WO2016145775A1 - 柔性导电振膜、柔性振动传感器及其制备方法和应用 - Google Patents
柔性导电振膜、柔性振动传感器及其制备方法和应用 Download PDFInfo
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- WO2016145775A1 WO2016145775A1 PCT/CN2015/086829 CN2015086829W WO2016145775A1 WO 2016145775 A1 WO2016145775 A1 WO 2016145775A1 CN 2015086829 W CN2015086829 W CN 2015086829W WO 2016145775 A1 WO2016145775 A1 WO 2016145775A1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01H—MEASUREMENT OF MECHANICAL VIBRATIONS OR ULTRASONIC, SONIC OR INFRASONIC WAVES
- G01H11/00—Measuring mechanical vibrations or ultrasonic, sonic or infrasonic waves by detecting changes in electric or magnetic properties
- G01H11/06—Measuring mechanical vibrations or ultrasonic, sonic or infrasonic waves by detecting changes in electric or magnetic properties by electric means
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01P—MEASURING LINEAR OR ANGULAR SPEED, ACCELERATION, DECELERATION, OR SHOCK; INDICATING PRESENCE, ABSENCE, OR DIRECTION, OF MOVEMENT
- G01P5/00—Measuring speed of fluids, e.g. of air stream; Measuring speed of bodies relative to fluids, e.g. of ship, of aircraft
- G01P5/08—Measuring speed of fluids, e.g. of air stream; Measuring speed of bodies relative to fluids, e.g. of ship, of aircraft by measuring variation of an electric variable directly affected by the flow, e.g. by using dynamo-electric effect
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- the invention relates to a vibration sensor, in particular to a flexible vibration sensor based on a flexible material, a nano material and a microstructure, a preparation method and application thereof, and belongs to the technical field of sensors and smart materials.
- the vibration sensor is one of the key components in the testing technology. Its function is mainly to receive the mechanical quantity and convert it into a proportional amount of electricity. Because it is also an electromechanical conversion device. Therefore, it is also called a transducer, a vibrator, and the like.
- the vibration sensor does not directly convert the original mechanical quantity to be measured into electricity. Instead, it takes the original mechanical quantity to be measured as the input of the vibration sensor, and then receives it by the mechanical receiving part to form another mechanical quantity suitable for transformation. Finally, the electromechanical conversion part converts it into electricity.
- the conventional vibration sensor has defects such as inflexibility, large volume, and large power consumption, and is difficult to apply to a wearable device.
- One of the objects of the present invention is to provide a flexible conductive diaphragm which can be used as a transducer in a wearable device or the like to convert mechanical energy into an electrical signal for detection, and has flexibility, flexibility, stability, and work. Low voltage, low power consumption, high sensitivity, and short response time.
- Another object of the present invention is to provide a method for preparing the flexible conductive diaphragm, which has the characteristics of simple process and easy implementation.
- a third object of the present invention is to provide a flexible vibration sensor based on the flexible conductive diaphragm that can be easily integrated in a wearable device.
- a fourth object of the present invention is to provide a wearable device based on the flexible vibration sensor.
- the technical solution adopted by the present invention includes:
- a flexible conductive diaphragm comprising at least one conductive film, the conductive film comprising a flexible support layer, a flexible sensitive layer stacked on the flexible support layer, a flexible conductive layer stacked on the flexible sensitive layer, and the flexible An electrode electrically connected to the conductive layer.
- the flexible conductive diaphragm includes two or more of the conductive films stacked, wherein the flexible conductive layers of adjacent conductive films contact each other to form a resistance-adjustable contact resistance layer.
- the flexible conductive diaphragm comprises a plurality of stacked conductive films, and two or more contact resistance layers are formed between the plurality of conductive films.
- the flexible sensitive layer is directly disposed on the surface of the flexible support layer and is fixedly connected to the flexible support layer.
- the flexible sensitive layer is bonded and fixed to the flexible support layer; and/or the flexible sensitive layer and the flexible support layer are bonded to each other by a polymer crosslinking reaction.
