WO2014040451A1 - 压电驻极体薄膜及其制备方法 - Google Patents

压电驻极体薄膜及其制备方法 Download PDF

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WO2014040451A1
WO2014040451A1 PCT/CN2013/079680 CN2013079680W WO2014040451A1 WO 2014040451 A1 WO2014040451 A1 WO 2014040451A1 CN 2013079680 W CN2013079680 W CN 2013079680W WO 2014040451 A1 WO2014040451 A1 WO 2014040451A1
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template
film
piezoelectric electret
nanowire
polymer
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PCT/CN2013/079680
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English (en)
French (fr)
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范凤茹
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纳米新能源（唐山）有限责任公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • H10N30/08—Shaping or machining of piezoelectric or electrostrictive bodies
    • H10N30/084—Shaping or machining of piezoelectric or electrostrictive bodies by moulding or extrusion
    • 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
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/098—Forming organic materials
    • 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
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/857—Macromolecular compositions

Definitions

  • the invention relates to a piezoelectric electret film and a preparation method thereof, in particular to a piezoelectric electret film manufactured by template processing and a preparation method thereof. Background technique
  • the common dielectric will be polarized under the action of an external electric field. When the external electric field is removed, the polarization of the dielectric disappears.
  • An electret is a dielectric with a long-term charge. Its charge can be a polarized charge that is "frozen” due to polarization, or it can be a positive or negative charge trapped in a "trap” on the surface or in the body, and magnetized with a steel rod. After that, the residual magnetization becomes similar to that of a permanent magnet. People also call a dielectric with a long-lasting charge called a permanent electric body, which is customarily called an electret.
  • Electrets are used in industrial technology, medicine, biology, etc., mainly including electret microphones, electret air filters, and fax image recording.
  • Electret can be made into medical materials, such as China's first anti-inflammatory analgesic membrane for the treatment of pain, has achieved good results, won the international Eureka invention gold medal, and has been mass-produced; due to the electric field formed by the electret The role of thrombosis, so it is hopeful to become a material for artificial blood vessels and so on.
  • the materials prepared are no longer made of a mixture of natural materials, but a large number of artificially produced polymer materials, such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF).
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • the heating temperature should be slightly higher than the glass transition temperature of the polymer (polytetrafluoroethylene about 150-200 ° C)
  • the electric field used is about 0.1-1 kV per centimeter
  • the polarization time is about a few minutes. Until 1 hour, keep the temperature constant during this period.
  • the preparation method includes, in addition to the thermal polarization method, a corona method, an electron ray method, and a liquid contact method.
  • porous piezoelectric electret is a porous structure polymer film material/structure with excess charge. Porous piezoelectric electret film has superior piezoelectric properties, and its piezoelectric constant in the thickness direction is usually several hundred pC/N, which is equivalent to or higher than the piezoelectric constant of piezoelectric ceramics. It is a new type of electromechanical sensing. Material Material / structure. Coupled with the flexibility of the polymer, large-area film formation, and low cost, the porous piezoelectric electret film material has important application prospects in flexible functional electronic devices and electromechanical smart sensor devices.
  • the technical problem to be solved by the present invention is to provide a method for preparing a piezoelectric electret film having a pore size up to a nanometer level and a piezoelectric electret film obtained by the nanowire template.
  • a method for preparing a piezoelectric electret film comprising the steps of:
  • step (1) (2) combining at least one first polymer film dried in step (1) with the second polymer film to form a cavity;
  • the cavity has a width of 50 nm to 500 nm, a depth of 100 ⁇ -3 ⁇ , and a cavity spacing of 100 nm to 500 nm.
  • the template removal described in step (1) is removed by etching the nanowires.
  • the template of the oxidized nanowire array structure is removed by using a dilute acid, and the template of the silicon nanowire array structure is removed by using a mixed solution of hydrogen fluoride and hydrogen peroxide.
  • the template having the nanowires in the step (1) is a template of a silicon nanowire array structure or a template vertically grown with an oxidized nanowire array structure, and the cross-sectional shape of the nanowires is selected from a regular rectangle and a hexagon. , round or square
  • the template having the nanowires in the step (1) is a template of a silicon nanowire array structure or a template in which an oxidized nanowire array structure is vertically grown, and the cross-sectional shape of the nanowires is selected from an irregular shape.
  • the coating method of the step (1) is spin coating or electrostatic spraying.
  • step (1) the coating thickness of the polymer is greater than the height of the nanowire.
  • polymer is selected from one or more of the following polymer groups: polyvinylidene fluoride
  • PVDF fluorinated ethylene propylene copolymer
  • FEP fluorinated ethylene propylene copolymer
  • PFA soluble polytetrafluoroethylene
  • PCTFE polychlorotrifluoroethylene
  • PP polypropylene
  • PE polyethylene
  • PE polyimine
  • PI And polyethylene terephthalate PET
  • step (2) is selected from one or more of the following: laminating, bonding, clamping, clamping, screwing, riveting or welding.
  • the first polymer film and the second polymer film are made of the same material.
  • the template of the oxidized nanowire array structure is prepared by the following method: synthesizing the oxidized nanowire array by hydrothermal method, and then annealing and annealing to obtain a template of the oxidized nanowire array structure; wherein, the silicon nanowire
  • the template of the array structure is prepared by wet etching, and the clean silicon wafer is directly immersed and etched in a mixed solution of hydrogen fluoride and silver nitrate to obtain a template of the silicon nanowire array structure.
  • the gas is flushed into the cavity of the piezoelectric electret, and the gas is preferably pure nitrogen.
  • a piezoelectric electret film characterized in that the film comprises a first polymer film (1) having nanowire holes bonded to a surface of the at least one first polymer film (1) having nanowire holes a second polymer film (3), a cavity formed between the first polymer film (1) and the second polymer film (3) (2), and forming opposite charges distributed on the upper and lower surfaces in the cavity by polarization; wherein the formation of the nanowire holes is achieved by coating the polymer solution on a template having nanowires.
  • the cavity has a width of 50 nm to 500 nm, a depth of 100 ⁇ -3 ⁇ , and a cavity pitch of 100 nm to 500 nm.
  • a piezoelectric element comprising at least one of the piezoelectric electret films.
  • the invention has the beneficial effects that: the invention forms a piezoelectric electret film by using a nanowire template to form a piezoelectric electret film with a cavity reaching a nanometer level, and an increase in the specific surface area of the film is advantageous for storing more stable charges. , thereby obtaining a larger piezoelectric constant d33.
  • the present invention not only realizes the size of the cavity to the nanometer level, but also improves the piezoelectric constant of the electret piezoelectric film by optimizing various influence factors such as materials.
  • the invention directly forms a closed structure without enclosing the piezoelectric electret film, and various piezoelectric electret films can be obtained by selecting a template, which can be operated in a tube, saves cost, and can be large-scale
  • the production and the obtained piezoelectric electret film have good performance, and have wide application prospects in self-driven generators and pressure sensors.
  • Figure 1 is a cross-sectional view of a piezoelectric electret film in a specific embodiment of the present invention.
  • Figure 2 Nanowire template for a piezoelectric electret film of an embodiment of the present invention.
  • Figure 3 Illustration of the stripping of the first polymer film with the nanowire template.
  • Figure 4 Appearance of the piezoelectric electret film of the present invention.
  • Figure 5 is a cross-sectional view of a piezoelectric electret film in another embodiment of the present invention.
  • the numbers in the figure are: 1-first polymer film, 2-cavity, 3-second polymer film, 4-nanowire, 5-nanowire template substrate, 6-first polymer layer a , 7 - first polymer layer b, 8- first layer cavity, 9 - second layer cavity.
