the high specific area makes it conformal contact with the flexible substrate, so that the sensor has high sensitivity and high stability.
  • the pressure sensor in this embodiment has high sensitivity characteristics. As shown in FIG. 7, the sensor has a sensitivity of 19.8 kPa -1 in a pressure range of less than 0.3 kPa; the pressure sensor in this embodiment has a low detection limit, such as As shown in FIG. 8, the sensor can detect a pressure of 0.6 Pa; the pressure sensor in this embodiment has high stability characteristics, as shown in FIG. 9, the sensor remains good after 35,000 cycles under a constant pressure of 150 Pa. stability.
  • This embodiment provides a flexible pressure sensor.
  • the structure of the flexible pressure sensor is the same as in the first embodiment.
  • the embodiment also provides a preparation method of the above flexible pressure sensor, and the specific steps are as follows:
  • Step 1 the precursor of the polydimethylsiloxane and the curing agent are uniformly mixed in a ratio of 10:1, and sprayed on the surface of the fresh green leaves of the washed and dried;
  • Step 2 After the surface of the blade is substantially flat, the polydimethylsiloxane is cured in an oven at 80 ° C for 3 hours, and the curing is completed, and the polydimethylsiloxane film is removed to obtain a microstructured substrate;
  • Step 3 The carbon nanotube film is directly extracted from the vertical carbon nanotube array, and the width is 2 cm. Placed on the surface of the copper foil, add ethanol, and the ethanol is evaporated to make the carbon nanotube film and the surface of the copper foil firmly bonded;
  • Step 4 the carbon nanotube film / copper foil is placed in a quartz tube, graphene is grown at 1050 ° C, the carbon source is methane, the inlet rate is 15 mL / min, and the growth time is 30 min;
  • Step 5 etching the copper foil substrate in a liquid phase to obtain a carbon nanotube/graphene film having a thickness of 30 nm;
  • Step 6 Transfer the carbon nanotube/graphene film to the flexible substrate
  • Step 7 Prepare an electrode at the edge of the sensitive layer.
  • the electrode 3 is a copper foil having a thickness of 25 ⁇ m and a width of 1 mm.
  • the electrode is bonded to the edge of the sensitive layer 2 by a conductive silver paste.
  • Step 8 Place two flexible substrates covered with the sensitive layer and the electrodes face to face, the two electrodes do not contact, and the direction of the carbon nanotubes in the two sensitive layers remains vertical;
  • Step 9 The encapsulating material polydimethylsiloxane encapsulates the device.
  • the pressure sensor in this embodiment has the characteristics of high sensitivity, high stability, and low detection limit. As shown in FIG. 10, the pressure sensor can be used to detect small mechanical forces such as bending force and torsion force; as shown in FIG. The pressure sensor can detect the slight pressure caused by the sound vibration, and the pressure sensor is attached to the skin of the human body pulse to detect the pressure of the human body pulse on the blood vessel wall, and realize the monitoring of the human body pulse.
  • This embodiment provides a flexible pressure sensor.
  • This embodiment provides a flexible pressure sensor.
  • the structure of the flexible pressure sensor is the same as in the first embodiment.
  • the embodiment also provides a preparation method of the above flexible pressure sensor, and the specific steps are as follows:
  • Step 1 the precursor of the polydimethylsiloxane and the curing agent are uniformly mixed in a ratio of 10:1, and sprayed on the surface of the fresh green leaves of the washed and dried;
  • Step 2 After the surface of the blade is substantially flat, the polydimethylsiloxane is cured in an oven at 70 ° C for 3 hours, and the curing is completed, and the polydimethylsiloxane film is removed to obtain a microstructured substrate.
  • the thickness of the flexible substrate is 250 ⁇ m;
  • Step 3 The carbon nanotube film is directly extracted from the vertical carbon nanotube array, placed on the surface of the copper foil, and ethanol is added dropwise, and the carbon nanotube film is firmly bonded to the surface of the copper foil after the alcohol is volatilized;
  • Step 4 the carbon nanotube film / copper foil is placed in a quartz tube, graphene is grown at 1050 ° C, the carbon source is methane, the inlet rate is 15 mL / min, and the growth time is 30 min;
  • Step 5 etching the copper foil substrate in a liquid phase to obtain a carbon nanotube/graphene film having a thickness of 30 nm;
  • Step 6 Transfer the carbon nanotube/graphene film to the flexible substrate
  • Step 7 Prepare an electrode at the edge of the sensitive layer.
  • the electrode 3 is a copper foil having a thickness of 25 ⁇ m and a width of 1 mm.
  • the electrode is bonded to the edge of the sensitive layer 2 by a conductive silver paste.
  • Step 8 Place two flexible substrates covered with the sensitive layer and the electrodes face to face, the two electrodes do not contact, and the directions of the carbon nanotubes in the two sensitive layers are kept parallel;
  • Step 9 The encapsulating material polydimethylsiloxane encapsulates the device.
  • the pressure sensor in this embodiment has high sensitivity and high stability characteristics. As shown in FIG. 12, the sensor has a sensitivity of 12.7 kPa -1 in a lower pressure range ( ⁇ 0.3 kPa).
  • This embodiment provides a flexible pressure sensor.
  • the structure of the flexible pressure sensor is the same as in the first embodiment.
  • the embodiment also provides a preparation method of the above flexible pressure sensor, and the specific steps are as follows:
  • Step 1 the precursor of the polydimethylsiloxane and the curing agent are uniformly mixed in a ratio of 10:1, and sprayed on the surface of the fresh green leaves of the washed and dried;
  • Step 2 After the surface of the blade is substantially flat, the surface of the polydimethylsiloxane is cured in an environment of 20 ° C for 24 hours, the curing is completed, and the polydimethylsiloxane film is removed to obtain a microstructured substrate having a thickness of 100 ⁇ m;
  • Step 3 The carbon nanotube film is directly extracted from the vertical carbon nanotube array and directly transferred to the flexible substrate;
  • Step 4 preparing an electrode at the edge of the sensitive layer, the electrode is a copper wire, the diameter is 100 ⁇ m, and is bonded to the edge of the sensitive layer by a conductive silver glue;
  • Step 5 placing two flexible substrates covered with the sensitive layer and the electrodes face to face, the two electrodes are not in contact, and the direction of the carbon nanotubes in the two sensitive layers is kept vertical;
  • Step 6 The encapsulating material polydimethylsiloxane encapsulates the device.
  • the sensitive layer of the invention is obtained by the carbon nanotube film, has high conductivity, high flexibility, and high specific area makes it conformal contact with the flexible substrate, so that the sensor has high sensitivity and high stability.
  • the flexible pressure sensor of this embodiment has a characteristic of higher sensitivity.
  • the flexible pressure sensor of the present embodiment has a sensitivity of 0.85 kPa -1 in a pressure range of less than 0.3 kPa.
  • This embodiment provides a flexible pressure sensor.
  • the structure of the flexible pressure sensor is the same as in the first embodiment.
  • the embodiment also provides a preparation method of the above flexible pressure sensor, and the specific steps are as follows:
  • Step 1 the precursor of the polydimethylsiloxane and the curing agent are uniformly mixed in a ratio of 10:1, and sprayed on the surface of the fresh green leaves of the washed and dried;
  • Step 2 After the surface of the blade is substantially flat, the polydimethylsiloxane is cured in an oven at 70 ° C for 3 hours, and the curing is completed, and the polydimethylsiloxane film is removed to obtain a microstructured substrate.
  • the thickness of the flexible substrate is 200 ⁇ m;
  • Step 3 placing the copper foil in a quartz tube, growing graphene at 1050 ° C, the carbon source is methane, the inlet rate is 5 mL / min, and the growth time is 60 min;
  • Step 4 spin coating polymethacrylate, liquid phase etching copper foil substrate, transferred to a flexible substrate;
  • Step 5 removing the polymethacrylate by acetone to obtain a graphene film
  • Step 6 Prepare an electrode at the edge of the sensitive layer.
  • the electrode is a copper foil with a thickness of 25 ⁇ m and a width of 1 mm.
  • the electrode is bonded to the edge of the sensitive layer by a conductive silver paste.
  • Step 7 Place two flexible substrates covered with sensitive layers and electrodes face to face, and the two electrodes are not in contact;
  • Step 8 The packaging material polydimethylsiloxane encapsulates the device.
  • the sensitive layer in this embodiment is obtained by graphene.
  • the graphene film can be in conformal contact with the microstructure substrate, and the generated wrinkles can effectively increase the sensitivity of the sensor, and the sensor has high sensitivity and high stability. .
  • the pressure sensor in this embodiment has characteristics of high sensitivity and high stability.
  • the flexible pressure sensor of the present embodiment has a sensitivity of 40.7 kPa -1 in a pressure range of less than 0.3 kPa.

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Abstract

A flexible pressure sensor and a fabricating method thereof. The flexible pressure sensor comprises: an upper flexible substrate (1) and a lower flexible substrate (1) arranged in parallel thereto; an upper sensitive layer (2) attached to a lower surface of the upper flexible substrate and maintaining a shape thereof, and a lower sensitive layer (2) attached to an upper surface of the lower flexible substrate and maintaining a shape thereof; and an upper electrode (3) arranged at the upper sensitive layer, and a lower electrode (3) arranged at the lower sensitive layer. The upper electrode and the lower electrode do not overlap with each other. A contactable area is formed between the upper sensitive layer and the lower sensitive layer. Both the lower surface of the upper flexible substrate and the upper surface of the lower flexible substrate comprise a plurality of multistage protrusions, and an average length of the multi-stage protrusions is 50-100 μm, and an average height thereof is 1-10 μm. The flexible pressure sensor contains the flexible substrate having the specific protruding microstructures obtained by using a die, increasing surface roughness, and significantly increasing sensitivity of the sensor.

Description

一种柔性压力传感器及其制备方法Flexible pressure sensor and preparation method thereof
交叉引用cross reference
本申请引用于2016年12月21日提交的专利名称为“一种柔性压力传感器及其制备方法”的第2016111942299号中国专利申请，其通过引用被全部并入本申请。The present application is hereby incorporated by reference in its entirety in its entirety in its entirety in its entirety in the the the the the the the the the the
技术领域Technical field
本发明涉及压力检测技术领域，更具体地，涉及一种柔性压力传感器及其制备方法。The invention relates to the field of pressure detection technology, and more particularly to a flexible pressure sensor and a preparation method thereof.