- the bonding strength of the flexible sensitive layer and the flexible supporting layer is sufficient to ensure that the flexible sensitive layer can be directly peeled off from the template of the flexible sensitive layer without being damaged.
- the flexible sensitive layer has a thickness of 0.1 to 200 ⁇ m, preferably 0.1 to 10 ⁇ m, and particularly preferably 1 ⁇ m.
- more than one flexible layer is further distributed between the flexible support layer and the flexible sensitive layer and/or between the flexible sensitive layer and the flexible conductive layer.
- a flexible sensitive layer and a flexible conductive layer are sequentially stacked on both sides of the flexible supporting layer.
- the surface of the flexible sensitive layer has an array microstructure
- the microstructure includes a non-planar microstructure including a pyramid shape, a quadrangular pyramid shape, a triangular pyramid shape, a hemispherical shape or a columnar microstructure. But it is not limited to this.
- the flexible conductive diaphragm comprises two or more superposed conductive films, wherein an apex of the non-planar microstructure of one flexible conductive layer is in electrical contact with the other flexible conductive layer that is mated.
- the apex of the non-planar microstructure of one of the flexible conductive layers is in electrical contact with the planar region of the other flexible conductive layer that is mated.
- the material of the flexible sensitive layer comprises a polymer material, such as polyethylene terephthalate, polydimethylsiloxane, polyimide, polyurethane, polyethylene.
- a polymer material such as polyethylene terephthalate, polydimethylsiloxane, polyimide, polyurethane, polyethylene.
- the alcohol, polyvinyl formal, polyethylene, etc. are not limited thereto, but polydimethylsiloxane is preferably used.
- the flexible conductive layer is made of a carbon nanotube film, and is prepared by spraying, and the obtained device has a sheet resistance of 0.1-100 k ⁇ / ⁇ .
- the electrode has a thickness of 1 to 10 ⁇ m.
- the material of the electrode is copper foil.
- the electrode and the flexible conductive layer are connected by a conductive adhesive.
- the preparation method of the flexible conductive diaphragm comprises:
- the template surface has a micropattern structure corresponding to the array microstructure distributed on the flexible sensitive layer.
- the step (2) comprises: surface treating the flexible support layer or the flexible sensitive layer, and then combining the flexible support layer with the flexible sensitive layer; wherein the surface treatment method comprises strong acid oxidation Treatment, plasma treatment or UV ozone treatment. Further, the surface treatment time may be 1 to 30 minutes.
- the cured or semi-cured flexible support layer is bonded to the cured or semi-cured flexible sensitive layer by a crosslinking reaction.
- the reaction is carried out under a vacuum atmosphere at a reaction temperature of 50 to 200 ° C for 30 minutes to 6 hours to complete the crosslinking reaction.
- the manner in which the flexible conductive layer is formed may include evaporation, chemical deposition, printing, spraying, sputtering, or the like.
- the method for preparing the electrode may include evaporation, chemical deposition, printing, spraying, sputtering, or the like.
- the flexible vibration sensor can be applied to fields such as fluid flow rate detection and sound recording.
- a novel flexible conductive diaphragm is constructed, in which the flexible support layer is fixedly connected with the flexible sensitive layer, especially by a cross-linking reaction, so that the flexible support layer can be directly sensitive during the preparation process.
- the layer is removed from the stencil, the stripping time is fast, and there is no damage. Therefore, the flexible sensitive layer can be very thin (as low as 0.1 ⁇ m), and the sensitivity is higher. Similar to the microphone, the sound can be detected in a non-contact condition. ;
- the flexible vibration sensor of the present invention combines flexible vibration sensing technology and novel micro-nano sensing technology, and has the characteristics of ultra-thin, ultra-light and flexible, and can be easily integrated into a wearable device, and the working voltage is Low, low power consumption, high sensitivity, and short response time provide excellent user experience.
