WO2020252833A1 - Multifunctional flexible piezoelectric composite thin film having ordered structure and manufacturing method therefor - Google Patents

Multifunctional flexible piezoelectric composite thin film having ordered structure and manufacturing method therefor Download PDF

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WO2020252833A1
WO2020252833A1 PCT/CN2019/095932 CN2019095932W WO2020252833A1 WO 2020252833 A1 WO2020252833 A1 WO 2020252833A1 CN 2019095932 W CN2019095932 W CN 2019095932W WO 2020252833 A1 WO2020252833 A1 WO 2020252833A1
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single crystal
ordered structure
composite film
piezoelectric
multifunctional flexible
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PCT/CN2019/095932
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French (fr)
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王一平
李雄杰
杨颖�
何亭睿
孙胜
盛云
陈朋
胡悫睿
维陶塔斯•奥斯塔瑟维修斯
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南京航空航天大学
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • H10N30/092—Forming composite 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
    • H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity

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  • the invention relates to the field of flexible piezoelectric materials, in particular to a multifunctional flexible piezoelectric composite film with an ordered structure and a preparation method thereof.
  • the functionalized film can use the internal sensor array to sense the effects of external forces and send out responses, these functions
  • the multi-functionality and stability of the functionalized film are poor.
  • the sensitivity of the functionalized film to external forces is significantly weakened.
  • the functionalized film stretched the miniature rubber resistance sensor into a molecular semiconductor crystal size and fabricated it into the substrate material.
  • the sensors are arrayed and made into a flexible and changeable functionalized film, which is used in robots and can measure pressure and temperature at the same time.
  • Chinese invention CN107123470A has developed a flexible and elastic functionalized film.
  • the conductive film includes a pre-stretched elastic substrate, elastic connectors and nanowires.
  • the elastic connector is located between the pre-stretched elastic substrate and the nanowire, and the elastic connector material is partially embedded in the nanowire to form a mixed transition zone to enhance the adhesion between the layers.
  • the functionalized film prepared by the invention has high sensitivity, the preparation method of the functionalized film is more complicated.
  • the Chinese invention CN108896219A has developed a flexible bionic functionalized film.
  • the sensing layer includes a piezoresistive layer and a thin film electrode.
  • the piezoresistive layer has a porous structure and uses elastomers to contact the piezoresistive layer and the thin film electrode.
  • the interface area is filled, the flexible bionic functionalized film can feel the presence of airflow and pressure, and the flexible bionic functionalized film has certain mechanical stability.
  • sensors mainly include capacitive, piezoresistive and friction sensing types.
  • piezoelectric pressure sensors are generally composed of piezoelectric polymers or inorganic functional materials and polymer matrix composites. So far, many functional materials with micro and nano structures, such as BaTiO 3 nanowires, Ge/Si nanowires, single-walled carbon nanotubes (SWNT) and PZT nanorod arrays, have proven that the device is under a small external pressure ( ⁇ 10kPa) has high sensitivity. Although these works have a good effect on improving the sensitivity of functionalized films, the preparation methods of nanowires, nanorods and microarrays are more complicated, with poor reproducibility and higher cost. Therefore, it has become an urgent problem to be solved.
  • the invention provides a multifunctional flexible piezoelectric composite film with an ordered structure and a preparation method thereof, which can prepare a flexible functionalized piezoelectric film with high sensitivity, and the preparation method has simple process and low cost.
  • the present invention adopts the following technical solutions:
  • a method for preparing a multifunctional flexible piezoelectric composite film with an ordered structure including:
  • preparation method of the ordered structure of the multifunctional flexible piezoelectric composite film further includes:
  • Gold electrodes are plated on the multifunctional flexible piezoelectric composite film with an ordered structure by ion sputtering, and wires are drawn on the upper and lower sides;
  • the polydimethylsiloxane and the curing agent are mixed at a weight ratio of 10:1, and spin-coated to cover the upper and lower sides of the electrode, and dried and cured at 80° C. to obtain the assembled piezoelectric film.
  • the polymer includes polyvinyl alcohol, polyvinylidene fluoride, polyvinylidene fluoride vinyl copolymer, polylactic acid, polydimethylsiloxane, polyurethane, polyacrylic resin, and polyolefin.
  • the solvent includes one or more of water, N,N-dimethylene formamide, and N-methylpyrrolidone.
  • the concentration of the polymer solution is 0.5-3wt%.
  • piezoelectric material single crystal microchips include barium titanate single crystal microchips, lead titanate single crystal microchips, lead magnesium niobate-lead titanate single crystal microchips, sodium niobate single crystal microchips, and niobic acid Potassium sodium single crystal microchips, lithium niobate single crystal microchips, lithium tantalate single crystal microchips, and quartz single crystal microchips.
  • the thickness of the piezoelectric material single crystal microplate is 1 nm-100 nm, and the length and width are 1 ⁇ m-10 ⁇ m.
  • the concentration of the piezoelectric single crystal microchip dispersion is 1 to 5 wt%.
  • the thickness of the assembled piezoelectric film is 1-1000 ⁇ m.
  • the invention also provides a multifunctional flexible piezoelectric composite film with an ordered structure, which is prepared by the above preparation method.
  • the orderly organic/inorganic hybrid flexible piezoelectric composite film formed by the layer-by-layer self-assembly method adopted in the present invention has the characteristics of high sensitivity, short response time and stable structure.
  • the functionalized film in the present invention has a simple preparation method, and avoids the use of nanomaterials such as expensive, difficult to process, and complex structure of microarrays, nanowires or nanorods.
  • these nano-materials with micro-nano structures have inevitable uneven distribution and low repeatability during processing.
  • the flat piezoelectric material single crystal microplates are easily aligned on the surface of the polymer, and the layers are similar to the organic/inorganic hybrid structure of mussel shells. This structure can not only improve the stability of the film
  • the piezoelectric material single crystal microplates with the orientation of adjacent layers can play a complementary role, so that the functionalized film of the present invention has high sensitivity and excellent mechanical properties.
  • the functionalized film can convert the vibration of the human vocal cord muscles into electrical signals, and generate corresponding electrical signals according to the differences in the pronunciation of the human vocal cords, and has repeatability and high reliability.