  • the invention provides a method for preparing a piezoelectric electret film, comprising the steps of: (1) coating a polymer solution on a template having nanowires, followed by drying; removing the template after drying to obtain nanowires a first polymer film of the pores; (2) combining at least one first polymer film dried in step (1) with the second polymer film to form a cavity; and (3) forming step (2) by polarization
  • the upper and lower surfaces of the cavity are distributed with opposite charges to form a piezoelectric electret film.
  • the step (1) is mainly a process of forming nanopores on the polymer film according to the needs of the final piezoelectric electret.
  • the thickness of the coating polymer is greater than the height of the nanowires on the template to ensure that the depth of the nanowire holes on the first polymer film obtained is consistent with the height of the nanowires on the template to satisfy the piezoelectric electret The need for body membranes.
  • the coating may be applied by spin coating or electrostatic spraying during the coating process to better control the thickness and uniformity of the coating.
  • the coating thickness mainly depends on the use of the prepared piezoelectric electret film, and different thicknesses are applied according to different requirements.
  • the template having nanowires is a template of a silicon nanowire array structure or a template vertically grown with an array of oxidized nanowires, and the cross-sectional shape of the nanowires is selected from a regular or irregular rectangle, a hexagon, and a circle. Shape or square.
  • the shape of each nanowire of the nanowire array is the same as the individual nanowire holes on the finally prepared first polymer film. In order to accurately control the shape and size of the nanowire holes, different nanowire templates can be selected as needed.
  • the polymer is selected from one or more of the following polymer groups: polyvinylidene fluoride (PVDF), fluorinated ethylene propylene copolymer (FEP), soluble polytetrafluoroethylene (PFA), polychlorotrifluoroethylene (PCTFE), polypropylene (PP), polyethylene (PE), polyimine (PI) and polyethylene terephthalate (PET); preferably polyvinylidene fluoride, preferably first and second
  • PVDF polyvinylidene fluoride
  • FEP fluorinated ethylene propylene copolymer
  • PFA soluble polytetrafluoroethylene
  • PCTFE polychlorotrifluoroethylene
  • PP polypropylene
  • PE polyethylene
  • PE polyimine
  • PET polyethylene terephthalate
  • the polymer solution in the step (1) is prepared by mixing a polymer with N, N-dimercaptophthalamide and sealing and dissolving, and preferably, the mixed solution is ultrasonicated for a period of time, preferably 30 minutes, after sealing.
  • the nanowire template of the present invention is a template of a nanowire array structure prepared by itself according to a conventional method as needed.
  • the method of separating the nanowire template from the piezoelectric electret film may be any method capable of separating the two, and it is preferably placed in a dilute hydrochloric acid solution for immersion, and the nanowire is partially etched and then peeled off.
  • step (2) is a process in which the final piezoelectric electret is physically formed, that is, a process in which the film layers are combined to form a cavity.
  • the manner of bonding is selected from one or more of the following: lamination, bonding, clamping, clamping, threading, riveting or welding.
  • the depth (height) at which the cavity is formed is 100 ⁇ - 3 ⁇ , which is the highest height of the cavity in the cross section in the vertical direction of the polymer layer, that is, the distance between the upper and lower surfaces in the cavity formed.
  • the width of the cavity is from 50 nm to 500 nm, and the width refers to the maximum width of the cavity in the cross section in the vertical direction of the polymer layer, and the cavity formed is in a range parallel to the direction of the layer.
  • the second polymer film and the first polymer film are used The materials are the same, the second polymer film is commercially available, or can be prepared by a conventional method for preparing a film in the art, and can also be obtained by a method similar to that of the first polymer film.
  • the piezoelectric electret film of the present invention has a smaller cavity and a larger specific surface area, which is advantageous for stabilizing the formed charge, thereby achieving a larger piezoelectric constant d33.
  • the step (3) is a functional requirement for making the film layer prepared above into a piezoelectric electret.
  • the electrode or electrode layer is applied to the piezoelectric electret film
  • the upper and lower surfaces of the cavity may be polarized by the corona discharge, and after the electrode or electrode layer is applied to the piezoelectric electret film, It can be directly charged by applying a voltage, which is more favorable for polarization when the gas is flushed into the cavity of the piezoelectric electret.
  • the present invention also provides a piezoelectric electret film comprising a first polymer film (1) having nanowire holes, and nanowire holes bonded to at least one first polymer film (1) a second polymer film (3) on the surface, a cavity (2) formed between the first polymer film (1) and the second polymer film (3), and distributed in the cavity by polarization formation The opposite charge of the surface; wherein the formation of nanowire pores is achieved by coating a polymer solution onto a template having nanowires.
  • Fig. 5 shows a piezoelectric electret film obtained by filming two first polymer films and a second polymer.
  • the invention further relates to a piezoelectric element comprising at least one of the above described piezoelectric electret films.
  • the piezoelectric element further includes an electrode layer coated on the first polymer film and/or the second polymer film, and/or connected to the first polymer film and/or the second polymer film electrode, ultimately forming two Electrodes.
  • the surface of the prepared piezoelectric electret film can be plated with a metal electrode by vacuum sputtering or evaporation. A voltage is applied to the metal electrodes on both sides of each layer of the piezoelectric electret film to polarize to form a ⁇ phase structure.
  • the magnitude of the voltage intensity is determined by the thickness of the film, and the average is 60 ⁇ / ⁇ , and the voltage is applied for one hour.
  • the polarized piezoelectric electret film has piezoelectric properties, and two metal film electrodes serve as output electrodes.
  • PVDF Polyvinylidene fluoride
  • d33 YE2730A Piezoelectric Ceramic Constant (d33) measuring instrument, manufactured by Jiangsu Lianneng Electronic Technology Co., Ltd.
  • the oxidation of the nanowire array After the oxidation of the nanowire array is completed, it is heat-annealed (temperature: 145-155 ° C), ultrasonically cleaned, dried with a nitrogen gas gun, and dried in a vacuum oven at 80 ° C for 1.5 hours to form a A template for the oxidation of nanowire arrays.
  • the oxidized nanowires on the template were determined to have a height of 3 ⁇ m, a cross section of a hexagon having a side length of about 200 nm, and an interval between the oxidized nanowires of 200 nm.
  • the PVDF solution prepared in the step 1) is uniformly and directly coated on the prepared template of the vertically grown oxidized nanowire array by spin coating, and the coating is controlled to dry.
  • the thickness of the rear PVDF film was 100 ⁇ m. After the coating was completed, it was dried in a vacuum desiccator at 80 ° C for 1 hour. After drying, it was placed in a dilute hydrochloric acid solution for 15 min, and then the template in which the oxidized nanowire array was vertically grown was removed to obtain a PVDF film having nanowire holes, which was the first polymer film.
  • Preparation of smooth second polymer film The above prepared PVDF solution is uniformly coated directly on the smooth substrate for growing the oxidized nanowire by spin coating, and the thickness of the PVDF film after drying is controlled by coating. It is 50 ⁇ . After the coating was completed, it was dried in a vacuum desiccator at a temperature of 80 ° C for 0.5 hour to obtain a smooth PVDF film having a thickness of 50 ⁇ m.
  • Preparation and performance formation of piezoelectric electret film The smooth PVDF film having a thickness of 50 ⁇ m obtained above was placed on the first polymer film prepared above, and laminated at a temperature of 150 ° C, after lamination The film thickness was 150 ⁇ m, forming a cavity.
  • the height of the cavity is 3 ⁇ m
  • the bottom surface is a hexagon having a side length of about 200 nm
  • the lateral spacing between the cavities is 200 nm, thereby preparing a piezoelectric electret.
  • the physical structure of the film Thereafter, both surfaces of the above-prepared PVDF composite film were subjected to sputtering by sputtering a 50 nm-thick aluminum electrode to form a piezoelectric element having a size of 4 cm x 4 cm. A voltage is applied to the electrodes on both sides of the PVDF composite membrane to polarize the PVDF to form a ⁇ phase structure.