背景技术Background technique
近年来，随着智能可穿戴电子的发展，柔性电子器件在医疗(人体生理信号检测和运动检测等)、能源、信息、军事等领域表现出巨大的应用前景。其中，压力传感器是将外界感受到的压力转变为电学等信号的一种电子器件，广泛应用到可穿戴电子设备中。为了实现人体生理信号等实时监测，压力传感器需要满足高柔性、高灵敏度、高稳定性、低检测限等高性能指标。然而，传统的大体积机械电子难以满足要求。因此，开发高性能柔性压力传感器成为柔性电子领域的重要前沿课题之一。In recent years, with the development of smart wearable electronics, flexible electronic devices have shown great application prospects in medical (human physiological signal detection and motion detection, etc.), energy, information, military and other fields. Among them, the pressure sensor is an electronic device that converts the pressure felt by the outside into a signal such as electricity, and is widely applied to wearable electronic devices. In order to realize real-time monitoring of human physiological signals, pressure sensors need to meet high performance indicators such as high flexibility, high sensitivity, high stability, and low detection limit. However, conventional large-volume mechatronics are difficult to meet the requirements. Therefore, the development of high-performance flexible pressure sensors has become one of the important frontier topics in the field of flexible electronics.
为获得高灵敏性的压力传感器件，研究者通常利用光刻等技术得到有微结构的硅模板，通过柔性聚合物的印模得到具有微结构的基底，在基底上覆盖导电活性物质，得到柔性压力传感器。韩国研究者通过聚二甲基硅氧烷印模硅模板得到金字塔状微结构，覆盖导电聚合物组装成压力传感器，灵敏度为4.88kPa-1(0.27～5.9kPa)，最低检测限为23Pa(Adv.Mater.2014,26,3451-3458)。微结构赋予传感器比较高的灵敏度，但模板制备过程复杂，价格较高且耗时长。另外，最低检测的压力还有待进一步优化。In order to obtain highly sensitive pressure sensor devices, researchers usually use a technique such as photolithography to obtain a microstructured silicon template. A flexible polymer is used to obtain a microstructured substrate, and the substrate is coated with a conductive active material to obtain flexibility. Pressure Sensor. Korean researchers obtained a pyramid-like microstructure through a polydimethylsiloxane stamped silicon template, and covered with a conductive polymer assembled into a pressure sensor with a sensitivity of 4.88 kPa -1 (0.27-5.9 kPa) and a minimum detection limit of 23 Pa (Adv). .Mater. 2014, 26, 3451-3458). The microstructure gives the sensor a relatively high sensitivity, but the template preparation process is complicated, expensive and time consuming. In addition, the minimum detection pressure has yet to be further optimized.
压力传感器中的敏感层一般以金属薄膜、金属纳米线、纳米碳材料、导电聚合物材料为主，纳米碳材料因其良好的柔性、化学稳定性、高导电性等优异性能得到广泛应用。澳大利亚莫纳什大学的研究者在具有微结构的基底上沉积纳米厚度的金箔用作压力传感器，但未用于人体相关生理信 号的检测(Small 2015,11,1886-1891)。中国科学院苏州纳米技术与纳米仿生研究所的张珽课题组利用碳纳米管薄膜作为传感器的敏感层，得到灵敏度为1.8kPa-1(<0.3kPa)、高稳定性的柔性压力传感器(Adv.Mater.2014,26,1336-1342)。该传感器的灵敏度有待提高，且敏感层与基底的结合需要退火处理。The sensitive layer in the pressure sensor is generally made of metal film, metal nanowire, nano carbon material and conductive polymer material. Nano carbon material is widely used due to its excellent flexibility, chemical stability and high conductivity. Researchers at Monash University in Australia deposited nano-thick gold foil on a microstructured substrate for use as a pressure sensor, but not for human-related physiological signals (Small 2015, 11, 1886-1891). Zhang Wei, a researcher at the Suzhou Institute of Nanotechnology and Nano-Bionics, Chinese Academy of Sciences, used carbon nanotube film as a sensitive layer of the sensor to obtain a flexible pressure sensor with a sensitivity of 1.8 kPa -1 (<0.3 kPa) and high stability (Adv.Mater). .2014,26,1336-1342). The sensitivity of the sensor needs to be improved, and the bonding of the sensitive layer to the substrate requires annealing.
因此，如何通过工艺简单、价格低廉、可大面积制备的方法得到具有微结构的基底，利用高导电、高比表面的活性材料实现与基底的良好接触，制备高柔性、高灵敏度、低检测限、高稳定性的压力传感器且用于人体生理信号检测是目前研究的重要课题。Therefore, how to obtain a microstructured substrate by a simple process, low cost, and large-area preparation method, and use a highly conductive, high specific surface active material to achieve good contact with the substrate to prepare a high flexibility, high sensitivity, and low detection limit. The high stability pressure sensor and its application for human physiological signal detection are important topics in current research.
发明内容Summary of the invention
本发明提供一种克服上述问题或者至少部分地解决上述问题的柔性压力传感器。The present invention provides a flexible pressure sensor that overcomes the above problems or at least partially solves the above problems.
所述柔性压力传感器包括相对平行设置的上柔性基底和下柔性基底，保形附着于所述上柔性基底下表面的上敏感层和保形附着于所述下柔性基底上表面的下敏感层；所述上敏感层上设有上电极，所述下敏感层上设有下电极，所述上电极和所述下电极相互不交叉，所述上敏感层和所述下敏感层之间形成可接触区域；所述上柔性基底的下表面和所述下柔性基底的上表面均含有多个多级凸起。The flexible pressure sensor includes an upper flexible substrate and a lower flexible substrate disposed in parallel, a top sensitive layer adhered to the lower surface of the upper flexible substrate, and a lower sensitive layer conformally attached to the upper surface of the lower flexible substrate; An upper electrode is disposed on the upper sensitive layer, a lower electrode is disposed on the lower sensitive layer, and the upper electrode and the lower electrode do not intersect each other, and the upper sensitive layer and the lower sensitive layer are formed a contact area; the lower surface of the upper flexible substrate and the upper surface of the lower flexible substrate each comprise a plurality of multi-level protrusions.
含有上述凸起微结构的柔性表面处于本发明特定的柔性压力传感器，极大地提高了表面粗糙度，使柔性压力传感器具有高灵敏度。The flexible surface containing the above-mentioned convex microstructure is in the specific flexible pressure sensor of the present invention, which greatly improves the surface roughness and makes the flexible pressure sensor have high sensitivity.
在本发明中，“保形”是指敏感层附着于凸起微结构的柔性基底表面时，凸起微结构的形状并未被掩盖而保持原来的凸起状态。In the present invention, "conformal" means that when the sensitive layer is attached to the surface of the flexible substrate of the convex microstructure, the shape of the convex microstructure is not masked to maintain the original convex state.
本发明中的“多个”指2个或2个以上。"Multiple" in the present invention means two or more.
本发明中的“多级”指在上柔性基底的下表面和下柔性基底的上表面的凸起有多个尺寸级别。本发明中，在所述表面含有多个高度为微米级的凸起，在所述微米级的凸起的表面还含有多个高度为纳米级的凸起。"Multi-stage" in the present invention means that the protrusions on the lower surface of the upper flexible substrate and the upper surface of the lower flexible substrate have a plurality of size levels. In the present invention, the surface contains a plurality of protrusions having a height of a micron order, and the surface of the micron-sized protrusions further includes a plurality of protrusions having a height of a nanometer order.
在本发明中，优选地，多级凸起的平均长度为50-100μm，平均高度为1-10μm，更优选地是，平均长度为50-70μm，平均高度为2-5μm。含有该多级凸起的柔性表面所制备得到的柔性压力传感器在低压力下具有很高的灵敏度。 In the present invention, preferably, the multistage projections have an average length of 50 to 100 μm, an average height of 1-10 μm, more preferably an average length of 50 to 70 μm, and an average height of 2 to 5 μm. The flexible pressure sensor prepared by the flexible surface containing the multi-stage protrusion has high sensitivity at low pressure.
在本发明中，为了得到上述结构的凸起，可以使用本领域中常用的方法来制备。为了更好地提高柔性压力传感器的灵敏度，所述凸起通过在所述表面印模表面积为1～30cm2的植物叶片或砂粒尺寸为0.5～20μm的砂纸制备得到。优选地，所述凸起通过在所述表面印模表面积为2～10cm2的植物叶片或砂粒尺寸为1～5μm的砂纸制备得到。In the present invention, in order to obtain the projections of the above structure, it can be produced by a method commonly used in the art. In order to better improve the sensitivity of the flexible pressure sensor, the projections are prepared by using a plant blade having a surface area of 1 to 30 cm 2 or a sandpaper having a grit size of 0.5 to 20 μm. Preferably, the protrusions are prepared by using a plant blade having a surface area of 2 to 10 cm 2 or a sandpaper having a grit size of 1 to 5 μm.
其中，植物叶片较优选为绿萝叶片。Among them, the plant leaves are more preferably green leaves.
本发明中的上下柔性基底可以采用本领域中常用的柔性材料制得，如聚二甲基硅氧烷、聚对苯二甲酸乙二醇酯或聚酰亚胺中的一种或多种。其中上下柔性基底材料可以不同，也可以相同。为了防止柔性压力传感器与皮肤接触后发生过敏、炎症，本发明的上下柔性基底均优选采用聚二甲基硅氧烷制得。The upper and lower flexible substrates in the present invention may be made of a flexible material commonly used in the art, such as one or more of polydimethylsiloxane, polyethylene terephthalate or polyimide. The upper and lower flexible substrate materials may be different or the same. In order to prevent allergy and inflammation of the flexible pressure sensor from coming into contact with the skin, the upper and lower flexible substrates of the present invention are preferably made of polydimethylsiloxane.
为了使柔性压力传感器具备优异的柔性和稳定性，上柔性基底和下柔性基底的厚度相同，均为30～3000μm，优选为100～500μm，更优选为200～300μm，最优选为250μm。In order to provide the flexible pressure sensor with excellent flexibility and stability, the upper flexible substrate and the lower flexible substrate have the same thickness of 30 to 3000 μm, preferably 100 to 500 μm, more preferably 200 to 300 μm, and most preferably 250 μm.