  • speech recognition systems There are potential applications in the field of speech recognition systems.
  • the functionalized film can also sense weak physiological signals of the human body, such as pulse, heartbeat, and exercise status, which can play an important role in the field of biomedicine.
  • the functionalized film prepared by the present invention has the advantages of high sensitivity, simple preparation method, and low cost, which provide the possibility for its practical application in the field of wearable devices and biomedicine.
  • Figure 1 is a plan view of the microstructure of a multifunctional flexible piezoelectric composite film with an ordered structure
  • Figure 2 is a three-dimensional view of the microstructure of a multifunctional flexible piezoelectric composite film with an ordered structure
  • Fig. 3 is a structural plan view of an ordered structure of a multifunctional flexible piezoelectric composite film after packaging.
  • the orderly organic/inorganic hybrid flexible piezoelectric composite film formed by the layer-by-layer self-assembly method adopted in the present invention has the characteristics of high sensitivity, short response time and stable structure.
  • the functionalized film in the present invention has a simple preparation method, and avoids the use of nanomaterials such as expensive, difficult to process, and complex structure of microarrays, nanowires or nanorods.
  • these nano-materials with micro-nano structures have inevitable uneven distribution and low repeatability during processing.
  • the flat piezoelectric material single crystal microplates are easily aligned on the surface of the polymer.
  • the layers are similar to the organic/inorganic hybrid structure between mussel shells. This structure can not only improve the film’s
  • the piezoelectric material single crystal microplates with stability and orientation of adjacent layers can play a complementary role, so that the functionalized film of the present invention has high sensitivity.
  • the functionalized film can convert the vibration of the human vocal cord muscles into electrical signals, and generate corresponding electrical signals according to the differences in the pronunciation of the human vocal cords, and has repeatability and high reliability.
  • speech recognition systems There are potential applications in the field of speech recognition systems.
  • the functionalized film can also sense weak physiological signals of the human body, such as pulse, heartbeat, and exercise status, which can play an important role in the field of biomedicine.
  • the functionalized film prepared by the present invention has the advantages of high sensitivity, simple preparation method, and low cost, which provide the possibility for its practical application in the field of wearable devices and biomedicine.

Abstract

The present invention relates to the field of flexible piezoelectric materials, and provides a multifunctional flexible piezoelectric composite thin film having an ordered structure and a manufacturing method therefor. A flexible functionalized piezoelectric thin film having high sensitivity can be manufactured, and the preparation method is simple in process and low in cost. The present invention comprises: dissolving a polymer powder in a solvent, and dispersing a piezoelectric single crystal platelet in a solvent to obtain a polymer solution and a piezoelectric single crystal platelet dispersion, respectively; putting a glass sheet into the polymer solution and leaving same to stand, and then drying the glass sheet; evenly and slowly dropping the piezoelectric single crystal platelet suspension on the surface of the glass sheet which is inclined and carries a thin layer of polymer, enabling the suspension to flow over the surface of the polymer, and then drying the glass sheet; cyclically performing the process above until a multifunctional flexible piezoelectric composite thin film having a multi-layer ordered structure is formed on the surface of the glass sheet. The present invention can be widely used in the fields of smart wearable devices, flexible robots, energy harvesting and biomedicine, etc.

Description

一种有序结构的多功能柔性压电复合薄膜及其制备方法Multifunctional flexible piezoelectric composite film with ordered structure and preparation method thereof 技术领域Technical field
本发明涉及柔性压电材料领域，尤其涉及一种有序结构的多功能柔性压电复合薄膜及其制备方法。The invention relates to the field of flexible piezoelectric materials, in particular to a multifunctional flexible piezoelectric composite film with an ordered structure and a preparation method thereof.
背景技术Background technique
近些年来，柔性可穿戴设备及人工智能领域得到迅猛发展，对其核心部件---传感器的要求也越来越高，而该种柔性传感器主要由一些具有特殊微结构的功能薄膜构成。高性能功能化薄膜的开发是柔性传感器领域的先决条件，功能薄膜本体的性能直接关系到机器人、医疗设备、人体假肢和可穿戴设备等载体的智能化和多功能化，并受到了多学科研究人员的高度重视。早在1991年，T.R.Jensen等人研制出了用于覆盖机器人表面的具有触觉功能的功能化薄膜，虽然该功能化薄膜能够利用内部的传感阵列感知外界力的作用并发出响应，但是这些功能化薄膜的多功能和稳定性较差，多次使用后，功能化薄膜对外界力响应的敏感度发生明显的削弱。随着传感技术的发展，在2004年，日本东京大学研发出一款具有触觉功能的柔性功能化薄膜，该功能化薄膜将微型橡胶电阻传感器拉制成分子半导体晶体大小并制作到衬底材料上，传感器形成阵列制作成柔性可改变形状的功能化薄膜，该功能化薄膜被用于机器人且能够同时测量压力和温度。但由于该传感器采用了电阻式压力传感器，且该功能化薄膜较薄，在同样的施加力的作用下，产生的单位力矩较小，因此，该功能化薄膜具有较差的灵敏度。中国发明CN107123470A研制出一种柔弹性功能化薄膜，该 导电薄膜包括预拉伸的弹性基底、弹性连接体和纳米线。弹性连接***于预拉伸的弹性基底和纳米导线之间，弹性连接体材料部分嵌入到纳米线中形成混合过渡区，用以增强层间的粘接性能。虽然该发明所制备的功能化薄膜具有较高的灵敏度，但该功能化薄膜的制备方法较为复杂。除此之外，中国发明CN108896219A研制出供一种柔性仿生功能化薄膜，其中传感层包括压阻层、薄膜电极，其中压阻层具有多孔结构，利用弹性体对压阻层与薄膜电极接触界面区域进行填充，该柔性仿生功能化薄膜能够感受气流和压力的存在，并且该柔性仿生功能化薄膜具有一定的力学稳定性。