- FIG. 1 is a schematic structural view of a double-layer flexible conductive diaphragm according to an embodiment of the present invention
- FIG. 2 is a schematic structural view of a multilayer flexible conductive diaphragm according to an embodiment of the present invention
- FIG. 3 is an SEM image of a surface array microstructure of a flexible sensitive layer in accordance with an embodiment of the present invention
- FIG. 4 is a graph showing voltage versus time for a response of a flexible vibration sensor to sound vibration according to an embodiment of the present invention
- FIG. 5 is a graph showing resistance versus time for a response of a flexible vibration sensor to a water flow rate according to an embodiment of the present invention
- FIG. 6 is a comparison diagram of sound response of a flexible vibration sensor having a thickness of 200 ⁇ m and 10 ⁇ m in a flexible sensitive layer according to an embodiment of the present invention.
- an embodiment of the invention relates to a two-layer flexible conductive diaphragm, wherein each conductive film comprises a flexible supporting layer 1 and a flexible sensitive layer 2 formed on an upper surface of the flexible supporting layer 1 to form Flexible sensitive layer
- the flexible conductive layer 3 on the second and the electrode 4 electrically connected to the flexible conductive layer 3.
- each structural layer can be as shown in the foregoing, and details are not described herein again.
- the conductive film can be prepared by the following method, namely:
- a thin layer of organic molecules (such as trimethylchlorosilane or perfluorooctyltrichlorosilane) is processed on a surface of a template such as a silicon wafer (such as vapor deposition or fumigation) to ensure a flexible layer on the surface of the template. Easy and complete separation from the template.
- an unpolymerized polymer prepolymer or a mixture of a plurality of polymer prepolymers on the organic molecular layer eg, polyethylene terephthalate, polyimide, polydimethylsiloxane
- the organic molecular layer eg, polyethylene terephthalate, polyimide, polydimethylsiloxane
- a mixture of one or more of polyurethane, polyvinyl alcohol, polyvinyl formal, and polyethylene to uniformly form a film of a flexible sensitive layer.
- the flexible sensitive layer and the flexible supporting layer are heated and treated in a vacuum environment for a period of time, and the flexible supporting layer and the flexible sensitive layer film are completely integrated, and then the flexible sensitive layer and the flexible supporting layer film which have been completely reacted together are
- the surface of the template is peeled off to form a microstructure by replicating the micropattern on the template onto the flexible sensitive layer.
- a conductive material is prepared on the flexible sensitive layer by using a spray gun.
- a spray gun For example, the surface topography of a typical device formed under the electron microscope is as shown in FIG.
- the flexible conductive layer is conformally attached to the surface of the flexible sensitive layer.
- a layer of electrode material is bonded to the flexible conductive layer by using a silver paste, and after a process such as curing, a single layer of the flexible conductive film can be formed.
- a plurality of conductive films are covered with each other, and the surface of the flexible conductive layer with the microstructure is partially in contact with each other to form a double-layer conductive diaphragm.
- a flexible vibration sensor is formed in the aforementioned flexible conductive diaphragm, which can detect fluid flow rate and sound recording.
- the inventors of the present invention made flexible sensitive layers and flexible support layers having different thicknesses by using various polymer materials listed in the foregoing, and found that when the thickness of the flexible supporting layer is above 1 ⁇ m, The flexible sensitive layer having a thickness of 0.1 ⁇ m or more can be peeled off from the aforementioned template completely without damage.
- the flexible sensitive layer when the thickness of the flexible sensitive layer is more than 200 micrometers, the sensitivity of the formed device is very poor, the signal-to-noise ratio is also very low, and the sound detecting performance is completely absent.
- FIG. 6 for a sound response test pattern of a flexible vibration sensor using a flexible sensitive layer consisting of polydimethylsiloxane or the like and having a thickness of 200 micrometers, respectively, at 15, 20, 25 At 30 seconds, the flexible vibration sensor is given a sound, and the device reacts little to sound, and referring to Fig. 6, when the flexible sensitive layer has a thickness of 10 ⁇ m, it exhibits a very high sensitivity.
- the flexible vibration sensor constructed by using the flexible conductive diaphragm of the present invention has excellent performance in terms of sensitivity, signal to noise ratio and the like.
- the smaller the thickness of the flexible sensitive layer the higher the sensitivity, signal-to-noise ratio, etc. performance.