  • the applied voltage intensity was determined by the thickness of the film, and the average was 60 ⁇ / ⁇ , and the application time was 1 hour.
  • the polarized PVDF film has piezoelectric properties, and the results of measuring the d33 coefficient after polarization are shown in Table 1.
  • the oxidation of the nanowire array After the oxidation of the nanowire array is completed, it is heat-annealed (temperature: 145-155 ° C), ultrasonically cleaned, dried with a nitrogen gas gun, and dried in a vacuum oven at 80 ° C for 1.5 hours to form a A template for the oxidation of nanowire arrays.
  • the oxidized nanowires on the template were determined to have a height of 3 ⁇ m, a cross section of a hexagon having a side length of about 200 nm, and an interval between the oxidized nanowires of 200 nm.
  • the PVDF solution prepared in the step 1) is uniformly and directly coated on the prepared template of the vertically grown oxidized nanowire array by spin coating, and the coating is controlled to be dried.
  • the thickness of the rear PVDF film was 100 ⁇ m.
  • an identical first polymer film b was prepared in the same manner as above to obtain two first polymer films.
  • Preparation and performance formation of piezoelectric electret film The surface of the first polymer film a without nanowire holes is laminated with the surface of the first polymer film b having nanowire holes, and the step (4) is prepared.
  • a smooth PVDF film having a thickness of 50 ⁇ m was placed on the surface of the first polymer film a prepared above having nanowire holes, followed by lamination at a temperature of 150 ° C, in the first polymer film a and the smooth PVDF film.
  • a first layer of cavities is formed between the first polymer film a and the first polymer film b to form a second layer of cavities (as shown in FIG. 5), and the lamination process is performed in a pure nitrogen atmosphere.
  • the combined film thickness was 250 ⁇ m.
  • the height of the first layer cavity and the second layer cavity are both 3 ⁇ , and the bottom surface is a hexagon having a side length of about 200 nm, and the lateral intervals between the cavities are At 200 nm, the physical structure of the piezoelectric electret film was prepared. Thereafter, the two surfaces of the above-prepared PVDF composite film were subjected to sputtering by sputtering a 50 nm-thick aluminum electrode to form a piezoelectric element having a size of 4 cm x 4 cm. A voltage is applied to the electrodes on both sides of the PVDF composite film to polarize the PVDF to form a ⁇ phase structure.
  • the applied voltage intensity was determined by the thickness of the film, and the average was 60 ⁇ / ⁇ , and the application time was 1 hour.
  • the polarized PVDF film has piezoelectric properties, and the results of measuring the d33 coefficient after polarization are shown in Table 1.
  • PET polyethylene terephthalate
  • Preparation of the template of the silicon nanowire array structure The preparation of the silicon nanowire template is carried out by wet etching, and the reaction temperature is controlled at 50 ° C with a constant temperature water bath, and the etching solution is selected to be 5 mol/L hydrofluoric acid and 0.02. A mixed solution of mol/L silver nitrate is used to etch the cleaned silicon wafer in an etching solution in time. After the reaction for 60 minutes, the silicon wafer was taken out, washed, and dried. The prepared silicon nanowires have a length of about 20 ⁇ m and a cross section of 50 nm in diameter, which finally forms a template for the silicon nanowire array structure.
  • the PET solution prepared in the step 1) is uniformly coated directly on the template of the prepared silicon nanowire array structure by spin coating, and the coated PET film is controlled to be dried. The thickness is 100 ⁇ m. After the coating was completed, it was dried in a vacuum desiccator at 80 ° C for 1 hour. After drying, it was placed in a mixed solution of hydrogen fluoride and hydrogen peroxide for 15 minutes to remove the template of the silicon nanowire array structure to obtain a PET film having nanowire holes, which is the first polymer film.
  • Preparation of a smooth second polymer film uniformly coating the above-prepared PET solution on a smooth substrate for etching silicon nanowires by spin coating, and controlling the thickness of the PET film after drying It is 50 ⁇ . After the coating was completed, it was dried in a vacuum desiccator at 80 ° C for 0.5 hours to obtain a smooth PET film having a thickness of 50 ⁇ m.
  • both surfaces of the above-prepared PET composite film were subjected to sputtering by sputtering a 50 nm-thick aluminum electrode to form a piezoelectric element having a size of 4 cm x 4 cm.
  • a voltage is applied to the electrodes on both sides of the PET composite film to polarize PET to form a ⁇ phase structure.
  • the applied voltage intensity was determined by the thickness of the film, and the average was 60 ⁇ / ⁇ , and the application time was 1 hour.
  • the polarized PET film has piezoelectric properties, and the results of the d33 coefficient after polarization are shown in Table 1.
  • the oxidation of the nanowire array After the oxidation of the nanowire array is completed, it is heat-annealed (temperature: 145-155 ° C), ultrasonically cleaned, dried with a nitrogen gas gun, and dried in a vacuum oven at 80 ° C for 1.5 hours to form a A template for the oxidation of nanowire arrays. It was determined that the height of the oxidized nanowire on the template was 2 ⁇ m, the cross section was a circle having a diameter of about 500 nm, and the interval between the nanowires was 500 nm.
  • the PE solution prepared in the above step 1) is uniformly and directly coated on the prepared template of the vertically grown oxidized nanowire array by spin coating, and the coating is controlled.
  • the thickness of the PE film after drying was 100 ⁇ m.
  • both surfaces of the above-prepared PE composite film were subjected to sputtering by sputtering a 5 nm thick aluminum electrode to form a piezoelectric element, and the size of the piezoelectric element after the cutting was 4 cm x 4 cm.
  • a voltage is applied to the electrodes on both sides of the PE composite membrane to polarize the PE to form a ⁇ phase structure.
  • the applied voltage intensity was determined by the thickness of the film, and the average was 60 ⁇ / ⁇ , and the application time was 1 hour.
  • the polarized ruthenium film has piezoelectric properties, and the results of measuring the d33 coefficient after polarization are shown in Table 1.
  • Example 5 1) Preparation of polymer solution: 2 g of PVDF was placed in a 100 mL beaker, 8 ml of dimercaptoacetamide (DMF) was weighed in a 10 mL measuring cylinder, and added to a beaker to dissolve PVDF (11.7 wt%), and then the beaker was used. The cling film is sealed, sonicated for 30 min, PVDF is completely dissolved, and it is ready for use.
  • DMF dimercaptoacetamide
  • Preparation of the first polymer film The above-prepared PVDF solution was uniformly coated directly by spin coating on a PDMS template having a rectangular parallelepiped array (commercially prepared, the template of the convex cuboid) The height is 60 ⁇ , the bottom surface is a square having a side length of 30 ⁇ m, and the interval between the protrusions is ⁇ ), and the coating is controlled so that the thickness of the PVDF film after drying is 100 ⁇ m. After the coating was completed, it was dried in a vacuum desiccator at 80 ° C for 1 hour. After drying, the PDMS template with the rectangular raised array is removed. A PVDF film having an array of pits is obtained, i.e., a first polymer film.
  • step 3 Preparation of smooth second polymer film:
  • the PVDF solution prepared in step 1) is uniformly coated directly on the smooth substrate for preparing the rectangular parallelepiped array by spin coating, and the coating is controlled to make the PVDF after drying.
  • the thickness of the film was 50 ⁇ m.
  • the two surfaces of the above-prepared PVDF composite film were subjected to sputtering by sputtering a 50 nm-thick aluminum electrode to form a piezoelectric element having a size of 4 cm x 4 cm.
  • a voltage is applied to the electrodes on both sides of the PVDF composite film to polarize the PVDF to form a ⁇ phase structure.
  • the applied voltage intensity was determined by the thickness of the film, and the average was 60 ⁇ / ⁇ , and the application time was 1 hour.