In recent years, the field of flexible wearable devices and artificial intelligence has been rapidly developed, and the requirements for its core components-sensors are getting higher and higher, and this kind of flexible sensors is mainly composed of some functional films with special microstructures. The development of high-performance functional films is a prerequisite in the field of flexible sensors. The performance of functional films is directly related to the intelligent and multi-functionalization of carriers, such as robots, medical equipment, human prostheses and wearable devices, and has been subject to multidisciplinary research. High attention of personnel. As early as 1991, TRJensen et al. developed a functionalized film with tactile functions for covering the surface of a robot. Although the functionalized film can use the internal sensor array to sense the effects of external forces and send out responses, these functions The multi-functionality and stability of the functionalized film are poor. After repeated use, the sensitivity of the functionalized film to external forces is significantly weakened. With the development of sensing technology, in 2004, the University of Tokyo in Japan developed a flexible functionalized film with tactile function. The functionalized film stretched the miniature rubber resistance sensor into a molecular semiconductor crystal size and fabricated it into the substrate material. Above, the sensors are arrayed and made into a flexible and changeable functionalized film, which is used in robots and can measure pressure and temperature at the same time. However, because the sensor uses a resistive pressure sensor and the functionalized film is thinner, the unit torque generated by the same applied force is small, so the functionalized film has poor sensitivity. Chinese invention CN107123470A has developed a flexible and elastic functionalized film. The conductive film includes a pre-stretched elastic substrate, elastic connectors and nanowires. The elastic connector is located between the pre-stretched elastic substrate and the nanowire, and the elastic connector material is partially embedded in the nanowire to form a mixed transition zone to enhance the adhesion between the layers. Although the functionalized film prepared by the invention has high sensitivity, the preparation method of the functionalized film is more complicated. In addition, the Chinese invention CN108896219A has developed a flexible bionic functionalized film. The sensing layer includes a piezoresistive layer and a thin film electrode. The piezoresistive layer has a porous structure and uses elastomers to contact the piezoresistive layer and the thin film electrode. The interface area is filled, the flexible bionic functionalized film can feel the presence of airflow and pressure, and the flexible bionic functionalized film has certain mechanical stability.
从功能化薄膜的组成和结构来看，传感器主要有电容式，压阻式和摩擦传感式，除上述外，对压电式功能薄膜的研究很少。压电式压力传感器一般由压电聚合物或无机功能材料与聚合物基体复合而成。到目前为止，许多微纳米结构功能材料，如BaTiO 3纳米线、Ge/Si纳米线、单壁碳纳米管(SWNT)和PZT纳米棒阵列，已证明，该器件在微小的外压状态下(<10kPa)具有很高的灵敏度。尽管这些工作对提高功能化薄膜的灵敏度有很好的效果，但是，纳米线、纳米棒以及微阵列的制备方法较为复杂、可重复性较差及成本较高。因此，成为为亟待解决的问题。 From the perspective of the composition and structure of functionalized films, sensors mainly include capacitive, piezoresistive and friction sensing types. In addition to the above, few studies have been done on piezoelectric functional films. Piezoelectric pressure sensors are generally composed of piezoelectric polymers or inorganic functional materials and polymer matrix composites. So far, many functional materials with micro and nano structures, such as BaTiO 3 nanowires, Ge/Si nanowires, single-walled carbon nanotubes (SWNT) and PZT nanorod arrays, have proven that the device is under a small external pressure ( <10kPa) has high sensitivity. Although these works have a good effect on improving the sensitivity of functionalized films, the preparation methods of nanowires, nanorods and microarrays are more complicated, with poor reproducibility and higher cost. Therefore, it has become an urgent problem to be solved.
发明内容Summary of the invention
本发明提供一种有序结构的多功能柔性压电复合薄膜及其制备方法，能够制备出一种敏感度高的柔性功能化压电薄膜，并且制备方法工艺简单、低成本。The invention provides a multifunctional flexible piezoelectric composite film with an ordered structure and a preparation method thereof, which can prepare a flexible functionalized piezoelectric film with high sensitivity, and the preparation method has simple process and low cost.
为达到上述目的，本发明采用如下技术方案：To achieve the above objective, the present invention adopts the following technical solutions:
一种有序结构的多功能柔性压电复合薄膜的制备方法，包括：A method for preparing a multifunctional flexible piezoelectric composite film with an ordered structure, including:
S1、将聚合物粉末溶解于溶剂中，将压电单晶微片分散到溶剂中，分别得到聚合物溶液和压电单晶微片分散液；S1. Dissolve polymer powder in a solvent, and disperse piezoelectric single crystal microchips in the solvent to obtain polymer solution and piezoelectric single crystal microchip dispersion respectively;
S2、将玻璃片***聚合物溶液中静置，再将玻璃片烘干，玻璃片表面形成聚合物覆膜；S2. Insert the glass sheet into the polymer solution and let it stand, and then dry the glass sheet to form a polymer film on the surface of the glass sheet;
S3、将压电单晶微片悬浊液均匀缓慢地滴到玻璃片表面，使压电单晶微片在所述聚合物覆膜表面以晶面00l方向平铺取向，再将玻璃片烘干；S3. Drop the suspension of piezoelectric single crystal microchips uniformly and slowly onto the surface of the glass sheet, so that the piezoelectric single crystal microchips are oriented in the direction of crystal plane 00l on the surface of the polymer film, and then the glass sheet is dried. dry;
S4、循环执行S2-S3，直到玻璃片表面形成有序结构的多功能柔性压电复合薄膜。S4. Repeat S2-S3 until a multifunctional flexible piezoelectric composite film with an ordered structure is formed on the surface of the glass sheet.
进一步的，的有序结构的多功能柔性压电复合薄膜的制备方法还包括：Further, the preparation method of the ordered structure of the multifunctional flexible piezoelectric composite film further includes:
在有序结构的多功能柔性压电复合薄膜上通过离子溅射镀上金电极，并在上下两面引出导线；Gold electrodes are plated on the multifunctional flexible piezoelectric composite film with an ordered structure by ion sputtering, and wires are drawn on the upper and lower sides;
将聚二甲基硅氧烷与固化剂以重量比10:1进行混合，并旋涂覆盖于电极的上下两面，在80℃下烘干固化，得到组装完成的压电薄膜。The polydimethylsiloxane and the curing agent are mixed at a weight ratio of 10:1, and spin-coated to cover the upper and lower sides of the electrode, and dried and cured at 80° C. to obtain the assembled piezoelectric film.