- the flexible vibration sensor when a typical flexible vibration sensor of the present invention is placed at a speaker port, the flexible vibration sensor automatically collects a sound signal when the speaker emits sound, and converts the sound signal into a voltage signal output, and the obtained signal is The original sound signal is highly shaped.
- the invention utilizes a flexible multilayer conductive diaphragm as a core component of the flexible vibration sensor to sense vibration. Compared with the conventional vibration sensor, the sensitivity of the device is greatly improved, the thickness and quality of the device are reduced, and the bendability is good.
- the flexible vibration sensor can be integrated into the wearable device to achieve fluid flow rate detection, sound recording and the like.
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Abstract
一种柔性导电振膜及其制备方法以及基于所述柔性导电振膜的柔性振动传感器，柔性导电振膜包含至少一导电薄膜，所述导电薄膜包括柔性支撑层（1）、叠设于柔性支撑层（1）上的柔性敏感层（2），叠设于柔性敏感层（2）上的柔性导电层（3）以及与所述柔性导电层（3）电性连接的电极（4）。通过采用柔性材料、纳米材料和阵列式微结构等技术的组合，使得所获柔性振动传感器具有灵敏度高、制备成本低、重量轻、厚度薄、体积小、可折叠弯曲等特点，可应用于可穿戴、可贴敷电子设备之中。
Description
本发明涉及一种振动传感器，特别是涉及一种基于柔性材料、纳米材料和微结构的柔性振动传感器及其制备方法和应用，属于传感器和智能材料技术领域。
随着可穿戴设备的快速发展和制造技术的不断进步，柔性智能器件成为一项重要的研究领域。它涉及材料学、微电子技术、微机电技术、纳米技术、电路与系统以及传感技术等多学科的综合性技术，其应用已经成为众多跨国公司相继重点的研发领域。柔性的压力传感器，显示器，储能器等都有相应的产品问世。然而作为一种重要物理参数的传感器—振动传感器，却鲜有柔性器件的报道。
另一方面，振动传感器在测试技术中是关键部件之一，它的作用主要是将机械量接收下来，并转换为与之成比例的电量。由于它也是一种机电转换装置。所以也被称为换能器、拾振器等。振动传感器并不是直接将原始要测的机械量转变为电量，而是将原始要测的机械量做为振动传感器的输入量，然后由机械接收部分加以接收，形成另一个适合于变换的机械量，最后由机电变换部分再将其变换为电量。但是传统振动传感器存在无法弯曲、体积大、功耗大等缺陷，难以应用于可穿戴设备中。
发明内容
本发明的目的之一在于提供一种柔性导电振膜，其可作为换能器而应用于可穿戴设备等之中将机械能转化为电信号加以检测，且具有柔性易弯曲、稳定性佳、工作电压低、功耗低、灵敏度高、响应时间短等优点。