  • the polarized PVDF film has piezoelectric properties, and the results of measuring the d33 coefficient after polarization are shown in Table 1.

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Abstract

压电驻极体薄膜的制备方法，将聚合物溶液涂覆在具有纳米线的模板上，进行干燥；后将该模板移除得到具有纳米线孔的第一聚合物膜（1）；将干燥后的至少一个第一聚合物膜（1）与第二聚合物膜（3）结合形成空腔（2）；通过极化使空腔（2）内上下表面分布相反电荷，形成压电驻极体薄膜。上述制备方法制备得到的压电驻极体薄膜。还提供了压电驻极体薄膜，包括具有纳米线孔的第一聚合物膜（1），结合在至少一个第一聚合物膜（1）的具有纳米线孔的表面上的第二聚合物膜（3），在第一聚合物膜（1）与第二聚合物膜（3）之间形成空腔（2），以及通过极化形成分布于空腔（2）内上下表面的相反电荷；纳米线孔的形成是通过将聚合物溶液涂覆在具有纳米线的模板上实现的。还提供了由驻极体薄膜形成的压电元件。

Description

压电驻极体薄膜及其制备方法
技术领域
本发明涉及一种压电驻极体薄膜及其制备方法，特别涉及一种通过模板加 工制造的压电驻极体薄膜及其制备方法。 背景技术
常见的电介质在外电场作用下会发生极化， 当去除外电场后， 电介质的极 化现象也随之消失。驻极体是具有长久电荷的电介质， 它的电荷可以是因极化 而被"冻结"的极化电荷， 也可以是陷入表面或体内"陷阱" 中的正、 负电荷， 与钢棒经磁化后具有剩余磁化强度成为永磁体类似，人们也把具有长久保留电 荷的电介质叫永电体， 习惯上称为驻极体。
驻极体在工业技术、 医学、 生物学等领域都有应用， 主要有驻极体传声 器、驻极体空气过滤器和传真图像记录等。 驻极体可制成医用材料， 如我国首 创的消炎止痛膜用于治疗伤痛，已取得良好的疗效，获得国际尤里卡发明金奖， 并已批量生产； 由于驻极体形成的电场有阻止血栓形成的作用， 因此有希望成 为人造血管的材料等等。
随着人们对驻极体的研究和应用， 制备的材料不再用天然材料的混合物， 而是大量使用人工制造的聚合物材料， 如聚四氟乙烯 (PTFE), 聚偏氟乙烯 (PVDF)等， 聚合物驻极体具有更好的荷电能力和优良的机械性能， 可制成微 米量级的薄膜。用热极化法制备时，加热温度应稍高于聚合物的玻璃化温度 (聚 四氟乙烯约 150-200 °C), 所用电场约 0.1-1千伏每厘米， 极化时间约几分钟到 1小时， 此期间保持恒温。 而制备方法除热极化法之外， 还有电晕法、 电子射 线法和液体接触法等。
近年来有多篇文献公开了封闭的外层和多孔或者穿孔的中间层组成的多 层系统。 多孔压电驻极体是带有过剩电荷的孔洞结构聚合物薄膜材料 /结构。 多孔压电驻极体薄膜具有优越的压电性能， 其厚度方向的压电常数通常达到 数百 pC/N, 与压电陶瓷的压电常数相当甚至更高， 是一种新型的机电传感材 料 /结构。 再加上拥有聚合物的柔顺性、 可大面积成膜、 低成本的优点， 使得 多孔压电驻极体薄膜材料在柔性功能电子器件和机电智能传感器件方面具有 重要应用前景。
最近公开的具有多孔或穿孔中间层的层系统经常具有比上述系统大出很 多的压电常数，但是这些中间层是不能与固体外层可靠的层合。 而且对中间层 的穿孔通常是非常耗时的。特别是将空腔的大小做到纳米级在现有技术中是很 难实现的。 纳米级的空腔具有很高的内比表面， 应用到驻极体薄膜中， 可以更 有效的存储电荷， 使得驻极体薄膜在形变过程中， 输出的电能更大。 然而由于 规则纳米线阵列的制备具有一定的难度， 需要借助一些昂贵的仪器，制作成本 太！ ¾。
现有技术中， 由于没有合适的模板或者方法可以将空腔的大小做到纳米 级， 所以亟需开发一种筒便的、 廉价的， 能大规模生产具有纳米级空腔的压电 驻极体薄膜。 发明内容
本发明解决技术问题是：提供一种通过纳米线模板制备得到的孔腔达到纳 米级的压电驻极体薄膜的方法及其得到的压电驻极体薄膜。
具体来说， 本发明是通过如下技术方案实现的：
一种压电驻极体薄膜的制备方法， 其特征在于， 包括如下步骤：
( 1 )将聚合物溶液涂覆在具有纳米线的模板上， 之后进行干燥； 干燥后 将该模板移除得到具有纳米线孔的第一聚合物膜；
( 2 )将步骤（ 1 )干燥后的至少一个第一聚合物膜与第二聚合物膜结合形 成空腔； 以及
( 3 )通过极化使步骤（ 2 )形成的空腔内上下表面分布相反电荷， 从而形 成压电驻极体薄膜。
其中， 空腔的宽度为 50nm-500nm, 深度为 100ηηι-3μηι, 空腔间距为 100 nm-500nm„
其中， 步骤（1 )所述的模板移除是通过将纳米线蚀刻进行移除。 其中，氧化辞纳米线阵列结构的模板采用稀酸进行移除，硅纳米线阵列结 构的模板采用氟化氢和双氧水的混合溶液进行移除。
其中， 在步骤（1 )所述具有纳米线的模板是硅纳米线阵列结构的模板或 垂直生长有氧化辞纳米线阵列结构的模板，所述纳米线的断面形状选自规则矩 形、 六边形、 圓形或正方形
其中， 在步骤（1 )所述具有纳米线的模板是硅纳米线阵列结构的模板或 垂直生长有氧化辞纳米线阵列结构的模板，所述纳米线的断面形状选自不规则 的形状。
其中， 步骤（1 )所述涂覆的方式是旋转涂覆或静电喷涂。
其中， 步骤（1 ) 中， 聚合物的涂覆厚度大于纳米线的高度。
其中， 所述聚合物选自如下聚合物组中的一种或几种： 聚偏氟乙烯
( PVDF )、 氟化乙烯丙烯共聚物 (FEP)、 可溶性聚四氟乙烯 (PFA)、 聚三氟氯乙 烯 (PCTFE)、 聚丙烯 (PP)、 聚乙烯 (PE)、 聚酞亚胺 (PI)和聚对苯二曱酸乙二酯 (PET)。
其中， 步骤（2 ) 中结合的方式选自如下方式的一种或几种： 层合、 粘合、 夹紧、 钳夹、 螺纹连接、 铆接或焊接。
其中， 所述第一聚合物膜和第二聚合物膜材质相同。
其中，氧化辞纳米线阵列结构的模板是通过如下方法制备得到的： 通过水 热法合成氧化辞纳米线阵列，之后对其加热退火，得到氧化辞纳米线阵列结构 的模板； 其中， 硅纳米线阵列结构的模板的制备方法是采用湿法刻蚀的方法， 直接将干净的硅片在氟化氢和硝酸银的混合溶液中浸泡刻蚀，得到硅纳米线阵 列结构的模板。
其中， 在步骤（ 2 )后和步骤（ 3 )之间， 将气体沖入压电驻极体的空腔内， 所述的气体优选纯氮气。
一种通过所述的制备方法制备得到的压电驻极体薄膜。
一种压电驻极体薄膜，其特征在于，该薄膜包括具有纳米线孔的第一聚合 物膜（ 1 ) , 结合在至少一个第一聚合物膜（ 1 ) 的具有纳米线孔的表面上的第 二聚合物膜（ 3 ), 在第一聚合物膜（ 1 )与第二聚合物膜（ 3 )之间形成的空腔 ( 2 ), 以及通过极化形成分布于空腔内上下表面的相反电荷； 其中纳米线孔的 形成是通过将聚合物溶液涂覆在具有纳米线的模板上实现的。