进一步的，聚合物包括聚乙烯醇、聚偏氟乙烯、聚偏氟乙烯基共聚物、聚乳酸、聚二甲基硅氧烷、聚氨酯、聚丙烯酸树脂、聚烯烃。Further, the polymer includes polyvinyl alcohol, polyvinylidene fluoride, polyvinylidene fluoride vinyl copolymer, polylactic acid, polydimethylsiloxane, polyurethane, polyacrylic resin, and polyolefin.
进一步的，溶剂包括水、N,N-二亚甲基甲酰胺、N-甲基吡咯烷酮的一种或多种。Further, the solvent includes one or more of water, N,N-dimethylene formamide, and N-methylpyrrolidone.
进一步的，聚合物溶液的浓度为0.5～3wt％。Further, the concentration of the polymer solution is 0.5-3wt%.
进一步的，压电材料单晶微片包括钛酸钡单晶微片、钛酸铅单晶 微片、铌镁酸铅-钛酸铅单晶微片、铌酸钠单晶微片、铌酸钾钠单晶微片、铌酸锂单晶微片、钽酸锂单晶微片、石英单晶微片。Further, piezoelectric material single crystal microchips include barium titanate single crystal microchips, lead titanate single crystal microchips, lead magnesium niobate-lead titanate single crystal microchips, sodium niobate single crystal microchips, and niobic acid Potassium sodium single crystal microchips, lithium niobate single crystal microchips, lithium tantalate single crystal microchips, and quartz single crystal microchips.
进一步的，压电材料单晶微片的厚度为1nm～100nm，长和宽为1μm～10μm。Further, the thickness of the piezoelectric material single crystal microplate is 1 nm-100 nm, and the length and width are 1 μm-10 μm.
进一步的，压电单晶微片分散液的浓度为1～5wt％。Further, the concentration of the piezoelectric single crystal microchip dispersion is 1 to 5 wt%.
进一步的，组装完成的压电薄膜厚度为1-1000μm。Further, the thickness of the assembled piezoelectric film is 1-1000 μm.
本发明还提供一种有序结构的多功能柔性压电复合薄膜，由上述制备方法制得。The invention also provides a multifunctional flexible piezoelectric composite film with an ordered structure, which is prepared by the above preparation method.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明采用的层层自组装法形成的有序化有机/无机杂化的柔性压电复合薄膜，该功能化薄膜具有高度的灵敏度、响应时间短以及结构稳定等特点，相比于传统的电容式、电阻式及有机晶体管式传感器，本发明中的功能化薄膜具有制备方法简单，避免了昂贵、难加工、结构复杂的微阵列、纳米线或纳米棒等纳米材料的使用。The orderly organic/inorganic hybrid flexible piezoelectric composite film formed by the layer-by-layer self-assembly method adopted in the present invention has the characteristics of high sensitivity, short response time and stable structure. Compared with traditional capacitors Type, resistance type and organic transistor type sensors, the functionalized film in the present invention has a simple preparation method, and avoids the use of nanomaterials such as expensive, difficult to process, and complex structure of microarrays, nanowires or nanorods.
并且，这些具有微纳结构的纳米材料在加工过程中存在着不可避免的分布不均和重复性低等问题。而本发明中平铺的压电材料单晶微片容易在聚合物表面取向排列，层与层之间类似于贻贝贝壳的有机/无机杂化的结构，该种结构不仅能提高薄膜的稳定性，且相邻层取向的压电材料单晶微片能起到互补作用，使得本发明的功能化薄膜具有高敏感度和优异的力学性能。Moreover, these nano-materials with micro-nano structures have inevitable uneven distribution and low repeatability during processing. In the present invention, the flat piezoelectric material single crystal microplates are easily aligned on the surface of the polymer, and the layers are similar to the organic/inorganic hybrid structure of mussel shells. This structure can not only improve the stability of the film The piezoelectric material single crystal microplates with the orientation of adjacent layers can play a complementary role, so that the functionalized film of the present invention has high sensitivity and excellent mechanical properties.
另一方面，该功能化薄膜能将人体的声带肌肉的震动转换为电信号，根据人体声带发音的差异产生相应的电信号，并且具有可重复性 和较高的可靠性，在人工智能中的语音识别***领域具有潜在的应用。On the other hand, the functionalized film can convert the vibration of the human vocal cord muscles into electrical signals, and generate corresponding electrical signals according to the differences in the pronunciation of the human vocal cords, and has repeatability and high reliability. There are potential applications in the field of speech recognition systems.
除此之外，该功能化薄膜也能感知人体微弱的生理信号，例如，脉搏、心跳以及运动情况，能在生物医学领域中发挥重要的作用。In addition, the functionalized film can also sense weak physiological signals of the human body, such as pulse, heartbeat, and exercise status, which can play an important role in the field of biomedicine.
综上所述，本发明所制备的功能化薄膜具有的高度敏感性、制备方法简单以及低成本等优势，为其在可穿戴设备及生物医学领域的实际应用提供了可能。In summary, the functionalized film prepared by the present invention has the advantages of high sensitivity, simple preparation method, and low cost, which provide the possibility for its practical application in the field of wearable devices and biomedicine.
附图说明Description of the drawings
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。In order to explain the technical solutions in the embodiments of the present invention more clearly, the following will briefly introduce the drawings needed in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative work.
图1是有序结构的多功能柔性压电复合薄膜微结构平面图；Figure 1 is a plan view of the microstructure of a multifunctional flexible piezoelectric composite film with an ordered structure;
图2是有序结构的多功能柔性压电复合薄膜微结构三维图；Figure 2 is a three-dimensional view of the microstructure of a multifunctional flexible piezoelectric composite film with an ordered structure;
图3是有序结构的多功能柔性压电复合薄膜封装后的结构平面图。Fig. 3 is a structural plan view of an ordered structure of a multifunctional flexible piezoelectric composite film after packaging.
具体实施方式Detailed ways
为使本领域技术人员更好地理解本发明的技术方案，下面结合具体实施方式对本发明作进一步详细描述。In order to enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be further described in detail below in conjunction with specific embodiments.