本发明的目的之二在于提供一种制备所述柔性导电振膜的方法，具有工艺简单易于实施等特点。
本发明的目的之三在于提供一种基于所述柔性导电振膜的柔性振动传感器，其能够方便地整合在可穿戴设备中。
本发明的目的之四在于提供一种基于所述柔性振动传感器的可穿戴设备。
为实现前述发明目的，本发明采用的技术方案包括：
一种柔性导电振膜，包含至少一导电薄膜，所述导电薄膜包括柔性支撑层，叠设于柔性支撑层上的柔性敏感层，叠设于柔性敏感层上的柔性导电层以及与所述柔性导电层电性连接的电极。
作为较佳实施方案之一，所述柔性导电振膜包括叠加的两个以上所述导电薄膜，其中相邻导电薄膜的柔性导电层相互接触形成电阻可调的接触电阻层。
进一步的，所述柔性导电振膜包括叠加的复数个导电薄膜，该复数个导电薄膜之间形成有两个以上接触电阻层。
作为较佳实施方案之一，所述柔性敏感层直接设置于柔性支撑层表面，并与柔性支撑层固定连接。
进一步的，所述柔性敏感层与柔性支撑层粘接固定；和/或，所述柔性敏感层与柔性支撑层通过聚合物交联反应而相互结合。
进一步的，所述柔性敏感层与柔性支撑层的结合强度足以保证柔性敏感层能够被从柔性敏感层的模板上直接剥离而不破损。
进一步的，所述柔性敏感层的厚度为0.1～200μm，优选为0.1-10μm，尤其优选为1μm。
较为优选的，所述柔性支撑层与柔性敏感层之间和/或所述柔性敏感层与柔性导电层之间还分布有一层以上柔性层。
作为较佳实施方案之一，所述柔性支撑层的两侧面上均依次叠设有柔性敏感层和柔性导电层。
优选的，所述柔性支撑层的材质为聚乙烯，厚度为1-10μm。
进一步的，所述柔性敏感层表面具有阵列式微结构，所述微结构包括非平面微结构，所述非平面微结构包括金字塔形、四棱锥形、三棱锥形、半球型或柱形微结构，但不限于此。
优选的，所述微结构为金字塔形四棱锥，每个锥体的底面为边长为1-200μm的正方形，侧面与底面的夹角为0-90°，优选为54.7°，锥体间距为1-200μm。
作为较佳实施方案之一，所述柔性导电层共形附着于所述柔性敏感层表面。
进一步的，所述柔性导电振膜包括叠加的两个以上所述导电薄膜，其中一柔性导电层的非平面微结构的顶点与相配合的另一柔性导电层电性接触。
更进一步的，其中一柔性导电层的非平面微结构的顶点与相配合的另一柔性导电层的平面区域电性接触。
进一步的，所述柔性敏感层的材质包括高分子材料，例如可选自聚对苯二甲酸乙二醇酯、聚二甲基硅氧烷、聚酰亚胺、聚氨基甲酸酯、聚乙烯醇、聚乙烯醇缩甲醛、聚乙烯等，但不限于此，但优选采用聚二甲基硅氧烷。
进一步的，所述柔性支撑层的材质包括高分子材料，例如可选自聚对苯二甲酸乙二醇酯、聚二甲基硅氧烷、聚酰亚胺、聚氨基甲酸酯、聚乙烯醇、聚乙烯醇缩甲醛、聚乙烯等，但不限于此。
进一步的，所述柔性导电层的材质包括导电材料或导电材料与非导电材料的组合，例如，其中所述导电材料至少选自碳纳米管、石墨烯、金属纳米线、导电聚合物材料，而所述非导电材料包括聚合物，例如所述聚合物可选自聚二甲基硅氧烷、聚对苯二甲酸乙二醇酯、聚酰亚胺、聚氨基甲酸酯、聚乙烯醇、聚乙烯醇缩甲醛、聚乙烯等，但均不限于此。
优选的，所述柔性导电层的材质为碳纳米管薄膜，制备方式为喷涂，而所获相应器件的方块电阻为0.1-100kΩ/□。
进一步的，所述电极的材质包括金属或非金属导电材料，例如所述金属可选自金、铂、镍、银(例如银纳米线)、铟、铜、铝，所述非金属可选自碳纳米管、石墨烯，但均不限于此。
较为优选的，所述电极厚度为1～10μm。优选的，所述电极的材质为铜箔。
作为可行实施方案之一，所述电极与柔性导电层通过导电胶连接。
所述柔性导电振膜的制备方法包括：
(1)提供柔性敏感层的模板，并在所述模板表面形成柔性敏感层；
(2)在柔性敏感层上形成柔性支撑层；
(3)将所述柔性敏感层及柔性支撑层自所述模板上剥离；