本发明上下柔性基底表面的凸起微结构可以用印模制得，具体步骤为：The convex microstructure of the upper and lower flexible substrate surface of the present invention can be obtained by using an impression, and the specific steps are as follows:
将上柔性基底和下柔性基底的前驱体溶液分别滴加在产生所述凸起的结构的器件表面，印模，固化后分别得到含有所述凸起的上柔性基底和含有所述凸起的下柔性基底。Depositing a precursor solution of the upper flexible substrate and the lower flexible substrate onto the surface of the device for producing the raised structure, stamping, curing, respectively, to obtain an upper flexible substrate containing the protrusions and containing the protrusions Lower flexible substrate.
即将柔性基底的前驱体溶液滴加在产生所述凸起微结构的器件表面，滴在植物叶片或砂粒尺寸为0.5～20μm的砂纸的表面，印模固化即得。That is, the precursor solution of the flexible substrate is dropped on the surface of the device which produces the convex microstructure, and is dropped on the surface of the plant leaf or the sandpaper having a sand particle size of 0.5 to 20 μm, and the stamp is solidified.
为了使含有凸起的器体的结构能够完整地被印制下来，增加柔性基底表面的粗糙度，在印模过程中，温度通常为20～150℃，时间为10min～24h，优选地，温度为70～80℃，时间为2h～3h。In order to enable the structure of the convex body to be completely printed, the roughness of the surface of the flexible substrate is increased. During the stamping process, the temperature is usually 20 to 150 ° C, and the time is 10 min to 24 h, preferably, the temperature. It is 70-80 ° C and the time is 2 h ~ 3 h.
本发明中的上下敏感层可以为石墨烯薄膜或碳纳米管/石墨烯复合薄膜。本发明的上下敏感层可以为同一种物质所形成的膜，也可以为不同物质所形成的膜。为了提高柔性压力传感器在低压力下的灵敏度，上下敏感层为同一种物质，优选均为石墨烯薄膜或碳纳米管/石墨烯复合薄膜。The upper and lower sensitive layers in the present invention may be a graphene film or a carbon nanotube/graphene composite film. The upper and lower sensitive layers of the present invention may be a film formed of the same substance or a film formed of different substances. In order to improve the sensitivity of the flexible pressure sensor under low pressure, the upper and lower sensitive layers are the same substance, preferably both graphene film or carbon nanotube/graphene composite film.
其中，本发明敏感层为石墨烯薄膜或碳纳米管/石墨烯复合薄膜时，石墨烯可以为单层或多层。 Wherein, when the sensitive layer of the present invention is a graphene film or a carbon nanotube/graphene composite film, the graphene may be a single layer or a plurality of layers.
当上下敏感层均为碳纳米管/石墨烯复合薄膜时，得到的柔性压力传感器可以在较低压力下也具有较高的灵敏度。更优选地是，上敏感层中碳纳米管和下敏感层中碳纳米管阵列相互平行或垂直。最优选地是，上敏感层中碳纳米管阵列和下敏感层中碳纳米管阵列相互垂直。此时，得到的柔性压力传感器在小于0.3kPa的压力范围内，该传感器具有至少19.8kPa-1的灵敏度。When the upper and lower sensitive layers are both carbon nanotube/graphene composite films, the obtained flexible pressure sensor can also have higher sensitivity at lower pressure. More preferably, the carbon nanotube arrays in the upper sensitive layer and the carbon nanotube array in the lower sensitive layer are parallel or perpendicular to each other. Most preferably, the array of carbon nanotubes in the array of carbon nanotubes and the lower layer of the upper sensitive layer are perpendicular to each other. At this point, the resulting flexible pressure sensor has a sensitivity of at least 19.8 kPa -1 in a pressure range of less than 0.3 kPa.
当上下敏感层均为石墨烯薄膜时，得到的柔性压力传感器可以在较低压力下具有较高的灵敏度，得到的柔性压力传感器在小于0.3kPa的压力范围内，该传感器具有至少40kPa-1的灵敏度。When the upper and lower sensitive layers are graphene films, the obtained flexible pressure sensor can have higher sensitivity at a lower pressure, and the obtained flexible pressure sensor has a pressure range of less than 0.3 kPa, and the sensor has at least 40 kPa -1 . Sensitivity.
本发明中的上敏感层和下敏感层的厚度可以相同或不同，优选地将两者的厚度设为相同，均为0.34～100nm，优选地，当敏感层均为碳纳米管/石墨烯复合薄膜时，厚度优选为30～50nm；当敏感层均为石墨烯薄膜时，厚度优选为0.34～10nm。在本发明中，也可以使用宽度均为0.1～10cm的敏感层。本发明的上下敏感层分别完全保形附着于所述上下柔性基底表面，其宽度与柔性基底的宽度相对应。The thickness of the upper sensitive layer and the lower sensitive layer in the present invention may be the same or different, and preferably the thickness of both is the same, both being 0.34 to 100 nm, preferably, when the sensitive layer is a carbon nanotube/graphene composite In the case of a film, the thickness is preferably from 30 to 50 nm; when the sensitive layer is a graphene film, the thickness is preferably from 0.34 to 10 nm. In the present invention, a sensitive layer having a width of 0.1 to 10 cm can also be used. The upper and lower sensitive layers of the present invention are each completely conformally attached to the upper and lower flexible substrate surfaces, the width of which corresponds to the width of the flexible substrate.
本发明的上下敏感层可以用本领域中常用的方法制备得到。当敏感层为碳纳米管/石墨烯薄膜时，可以使用化学气相沉积法制得。为了得到与柔性基底保形接触的敏感层，本发明的化学气相沉积法的步骤如下：The upper and lower sensitive layers of the present invention can be prepared by methods conventional in the art. When the sensitive layer is a carbon nanotube/graphene film, it can be obtained by chemical vapor deposition. In order to obtain a sensitive layer in conformal contact with the flexible substrate, the steps of the chemical vapor deposition method of the present invention are as follows:
将由碳纳米管阵列抽出的碳纳米管薄膜纺在铜箔或镍箔表面，再在其表面生长石墨烯，碳源的进气速率为1～50mL/min，石墨烯的生长时间为5-120min，生长温度为900～1060℃。优选地，进气速率为15～30mL/min，石墨烯的生长时间为30～60min，生长温度为1000～1050℃。碳源优选使用甲烷。The carbon nanotube film extracted from the carbon nanotube array is spun on the surface of the copper foil or the nickel foil, and graphene is grown on the surface thereof. The carbon source has an inlet rate of 1 to 50 mL/min, and the graphene growth time is 5 to 120 min. The growth temperature is 900 to 1060 °C. Preferably, the intake rate is 15 to 30 mL/min, the graphene growth time is 30 to 60 min, and the growth temperature is 1000 to 1050 °C. Methane is preferably used as the carbon source.
当敏感层为碳纳米管薄膜时，可以直接从碳纳米管垂直阵列中抽出得到。When the sensitive layer is a carbon nanotube film, it can be directly extracted from the vertical array of carbon nanotubes.
当敏感层为石墨烯薄膜时，可以使用化学气相沉积法制得。具体步骤如下：When the sensitive layer is a graphene film, it can be obtained by chemical vapor deposition. Specific steps are as follows:
将铜箔或镍箔的表面生长石墨烯，碳源的进气速率为1～50mL/min，石墨烯的生长时间为5-120min，生长温度为900～1060℃。优选地，进气速率为5～15mL/min，石墨烯的生长时间为60～90min，生长温度为 1000～1050℃。The graphene is grown on the surface of the copper foil or the nickel foil, the carbon source has an inlet rate of 1 to 50 mL/min, the graphene growth time is 5 to 120 min, and the growth temperature is 900 to 1060 °C. Preferably, the inlet rate is 5-15 mL/min, the growth time of graphene is 60-90 min, and the growth temperature is 1000 ~ 1050 ° C.
将上述方法所生成的石墨稀薄膜敏感层转移至柔性基底上时，有额外的褶皱生成，使得得到的柔性压力传感器的灵敏度得到更大幅度的提升。When the graphite thin film sensitive layer generated by the above method is transferred onto the flexible substrate, additional wrinkles are generated, so that the sensitivity of the obtained flexible pressure sensor is further improved.
在保证不交叉的前提下，本发明的上下电极可以分别设在上下敏感层的中部或是边部。优选地，将本发明的上电极设在上敏感层的边部，下电极设在下敏感层的边部，其中，上下电极不交叉，较优选地是，上电极设在上敏感层的边缘处，下电极设在下敏感层的远离上电极的一边的边缘处。其中，上下电极均优选为一个。The upper and lower electrodes of the present invention may be respectively disposed at the middle or the side of the upper and lower sensitive layers under the premise of not intersecting. Preferably, the upper electrode of the present invention is disposed at a side of the upper sensitive layer, and the lower electrode is disposed at a side of the lower sensitive layer, wherein the upper and lower electrodes do not intersect, and more preferably, the upper electrode is disposed at an edge of the upper sensitive layer The lower electrode is disposed at an edge of the lower sensitive layer away from the side of the upper electrode. Among them, the upper and lower electrodes are preferably one.
通常将上柔性基底和下柔性基底面对面设置，使上敏感层和下敏层之间通过凸起微结构而接触，实现导通。The upper flexible substrate and the lower flexible substrate are generally disposed face to face such that the upper sensitive layer and the lower sensitive layer are contacted by the convex microstructure to achieve conduction.
本发明的上下电极可以采用同样厚度的同样材料制得，也可以采用不同厚度的不同材料制得，本发明优选采用同样厚度电极层。上下电极可以采用厚度为0.25～3mm的导电无纺布、0.25～3mm的碳化纺织品、厚度为1～500μm的铜箔或直径为10～1000μm的铜丝制得。本发明中优选采用厚度为25～50μm和宽度为1～2mm的铜箔或直径为50～150μm的铜丝制得。其中，铜丝较优选为100μm。The upper and lower electrodes of the present invention may be made of the same material of the same thickness or may be made of different materials of different thicknesses, and the electrode layer of the same thickness is preferably used in the present invention. The upper and lower electrodes can be made of a conductive nonwoven fabric having a thickness of 0.25 to 3 mm, a carbonized textile of 0.25 to 3 mm, a copper foil having a thickness of 1 to 500 μm, or a copper wire having a diameter of 10 to 1000 μm. In the present invention, a copper foil having a thickness of 25 to 50 μm and a width of 1 to 2 mm or a copper wire having a diameter of 50 to 150 μm is preferably used. Among them, the copper wire is more preferably 100 μm.
