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In recent years, the flexible piezoresistive pressure sensor has attracted widespread attention due to the trend of improved wearable electronics applied to the field of electronic skin, disease diagnosis, motion detection and health monitoring. Here in this paper, the latest progress of the exploitation of flexible piezoresistive pressure sensors is reviewed in terms of sensing mechanism, selection of sensing materials, structural design and their advanced application. Firstly, the sensing mechanism of piezoresistive pressure sensors is generally introduced from the band structure of semiconductor materials, seepage theory and tunneling effect of conductive polymer composites and changes in interface contact resistance. Based on these sensing mechanisms, various flexible piezoresistive pressure sensors with high sensitivity, broad sensing range and fast response time have been developed. The selection of composition materials and microstructural design in flexible piezoresistive pressure sensor to implement the optimization of sensing performance are emphatically presented in this review. The composition materials including organic polymer material and inorganic nanomaterial based on two-dimensional (2D) materials such as graphene and MXene are intensively exhibited. In addition to the above characteristics, these kinds of pressure sensors exhibit high mechanical reversibility and low detection limit, which is essential for detecting the minor motions like respiratory rate and pulse. Moreover, the well-designed structures applied to the composition analysis are also overviewed, such as the sea urchin-like structure, spongy porous structure and regular structure. Various designed structures provide further properties like stability for the flexible pressure sensor. However, comparing with traditional pressure sensor, the mass production and application of flexible pressure sensor are confronting several barriers, like the high cost of raw materials and relatively complex manufacturing processes. How to achieve the low cost and low energy consumption simultaneously on the basis of excellent performance is still a challenge to expanding the applications of flexible pressure sensor. Novel sensing mechanism, functional materials and synthetic integration are expected to be developed in the future. And also, the potential application of flexible pressure sensor will be further expanded after endowing it with more functions.
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图 1 (a)半导体硅在[111]和[100]波数方向的导带和价带[34]; (b)化合物CsAuBr3在27 ℃下, 45 GPa压力范围内电阻率的变化[35]; (c)石墨烯片层沿指定方向均匀拉伸或压缩[38]; (d)通过按压导电聚合物复合材料降低电阻率的示意图[45]; (e) 相邻纳米线之间的不同电接触情况[50]
Figure 1. (a) Conduction band and valence band in silicon along [111] and [100] κ-directions[34]; (b) Evolution of the resistivity of CsAuBr3 at 27 ℃ in a pressure range up to 45 GPa[35]; (c) the graphene sheet is uniformly stretched or compressed along a prescribed direction[38]; (d) schematic illustration of decrease in resistivity by pressing a conductive polymer composite[45]; (e) different electrical interconnections between two adjacent NWs[45].
图 2 基于界面接触电阻的变化 (a)两种固体材料接触界面的示意图[54]; (b)电极-活性层接触型压力传感器的工作机理[58]; (c) PEI-CNT涂层的非导电纤维在外加压力下的传感机理[59]
Figure 2. Change based on interface contact resistance: (a) Schematic diagram of a bulk electrical interface[54]; (b) working mechanism of pressure sensor of electrode-active layer contact type[58]; (c) PEI-CNT coated non-conductive fibers under applied pressure showing the proposed sensing mechanism[59].
图 3 柔性压阻式压力传感器活性层材料、微结构类型及应用概述. 柔性压阻式压力传感器活性层材料的组分包括: 碳基纳米材料[60]、金属基纳米材料[61]、导电聚合物[62]、绝缘弹性体[63]等; 柔性压阻式压力传感器微结构设计类型包括: 单一微凸体结构(如金字塔结构[64])、复合微凸体结构(如多孔金字塔结构[65]、互锁结构[48]等)及三维多孔结构[66]; 柔性压阻式压力传感器主要应用于电子皮肤感知[67]和健康检测[68]等领域
Figure 3. Overview of flexible piezoresistive pressure sensor active layer materials, microstructure types and application. The components of the active layer materials of flexible piezoresistive pressure sensors include carbon nanomaterials[60], metal materials[61], conductive polymers[62], insulating elastomers[63]; The microstructure types of flexibility piezoresistive pressure sensor include single microstructure (such as pyramid structure[64]), composite microstructure (such as porous pyramid structure[65], interlocking structure[48]) and 3D porous structure[66]; and the application of flexible piezoresistive pressure sensor: electronic skin[67] and health monitoring[68].
图 4 柔性压阻式压力传感器常用的代表性活性层材料 (a), (b) 海胆状金属基纳米颗粒和弹性体应用于柔性压阻式压力传感器的制备[61]; (c), (d)碳基材料(CNTs)应用于柔性压阻式压力传感器的制备[94]; (e), (f) 碳基材料二维MXene应用于柔性压阻式压力传感器的制备[60]; (g), (h) 导电聚合物PEDOT:PSS应用于柔性压阻式压力传感器的制备[115,116]
Figure 4. Typical active layer materials for flexible piezoresistive pressure sensors: (a), (b) Sea urchin-like metal-based nanoparticles and elastomers are used in the preparation of flexible piezoresistive pressure sensors[61]; (c), (d) carbon-based material(CNTs) used in the preparation of flexible piezoresistive pressure sensors[94]; (e), (f) carbon-based material(MXene) used in the preparation of flexible piezoresistive pressure sensors[60]; (g), (h) conductive polymer(PEDOT:PSS) applied to the preparation of flexible piezoresistive pressure sensor[115,116].