实施例1：Example 1:
首先将0.5g聚偏氟乙烯共聚物P(VDF-TrFE)粉末溶解于100mL N,N-二甲基甲酰胺(DMF)溶剂中，备用，然后将0.5g BaTiO 3单晶微片分散到50mL DMF(N,N-Dimethylformamide N,N-二甲基甲酰胺)溶剂中，经过超声、搅拌形成压电单晶微片的悬浊液，然后将洁净的玻璃片***上述P(VDF-TrFE)溶液中，静置3分钟后，烘干，然后用滴管吸取10mL BaTiO 3单晶微片悬浊液均匀缓慢地滴到倾斜的上述 玻璃片，烘干玻璃片。将玻璃片***P(VDF-TrFE)溶液后再滴加单晶微片悬浊液烘干的流程如此往复150次，形成有序结构的多功能柔性压电复合薄膜，如图1、2所示。 First, dissolve 0.5 g of polyvinylidene fluoride copolymer P (VDF-TrFE) powder in 100 mL of N,N-dimethylformamide (DMF) solvent, and then disperse 0.5 g of BaTiO 3 single crystal microplates to 50 mL In DMF (N,N-Dimethylformamide N,N-Dimethylformamide) solvent, ultrasonic and stirring are carried out to form a suspension of piezoelectric single crystal microchips, and then the clean glass plate is inserted into the above P(VDF-TrFE) In the solution, let it stand for 3 minutes, then dry, and then use a dropper to suck 10 mL of BaTiO 3 single crystal microplate suspension evenly and slowly drop it onto the inclined glass slide, and then dry the glass slide. The process of inserting the glass slide into the P(VDF-TrFE) solution and then dropping the monocrystalline microchip suspension to dry it is repeated 150 times to form a multifunctional flexible piezoelectric composite film with an ordered structure, as shown in Figures 1 and 2 Show.
通过磁控溅射，在复合薄膜上下表面均匀镀上金电极，并在上下两面引出导线。然后将聚二甲基硅氧烷与固化剂以重量比10:1进行混合，并旋涂覆盖于电极的上下两面，在80℃的烘箱中固化10h，封装后的结构图如图3所示。封装完成后，进行器件的灵敏性测试。Through magnetron sputtering, gold electrodes are evenly plated on the upper and lower surfaces of the composite film, and wires are drawn on the upper and lower sides. Then mix the polydimethylsiloxane and the curing agent at a weight ratio of 10:1, and spin coating to cover the upper and lower sides of the electrode, and cure in an oven at 80°C for 10 hours. The structure diagram after packaging is shown in Figure 3. . After the packaging is completed, the sensitivity test of the device is performed.
实施例2：Example 2:
首先将0.5g PVA(polyvinyl alcohol聚乙烯醇)粉末溶解于100mL去离子水中，备用，然后将0.5g BaTiO 3单晶微片分散到50mL去离子水中，经过超声、搅拌形成压电单晶微片的悬浊液，然后将洁净的玻璃片***上述PVA水溶液中，静置3分钟后，烘干，然后用滴管吸取10mL BaTiO 3单晶微片悬浊液均匀缓慢地滴到倾斜的上述玻璃片，烘干。将玻璃片***PVA溶液后再滴加单晶微片悬浊液烘干的流程如此往复150次，形成有序结构的多功能柔性压电复合薄膜。 First, dissolve 0.5g of PVA (polyvinyl alcohol) powder in 100mL of deionized water, and then disperse 0.5g of BaTiO 3 single crystal microchips into 50mL of deionized water, and form piezoelectric single crystal microchips through ultrasound and stirring. Then insert the clean glass slide into the above-mentioned PVA aqueous solution, let it stand for 3 minutes, dry it, and then use a dropper to suck 10mL of BaTiO 3 single crystal microplate suspension and drop it evenly and slowly onto the inclined glass Slices, drying. The process of inserting the glass sheet into the PVA solution and then dropping the monocrystalline microchip suspension for drying is repeated 150 times to form a multifunctional flexible piezoelectric composite film with an ordered structure.
通过磁控溅射，在复合薄膜上下表面均匀镀上金电极，并在上下两面引出导线。然后将聚二甲基硅氧烷与固化剂以重量比10:1进行混合，并旋涂覆盖于电极的上下两面，在80℃的烘箱中固化10h。封装完成后，进行器件的灵敏性测试。Through magnetron sputtering, gold electrodes are evenly plated on the upper and lower surfaces of the composite film, and wires are drawn on the upper and lower sides. Then, the polydimethylsiloxane and the curing agent were mixed in a weight ratio of 10:1, and spin-coated to cover the upper and lower sides of the electrode, and cured in an oven at 80°C for 10 hours. After the packaging is completed, the sensitivity test of the device is performed.
实施例3：Example 3:
首先将0.5g P(VDF-TrFE)粉末溶解于100mL DMF溶剂中，备用，然后将0.5g PbTiO 3单晶微片分散到50mL DMF溶剂中，经过超声、 搅拌形成PbTiO 3单晶微片的悬浊液，然后将洁净的玻璃片***上述P(VDF-TrFE)溶液中，静置3分钟后，烘干，然后用滴管吸取10mL PbTiO 3单晶微片悬浊液均匀缓慢地滴到倾斜的上述玻璃片，烘干。将玻璃片***P(VDF-TrFE)溶液后再滴加单晶微片悬浊液烘干的流程如此往复150次，形成有序结构的多功能柔性压电复合薄膜。 First dissolve 0.5g P(VDF-TrFE) powder in 100mL DMF solvent, and then disperse 0.5g PbTiO 3 single crystal microchips in 50mL DMF solvent, and form a suspension of PbTiO 3 single crystal microchips through ultrasound and stirring. Then insert the clean glass slide into the above P(VDF-TrFE) solution, let it stand for 3 minutes, dry it, and then use a dropper to suck 10mL PbTiO 3 single crystal microchip suspension evenly and slowly drop it to the tilt The above glass pieces are dried. The process of inserting the glass sheet into the P (VDF-TrFE) solution and then dropping the monocrystalline microchip suspension for drying is repeated 150 times to form an ordered structure of the multifunctional flexible piezoelectric composite film.