(4)在所述柔性敏感层上形成柔性导电层，以及在所述柔性导电层上电性连接电极。
进一步的，所述模板表面具有与分布在柔性敏感层上的阵列式微结构相应的微图案结构。
作为较佳实施方案之一，步骤(1)包括：在所述模板表面先设置至少一脱模剂层，再在所述脱模剂层上形成所述柔性敏感层，所述脱模剂包括三甲基氯硅烷或者全氟辛基三氯硅烷。
作为较佳实施方案之一，步骤(2)包括：对所述柔性支撑层或柔性敏感层进行表面处理，之后将所述柔性支撑层与柔性敏感层结合；其中采用的表面处理方式包括强酸氧化处理、等离子处理或紫外臭氧处理方式。进一步的，表面处理的时间可以为1～30min。
作为较佳实施方案之一，步骤(2)还包括：
将所述柔性支撑层与柔性敏感层粘接而使该两者结合；或者
使固化或半固化的柔性支撑层与固化或半固化的柔性敏感层通过交联反应而结合。例如，在真空环境下，于反应温度为50～200℃的条件下反应30min～6h而使交联反应充分。
进一步的，所述柔性导电层的形成方式可包括蒸镀、化学沉积、打印、喷涂或溅射等。
进一步的，所述电极的制备方法可以包括蒸镀、化学沉积、打印、喷涂或溅射等。
一种柔性振动传感器，包含所述的柔性导电振膜。
所述柔性振动传感器可应用于流体流速检测和声音录取等领域。
一种可穿戴或可贴敷设备，包含所述的柔性导电振膜或所述的柔性振动传感器。
与现有技术相比，本发明的优点包括：
(1)构建了一种新型的柔性导电振膜，其中柔性支撑层与柔性敏感层固定连接，特别是通过交联反应结合在一起，因而在制备过程中可以借助柔性支撑层而直接将柔性敏感层从模板上取下，剥离时间快，无损伤，因而柔性敏感层可以很薄(可低至0.1μm)，敏感度更高，类似于麦克风，在非接触情况下即可实现对声音的检测；
(2)构建了一种柔性振动传感器，其主要组件可以采用廉价的碳纳米管和高分子聚合物等作为原料，制备工艺简单，无需高温过程，制备成本低，同时使用纳米材料和独特的微结构，还可增加器件的灵敏度和稳定性；
(3)本发明的柔性振动传感器中融合了柔性振动传感技术与新型微纳传感技术，具有超薄、超轻和可弯曲的特点，能够方便地整合在可穿戴设备上，且工作电压低、功耗低、灵敏度高、响应时间短，能带来优良的用户体验。
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述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中记载的一些实施例，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他的附图。
图1为本发明一实施例中双层柔性导电振膜结构示意图；
图2为本发明一实施例中多层柔性导电振膜结构示意图；
图3为本发明一实施例中柔性敏感层表面阵列式微结构的SEM图；
图4为本发明一实施例中柔性振动传感器对声音振动的响应对应的电压随时间的变化曲线图；
图5为本发明一实施例中柔性振动传感器对水流流速的响应对应的电阻随时间的变化曲线图；
图6为本发明一实施例中柔性敏感层厚度为200μm、10μm的柔性振动传感器对声音响应的对比图。
鉴于现有技术中的不足，本案发明人经长期研究和大量实践，得以提出本发明的技术方案。下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行详细的描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
请参阅图1，在本发明的一实施例中涉及一种双层柔性导电振膜，其中的每层导电薄膜包括柔性支撑层1、形成于柔性支撑层1上表面的柔性敏感层2，形成于柔性敏感层
2上的柔性导电层3以及电性连接于柔性导电层3上的电极4。
其中，各结构层的材质可如前文所示，此处不再赘述。
进一步的，所述导电薄膜可通过如下方法制备，即：