可以使用本领域中常见的方法将电极设在敏感层的边部，通常使用导电银胶粘接在敏感层的边缘处。The electrodes can be placed on the edges of the sensitive layer using methods commonly found in the art, typically bonded to the edges of the sensitive layer using a conductive silver paste.
为了得到在较低压力下也具有高灵敏度的柔性压力传感器，本发明的柔性压力传感器优选为：In order to obtain a flexible pressure sensor that also has high sensitivity at lower pressures, the flexible pressure sensor of the present invention preferably:
包括相对平行设置的聚二甲基硅氧烷上柔性基底和聚二甲基硅氧烷下柔性基底，保形附着于所述上柔性基底下表面的碳纳米管/石墨烯复合薄膜上敏感层和保形附着于所述下柔性基底上表面的碳纳米管/石墨烯复合薄膜下敏感层；所述上敏感层和所述下敏感层上分别设有上电极和下电极，所述上电极和所述下电极相互不交叉，所述上敏感层和所述下敏感层之间形成可接触区域；所述上柔性表面的下表面和所述下柔性基底的上表面均含有多个多级凸起；所述上柔性基底和所述下柔性基底的厚度均为200～300μm；所述上敏感层中碳纳米管和所述下敏感层中碳纳米管的阵列相互平行或垂直；所述上敏感层和所述下敏感层的厚度均为30～50nm。该柔性压力传感器在小于0.3kPa的压力范围内，该传感器具有至少12.7kPa-1 的灵敏度。The flexible substrate on the polydimethylsiloxane and the flexible substrate under the polydimethylsiloxane are disposed in a relatively parallel arrangement, and the sensitive layer on the carbon nanotube/graphene composite film conformally adhered to the lower surface of the upper flexible substrate And a carbon nanotube/graphene composite film lower sensitive layer adhered to the upper surface of the lower flexible substrate; an upper electrode and a lower electrode respectively disposed on the upper sensitive layer and the lower sensitive layer, the upper electrode And the lower electrode do not cross each other, a contactable region is formed between the upper sensitive layer and the lower sensitive layer; the lower surface of the upper flexible surface and the upper surface of the lower flexible substrate each have a plurality of levels a protrusion; the upper flexible substrate and the lower flexible substrate each having a thickness of 200 to 300 μm; wherein the carbon nanotubes in the upper sensitive layer and the array of carbon nanotubes in the lower sensitive layer are parallel or perpendicular to each other; The upper sensitive layer and the lower sensitive layer each have a thickness of 30 to 50 nm. The flexible pressure sensor has a sensitivity of at least 12.7 kPa -1 in a pressure range of less than 0.3 kPa.
为了进一步地提高柔性压力传感器的灵敏度，本发明的柔性压力传感器优选为：In order to further increase the sensitivity of the flexible pressure sensor, the flexible pressure sensor of the present invention is preferably:
包括相对平行设置的聚二甲基硅氧烷上柔性基底和聚二甲基硅氧烷下柔性基底，保形附着于所述上柔性基底下表面的石墨烯薄膜上敏感层和保形附着于所述下柔性基底上表面的石墨烯薄膜下敏感层；所述上敏感层和所述下敏感层上分别设有上电极和下电极，所述上电极和所述下电极相互不交叉，所述上敏感层和所述下敏感层之间形成可接触区域；所述上柔性表面的下表面和所述下柔性基底的上表面均含有多个多级凸起；所述上柔性基底和所述下柔性基底的厚度均为200～300μm；所述上敏感层和所述下敏感层的厚度均为0.34～10nm。该柔性压力传感器在小于0.3kPa的压力范围内，该传感器具有至少40kPa-1的灵敏度。The invention comprises a flexible substrate on a polydimethylsiloxane and a flexible substrate under a polydimethylsiloxane disposed in parallel, and a sensitive layer adhered to the graphene film attached to the lower surface of the upper flexible substrate and conformally attached thereto a lower graphene film under the upper flexible substrate; an upper electrode and a lower electrode respectively disposed on the upper sensitive layer and the lower sensitive layer, wherein the upper electrode and the lower electrode do not cross each other Forming a contactable region between the sensitive layer and the lower sensitive layer; the lower surface of the upper flexible surface and the upper surface of the lower flexible substrate each comprise a plurality of multi-level protrusions; the upper flexible substrate and the The thickness of the flexible substrate is 200-300 μm; the thickness of the upper sensitive layer and the lower sensitive layer are both 0.34-10 nm. The flexible pressure sensor has a sensitivity of at least 40 kPa -1 in a pressure range of less than 0.3 kPa.
同时，本发明的柔性压力传感器在100Pa以上的压力下，传感器经过30000次循环后仍然保持良好的稳定性。更优选地，在150Pa恒定压力下，传感器经过35000次循环后仍然保持良好的稳定性。At the same time, the flexible pressure sensor of the present invention maintains good stability after 30,000 cycles under a pressure of 100 Pa or more. More preferably, the sensor maintains good stability after 35,000 cycles at a constant pressure of 150 Pa.
本发明的柔性压力传感器还可以包括封装层，可以采用本领域中常用的材料，优选地，封装层采用聚二甲基硅氧烷、聚丙烯、聚乙烯、环氧树脂中的一种或多种制得。为了防止柔性压力传感器与皮肤接触后发生过敏、炎症，封装层优选采用聚二甲基硅氧烷制得。The flexible pressure sensor of the present invention may further comprise an encapsulating layer, which may be made of materials commonly used in the art. Preferably, the encapsulating layer is one or more of polydimethylsiloxane, polypropylene, polyethylene, epoxy resin. Made. In order to prevent allergies and inflammation of the flexible pressure sensor from coming into contact with the skin, the encapsulating layer is preferably made of polydimethylsiloxane.
根据本发明的一个方面，提供了柔性压力传感器的制备方法，所述方法包括：According to an aspect of the invention, a method of preparing a flexible pressure sensor is provided, the method comprising:
1)将所述上柔性基底和所述下柔性基底的前驱体溶液分别滴加在含有所述凸起的器件的表面上，印模，固化后分别得到含有所述凸起的上柔性基底和含有所述凸起的下柔性基底；其中，所述印模过程中温度为20～150℃，时间为10min～24h；1) respectively, the precursor solutions of the upper flexible substrate and the lower flexible substrate are dropped on the surface of the device containing the protrusions, and the stamps are solidified to obtain an upper flexible substrate containing the protrusions, respectively. a lower flexible substrate comprising the protrusion; wherein the temperature during the stamping process is 20 to 150 ° C, and the time is 10 min to 24 h;
2)将所述上敏感层和所述下敏感层分别转移至步骤1)中含有所述凸起的上柔性基底的下表面和含有所述凸起的下柔性基底上表面，在所述上敏感层和所述下敏感层上分别设置所述上电极和所述下电极；2) transferring the upper sensitive layer and the lower sensitive layer to the lower surface of the upper flexible substrate containing the protrusions in step 1) and the upper surface of the lower flexible substrate containing the protrusions, The upper electrode and the lower electrode are respectively disposed on the sensitive layer and the lower sensitive layer;
3)将步骤2)中上柔性基底和下柔性基底相对平行设置，使得所述上敏感层和所述下敏感层形成可接触区域。 3) The upper flexible substrate and the lower flexible substrate in step 2) are disposed in parallel so that the upper sensitive layer and the lower sensitive layer form a contactable region.
其中，对于步骤1)，所述器件为植物叶片或砂粒尺寸为0.5～20μm的砂纸，即将上柔性基底和所述下柔性基底的前驱体溶液分别滴加在植物叶片或砂粒尺寸为0.5～20μm的砂纸的表面上，印模，固化，分别得到含有所述凸起的上柔性基底和含有所述凸起的下柔性基底。Wherein, for the step 1), the device is a plant blade or a sandpaper having a sand particle size of 0.5-20 μm, that is, the precursor solution of the upper flexible substrate and the lower flexible substrate is respectively added to the plant blade or the sand particle size is 0.5-20 μm. On the surface of the sandpaper, the stamp is cured to obtain an upper flexible substrate containing the protrusions and a lower flexible substrate containing the protrusions, respectively.
当未施加压力时，上敏感层和下敏感层通过凸起接触，当施加一定压力时，上敏感层和下敏感层接触面积增大，从而使电流变大，实现压力的检测。When no pressure is applied, the upper sensitive layer and the lower sensitive layer are contacted by the protrusions, and when a certain pressure is applied, the contact area of the upper sensitive layer and the lower sensitive layer is increased, so that the current is increased, and the pressure is detected.
优选地，还包括有封装材料，具体步骤为使用封装材料将上述器件封装。Preferably, an encapsulating material is further included, and the specific step is to package the above device using the encapsulating material.
本发明的柔性压力传感器中上柔性基底和下柔性基底优选相同，微结构优选相同，上敏感层和下敏感层优选相同，上电极与下电极相同，即在制备过程中，可以先制备含有微结构的上柔性基底和含有上电极的上敏感层，将两者结合在一起成一个传感单元，再使用上述同样的方法制备含有微结构的下柔性基底和含有下电极的下敏感层，将其结合在一起成另一个传感单元，再将两个传感单元按需要放置，即使得上柔性基底和下柔性基底彼此平行相对设置，从而使得上敏感层和下敏感层之间形成可接触区域。In the flexible pressure sensor of the present invention, the upper flexible substrate and the lower flexible substrate are preferably the same, the microstructure is preferably the same, the upper sensitive layer and the lower sensitive layer are preferably the same, and the upper electrode is the same as the lower electrode, that is, in the preparation process, the micro-preparation can be prepared first. The upper flexible substrate of the structure and the upper sensitive layer containing the upper electrode are combined to form a sensing unit, and the lower flexible substrate containing the microstructure and the lower sensitive layer containing the lower electrode are prepared by the same method as described above. They are combined into another sensing unit, and then the two sensing units are placed as needed, such that the upper flexible substrate and the lower flexible substrate are disposed in parallel with each other such that contact is formed between the upper sensitive layer and the lower sensitive layer. region.
本发明的另一个方面，还提供了柔性压力传感器用于制备检测微小机械力、声音振动和/或脉搏的监测器的制备中。In another aspect of the invention, a flexible pressure sensor is also provided for use in preparing a monitor for detecting minute mechanical forces, acoustic vibrations, and/or pulses.