其中， 空腔的宽度为 50nm-500nm, 深度为 100ηηι-3μηι, 空腔间距为 100 nm-500nm。 一种压电元件， 包括至少一个所述的压电驻极体薄膜。
本发明的有益效果是： 本发明通过使用纳米线模板形成压电驻极体薄膜， 形成空腔达到纳米级的压电驻极体薄膜，薄膜内比表面的增加有利于存储更多 的稳定电荷， 从而得到更大的压电常数 d33。 本发明不仅实现了将空腔的大小 做到了纳米级别， 而且通过对材料等各种影响因素的优化，将驻极体压电薄膜 的压电常数提高了很多。本发明直接形成封闭结构， 而不需要对压电驻极体薄 膜进行封闭，通过对模板的选择制备可以得到各种压电驻极体薄膜， 筒化了操 作， 节约了成本， 并可以大规模生产， 并且得到的压电驻极体薄膜性能较好， 在自驱动发电机以及压力传感器等方面有着广泛的应用前景。 附图说明
图 1 : 本发明的一种具体实施方式中的压电驻极体薄膜的截面图。
图 2: 本发明的一种具体实施方式的压电驻极体薄膜所用的纳米线模板。 图 3: 将第一聚合物膜与纳米线模板进行剥离的图示。
图 4 ： 本发明压电驻极体薄膜的外观图。
图 5: 本发明另一种具体实施方式中压电驻极体薄膜的截面图。
其中， 图中编号分别为： 1-第一聚合物膜， 2-空腔， 3-第二聚合物膜， 4- 纳米线， 5-纳米线模板的基板， 6-第一聚合物层 a, 7-第一聚合物层 b, 8-第一 层空腔， 9-第二层空腔。 具体实施方式
本发明提供了一种压电驻极体薄膜的制备方法， 包括步骤： （1 )将聚合物 溶液涂覆在具有纳米线的模板上，之后进行干燥； 干燥后将模板移除得到具有 纳米线孔的第一聚合物膜； （2 )将步骤（1 )干燥后的至少一个第一聚合物膜 与第二聚合物膜结合形成空腔； 以及（ 3 )通过极化使步骤（ 2 )形成的空腔内 上下表面分布相反电荷， 从而形成压电驻极体薄膜。 下面结合附图 1-5 对本发明的压电驻极体薄膜及其制备方法进行详细说 明。
其中， 步骤（1 )主要是根据最终压电驻极体的需要在聚合物膜上形成纳 米孔的过程。 在该步骤中， 涂覆聚合物的厚度大于模板上纳米线高度， 以确保 得到的第一聚合物膜上的纳米线孔的深度与模板上纳米线的高度一致，以满足 作为压电驻极体膜的需要。优选在涂覆的过程中可以使用旋转涂覆或静电喷涂 的方式进行涂覆， 以更好地控制涂覆的厚度和均勾度。 其中， 涂覆厚度主要取 决于所制备的压电驻极体薄膜的用途，根据不同的要求涂覆不同的厚度。其中， 所述具有纳米线的模板为硅纳米线阵列结构的模板或垂直生长有氧化辞纳米 线阵列的模板， 所述纳米线的断面形状选自规则或不规则的矩形、 六边形、 圓 形或正方形。该纳米线阵列的各纳米线的形状与最终制备的第一聚合物膜上的 各个纳米线孔相同。为了精确控制纳米线孔的形状和尺寸，可以根据需要选择 不同的纳米线模板。
所述聚合物选自如下聚合物组中的一种或几种： 聚偏氟乙烯（PVDF )、 氟 化乙烯丙烯共聚物 (FEP)、 可溶性聚四氟乙烯 (PFA)、 聚三氟氯乙烯 (PCTFE)、 聚丙烯 (PP)、 聚乙烯 (PE)、 聚酞亚胺 (PI)和聚对苯二曱酸乙二酯 (PET); 优选为 聚偏氟乙烯， 优选第一、 第二聚合物膜所用的聚合物材料相同。 其中步骤（1 ) 所述聚合物溶液是将聚合物与 N, N-二曱基曱酰胺混合后进行密封溶解制成， 优选在密封后对混合溶液进行超声一段时间， 优选为 30min。 本发明的纳米线 模板，是根据需要按照常规方法自己制备的纳米线阵列结构的模板。 关于纳米 线模板与压电驻极体薄膜进行分离的方式可以是任意的能将两者分开的方式， 优选将其放进稀盐酸溶液中进行浸泡， 将纳米线进行部分蚀刻后进行剥离。
其中， 步骤（2 )是最终压电驻极体在物理上成型的过程， 即将薄膜层结 合形成空腔的过程。 在该步骤中， 结合的方式选自如下方式中的一种或几种： 层合、 粘合、 夹紧、 钳夹、 螺纹连接、 铆接或焊接。 形成空腔的深度（高度） 为 100ηηι-3μηι, 所述的深度是指在聚合层垂直方向上的截面上空腔的最高高 度， 也就是形成的空腔内上下表面之间的距离。 空腔的宽度为 50nm -500nm, 所述的宽度是指在聚合层垂直方向上的截面上空腔的最大宽度，形成的空腔在 平行于层方向上距离的范围。其中所述的第二聚合物膜与第一聚合物膜所用的 材料相同，第二聚合物膜可以通过商购得到，也可以通过本领域常规的制备膜 的方法制备得到，还可以通过与第一聚合膜类似的方法得到。本发明的压电驻 极体薄膜中的空腔更小， 比表面积更大， 有利于形成的电荷稳定， 从而取得更 大的压电常数 d33。
其中， 步骤（3 )是使上述制备的薄膜层成为压电驻极体的功能要求。 其 中在将电极或电极层施加到压电驻极体薄膜上之前，可以依靠电晕放电使空腔 内上下表面相对侧极化，在将电极或电极层施加到压电驻极体薄膜后，可以通 过施加电压使其直接带电， 当将气体沖入压电驻极体的空腔内， 更加有利于极 化。
另外，本发明还提供了一种压电驻极体薄膜，该薄膜包括具有纳米线孔的 第一聚合物膜（ 1 ), 结合在至少一个第一聚合物膜（ 1 ) 的具有纳米线孔的表 面上的第二聚合物膜（ 3 ) , 在第一聚合物膜（ 1 )与第二聚合物膜（ 3 )之间形 成的空腔（2 ), 以及通过极化形成分布于空腔表面的相反电荷； 其中纳米线孔 的形成是通过将聚合物溶液涂覆在具有纳米线的模板上实现的。当存在多个第 一聚合物层时得到的效果很好，其中图 5所示为两层第一聚合物膜与第二聚合 物膜合得到的压电驻极体薄膜。
本发明还涉及一种压电元件， 包括至少一种上述的压电驻极体薄膜。该压 电元件还包括涂覆在第一聚合物膜和 /或第二聚合物膜上的电极层， 和 /或连接 在第一聚合物膜和 /或第二聚合物膜电极， 最终形成两个电极。 制备好的压电 驻极体薄膜表面可以真空溅射法或蒸镀法镀金属电极。在每一层压电驻极体薄 膜的两侧金属电极上加电压使其极化形成 β相结构。电压强度的大小由膜的厚 度决定， 平均是 60ν/μηι, 施加电压时间一小时。 极化后的压电驻极体薄膜具 有了压电性能， 两个金属薄膜电极作为输出电极。 实施例
首先，对下面实施例中制备压电驻极体薄膜和压电元件中所用的试剂和测 定方法进行如下说明：
Ν, Ν-二曱基曱酰胺（DMF ) ： 商购， 纯度为 98%。 聚偏氟乙烯（PVDF ) ： PVDF原料购自上海 3F新材料股份有限公司， 型号为 FR904。
d33 的测定： YE2730A 压电陶瓷常数 (d33 )测量仪， 江苏联能电子技术 有限公司制造。
稀盐酸的配制： 采用商购的浓盐酸加入水， 配制成质量分数为 10% ( g/g ) 的稀盐酸。 实施例 1
1 ) 聚合物溶液的制备： 将 lg的 PVDF放入 lOOmL烧杯中， 用 10mL量 筒量取 8ml的二曱基乙酰胺 ( DMF ), 加入到烧杯中溶解 PVDF ( 11.7 wt% ), 之后将烧杯用保鲜膜封住， 超声处理 30min, PVDF全部溶解， 待用。