S1、在模板表面形成一层有机物分子层
在硅晶片等模板表面加工处理(如气相沉积或者熏涂)一层薄薄的有机物分子层(例如三甲基氯硅烷或者全氟辛基三氯硅烷)，以保证在模板表面的柔性敏感层与模板能轻易、完整的分离。
S2、在有机物分子层上形成柔性敏感层
接着在有机物分子层上旋涂未聚合的高分子前聚体或多种聚合物前聚体的混合物(如聚对苯二甲酸乙二醇酯、聚酰亚胺、聚二甲基硅氧烷、聚氨基甲酸酯、聚乙烯醇、聚乙烯醇缩甲醛、聚乙烯中的一种或多种混合物)使之均匀形成一层柔性敏感层薄膜。
S4、对柔性支撑层支撑进行表面处理
将柔性支撑层薄膜进行表面处理，处理方式为强酸氧化处理，等离子处理和紫外臭氧处理三者中任意一种或几种的综合。
S5、在柔性敏感层上形成柔性支撑层
再在上述柔性敏感层薄膜表面上叠设已经表面处理过的柔性支撑层。
S6、热处理，将固化后的柔性敏感层和柔性支撑层从模板上剥离
将柔性敏感层和柔性支撑层在真空环境下加热处理一段时间，待上述柔性支撑层和柔性敏感层薄膜完全融为一体，接下来把已经完全反应到一起的柔性敏感层和柔性支撑层薄膜从模板表面剥离下来，从而将模板上的微图案复形到柔性敏感层上制备出微结构。
S7、在柔性敏感层上形成柔性导电层
再用喷枪在柔性敏感层上制备一层导电材料，例如，由此形成的一典型器件在电镜下的表面形貌如图3所示。
作为较佳实施方案之一，所述柔性导电层共形附着于所述柔性敏感层表面。
S8、在柔性导电层上形成电极
再在柔性导电层上利用银浆粘结上一层电极材料，经固化等工序后，即可形成单层的柔性导电薄膜。
S9、形成双层导电振膜
最后将多个导电薄膜相互覆盖在一起，柔性导电层带有微结构的表面相互部分接触，形成双层导电振膜。
作为较佳实施方案之一，其中一柔性导电层的非平面微结构的顶点与相配合的另一柔性导电层电性接触。通过采用这样的设计，可产生更少的接触位点，从而进一步提升灵敏度。
取前述柔性导电振膜中制成柔性振动传感器，可以其检测流体流速和声音录取。
在前述工艺中，本案发明人采用前文所列出的各种高分子材料分别制成了厚度不同的柔性敏感层、柔性支撑层，并且发现，当柔性支撑层的厚度在1μm以上时，能使厚度在0.1μm以上的柔性敏感层均能完全无损伤的被从前述模板上剥离。
而作为鲜明的对比，当未采用柔性支撑层时，换言之，若省略步骤S4、S5，则当柔性敏感层的厚度在200μm以下时，在将柔性敏感层自模板上剥离时，几乎无法避免柔性敏感层的破损。
但是，无论采用何种高分子材料形成柔性敏感层，当柔性敏感层厚度大于200微米时，形成的器件的灵敏度均很差，信噪比亦非常低，已然完全不具备检测声音的性能。例如，请参阅图6所示系利用主要由聚二甲基硅氧烷等组成的、厚度为200微米的柔性敏感层的柔性振动传感器对声音的响应测试图谱，当分别在15、20、25、30秒时给予该柔性振动传感器一个声音，器件对声音的反应很小，而再请参阅图6，当柔性敏感层厚度为10微米时，其展示出非常高的灵敏度。
而利用本发明柔性导电振膜构建的柔性振动传感器则在灵敏度、信噪比等方面均有优异的表现。尤其是，在柔性敏感层厚度越小时，其灵敏度、信噪比等性能会相应的大幅提升。
例如，请参阅图4，当将本发明的一种典型的柔性振动传感器放置在扬声器口，当扬声器发声时柔性振动传感器会自动收集声音信号，将声音信号转换成为电压信号输出，得到的信号与原始声音信号形似度高。
再将该柔性振动传感器放置在水箱中，利用注射剂和步进电机产生恒定的水流。因为不同流速的水流会使得器件产生不同的振动强度，所以器件对不同流速的水流有不同
的响应，将这种响应转换成为电阻信号输出，可以获得如图5所示曲线，其中当水流流速不同时，柔性振动传感器检测出的信号强度也不同，随着水流流速增大，信号强度也增大。据此，可以利用该柔性振动传感器检测流体的流速。
易于想到的，还可将多个导电薄膜叠加，由此形成多层柔性导电振膜，其结构可参阅图2所示。且通过采用与前述方式类同的方式对由这些多层柔性导电振膜形成的器件进行测试，亦可发现其具有优良灵敏度和信噪比。