本发明的柔性压力传感器具有较高的灵敏度和低检测限，当压力小于0.3kPa的压力范围内，该传感器具有至少12.7kPa-1的灵敏度，优选具有19.8kPa-1的灵敏度，更优选具有40.7kPa-1的灵敏度。本发明的柔性压力传感器可以检测不大于0.6Pa的压力。The flexible pressure sensor of the present invention has a high sensitivity and a low detection limit. The sensor has a sensitivity of at least 12.7 kPa -1 , preferably a sensitivity of 19.8 kPa -1 , more preferably 40.7, when the pressure is less than 0.3 kPa. Sensitivity of kPa -1 . The flexible pressure sensor of the present invention can detect a pressure of not more than 0.6 Pa.
本发明的柔性压力传感器因其良好的灵敏度和稳定性，可以用于检测弯曲力、扭转力等微小机械力，可以用于检测声音振动引起的微小压力，也可以将其贴附在人体脉搏处，用于检测人体脉搏对血管壁的压力，实现人体脉搏的检测。The flexible pressure sensor of the invention can be used for detecting small mechanical forces such as bending force and torsion force because of its good sensitivity and stability, and can be used for detecting small pressure caused by sound vibration, and can also be attached to the pulse of the human body. It is used to detect the pressure of the human body pulse on the blood vessel wall and realize the detection of the human body pulse.
本申请提出的柔性压力传感器含有通过印模得到含有特定多级凸起微结构的柔性基底，极大地增加了表面粗糙度，较大的提高了传感器的灵敏度；本发明使用了高导电性、高比表面积的石墨烯薄膜或碳纳米管/石墨 烯薄膜作为敏感层，很好地实现了和具有凸起微结构的柔性基底的保形接触，提高了压力传感器的灵敏度和稳定性，实现了微小压力的检测，可用于微小机械力、声音振动、脉搏的监测。The flexible pressure sensor proposed by the present application comprises a flexible substrate containing a specific multi-stage convex microstructure by an impression, which greatly increases the surface roughness and greatly improves the sensitivity of the sensor; the invention uses high conductivity and high Specific surface area of graphene film or carbon nanotube/graphite As a sensitive layer, the ene film can achieve conformal contact with a flexible substrate with a convex microstructure, improve the sensitivity and stability of the pressure sensor, and realize the detection of small pressure, which can be used for micro mechanical force and sound vibration. Pulse monitoring.
附图说明DRAWINGS
图1为根据本发明一个优选实施例中柔性压力传感器的结构示意图；1 is a schematic structural view of a flexible pressure sensor in accordance with a preferred embodiment of the present invention;
图2为根据本发明实施例1中具有凸起微结构的柔性基底扫描电子显微镜照片；2 is a scanning electron micrograph of a flexible substrate having a convex microstructure in Example 1 according to the present invention;
图3为根据本发明实施例1具有凸起微结构的柔性基底中多级凸起结构的光学显微镜照片(a)、扫描电子显微镜照片(b)和原子力显微镜照片(c,d)；3 is an optical micrograph (a), a scanning electron micrograph (b), and an atomic force microscope photograph (c, d) of a multi-stage convex structure in a flexible substrate having a convex microstructure according to Embodiment 1 of the present invention;
图4为根据本发明实施例1中柔性压力传感器的敏感层材料碳纳米管/石墨烯薄膜的扫描电子显微镜照片、透射电子显微镜照片和拉曼表征图；4 is a scanning electron micrograph, a transmission electron micrograph, and a Raman characterization diagram of a carbon nanotube/graphene film of a sensitive layer material of a flexible pressure sensor according to Embodiment 1 of the present invention;
图5为根据本发明实施例1中柔性压力传感器中敏感层材料碳纳米管/石墨烯薄膜的透光度和导电性图；5 is a graph showing transmittance and conductivity of a carbon nanotube/graphene film of a sensitive layer material in a flexible pressure sensor according to Embodiment 1 of the present invention;
图6为根据本发明实施例1中柔性压力传感器中敏感层材料碳纳米管/石墨烯薄膜与所述含有微结构的柔性基底完全贴合的扫描电子显微镜照片；6 is a scanning electron micrograph of a carbon nanotube/graphene film of a sensitive layer material and a flexible substrate containing the microstructure in a flexible pressure sensor according to Embodiment 1 of the present invention;
图7为根据本发明实施例1中柔性压力传感器灵敏度与压力的关系曲线图；Figure 7 is a graph showing the relationship between sensitivity and pressure of a flexible pressure sensor according to Embodiment 1 of the present invention;
图8为根据本发明实施例1中柔性压力传感器的低检测限测试图；8 is a low detection limit test chart of a flexible pressure sensor according to Embodiment 1 of the present invention;
图9为根据本发明实施例1中柔性压力传感器的长时间的稳定性测试图；9 is a long-term stability test chart of a flexible pressure sensor according to Embodiment 1 of the present invention;
图10为根据本发明实施例2中柔性压力传感器用于微小机械力检测的测试图；Figure 10 is a test diagram of a flexible pressure sensor for micro mechanical force detection according to Embodiment 2 of the present invention;
图11为根据本发明实施例2中柔性压力传感器用于声音振动和脉搏的监测图；Figure 11 is a monitoring diagram of a flexible pressure sensor for sound vibration and pulse according to Embodiment 2 of the present invention;
图12为根据本发明实施例3中柔性压力传感器的灵敏度与压力的关系曲线图；Figure 12 is a graph showing the relationship between sensitivity and pressure of a flexible pressure sensor according to Embodiment 3 of the present invention;
图13为根据本发明实施例4中柔性压力传感器的灵敏度与压力的关系曲线图； Figure 13 is a graph showing the relationship between sensitivity and pressure of a flexible pressure sensor according to Embodiment 4 of the present invention;
图14为根据本发明实施例5中敏感层石墨烯在含有微结构的柔性基底的扫描电子显微镜照片；Figure 14 is a scanning electron micrograph of a sensitive layer of graphene in a flexible substrate containing a microstructure according to Embodiment 5 of the present invention;
图15为根据本发明实施例5中柔性压力传感器的灵敏度与压力的关系曲线。Figure 15 is a graph showing the sensitivity versus pressure of a flexible pressure sensor in accordance with Example 5 of the present invention.
具体实施方式detailed description
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。The specific embodiments of the present invention are further described in detail below with reference to the drawings and embodiments. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
实施例1Example 1
本实施例提供了一种柔性压力传感器，包括相对平行设置的上柔性基底和下柔性基底，保形附着于上柔性基底下表面的上敏感层和保形附着于所述下柔性基底上表面的下敏感层；所述上敏感层上设有上电极，所述下敏感层上设有下电极，所述上电极和所述下电极分别设在所述上敏感层的边部和所述下敏感层的边部，上电极和下电极相互不交叉；所述上敏感层和所述下敏感层之间形成可接触区域。在上柔性基底和下柔性基底外含有封装层4，如图1所示。其中，上柔性基底和下柔性基底相同，均为含有新鲜绿萝叶片凸起微结构的聚二甲基硅氧烷薄膜，见图1中柔性基底层1，上敏感层和下敏感层相同，均为碳纳米管/石墨烯薄膜，见图1中敏感层2，其中，上敏感层和下敏感层中碳纳米管方向保持垂直，上电极与下电极相同，均采用厚度为25μm和宽度为1mm的铜箔制得，见图1中电极3。The present embodiment provides a flexible pressure sensor comprising an upper flexible substrate and a lower flexible substrate disposed in parallel, a top sensitive layer conformally attached to the lower surface of the upper flexible substrate, and a conformal adhesion to the upper surface of the lower flexible substrate a lower sensitive layer; an upper electrode is disposed on the upper sensitive layer, a lower electrode is disposed on the lower sensitive layer, and the upper electrode and the lower electrode are respectively disposed at a side of the upper sensitive layer and the lower portion The edge of the sensitive layer, the upper electrode and the lower electrode do not cross each other; a contactable region is formed between the upper sensitive layer and the lower sensitive layer. The encapsulation layer 4 is contained outside the upper flexible substrate and the lower flexible substrate, as shown in FIG. Wherein, the upper flexible substrate and the lower flexible substrate are the same, both are polydimethylsiloxane films containing the convex microstructure of the fresh green radish leaves, as shown in the flexible substrate layer 1 in FIG. 1, the upper sensitive layer and the lower sensitive layer are the same, both For the carbon nanotube/graphene film, see the sensitive layer 2 in FIG. 1, wherein the direction of the carbon nanotubes in the upper sensitive layer and the lower sensitive layer is kept perpendicular, and the upper electrode is the same as the lower electrode, and both have a thickness of 25 μm and a width of 1 mm. Made of copper foil, see electrode 3 in Figure 1.
本实施例同时还提供了上述柔性压力传感器的制备方法，具体步骤如下：The embodiment also provides a preparation method of the above flexible pressure sensor, and the specific steps are as follows:
步骤1、将聚二甲基硅氧烷的前驱体和固化剂按照10:1的比例混合均匀，滴涂在清洗、吹干的新鲜绿萝叶片表面； Step 1, the precursor of the polydimethylsiloxane and the curing agent are uniformly mixed in a ratio of 10:1, and sprayed on the surface of the fresh green leaves of the washed and dried;
步骤2、待聚二甲基硅氧烷在叶片表面基本平整后，置于70℃烘箱中固化3h，固化完成，取下聚二甲基硅氧烷薄膜，得到具有微结构的基底，其中，柔性基底的厚度为250μm；Step 2: After the surface of the blade is substantially flat, the polydimethylsiloxane is cured in an oven at 70 ° C for 3 hours, and the curing is completed, and the polydimethylsiloxane film is removed to obtain a microstructured substrate. The thickness of the flexible substrate is 250 μm;
步骤3、碳纳米管薄膜由垂直碳纳米管阵列直接抽出，宽度为2cm，放置在铜箔表面，滴加乙醇，待乙醇挥发使碳纳米管薄膜与铜箔表面结合牢固；Step 3: The carbon nanotube film is directly extracted from the vertical carbon nanotube array, and has a width of 2 cm. The surface of the carbon nanotube film is placed on the surface of the copper foil, and ethanol is added dropwise. When the ethanol is volatilized, the carbon nanotube film is firmly bonded to the surface of the copper foil;
步骤4、将碳纳米管薄膜/铜箔放置在石英管中，1050℃生长石墨烯， 碳源为甲烷，进气速率为15mL/min，生长时间为30min； Step 4. Place the carbon nanotube film/copper foil in a quartz tube and grow graphene at 1050 ° C. The carbon source is methane, the inlet rate is 15 mL/min, and the growth time is 30 min;
步骤5、液相刻蚀铜箔基底，得到碳纳米管/石墨烯薄膜，厚度为30nm； Step 5, etching the copper foil substrate in a liquid phase to obtain a carbon nanotube/graphene film having a thickness of 30 nm;
步骤6、转移碳纳米管/石墨烯薄膜到柔性基底； Step 6. Transfer the carbon nanotube/graphene film to the flexible substrate;
步骤7、在所述敏感层边缘处制备电极，所述电极3为铜箔，厚度为25μm，宽度为1mm，通过导电银胶粘接在敏感层2的边缘位置；Step 7. Prepare an electrode at the edge of the sensitive layer. The electrode 3 is a copper foil having a thickness of 25 μm and a width of 1 mm. The electrode is bonded to the edge of the sensitive layer 2 by a conductive silver paste.