通过磁控溅射，在电复合薄膜上下表面均匀镀上金电极，并在上下两面引出导线。然后将聚二甲基硅氧烷与固化剂以重量比10:1进行混合，并旋涂覆盖于电极的上下两面，在80℃的烘箱中固化10h。封装完成后，进行器件的灵敏性测试。Through magnetron sputtering, gold electrodes are evenly plated on the upper and lower surfaces of the electric composite film, and wires are drawn on the upper and lower sides. Then, the polydimethylsiloxane and the curing agent were mixed in a weight ratio of 10:1, and spin-coated to cover the upper and lower sides of the electrode, and cured in an oven at 80°C for 10 hours. After the packaging is completed, the sensitivity test of the device is performed.
实施例4：Example 4:
首先将0.5g PVA粉末溶解于100mL去离子水中，备用，然后将0.5g Pb(Mg 1/3Nb 2/3)O 3-PbTiO 3单晶微片分散到50mL去离子水中，经过超声、搅拌形成Pb(Mg 1/3Nb 2/3)O 3-PbTiO 3单晶微片的悬浊液，然后将洁净的玻璃片***上述PVA水溶液中，静置3分钟后，烘干，然后用滴管吸取10mL Pb(Mg 1/3Nb 2/3)O 3-PbTiO 3单晶微片悬浊液均匀缓慢地滴到倾斜的上述玻璃片，烘干。将玻璃片***PVA溶液后再滴加单晶微片悬浊液烘干的流程如此往复150次，形成有序结构的多功能柔性压电复合薄膜。 First dissolve 0.5g of PVA powder in 100mL of deionized water, and then disperse 0.5g of Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 single crystal microplates into 50mL of deionized water. A suspension of Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 single crystal microplates is formed, and then the clean glass slides are inserted into the above-mentioned PVA aqueous solution, and after standing for 3 minutes, they are dried, and then dripped Pipette 10 mL of Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 single crystal microplate suspension evenly and slowly onto the inclined glass slide, and dry. The process of inserting the glass sheet into the PVA solution and then dropping the monocrystalline microchip suspension for drying is repeated 150 times to form a multifunctional flexible piezoelectric composite film with an ordered structure.
通过磁控溅射，在复合薄膜上下表面均匀镀上金电极，并在上下两面引出导线。然后将聚二甲基硅氧烷与固化剂以重量比10:1进行混合，并旋涂覆盖于电极的上下两面，在80℃的烘箱中固化10h。封装完成后，进行器件的灵敏性测试。Through magnetron sputtering, gold electrodes are evenly plated on the upper and lower surfaces of the composite film, and wires are drawn on the upper and lower sides. Then, the polydimethylsiloxane and the curing agent were mixed in a weight ratio of 10:1, and spin-coated to cover the upper and lower sides of the electrode, and cured in an oven at 80°C for 10 hours. After the packaging is completed, the sensitivity test of the device is performed.
实施例5：Example 5:
首先将3g聚二甲基硅氧烷与0.3g固化剂均匀混合，备用，然后将0.5g Pb(Mg 1/3Nb 2/3)O 3-PbTiO 3单晶微片分散到50mL DMF溶剂中，经过超声、搅拌形成Pb(Mg 1/3Nb 2/3)O 3-PbTiO 3单晶微片的悬浊液，然后将洁净的玻璃片***上述聚二甲基硅氧烷混合溶胶中，静置3分钟后，100℃固化3h，然后用滴管吸取10mL Pb(Mg 1/3Nb 2/3)O 3-PbTiO 3单晶微片悬浊液均匀缓慢地滴到倾斜的上述玻璃片，烘干。将玻璃片***聚二甲基硅氧烷溶液后再滴加单晶微片悬浊液烘干的流程如此往复150次，形成有序结构的多功能柔性压电复合薄膜。 First, mix 3g of polydimethylsiloxane and 0.3g of curing agent uniformly, and then disperse 0.5g of Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 single crystal microchips into 50mL of DMF solvent. After ultrasonic and stirring, a suspension of Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 single crystal microplates is formed, and then the clean glass pieces are inserted into the above-mentioned polydimethylsiloxane mixed sol, After standing for 3 minutes, solidify at 100°C for 3 hours, and then use a dropper to suck 10 mL of Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 single crystal microplate suspension evenly and slowly onto the inclined glass slide ,drying. The process of inserting the glass sheet into the polydimethylsiloxane solution and then dropping the monocrystalline microchip suspension for drying is repeated 150 times to form a multifunctional flexible piezoelectric composite film with an ordered structure.
通过磁控溅射，在复合薄膜上下表面均匀镀上金电极，并在上下两面引出导线。然后将聚二甲基硅氧烷与固化剂以重量比10:1进行混合，并旋涂覆盖于电极的上下两面，在80℃的烘箱中固化10h。封装完成后，进行器件的灵敏性测试。Through magnetron sputtering, gold electrodes are evenly plated on the upper and lower surfaces of the composite film, and wires are drawn on the upper and lower sides. Then, the polydimethylsiloxane and the curing agent were mixed in a weight ratio of 10:1, and spin-coated to cover the upper and lower sides of the electrode, and cured in an oven at 80°C for 10 hours. After the packaging is completed, the sensitivity test of the device is performed.
对比例1：Comparative example 1:
首先将0.5g P(VDF-TrFE)粉末溶解于100mL DMF溶剂中，备用，然后将0.5g BaTiO 3微米粒子分散到50mL DMF溶剂中，经过超声、搅拌形成BaTiO 3微米粒子的悬浊液，然后将洁净的玻璃片***上述P(VDF-TrFE)溶液中，静置3分钟后，烘干，然后用滴管吸取10mL BaTiO 3微米粒子悬浊液均匀缓慢地滴到倾斜的上述玻璃片，烘干。将玻璃片***P(VDF-TrFE)溶液后再滴加微米粒子悬浊液烘干的流程如此往复150次，形成有序结构的多功能柔性压电复合薄膜。 First, dissolve 0.5g P(VDF-TrFE) powder in 100mL DMF solvent, and then disperse 0.5g BaTiO 3 micron particles in 50mL DMF solvent, and form a suspension of BaTiO 3 micron particles through ultrasound and stirring. Insert the clean glass slide into the above-mentioned P(VDF-TrFE) solution, let it stand for 3 minutes, dry it, and then use a dropper to suck 10 mL of BaTiO 3 micron particle suspension evenly and slowly drop it onto the inclined glass slide, and bake dry. The process of inserting the glass sheet into the P (VDF-TrFE) solution and then dropping the micro-particle suspension for drying is repeated 150 times to form a multifunctional flexible piezoelectric composite film with an ordered structure.