本发明利用柔性多层导电振膜作为柔性振动传感器的核心部件对振动进行传感，相比较传统的振动传感器，大大提高了器件的灵敏度，降低了器件的厚度和质量，具有良好的可弯曲性，使得柔性振动传感器能够被整合与可穿戴设备中，达到流体流速检测，声音的录取等目的。
需要说明的是，在本文中，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。
以上所述仅是本发明的具体实施方式，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (16)
- 一种柔性导电振膜，其特征在于包含至少一导电薄膜，所述导电薄膜包括柔性支撑层，叠设于柔性支撑层上的柔性敏感层，叠设于柔性敏感层上的柔性导电层以及与所述柔性导电层电性连接的电极。
- 根据权利要求1所述的柔性导电振膜，其特征在于包括叠加的两个以上所述导电薄膜，其中相邻导电薄膜的柔性导电层相互接触形成电阻可调的接触电阻层。
- 根据权利要求2所述的柔性导电振膜，其特征在于包括叠加的复数个导电薄膜，该复数个导电薄膜之间形成有两个以上接触电阻层。
- 根据权利要求1-3中任一项所述的柔性导电振膜，其特征在于所述柔性敏感层与柔性支撑层的结合强度足以保证柔性敏感层能够被从柔性敏感层的模板上直接剥离而不破损。
- 根据权利要求4所述的柔性导电振膜，其特征在于所述柔性敏感层与柔性支撑层粘接固定；或者，所述柔性敏感层与柔性支撑层通过聚合物交联反应而相互结合。
- 根据权利要求1-3、5中任一项所述的柔性导电振膜，其特征在于所述柔性敏感层的厚度为0.1～200μm。
- 根据权利要求1-3、5中任一项所述的柔性导电振膜，其特征在于所述柔性支撑层与柔性敏感层之间和/或所述柔性敏感层与柔性导电层之间还分布有一层以上柔性层。
- 根据权利要求1-3、5中任一项所述的柔性导电振膜，其特征在于所述柔性敏感层表面具有阵列式微结构，所述微结构包括非平面微结构，所述非平面微结构包括金字塔形、四棱锥形、三棱锥形、半球型或柱形微结构。
- 根据权利要求8所述的柔性导电振膜，其特征在于所述柔性导电层共形附着于所述柔性敏感层表面。
- 根据权利要求9所述的柔性导电振膜，其特征在于它包括叠加的两个以上所述导电薄膜，其中一柔性导电层的非平面微结构的顶点与相配合的另一柔性导电层电性接触。
- 根据权利要求10所述的柔性导电振膜，其特征在于，其中一柔性导电层的非平 面微结构的顶点与相配合的另一柔性导电层的平面区域电性接触。
- 根据权利要求1-3、5、9-11中任一项所述的柔性导电振膜，其特征在于所述柔性敏感层或所述柔性支撑层的材质包括高分子材料，所述的高分子材料至少选自聚对苯二甲酸乙二醇酯、聚二甲基硅氧烷、聚酰亚胺、聚氨基甲酸酯、聚乙烯醇、聚乙烯醇缩甲醛、聚乙烯。
- 权利要求1-12中任一项所述柔性导电振膜的制备方法，其特征在于包括：(1)提供柔性敏感层的模板，并在所述模板表面形成柔性敏感层；(2)在柔性敏感层上形成柔性支撑层；(3)将所述柔性敏感层及柔性支撑层自所述模板上剥离；(4)在所述柔性敏感层上形成柔性导电层，以及在所述柔性导电层上电性连接电极。
- 根据权利要求13所述柔性导电振膜的制备方法，其特征在于步骤(2)包括：对所述柔性支撑层或柔性敏感层进行表面处理，之后将所述柔性支撑层与柔性敏感层结合；其中采用的表面处理方式包括强酸氧化处理、等离子处理或紫外臭氧处理方式。
- 一种柔性振动传感器，其特征在于包含权利要求1-12中任一项所述的柔性导电振膜。
- 一种可穿戴或可贴敷设备，其特征在于包含权利要求1-12中任一项所述的柔性导电振膜或权利要求15所述的柔性振动传感器。
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