图 5 一种制备工艺: 在金字塔表面涂覆一层PEDOT:PSS薄膜, 电路模型用于推导传感器的传感原理, 它依赖于金字塔的几何形状对压力的响应的变化[64]; (b) 金字塔结构传感器在拉伸时的压力响应及其线性压力灵敏度[64]; (c) 具有不同表面形貌的单一微凸体结构的压力传感原理示意图[32]; (d) 对压力进行响应时的相对电流变化[32]; (e) 压力作用下不同微结构的有限元建模分析[124]; (f)传感器单元的接触面积随压力的变化[124]; (g) 不同几何形状结构: 金字塔、半球、纳米线等在5 kPa外载荷下的压力分布[125]; (h) RDS微结构在5 kPa外载荷下的压力分布[125]; (i) 具有不同表面微结构传感器的电阻随压力变化的模拟结果[125]
Figure 5. (a) Fabrication process showing a processing step that is first introduced: a PEDOT:PSSthin film coating the pyramid surface.Circuit model used to derive the sensing principle of the sensor, which relies on the change of the pyramid’s geometry in response to pressure[64]; (b) pressure responses of pyramid-structured sensors when stretched and their respective linear pressure sensitivities[64]; (c) a schematic illustration of the pressure-sensing principle of single microstructured e-skins with different surface morphologies[32]; (d) relative current changes in response to normal pressure[32]; (e) FEM analysis of different microstructures under pressure[124]; (f) contact area of a sensor cell as a function of pressure[124]; (g) the pressure distribution of the simulation results for different geometries: pyramid, hemisphere, nanowire at an external loading pressure of 5 kPa[125]; (h) the pressure distribution of the simulation results for RDS microstructure at an external loading pressure of 5 kPa[125]; (i) the simulation results of resistance variation versus applied pressure for different surface microstructures[125].
图 6 (a)简述了电子皮肤的工作原理. 外部压力集中应力在接触点, 使互锁型微结构变形, 从而导致接触面积和隧穿电流的增加[48]; (b) 质量分数为8%碳纳米管的不同传感器结构的压力敏感性比较: 平面型(黑色)、半球型(红色)和互锁型微结构(蓝色)[48]; (c) 具有互锁结构的Ti3C2/天然微囊体生物复合薄膜柔性传感器示意图[126]; (d) 手指不同角度弯曲时, Ti3C2/天然微囊体柔性传感器的相对电流变化[126]; (e)分层结构的石墨烯/PDMS的单个结构图像, 传感器组装的示意图及压力传感器的工作原理[99]; (f)基于PPy接枝多孔金字塔介质层的压力传感器结构[65]; (g)基于PPy接枝多孔/固体金字塔介质层的压力传感器的电流随压力变化关系[65]
Figure 6. (a) Schematic showing the working principle of the electronic skin. The external pressure concentrates stress at the contact spots, deforming the microdomes, which in turn causes an increase in the contact area and the tunneling currents[48]; (b) the comparison of pressure sensitivities of different sensor structures for 8 wt%: planar (black), microdome (red), and interlocked microdome (blue)[48]; (c) schematic illustration of the Ti3C2/NMC biocomposite film-based flexible sensors with interlocked structure[126]; (d) relative current change of Ti3C2/NMC flexible sensor in response to various angle bending[126]; (e) image of the individual structure of hierarchically structured graphene/PDMS Array, and schematic illustration of sensor assembly and operating principle of the pressure sensor[99]; (f) schematic of contact resistance-based pressure sensor based on PPy-grafted porous pyramid dielectric layer[65]; (g) relative change in current versus pressure ofthe contact resistance-based pressure sensor based on PPy-grafted porous pyramid dielectric layer and solid pyramid dielectric layer[65].
图 7 (a) 具有中空结构的石墨烯复合材料的制备工艺[98]; (b) MXene基海绵的制备工艺[127]; (c) 加载-卸载1万次循环的MXene基压力传感器的稳定性能[127]; (d)发泡石墨烯传感器的制备说明[128]; (e) 发泡石墨烯传感器的压力-响应曲线[128]
Figure 7. (a) Fabrication process of hollow-structured graphene composite[98]; (b) schematic illustration of fabrication procedure of MXene-sponge[127]; (c) stability performance of the pressure sensor with loading-unloading 10000 cycles[127]; (d) illustrations for the preparation of sparkling graphene block[128]; (e) pressure-response curve for the sparkling graphene block[128].
图 8 (a)“MXene基仿生皮肤”的设计与组装[67], MXene基压阻传感器阵列及相应压力分布的检测, 压力传感器用于检测机器人运动行为; (b)信号以电流变化的形式响应来自弯曲手指、弯曲手腕、腕部脉搏、吞咽动作等[67]; (c)无线健康监测系统在行走和跑步过程中的应用图像[29]
Figure 8. (a) Design and assembly of piezoresistive sensors with bionic spinous microstructure, photograph of the array of MXene-based piezoresistive sensor and detection of the corresponding pressure distributions, and photograph of the pressure sensor assembled on a robot and detection of its response to the motion behavior[67]; (b) the signal responses in the form of current changes come from finger bending, wrist bending, wrist pulse, throat swallowing[67]; (c)image of wireless health monitoring system applied during the process of walking and running[29].
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