通过磁控溅射，在复合薄膜上下表面均匀镀上金电极，并在上下 两面引出导线。然后将聚二甲基硅氧烷与固化剂以重量比10:1进行混合，并旋涂覆盖于电极的上下两面，在80℃的烘箱中固化10h。封装完成后，进行器件的灵敏性测试。By magnetron sputtering, gold electrodes are evenly plated on the upper and lower surfaces of the composite film, and wires are drawn on the upper and lower surfaces. Then, the polydimethylsiloxane and the curing agent were mixed in a weight ratio of 10:1, and spin-coated to cover the upper and lower sides of the electrode, and cured in an oven at 80°C for 10 hours. After the packaging is completed, the sensitivity test of the device is performed.
对比例2：Comparative example 2:
首先将0.5g P(VDF-TrFE)粉末溶解于100mL DMF溶剂中，然后将洁净的玻璃片***上述P(VDF-TrFE)溶液中，静置3分钟后，烘干，将玻璃片***P(VDF-TrFE)溶液后再烘干的流程如此往复150次，形成柔性压电薄膜。First dissolve 0.5g P(VDF-TrFE) powder in 100mL DMF solvent, then insert the clean glass slide into the above P(VDF-TrFE) solution, let it stand for 3 minutes, dry it, and insert the glass slide into P( The process of drying after the solution of VDF-TrFE) reciprocates 150 times to form a flexible piezoelectric film.
通过磁控溅射，在压电薄膜上下表面均匀镀上金电极，并在上下两面引出导线。然后将聚二甲基硅氧烷与固化剂以重量比10:1进行混合，并旋涂覆盖于电极的上下两面，在80℃的烘箱中固化10h。封装完成后，进行器件的灵敏性测试。Through magnetron sputtering, gold electrodes are evenly plated on the upper and lower surfaces of the piezoelectric film, and wires are drawn on the upper and lower surfaces. Then, the polydimethylsiloxane and the curing agent were mixed in a weight ratio of 10:1, and spin-coated to cover the upper and lower sides of the electrode, and cured in an oven at 80°C for 10 hours. After the packaging is completed, the sensitivity test of the device is performed.
上述实施例和对比例制备出的薄膜的灵敏度测试结果如下：The sensitivity test results of the films prepared in the foregoing examples and comparative examples are as follows:
表1.不同实施例和对比例样品的灵敏度及电学响应Table 1. Sensitivity and electrical response of samples of different examples and comparative examples
Figure PCTCN2019095932-appb-000001
Figure PCTCN2019095932-appb-000001
本发明的有益效果是：The beneficial effects of the present invention are:
本发明采用的层层自组装法形成的有序化有机/无机杂化的柔性压电复合薄膜，该功能化薄膜具有高度的灵敏度、响应时间短以及结 构稳定等特点，相比于传统的电容式、电阻式及有机晶体管式传感器，本发明中的功能化薄膜具有制备方法简单，避免了昂贵、难加工、结构复杂的微阵列、纳米线或纳米棒等纳米材料的使用。The orderly organic/inorganic hybrid flexible piezoelectric composite film formed by the layer-by-layer self-assembly method adopted in the present invention has the characteristics of high sensitivity, short response time and stable structure. Compared with traditional capacitors Type, resistance type and organic transistor type sensors, the functionalized film in the present invention has a simple preparation method, and avoids the use of nanomaterials such as expensive, difficult to process, and complex structure of microarrays, nanowires or nanorods.
并且，这些具有微纳结构的纳米材料在加工过程中存在着不可避免的分布不均和重复性低等问题。而本发明中平铺的压电材料单晶微片容易在聚合物表面取向排列，层与层之间类似于贻贝贝壳间的有机/无机杂化的结构，该种结构不仅能提高薄膜的稳定性，且相邻层取向的压电材料单晶微片能起到互补作用，使得本发明的功能化薄膜具有高敏感度。Moreover, these nano-materials with micro-nano structures have inevitable uneven distribution and low repeatability during processing. In the present invention, the flat piezoelectric material single crystal microplates are easily aligned on the surface of the polymer. The layers are similar to the organic/inorganic hybrid structure between mussel shells. This structure can not only improve the film’s The piezoelectric material single crystal microplates with stability and orientation of adjacent layers can play a complementary role, so that the functionalized film of the present invention has high sensitivity.
另一方面，该功能化薄膜能将人体的声带肌肉的震动转换为电信号，根据人体声带发音的差异产生相应的电信号，并且具有可重复性和较高的可靠性，在人工智能中的语音识别***领域具有潜在的应用。On the other hand, the functionalized film can convert the vibration of the human vocal cord muscles into electrical signals, and generate corresponding electrical signals according to the differences in the pronunciation of the human vocal cords, and has repeatability and high reliability. There are potential applications in the field of speech recognition systems.
除此之外，该功能化薄膜也能感知人体微弱的生理信号，例如，脉搏、心跳以及运动情况，能在生物医学领域中发挥重要的作用。In addition, the functionalized film can also sense weak physiological signals of the human body, such as pulse, heartbeat, and exercise status, which can play an important role in the field of biomedicine.
综上所述，本发明所制备的功能化薄膜具有的高度敏感性、制备方法简单以及低成本等优势，为其在可穿戴设备及生物医学领域的实际应用提供了可能。In summary, the functionalized film prepared by the present invention has the advantages of high sensitivity, simple preparation method, and low cost, which provide the possibility for its practical application in the field of wearable devices and biomedicine.