2 )氧化辞纳米线阵列结构的模板的制备： 采用 O.lmol/L浓度的由等摩尔 的环六亚曱基四胺 ( HMTA )和硝酸辞六水合物（ ΖηΝ03·6(Η20) )组成的培养 液， 将预先准备的生长有氧化辞种子层的基板硅片面朝下， 放在培养液顶部， 在水浴环境中生长 5小时， 得到长度为 3μηι的氧化辞纳米线阵列。 完成氧化 辞纳米线阵列生长后， 对其进行加热退火（温度为 145-155°C ), 经超声清洗 后用氮气枪吹干，置于 80°C真空干燥箱中干燥 1.5小时，最终形成具有氧化辞 纳米线阵列的模板。 经测定， 该模板上的氧化辞纳米线的高度为 3μηι, 截面 是边长约为 200nm的六边形， 氧化辞纳米线之间的间隔为 200nm。
3 ) 第一聚合物膜的制备： 将步骤 1 ) 中配好的 PVDF溶液通过旋转涂覆 均匀直接地涂覆在制备好的垂直生长有氧化辞纳米线阵列的模板上，控制涂覆 使干燥后 PVDF膜的厚度为 100μηι。 涂覆完毕后， 将其置于真空干燥器中在 80°C温度下干燥 1小时。 干燥后， 将其放置在稀盐酸溶液中 15min, 之后将垂 直生长有氧化辞纳米线阵列的模板移除，得到具有纳米线孔的 PVDF膜， 即为 第一聚合物膜。
4 ) 光滑的第二聚合物膜的制备： 将上述配好的 PVDF溶液通过旋转涂覆 均匀直接地涂覆在生长氧化辞纳米线用的平滑基板上， 控制涂覆使干燥后 PVDF膜的厚度为 50μηι。 涂覆完毕后， 将其置于真空干燥器中在 80°C温度下 干燥 0.5小时， 得到厚度为 50μηι的光滑 PVDF膜。 5 )压电驻极体膜的制备及性能形成： 将上述得到的厚度为 50μηι的光滑 PVDF膜放置在上述制备的第一聚合物膜上在 150°C温度下进行层合， 层合后 的薄膜厚度为 150μηι, 形成了空腔。 在垂直于层合面的截面上， 该空腔的高 度为 3μηι,底面是边长约为 200nm的六边形，空腔之间横向的间隔均为 200nm, 从而制备得到了压电驻极体薄膜物理结构。之后将上述制备好的 PVDF复合膜 的两个表面通过真空溅射法溅射 50nm厚度的铝电极形成压电元件，所述剪裁 之后的压电元件大小为 4cmx4cm。 在 PVDF 复合膜的两侧电极上加电压使 PVDF极化形成 β相结构。 所施加电压强度由膜的厚度决定， 平均是 60ν/μηι, 施加时间为 1 小时。 极化后的 PVDF膜就具有了压电性能， 极化后测定 d33 系数结果见表 1。 实施例 2
1 )聚合物溶液的制备： 将 2g的 PVDF放入 150mL烧杯中， 用 20mL量 筒量取 15ml的二曱基乙酰胺（ DMF ), 加入到烧杯中溶解 PVDF ( 11.7wt% ), 之后将烧杯用保鲜膜封住， 超声处理 30min, PVDF全部溶解， 待用。
2 )氧化辞纳米线阵列结构的模板的制备： 采用 0.1mol/L浓度的由等摩尔 的环六亚曱基四胺 ( HMTA )和硝酸辞六水合物（ ΖηΝ03·6(Η20) )组成的培养 液，将预先准备的生长有氧化辞种子层的两块基板硅片面朝下，放在培养液顶 部， 在水浴环境中生长 5小时， 得到长度为 3μηι的氧化辞纳米线阵列。 完成 氧化辞纳米线阵列生长后， 对其进行加热退火（温度为 145-155°C ), 经超声 清洗后用氮气枪吹干， 置于 80°C真空干燥箱中干燥 1.5小时，最终形成具有氧 化辞纳米线阵列的模板。 经测定， 该模板上的氧化辞纳米线的高度为 3μηι, 截面是边长约为 200nm的六边形， 氧化辞纳米线之间的间隔为 200nm。
3 )第一聚合物膜的制备： 将步骤 1 ) 中配好的 PVDF溶液通过旋转涂覆 均匀直接地涂覆在制备好的垂直生长有氧化辞纳米线阵列的模板上，控制涂覆 使干燥后 PVDF膜的厚度为 100μηι。 涂覆完毕后， 将其置于真空干燥器中在 80°C温度下干燥 1小时。 干燥后， 将其放置在稀盐酸溶液中 15min, 之后将垂 直生长有氧化辞纳米线阵列的模板移除，得到具有纳米线孔的 PVDF膜， 即为 第一聚合物膜 a,按照与上述相同的方法，再制备一块相同的第一聚合物膜 b, 共得到两块第一聚合物膜。
4 ) 光滑的第二聚合物膜的制备： 将上述配好的 PVDF溶液通过旋转涂覆 均匀直接地涂覆在生长氧化辞纳米线用的平滑基板上， 控制涂覆使干燥后 PVDF膜的厚度为 50μηι。 涂覆完毕后， 将其置于真空干燥器中在 80°C下干燥 0.5小时， 得到厚度为 50μηι的光滑 PVDF膜。
5 )压电驻极体膜的制备及性能形成： 将第一聚合物膜 a没有纳米线孔的 表面与第一聚合物膜 b 具有纳米线孔的表面层合放置， 将步骤（4 )制备的厚 度为 50μηι的光滑 PVDF膜放置在上述制备的第一聚合膜 a的具有纳米线孔的 表面上， 之后在 150°C温度下进行层合， 在第一聚合物膜 a与光滑的 PVDF膜 之间形成第一层空腔，在第一聚合物膜 a与第一聚合物膜 b之间形成第二层空 腔（如图 5所示），层合过程在纯氮气氛围中进行,层合后的薄膜厚度为 250μηι。 在垂直于层合面的截面上， 该第一层空腔和第二层空腔的高度均为 3μηι, 底 面均是边长约为 200nm的六边形， 空腔之间横向的间隔均为 200nm, 从而制 备得到了压电驻极体薄膜物理结构。之后将上述制备好的 PVDF复合膜的两个 表面通过真空溅射法溅射 50nm厚度的铝电极形成压电元件，所述剪裁之后的 压电元件大小为 4cmx4cm。 在 PVDF复合膜的两侧电极上加电压使 PVDF极 化形成 β相结构。 所施加电压强度由膜的厚度决定， 平均是 60ν/μηι, 施加时 间为 1小时。极化后的 PVDF膜就具有了压电性能，极化后测定 d33系数结果 见表 1。 实施例 3
1 )聚合物溶液的制备：将 30g的聚对苯二曱酸乙二酯 (PET)放入 lOOmL烧 杯中， 用 20mL量筒量取 15ml的苯酚， 加入到烧杯中溶解 PET ( 61.3 wt% ), 之后将烧杯用保鲜膜封住， 超声处理 30min, PET全部溶解， 待用。
2 )硅纳米线阵列结构的模板的制备： 硅纳米线模板的制备采用湿法刻蚀 的方法， 用恒温水浴锅控制反应温度在 50°C , 刻蚀溶液选择 5mol/L 氢氟酸 与 0.02 mol/L硝酸银的混合溶液， 将清洗好的硅片及时放入刻蚀溶液中刻蚀。 反应 60分钟之后， 将硅片取出， 清洗干净， 烘干。 制备的硅纳米线长度为 20 μηι左右，截面是直径为 50 nm的圓形，最终形成了硅纳米线阵列结构的模板。
3 ) 第一聚合物膜的制备： 将步骤 1 ) 中配好的 PET溶液通过旋转涂覆均 匀直接地涂覆在制备好的硅纳米线阵列结构的模板上，控制涂覆使干燥后 PET 膜的厚度为 100μηι。 涂覆完毕后， 将其置于真空干燥器中在 80°C温度下干燥 1小时。 干燥后， 将其放置在在氟化氢和双氧水的混合溶液中 15min, 即可将 硅纳米线阵列结构的模板移除， 得到具有纳米线孔的 PET膜， 即为第一聚合 物膜。