步骤8、将两片覆盖有敏感层、电极的柔性基底面对面放置，两个电极不发生接触，两敏感层中碳纳米管的方向保持垂直； Step 8. Place two flexible substrates covered with the sensitive layer and the electrodes face to face, the two electrodes do not contact, and the direction of the carbon nanotubes in the two sensitive layers remains vertical;
步骤9、封装材料聚二甲基硅氧烷将器件封装。Step 9. The encapsulating material polydimethylsiloxane encapsulates the device.
含有绿萝叶片凸起微结构的聚二甲基硅氧烷柔性基底的扫描电子显微镜照片见图2。该柔性基底表面的凸起为多级，有微米级和纳米级的凸起，其中，纳米级凸起存在微米级凸起的表面，多级凸起的平均长度为50-70μm，平均高度为2-5μm，见图3。本实施中的敏感层通过复合碳纳米管和石墨烯得到，如图4所示，碳纳米管与石墨烯融合在一起，石墨烯主要是少层结构。如图5和图6所示，复合薄膜具有高导电性、柔性和透明性，高比面积使其与柔性基底保形接触，使传感器具有高灵敏度和高稳定性。本实施例中的压力传感器具有高灵敏度特性，如图7所示，在小于0.3kPa的压力范围内，该传感器具有19.8kPa-1的灵敏度；本实施例中的压力传感器具有低检测限，如图8所示，该传感器可检测0.6Pa的压力；本实施例中的压力传感器具有高稳定性的特点，如图9所示，在150Pa恒定压力下，传感器经过35000次循环后仍然保持良好的稳定性。A scanning electron micrograph of a polydimethylsiloxane flexible substrate containing raised microstructures of green leaves is shown in Figure 2. The surface of the flexible substrate has a plurality of protrusions, and has micron-level and nano-scale protrusions, wherein the nano-scale protrusions have micro-scale convex surfaces, and the multi-level protrusions have an average length of 50-70 μm, and the average height is 2-5μm, see Figure 3. The sensitive layer in the present embodiment is obtained by combining carbon nanotubes and graphene. As shown in FIG. 4, the carbon nanotubes are fused with graphene, and the graphene is mainly a small layer structure. As shown in FIG. 5 and FIG. 6, the composite film has high conductivity, flexibility and transparency, and the high specific area makes it conformal contact with the flexible substrate, so that the sensor has high sensitivity and high stability. The pressure sensor in this embodiment has high sensitivity characteristics. As shown in FIG. 7, the sensor has a sensitivity of 19.8 kPa -1 in a pressure range of less than 0.3 kPa; the pressure sensor in this embodiment has a low detection limit, such as As shown in FIG. 8, the sensor can detect a pressure of 0.6 Pa; the pressure sensor in this embodiment has high stability characteristics, as shown in FIG. 9, the sensor remains good after 35,000 cycles under a constant pressure of 150 Pa. stability.
实施例2Example 2
本实施例提供了一种柔性压力传感器。该柔性压力传感器的结构与实施例1中相同。This embodiment provides a flexible pressure sensor. The structure of the flexible pressure sensor is the same as in the first embodiment.
本实施例同时还提供了上述柔性压力传感器的制备方法，具体步骤如下：The embodiment also provides a preparation method of the above flexible pressure sensor, and the specific steps are as follows:
步骤1、将聚二甲基硅氧烷的前驱体和固化剂按照10:1的比例混合均匀，滴涂在清洗、吹干的新鲜绿萝叶片表面； Step 1, the precursor of the polydimethylsiloxane and the curing agent are uniformly mixed in a ratio of 10:1, and sprayed on the surface of the fresh green leaves of the washed and dried;
步骤2、待聚二甲基硅氧烷在叶片表面基本平整后，置于80℃烘箱中固化3h，固化完成，取下聚二甲基硅氧烷薄膜，得到具有微结构的基底；Step 2: After the surface of the blade is substantially flat, the polydimethylsiloxane is cured in an oven at 80 ° C for 3 hours, and the curing is completed, and the polydimethylsiloxane film is removed to obtain a microstructured substrate;
步骤3、碳纳米管薄膜由垂直碳纳米管阵列直接抽出，宽为2cm，放 置在铜箔表面，滴加乙醇，待乙醇挥发使碳纳米管薄膜与铜箔表面结合牢固；Step 3: The carbon nanotube film is directly extracted from the vertical carbon nanotube array, and the width is 2 cm. Placed on the surface of the copper foil, add ethanol, and the ethanol is evaporated to make the carbon nanotube film and the surface of the copper foil firmly bonded;
步骤4、将碳纳米管薄膜/铜箔放置在石英管中，1050℃生长石墨烯，碳源为甲烷，进气速率为15mL/min，生长时间为30min； Step 4, the carbon nanotube film / copper foil is placed in a quartz tube, graphene is grown at 1050 ° C, the carbon source is methane, the inlet rate is 15 mL / min, and the growth time is 30 min;
步骤5、液相刻蚀铜箔基底，得到碳纳米管/石墨烯薄膜，厚度为30nm； Step 5, etching the copper foil substrate in a liquid phase to obtain a carbon nanotube/graphene film having a thickness of 30 nm;
步骤6、转移碳纳米管/石墨烯薄膜到柔性基底； Step 6. Transfer the carbon nanotube/graphene film to the flexible substrate;
步骤7、在所述敏感层边缘处制备电极，所述电极3为铜箔，厚度为25μm，宽度为1mm，通过导电银胶粘接在敏感层2的边缘位置；Step 7. Prepare an electrode at the edge of the sensitive layer. The electrode 3 is a copper foil having a thickness of 25 μm and a width of 1 mm. The electrode is bonded to the edge of the sensitive layer 2 by a conductive silver paste.
步骤8、将两片覆盖有敏感层、电极的柔性基底面对面放置，两个电极不发生接触，两敏感层中碳纳米管的方向保持垂直； Step 8. Place two flexible substrates covered with the sensitive layer and the electrodes face to face, the two electrodes do not contact, and the direction of the carbon nanotubes in the two sensitive layers remains vertical;
步骤9、封装材料聚二甲基硅氧烷将器件封装。Step 9. The encapsulating material polydimethylsiloxane encapsulates the device.
本实施例中的压力传感器具有高灵敏度、高稳定性、低检测限的特性，如图10所示，所述压力传感器可用于检测弯曲力、扭转力等微小机械力；如图11所示，所述压力传感器可以检测声音振动引起的微小压力，所述的压力传感器贴附在人体脉搏处的皮肤上，检测人体脉搏对血管壁的压力，实现人体脉搏的监测。The pressure sensor in this embodiment has the characteristics of high sensitivity, high stability, and low detection limit. As shown in FIG. 10, the pressure sensor can be used to detect small mechanical forces such as bending force and torsion force; as shown in FIG. The pressure sensor can detect the slight pressure caused by the sound vibration, and the pressure sensor is attached to the skin of the human body pulse to detect the pressure of the human body pulse on the blood vessel wall, and realize the monitoring of the human body pulse.
实施例3Example 3
本实施例提供了一种柔性压力传感器。本实施例提供了一种柔性压力传感器。该柔性压力传感器的结构与实施例1中相同。This embodiment provides a flexible pressure sensor. This embodiment provides a flexible pressure sensor. The structure of the flexible pressure sensor is the same as in the first embodiment.
本实施例同时还提供了上述柔性压力传感器的制备方法，具体步骤如下：The embodiment also provides a preparation method of the above flexible pressure sensor, and the specific steps are as follows:
步骤1、将聚二甲基硅氧烷的前驱体和固化剂按照10:1的比例混合均匀，滴涂在清洗、吹干的新鲜绿萝叶片表面； Step 1, the precursor of the polydimethylsiloxane and the curing agent are uniformly mixed in a ratio of 10:1, and sprayed on the surface of the fresh green leaves of the washed and dried;
步骤2、待聚二甲基硅氧烷在叶片表面基本平整后，置于70℃烘箱中固化3h，固化完成，取下聚二甲基硅氧烷薄膜，得到具有微结构的基底，所述柔性基底的厚度为250μm；Step 2: After the surface of the blade is substantially flat, the polydimethylsiloxane is cured in an oven at 70 ° C for 3 hours, and the curing is completed, and the polydimethylsiloxane film is removed to obtain a microstructured substrate. The thickness of the flexible substrate is 250 μm;
步骤3、碳纳米管薄膜由垂直碳纳米管阵列直接抽出，放置在铜箔表面，滴加乙醇，待乙醇挥发使碳纳米管薄膜与铜箔表面结合牢固；Step 3: The carbon nanotube film is directly extracted from the vertical carbon nanotube array, placed on the surface of the copper foil, and ethanol is added dropwise, and the carbon nanotube film is firmly bonded to the surface of the copper foil after the alcohol is volatilized;
步骤4、将碳纳米管薄膜/铜箔放置在石英管中，1050℃生长石墨烯，碳源为甲烷，进气速率为15mL/min，生长时间为30min； Step 4, the carbon nanotube film / copper foil is placed in a quartz tube, graphene is grown at 1050 ° C, the carbon source is methane, the inlet rate is 15 mL / min, and the growth time is 30 min;
步骤5、液相刻蚀铜箔基底，得到碳纳米管/石墨烯薄膜，厚度为30nm； Step 5, etching the copper foil substrate in a liquid phase to obtain a carbon nanotube/graphene film having a thickness of 30 nm;
步骤6、转移碳纳米管/石墨烯薄膜到柔性基底； Step 6. Transfer the carbon nanotube/graphene film to the flexible substrate;
步骤7、在所述敏感层边缘处制备电极，所述电极3为铜箔，厚度为25μm，宽度为1mm，通过导电银胶粘接在敏感层2的边缘位置；Step 7. Prepare an electrode at the edge of the sensitive layer. The electrode 3 is a copper foil having a thickness of 25 μm and a width of 1 mm. The electrode is bonded to the edge of the sensitive layer 2 by a conductive silver paste.