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求的保护范围为准。The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed in the present invention. All should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (10)

  1. 一种有序结构的多功能柔性压电复合薄膜的制备方法，其特征在于，包括：A method for preparing a multifunctional flexible piezoelectric composite film with an ordered structure, which is characterized in that it comprises:
    S1、将聚合物粉末溶解于溶剂中，将压电单晶微片分散到溶剂中，分别得到聚合物溶液和压电单晶微片分散液；S1. Dissolve polymer powder in a solvent, and disperse piezoelectric single crystal microchips in the solvent to obtain polymer solution and piezoelectric single crystal microchip dispersion respectively;
    S2、将玻璃片***所述聚合物溶液中静置，再将玻璃片烘干，玻璃片表面形成聚合物覆膜；S2. Insert the glass sheet into the polymer solution and let it stand, and then dry the glass sheet to form a polymer film on the surface of the glass sheet;
    S3、将压电单晶微片悬浊液均匀缓慢地滴到玻璃片表面，使压电单晶微片在所述聚合物覆膜表面以晶面00l方向平铺取向，再将所述玻璃片烘干；S3. Drop the piezoelectric single crystal microchip suspension evenly and slowly onto the surface of the glass sheet, so that the piezoelectric single crystal microchip is oriented in the direction of crystal plane 00l on the surface of the polymer coating, and then the glass Slice drying
    S4、循环执行S2-S3，直到所述玻璃片表面形成所述有序结构的多功能柔性压电复合薄膜。S4. Perform S2-S3 cyclically until the ordered structure of the multifunctional flexible piezoelectric composite film is formed on the surface of the glass sheet.
  2. 根据权利要求1所述的有序结构的多功能柔性压电复合薄膜的制备方法，其特征在于，还包括：The method for preparing a multifunctional flexible piezoelectric composite film with an ordered structure according to claim 1, characterized in that it further comprises:
    在所述有序结构的多功能柔性压电复合薄膜上通过离子溅射镀上金电极，并在上下两面引出导线；Gold electrodes are plated on the multifunctional flexible piezoelectric composite film with an ordered structure by ion sputtering, and wires are drawn on the upper and lower sides;
    将聚二甲基硅氧烷与固化剂以重量比10:1进行混合，并旋涂覆盖于所述电极的上下两面，在80℃下烘干固化，得到组装完成的压电薄膜。The polydimethylsiloxane and the curing agent are mixed in a weight ratio of 10:1, and spin-coated to cover the upper and lower sides of the electrode, and dried and cured at 80° C. to obtain the assembled piezoelectric film.
  3. 根据权利要求1所述的有序结构的多功能柔性压电复合薄膜的制备方法，其特征在于，所述的聚合物包括聚乙烯醇、聚偏氟乙烯、聚偏氟乙烯基共聚物、聚乳酸、聚二甲基硅氧烷、聚氨酯、聚丙烯酸树脂、聚烯烃。The method for preparing a multifunctional flexible piezoelectric composite film with an ordered structure according to claim 1, wherein the polymer includes polyvinyl alcohol, polyvinylidene fluoride, polyvinylidene fluoride copolymer, polyvinyl Lactic acid, polydimethylsiloxane, polyurethane, polyacrylic resin, polyolefin.
  4. 根据权利要求1所述的有序结构的多功能柔性压电复合薄膜的制备方法，其特征在于，所述溶剂包括水、N,N-二亚甲基甲酰胺、N-甲基吡咯烷酮溶剂中的一种或多种。The method for preparing a multifunctional flexible piezoelectric composite film with an ordered structure according to claim 1, wherein the solvent comprises water, N,N-dimethylene formamide, and N-methylpyrrolidone solvents. One or more of.
  5. 根据权利要求1所述的有序结构的多功能柔性压电复合薄膜的制备方法，其特征在于，所述聚合物溶液的浓度为0.5～3wt％。The method for preparing a multifunctional flexible piezoelectric composite film with an ordered structure according to claim 1, wherein the concentration of the polymer solution is 0.5-3wt%.
  6. 根据权利要求1所述的有序结构的多功能柔性压电复合薄膜的制备方法，其特征在于，所述压电材料单晶微片包括钛酸钡单晶微片、钛酸铅单晶微片、铌镁酸铅-钛酸铅单晶微片、铌酸钠单晶微片、铌酸钾钠单晶微片、铌酸锂单晶微片、钽酸锂单晶微片、石英单晶微片。The method for preparing a multifunctional flexible piezoelectric composite film with an ordered structure according to claim 1, wherein the piezoelectric material single crystal microplate comprises barium titanate single crystal microplate, lead titanate single crystal microplate Sheets, lead magnesium niobate-lead titanate single crystal microchips, sodium niobate single crystal microchips, potassium sodium niobate single crystal microchips, lithium niobate single crystal microchips, lithium tantalate single crystal microchips, quartz single晶微片.
  7. 根据权利要求1或6所述的有序结构的多功能柔性压电复合薄膜的制备方法，其特征在于，所述压电材料单晶微片的厚度为1nm～100nm，长和宽为1μm～10μm。The method for preparing a multifunctional flexible piezoelectric composite film with an ordered structure according to claim 1 or 6, characterized in that the thickness of the piezoelectric material single crystal microplate is 1 nm-100 nm, and the length and width are 1 μm- 10μm.
  8. 根据权利要求1所述的有序结构的多功能柔性压电复合薄膜的制备方法，其特征在于，所述压电单晶微片分散液的浓度为1～5wt％。The method for preparing a multifunctional flexible piezoelectric composite film with an ordered structure according to claim 1, wherein the concentration of the piezoelectric single crystal microchip dispersion is 1 to 5 wt%.
  9. 根据权利要求2所述的有序结构的多功能柔性压电复合薄膜的制备方法，其特征在于，所述组装完成的压电薄膜厚度为1-1000μm。The method for preparing a multifunctional flexible piezoelectric composite film with an ordered structure according to claim 2, wherein the thickness of the assembled piezoelectric film is 1-1000 μm.
  10. 一种有序结构的多功能柔性压电复合薄膜，其特征在于，由上述制备方法制得。A multifunctional flexible piezoelectric composite film with an ordered structure is characterized in that it is prepared by the above-mentioned preparation method.
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