4 )光滑的第二聚合物膜的制备： 将上述配好的 PET溶液通过旋转涂覆均 匀直接地涂覆在刻蚀硅纳米线用的平滑基板上， 控制涂覆使干燥后 PET膜的 厚度为 50μηι。 涂覆完毕后， 将其置于真空干燥器中在 80°C温度下干燥 0.5小 时， 得到厚度为 50μηιμηι的光滑 PET膜。
5 )压电驻极体膜的制备及性能形成： 将上述得到的厚度为 50μηι的光滑 PET膜放置在上述制备的第一聚合物膜上在 143 °C温度下进行层合，层合后的 薄膜厚度为 150μηιμηι, 形成了空腔。 在垂直于层合面的截面上， 该空腔的高 度为 lOOnm, 截面是直径为 50 nm的圓形， 空腔之间横向间隔均为 100 nm, 从而制备得到了压电驻极体薄膜物理结构。 之后将上述制备好的 PET复合膜 的两个表面通过真空溅射法溅射 50nm厚度的铝电极形成压电元件，所述剪裁 之后的压电元件大小为 4cmx4cm。 在 PET复合膜的两侧电极上加电压使 PET 极化形成 β相结构。 所施加电压强度由膜的厚度决定， 平均是 60ν/μηι, 施加 时间为 1小时。 极化后的 PET膜就具有了压电性能， 极化后测定 d33系数结 果见表 1。 实施例 4
1 )聚合物溶液的制备： 将 30g的 PE放入 lOOmL烧杯中， 用 10mL量筒 量取 8ml的十氢萘， 加入到烧杯中溶解 PE ( 80.6wt% ) , 之后将烧杯用保鲜 膜封住， 超声处理 30min, PE全部溶解， 待用。
2 )氧化辞纳米线阵列结构的模板的制备： 采用 O.lmol/L浓度的由等摩尔 的环六亚曱基四胺 ( HMTA )和硝酸辞六水合物（ ΖηΝ03·6(Η20) )组成的培养 液， 将预先准备的生长有氧化辞种子层的基板硅片面朝下， 放在培养液顶部， 在水浴环境中生长 5小时， 得到长度为 2μηι的氧化辞纳米线阵列。 完成氧化 辞纳米线阵列生长后， 对其进行加热退火（温度为 145-155°C ), 经超声清洗 后用氮气枪吹干，置于 80°C真空干燥箱中干燥 1.5小时，最终形成具有氧化辞 纳米线阵列的模板。 经测定， 该模板上的氧化辞纳米线的高度为 2μηι, 截面 是直径约为 500nm的圓形， 纳米线之间的间隔为 500nm。
3 )第一聚合物膜的制备： 将上述步骤 1 )中配好的 PE溶液通过旋转涂覆 均匀直接地涂覆在制备好的垂直生长有氧化辞纳米线阵列的模板上，控制涂覆 使干燥后 PE膜的厚度为 100μηιμηι。 涂覆完毕后， 将其置于真空干燥器中在 80°C温度下干燥 1小时。 干燥后， 将其放置在稀盐酸溶液中 15min, 即可将垂 直生长有氧化辞纳米线阵列的模板移除， 得到具有纳米线孔的 PE膜， 即为第 一聚合物膜。
4 ) 光滑的第二聚合物膜的制备： 将上述配好的 PE溶液通过旋转涂覆均 匀直接地涂覆在生长氧化辞纳米线用的平滑基板上， 控制涂覆使干燥后 PE膜 的厚度为 50μηιμηι。 涂覆完毕后， 将其置于真空干燥器中在 80°C温度下干燥 0.5小时， 得到厚度为 50μηιμηι的光滑 ΡΕ膜。
5 )压电驻极体膜的制备及性能形成： 将上述得到的厚度为 50μηιμηι的光 滑 ΡΕ膜放置在上述制备的第一聚合物膜上在 143 °C温度下进行层合， 层合后 的薄膜厚度为 150μηιμηι, 形成了空腔。 在垂直于层合面的截面上， 该空腔的 高度为 2μηιμηι, 底面是直径约为 500nm 的圓形， 空腔之间横向的间隔均为 500nm, 从而制备得到了压电驻极体薄膜物理结构。 之后将上述制备好的 PE 复合膜的两个表面通过真空溅射法溅射 5 Onm厚度的的铝电极形成压电元件， 所述剪裁之后的压电元件大小为 4cmx4cm。在 PE复合膜的两侧电极上加电压 使 PE极化形成 β相结构。 所施加电压强度由膜的厚度决定， 平均是 60ν/μηι, 施加时间为 1小时。 极化后的 ΡΕ膜就具有了压电性能， 极化后测定 d33系数 结果见表 1。 实施例 5 1 ) 聚合物溶液的制备： 将 2g的 PVDF放入 lOOmL烧杯中， 用 10mL量 筒量取 8ml的二曱基乙酰胺 ( DMF ) , 加入到烧杯中溶解 PVDF ( 11.7wt% ), 之后将烧杯用保鲜膜封住， 超声处理 30min, PVDF全部溶解， 待用。
2 ) 第一聚合物膜的制备： 将上述配好的 PVDF溶液通过旋转涂覆均匀直 接地涂覆在预先准备的具有长方体凸起阵列的 PDMS模板（商购的， 该模板 的凸起长方体的高度为 60μηιμηι,底面是边长为 30μηιμηι的正方形， 凸起之间 的间隔为 ΙΟμηιμηι )上， 控制涂覆使干燥后 PVDF膜的厚度为 100μηι。 涂覆完 毕后， 将其置于真空干燥器中在 80°C温度下干燥 1 小时。 干燥后， 将具有长 方体凸起阵列的 PDMS模板移除。 得到具有凹坑阵列的 PVDF膜， 即为第一 聚合物膜。
3 ) 光滑的第二聚合物膜的制备： 将步骤 1 ) 中配好的 PVDF溶液通过旋 转涂覆均匀直接地涂覆在制备长方体凸起阵列用的平滑基板上，控制涂覆使干 燥后 PVDF膜的厚度为 50μηι。 涂覆完毕后， 将其置于真空干燥器中在 80°C温 度下干燥 0.5小时， 得到厚度为 50μηι的光滑 PVDF膜。
4 )压电驻极体膜的制备及性能形成： 将上述得到的厚度为 50μηι的光滑 PVDF膜放置在上述制备的第一聚合物膜上在 150°C温度下进行层合， 层合后 的薄膜厚度为 150μηι, 形成了空腔。 在垂直于层合面的截面上， 该空腔的高 度为 60μηι, 宽度为 30μηι。 空腔之间横向和纵向的间隔均为 ΙΟμηι, 从而制备 得到了压电驻极体薄膜物理结构。之后将上述制备好的 PVDF复合膜的两个表 面通过真空溅射法溅射 50nm厚度的的铝电极形成压电元件，所述剪裁之后的 压电元件大小为 4cmx4cm。 在 PVDF复合膜的两侧电极上加电压使 PVDF极 化形成 β相结构。 所施加电压强度由膜的厚度决定， 平均是 60ν/μηι, 施加时 间为 1小时。极化后的 PVDF膜就具有了压电性能，极化后测定 d33系数结果 见表 1。
表 1 实施例 1-5制备的压电驻极体薄膜 d33系数的测定结果
Figure imgf000014_0001
通过上述实施例 1-5制备得到的压电驻极体薄膜 d33系数的测定结果，可 以看出实施例 2的多层的空腔比单层空腔的 d33系数高。通过上述结果可以看 出本发明的压电驻极体薄膜具有 4艮好的性能。通过实施例 1-4与实施例 5得到 的压电常数 d33的数值可以看出， 实施例 1-4制备的压电驻极体薄膜的 d33明 显高于实施例 5的 d33数值，这也充分证明了纳米级的压电驻极体空腔能够提 高压电驻极体薄膜的压电性能。