步骤8、将两片覆盖有敏感层、电极的柔性基底面对面放置，两电极不发生接触，两敏感层中碳纳米管的方向保持平行； Step 8. Place two flexible substrates covered with the sensitive layer and the electrodes face to face, the two electrodes do not contact, and the directions of the carbon nanotubes in the two sensitive layers are kept parallel;
步骤9、封装材料聚二甲基硅氧烷将器件封装。Step 9. The encapsulating material polydimethylsiloxane encapsulates the device.
本实施例中的压力传感器具有较高灵敏度、高稳定性的特性，如图12所示，所述传感器在较低压力范围内(<0.3kPa)具有12.7kPa-1的灵敏度。The pressure sensor in this embodiment has high sensitivity and high stability characteristics. As shown in FIG. 12, the sensor has a sensitivity of 12.7 kPa -1 in a lower pressure range (<0.3 kPa).
实施例4Example 4
本实施例提供了一种柔性压力传感器。该柔性压力传感器的结构与实施例1中相同。This embodiment provides a flexible pressure sensor. The structure of the flexible pressure sensor is the same as in the first embodiment.
本实施例同时还提供了上述柔性压力传感器的制备方法，具体步骤如下：The embodiment also provides a preparation method of the above flexible pressure sensor, and the specific steps are as follows:
步骤1、将聚二甲基硅氧烷的前驱体和固化剂按照10:1的比例混合均匀，滴涂在清洗、吹干的新鲜绿萝叶片表面； Step 1, the precursor of the polydimethylsiloxane and the curing agent are uniformly mixed in a ratio of 10:1, and sprayed on the surface of the fresh green leaves of the washed and dried;
步骤2、待聚二甲基硅氧烷在叶片表面基本平整后，置于20℃环境中固化24h，固化完成，取下聚二甲基硅氧烷薄膜，得到具有微结构的基底，厚度为100μm；Step 2: After the surface of the blade is substantially flat, the surface of the polydimethylsiloxane is cured in an environment of 20 ° C for 24 hours, the curing is completed, and the polydimethylsiloxane film is removed to obtain a microstructured substrate having a thickness of 100μm;
步骤3、碳纳米管薄膜由垂直碳纳米管阵列直接抽出，直接转移到柔性基底；Step 3: The carbon nanotube film is directly extracted from the vertical carbon nanotube array and directly transferred to the flexible substrate;
步骤4、在所述敏感层边缘处制备电极，所述电极为铜线，直径为100μm，通过导电银胶粘接在敏感层的边缘位置； Step 4, preparing an electrode at the edge of the sensitive layer, the electrode is a copper wire, the diameter is 100 μm, and is bonded to the edge of the sensitive layer by a conductive silver glue;
步骤5、将两片覆盖有敏感层、电极的柔性基底面对面放置，两个电极不发生接触，两敏感层中碳纳米管的方向保持垂直；Step 5: placing two flexible substrates covered with the sensitive layer and the electrodes face to face, the two electrodes are not in contact, and the direction of the carbon nanotubes in the two sensitive layers is kept vertical;
步骤6、封装材料聚二甲基硅氧烷将器件封装。 Step 6. The encapsulating material polydimethylsiloxane encapsulates the device.
本发明的敏感层通过碳纳米管薄膜得到，具有高导电性、高柔性，高比面积使其与柔性基底保形接触，使传感器具有高灵敏度和高稳定性。如图13所示，本实施例中的柔性压力传感器具有较高灵敏度的特性。本实施例的柔性压力传感器在小于0.3kPa的压力范围内，该传感器具有 0.85kPa-1的灵敏度。The sensitive layer of the invention is obtained by the carbon nanotube film, has high conductivity, high flexibility, and high specific area makes it conformal contact with the flexible substrate, so that the sensor has high sensitivity and high stability. As shown in FIG. 13, the flexible pressure sensor of this embodiment has a characteristic of higher sensitivity. The flexible pressure sensor of the present embodiment has a sensitivity of 0.85 kPa -1 in a pressure range of less than 0.3 kPa.
实施例5Example 5
本实施例提供了一种柔性压力传感器。该柔性压力传感器的结构与实施例1中相同。This embodiment provides a flexible pressure sensor. The structure of the flexible pressure sensor is the same as in the first embodiment.
本实施例同时还提供了上述柔性压力传感器的制备方法，具体步骤如下：The embodiment also provides a preparation method of the above flexible pressure sensor, and the specific steps are as follows:
步骤1、将聚二甲基硅氧烷的前驱体和固化剂按照10:1的比例混合均匀，滴涂在清洗、吹干的新鲜绿萝叶片表面； Step 1, the precursor of the polydimethylsiloxane and the curing agent are uniformly mixed in a ratio of 10:1, and sprayed on the surface of the fresh green leaves of the washed and dried;
步骤2、待聚二甲基硅氧烷在叶片表面基本平整后，置于70℃烘箱中固化3h，固化完成，取下聚二甲基硅氧烷薄膜，得到具有微结构的基底，所述柔性基底的厚度为200μm；Step 2: After the surface of the blade is substantially flat, the polydimethylsiloxane is cured in an oven at 70 ° C for 3 hours, and the curing is completed, and the polydimethylsiloxane film is removed to obtain a microstructured substrate. The thickness of the flexible substrate is 200 μm;
步骤3、将铜箔放置在石英管中，1050℃生长石墨烯，碳源为甲烷，进气速率为5mL/min，生长时间为60min； Step 3, placing the copper foil in a quartz tube, growing graphene at 1050 ° C, the carbon source is methane, the inlet rate is 5 mL / min, and the growth time is 60 min;
步骤4、旋涂聚甲基丙烯酸酯，液相刻蚀铜箔基底，转移至柔性基底； Step 4, spin coating polymethacrylate, liquid phase etching copper foil substrate, transferred to a flexible substrate;
步骤5、丙酮去除聚甲基丙烯酸酯，得到石墨烯薄膜； Step 5, removing the polymethacrylate by acetone to obtain a graphene film;
步骤6、在所述敏感层边缘处制备电极，所述电极为铜箔，厚度为25μm，宽度为1mm，通过导电银胶粘接在敏感层的边缘位置； Step 6. Prepare an electrode at the edge of the sensitive layer. The electrode is a copper foil with a thickness of 25 μm and a width of 1 mm. The electrode is bonded to the edge of the sensitive layer by a conductive silver paste.
步骤7、将两片覆盖有敏感层、电极的柔性基底面对面放置，两个电极不发生接触；Step 7. Place two flexible substrates covered with sensitive layers and electrodes face to face, and the two electrodes are not in contact;
步骤8、封装材料聚二甲基硅氧烷将器件封装。 Step 8. The packaging material polydimethylsiloxane encapsulates the device.
本实施例中的敏感层通过石墨烯得到，如图14所示，石墨烯薄膜可以与微结构基底保形接触，产生的褶皱可以有效增大传感器的灵敏度，使传感器具有高灵敏度和高稳定性。The sensitive layer in this embodiment is obtained by graphene. As shown in FIG. 14, the graphene film can be in conformal contact with the microstructure substrate, and the generated wrinkles can effectively increase the sensitivity of the sensor, and the sensor has high sensitivity and high stability. .
如图15所示，本实施例中的压力传感器具有高灵敏度、高稳定性的特性。本实施例的柔性压力传感器在小于0.3kPa的压力范围内，该传感器具有40.7kPa-1的灵敏度。As shown in Fig. 15, the pressure sensor in this embodiment has characteristics of high sensitivity and high stability. The flexible pressure sensor of the present embodiment has a sensitivity of 40.7 kPa -1 in a pressure range of less than 0.3 kPa.
最后，本申请的方法仅为较佳的实施方案，并非用于限定本发明的保护范围。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 Finally, the method of the present application is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims (10)

  1. 一种柔性压力传感器，包括：相对平行设置的上柔性基底和下柔性基底，保形附着于所述上柔性基底下表面的上敏感层和保形附着于所述下柔性基底上表面的下敏感层；所述上敏感层上设有上电极，所述下敏感层上设有下电极，所述上电极和所述下电极相互不交叉，所述上敏感层和所述下敏感层之间形成可接触区域；其特征在于，所述上柔性基底的下表面和所述下柔性基底的上表面均含有多个多级凸起，所述多级凸起的平均长度为50-100μm，平均高度为1-10μm。A flexible pressure sensor comprising: an upper flexible substrate and a lower flexible substrate disposed in parallel, an upper sensitive layer conformally attached to a lower surface of the upper flexible substrate, and a lower sensitivity conformally attached to an upper surface of the lower flexible substrate a layer; an upper electrode is disposed on the upper sensitive layer, and a lower electrode is disposed on the lower sensitive layer, the upper electrode and the lower electrode do not cross each other, and between the upper sensitive layer and the lower sensitive layer Forming a contactable region; wherein the lower surface of the upper flexible substrate and the upper surface of the lower flexible substrate each comprise a plurality of multi-level protrusions, the multi-stage protrusions having an average length of 50-100 μm, an average The height is 1-10 μm.
  2. 根据权利要求1所述的柔性压力传感器，其特征在于，所述多级凸起通过在所述表面印模表面积为1～30cm2的植物叶片或砂粒尺寸为0.5～20μm的砂纸制备得到；优选地，所述多级凸起通过在所述表面印模表面积为2～10cm2的植物叶片或砂粒尺寸为1～5μm的砂纸制备得到。The flexible pressure sensor according to claim 1, wherein the multi-stage projection is prepared by using a plant blade having a surface area of 1 to 30 cm 2 or a sandpaper having a grit size of 0.5 to 20 μm; The multi-stage projections are prepared by using a plant blade having a surface area of 2 to 10 cm 2 or a sandpaper having a grit size of 1 to 5 μm.
  3. 根据权利要求1-2中任一项所述的柔性压力传感器，其特征在于，所述上柔性基底和所述下柔性基底均采用聚二甲基硅氧烷、聚对苯二甲酸乙二醇酯或聚酰亚胺制得，优选均采用聚二甲基硅氧烷制得；The flexible pressure sensor according to any one of claims 1 to 2, wherein both the upper flexible substrate and the lower flexible substrate are made of polydimethylsiloxane or polyethylene terephthalate. Prepared from ester or polyimide, preferably prepared by using polydimethylsiloxane;
    和/或，所述上敏感层和所述下敏感层均为石墨烯薄膜或碳纳米管/石墨烯复合薄膜；And/or, the upper sensitive layer and the lower sensitive layer are both graphene film or carbon nanotube/graphene composite film;
    当所述上敏感层和所述下敏感层均为碳纳米管/石墨烯复合薄膜时，所述上敏感层中碳纳米管和所述下敏感层中碳纳米管的阵列相互平行或垂直。When the upper sensitive layer and the lower sensitive layer are both carbon nanotube/graphene composite films, the carbon nanotubes in the upper sensitive layer and the array of carbon nanotubes in the lower sensitive layer are parallel or perpendicular to each other.
  4. 根据权利要求1-3中任一项所述的柔性压力传感器，其特征在于，所述上柔性基底和所述下柔性基底的厚度均为30～3000μm，优选为100～500μm，更优选为200～300μm；The flexible pressure sensor according to any one of claims 1 to 3, wherein the upper flexible substrate and the lower flexible substrate each have a thickness of 30 to 3000 μm, preferably 100 to 500 μm, more preferably 200. ~300μm;
    和/或，所述上敏感层和所述下敏感层的厚度均为0.34～100nm，优选地，厚度均为0.34～10nm。And/or, the upper sensitive layer and the lower sensitive layer each have a thickness of 0.34 to 100 nm, and preferably have a thickness of 0.34 to 10 nm.
  5. 根据权利要求1-4中任一项所述的柔性压力传感器，其特征在于，所述上电极和所述下电极分别设在所述上敏感层的边部和所述下敏感层的边部，所述上电极和所述下电极均采用厚度为0.25～3mm的导电无纺布、0.25～3mm的碳化纺织品、厚度为1～500μm的铜箔或直径为10～1000μm的铜丝制得。 The flexible pressure sensor according to any one of claims 1 to 4, wherein the upper electrode and the lower electrode are respectively provided at a side of the upper sensitive layer and a side of the lower sensitive layer The upper electrode and the lower electrode are each made of a conductive nonwoven fabric having a thickness of 0.25 to 3 mm, a carbonized textile of 0.25 to 3 mm, a copper foil having a thickness of 1 to 500 μm, or a copper wire having a diameter of 10 to 1000 μm.
  6. 根据权利要求1所述的柔性压力传感器，其特征在于，所述压力传感器包括相对平行设置的聚二甲基硅氧烷上柔性基底和聚二甲基硅氧烷下柔性基底，保形附着于所述上柔性基底下表面的碳纳米管/石墨烯复合薄膜上敏感层和保形附着于所述下柔性基底上表面的碳纳米管/石墨烯复合薄膜下敏感层；所述上敏感层和所述下敏感层上分别设有上电极和下电极，所述上电极和所述下电极相互不交叉，所述上敏感层和所述下敏感层之间形成可接触区域；所述上柔性表面的下表面和所述下柔性基底的上表面均含有多个多级凸起；所述上柔性基底和所述下柔性基底的厚度均为200～300μm；所述上敏感层中碳纳米管和所述下敏感层中碳纳米管的阵列相互平行或垂直；所述上敏感层和所述下敏感层的厚度均为30～50nm；The flexible pressure sensor according to claim 1, wherein said pressure sensor comprises a flexible substrate on a polydimethylsiloxane disposed relatively in parallel and a flexible substrate under a polydimethylsiloxane, conformally attached thereto a sensitive layer on the carbon nanotube/graphene composite film on the lower surface of the upper flexible substrate and a lower sensitive layer of the carbon nanotube/graphene composite film adhered to the upper surface of the lower flexible substrate; the upper sensitive layer and An upper electrode and a lower electrode are respectively disposed on the lower sensitive layer, the upper electrode and the lower electrode do not intersect each other, and a contactable area is formed between the upper sensitive layer and the lower sensitive layer; The lower surface of the surface and the upper surface of the lower flexible substrate each comprise a plurality of multi-level protrusions; the upper flexible substrate and the lower flexible substrate each have a thickness of 200-300 μm; the carbon nanotubes in the upper sensitive layer And the array of carbon nanotubes in the lower sensitive layer are parallel or perpendicular to each other; the thickness of the upper sensitive layer and the lower sensitive layer are both 30 to 50 nm;
    或，所述压力传感器包括相对平行设置的聚二甲基硅氧烷上柔性基底和聚二甲基硅氧烷下柔性基底，保形附着于所述上柔性基底下表面的石墨烯薄膜上敏感层和保形附着于所述下柔性基底上表面的石墨烯薄膜下敏感层；所述上敏感层和所述下敏感层上分别设有上电极和下电极，所述上电极和所述下电极相互不交叉，所述上敏感层和所述下敏感层之间形成可接触区域；所述上柔性表面的下表面和所述下柔性基底的上表面均含有多个多级凸起；所述上柔性基底和所述下柔性基底的厚度均为200～300μm；所述上敏感层和所述下敏感层的厚度均为0.34～10nm。Alternatively, the pressure sensor comprises a flexible substrate on a polydimethylsiloxane disposed in parallel and a flexible substrate under a polydimethylsiloxane, which is conformally attached to the graphene film attached to the lower surface of the upper flexible substrate. a layer and a conformal layer of a graphene film attached to the upper surface of the lower flexible substrate; an upper electrode and a lower electrode respectively disposed on the upper sensitive layer and the lower sensitive layer, the upper electrode and the lower electrode The electrodes do not intersect each other, and a contactable region is formed between the upper sensitive layer and the lower sensitive layer; the lower surface of the upper flexible surface and the upper surface of the lower flexible substrate each include a plurality of multi-level protrusions; The thickness of the flexible substrate and the lower flexible substrate are both 200 to 300 μm; the thickness of the upper sensitive layer and the lower sensitive layer are both 0.34 to 10 nm.
  7. 根据权利要求1-6中任一项所述的柔性压力传感器，其特征在于，还包括封装层，所述封装层采用聚二甲基硅氧烷、聚丙烯、聚乙烯、环氧树脂中的一种或多种制得。The flexible pressure sensor according to any one of claims 1 to 4, further comprising an encapsulation layer, wherein the encapsulation layer is made of polydimethylsiloxane, polypropylene, polyethylene, epoxy resin One or more are made.
  8. 权利要求1-7中任一项所述的柔性压力传感器的制备方法，所述方法包括：The method of preparing a flexible pressure sensor according to any one of claims 1 to 7, the method comprising:
    1)将所述上柔性基底和所述下柔性基底的前驱体溶液分别滴加在产生所述凸起的器件的表面，印模，固化后分别得到含有所述凸起的上柔性基底和含有所述凸起的下柔性基底；其中，所述印模过程中温度为20～150℃，时间为10min～24h；1) respectively, the precursor solutions of the upper flexible substrate and the lower flexible substrate are dropped on the surface of the device for producing the protrusions, and the stamp is solidified to obtain an upper flexible substrate containing the protrusions and containing The raised lower flexible substrate; wherein the temperature during the stamping process is 20 to 150 ° C, and the time is 10 min to 24 h;
    2)将所述上敏感层和所述下敏感层分别转移至步骤1)中含有所述凸起的上柔性基底的下表面和含有所述凸起的下柔性基底上表面，在所述上敏感层和所述下敏感层分别设置所述上电极和所述下电极； 2) transferring the upper sensitive layer and the lower sensitive layer to the lower surface of the upper flexible substrate containing the protrusions in step 1) and the upper surface of the lower flexible substrate containing the protrusions, The upper layer and the lower electrode are respectively disposed on the sensitive layer and the lower sensitive layer;
    3)将步骤2)中上柔性基底和下柔性基底相对平行设置，使得所述上敏感层和所述下敏感层形成可接触区域。3) The upper flexible substrate and the lower flexible substrate in step 2) are disposed in parallel so that the upper sensitive layer and the lower sensitive layer form a contactable region.
  9. 根据权利要求8所述的制备方法，其特征在于，所述上敏感层和所述下敏感层均为碳纳米管/石墨烯复合薄膜；The preparation method according to claim 8, wherein the upper sensitive layer and the lower sensitive layer are both carbon nanotube/graphene composite films;
    所述碳纳米管/石墨烯复合薄膜的制备方法如下：The preparation method of the carbon nanotube/graphene composite film is as follows:
    将由碳纳米管阵列抽出的碳纳米管薄膜纺在金属表面，再在其表面生长石墨烯，碳源的进气速率为1～50mL/min，石墨烯的生长时间为5-120min，生长温度为900～1060℃；The carbon nanotube film extracted from the carbon nanotube array is spun on the metal surface, and graphene is grown on the surface thereof. The carbon source has an inlet rate of 1 to 50 mL/min, the graphene growth time is 5 to 120 min, and the growth temperature is 900～1060°C;
    优选地，所述上敏感层和所述下敏感层中碳纳米管的阵列相互平行或垂直。Preferably, the array of carbon nanotubes in the upper sensitive layer and the lower sensitive layer are parallel or perpendicular to each other.
  10. 根据权利要求8所述的制备方法，其特征在于，所述上敏感层和所述下敏感层均为石墨烯薄膜；The preparation method according to claim 8, wherein the upper sensitive layer and the lower sensitive layer are both graphene films;
    所述石墨烯薄膜的制备方法如下：The preparation method of the graphene film is as follows:
    在金属表面生长石墨烯，碳源的进气速率为1～50mL/min，石墨烯的生长时间为5-120min，生长温度为900～1060℃。 The graphene is grown on the metal surface, the carbon source has an inlet rate of 1 to 50 mL/min, the graphene growth time is 5 to 120 min, and the growth temperature is 900 to 1060 °C.
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