Claims

权 利 要 求 书
1. 一种压电驻极体薄膜的制备方法， 其特征在于， 包括如下步骤：
( 1 )将聚合物溶液涂覆在具有纳米线的模板上， 之后进行干燥； 干燥后 将该模板移除得到具有纳米线孔的第一聚合物膜；
( 2 )将步骤（ 1 )干燥后的至少一个第一聚合物膜与第二聚合物膜结合形 成空腔； 以及
( 3 )通过极化使步骤（ 2 )形成的空腔内上下表面分布相反电荷， 从而形 成压电驻极体薄膜。
2. 如权利要求 1 所述的压电驻极体薄膜的制备方法， 其中空腔的宽度为 50-500nm, 深度为 100ηηι-3μηι, 空月空间 巨为 100-500nm。
3. 如权利要求 1或 2所述的压电驻极体薄膜的制备方法， 其中步骤（ 1 ) 所述的模板移除是通过将纳米线蚀刻的方法进行移除。
4. 如权利要求 1-3 任一项所述的压电驻极体薄膜的制备方法， 其中在步 骤（1 )所述具有纳米线的模板是硅纳米线阵列结构的模板或垂直生长有氧化 辞纳米线阵列结构的模板， 所述纳米线的断面形状选自规则矩形、 六边形、 圓 形或正方形。
5. 如权利要求 1-3 任一项所述的压电驻极体薄膜的制备方法， 其中在步 骤（1 )所述具有纳米线的模板是硅纳米线阵列结构的模板或垂直生长有氧化 辞纳米线阵列结构的模板， 所述纳米线的断面形状选自不规则的形状。
6. 如权利要求 1-5 任一项所述的压电驻极体薄膜的制备方法， 其中步骤
( 1 ) 中， 聚合物的涂覆厚度大于纳米线的高度。
7. 如权利要求 1-6任一项所述的压电驻极体薄膜的制备方法， 其中所述 聚合物选自如下聚合物组中的一种或几种： 聚偏氟乙烯（PVDF )、 氟化乙烯丙 烯共聚物 (FEP)、可溶性聚四氟乙烯 (PFA)、聚三氟氯乙烯 (PCTFE)、聚丙烯 (PP)、 聚乙烯 (PE)、 聚酞亚胺 (PI)和聚对苯二曱酸乙二酯 (PET)。
8. 如权利要求 1-7任一项所述的压电驻极体薄膜的制备方法， 其中步骤
( 2 )中结合的方式选自如下方式中的一种或几种： 层合、 粘合、 夹紧、 钳夹、 螺纹连接、 铆接或焊接。
9. 如权利要求 1-8任一项所述的压电驻极体薄膜的制备方法， 其中所述 第一聚合物膜和第二聚合物膜材质相同。
10. 如权利要求 1-9任一项所述的压电驻极体薄膜的制备方法， 其中， 氧 化辞纳米线阵列结构的模板是通过如下方法制备得到的：通过水热法合成氧化 辞纳米线阵列，之后对其加热退火，得到氧化辞纳米线阵列结构的模板；其中， 硅纳米线阵列结构的模板的制备方法是采用湿法刻蚀的方法，直接将干净的硅 片在氟化氢和硝酸银的混合溶液中浸泡刻蚀， 得到硅纳米线阵列结构的模板。
11. 如权利要求 1-10任一项所述的压电驻极体薄膜的制备方法，其中在步 骤（ 2 )后和步骤（ 3 )之间， 将气体沖入压电驻极体的空腔内， 所述的气体优 选纯氮气。
12. 如权利要求 1-11任一项所述的压电驻极体薄膜的制备方法，其中步骤 ( 1 )所述涂覆的方式是旋转涂覆或静电喷涂。
13. 一种如权利要求 1-12任一项所述的制备方法制备得到的压电驻极体 薄膜。
14. 一种压电驻极体薄膜， 其特征在于， 该薄膜包括具有纳米线孔的第一 聚合物膜（ 1 ) , 结合在至少一个第一聚合物膜（ 1 ) 的具有纳米线孔的表面上 的第二聚合物膜（ 3 ) , 在第一聚合物膜（ 1 )与第二聚合物膜（ 3 )之间形成的 空腔（2 ), 以及通过极化形成分布于空腔内上下表面的相反电荷； 其中纳米线 孔的形成是通过将聚合物溶液涂覆在具有纳米线的模板上实现的。
15. 如权利要求 14所述的压电驻极体薄膜， 其特征在于， 其中空腔的宽 度为 50-500 nm, 深度为 100ηηι-3μηι, 空月空间 巨为 100-500nm。
16. —种压电元件， 其特征在于， 包括至少一个权利要求 13-15任一项所 述的压电驻极体薄膜。
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CN105788863B (zh) * 2016-02-29 2018-06-12 杭州电子科技大学 一种聚偏氟乙烯薄膜驻极体的制备方法
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CN108063183B (zh) * 2017-11-30 2019-07-12 西安交通大学 一种基于纳米压印制备封闭多孔压电驻极体俘能器的方法
CN110164693B (zh) * 2018-02-12 2022-02-11 北京纳米能源与系统研究所 驻极电极及其制备方法、驻极装置
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CN112606509B (zh) * 2020-12-16 2023-06-27 昆山微电子技术研究院 一种自极化复合驻极体-压电薄膜、其制备方法及压电薄膜传感器

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101654524A (zh) * 2008-03-10 2010-02-24 财团法人工业技术研究院 驻极体材料、驻极体扬声器及其制造方法
CN102415106A (zh) * 2009-04-24 2012-04-11 拜尔材料科学股份公司 生产电-机换能器的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8179026B2 (en) * 2008-09-04 2012-05-15 University Of Massachusetts Nanotubes, nanorods and nanowires having piezoelectric and/or pyroelectric properties and devices manufactured therefrom
EP2286988A1 (de) * 2008-12-13 2011-02-23 Bayer MaterialScience AG Ferroelektret-Zwei- und Mehrschichtverbund und Verfahren zu dessen Herstellung

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101654524A (zh) * 2008-03-10 2010-02-24 财团法人工业技术研究院 驻极体材料、驻极体扬声器及其制造方法
CN102415106A (zh) * 2009-04-24 2012-04-11 拜尔材料科学股份公司 生产电-机换能器的方法

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