柔性电子：大面积全纺织压力传感器用于检测人类移动和物理信号

文章：https://download.csdn.net/download/dss_dssssd/10874464

摘要：the textiles sensor unit achieves high sensitivity($14.4kP{a}^{-1}$),low detection limit(2 Pa), fast response(~24ms), low power consumption and mechanical stability under harsh deformations.

large-area sensor arrays are successfully fabricated on one textile substrate to spatially map tactile stimuli and can be directly incorporated into a fabric garment for stylish designs without sacrifice of comfort.

introduction

recently, intensive endeavors have been devoted to developing flexible pressure-sensitive devices.

A number of “skin-like” sensors[6] (e.g., electronic skins) have been realized by utilizing capacitive,[ 7] piezoelectric,[8] resistive,[9] or triboelectric[10] effects.

These pressure sensors based on ultrathin inorganic silicion[11], pressure-sensitive rubber[12], organic semi-conductors[13], conducting polymers[7a], ionic gels[14]离子凝胶, or self-powered systems[15] have been reported with high sensitivity and excellent flexibility.

However , either the fabrication process of these devices could be laborious（复杂的）, or their flat plastic or polymer substrates such as poly(ethylene terephthalate) (PET), polyimide (PI), poly(dimethylsiloxane) (PDMS), rubber, and paper[16] are still inappropriate for smart textiles.

纺织品是柔性压力传感器设计的理想载体，尤其适用于医疗和人类活动检测目的的可穿戴电子产品，因为纺织品具有吸湿性、柔软性、透气性和对人体皮肤的舒适性.Textiles are ideal vehicles for the design of flexible pressure sensors, especially for wearable electronics with detection purposes of healthcare and human activities , since textile are hygroscopic, soft, breathable, and comfortable to human skin.[17]

Recently, resistive textile-based pressure sensors have been reported with the aid of various nanomaterials, such as fiber-shaped carbon nanotubes(CNT)[2b, 18], gaphene[19], graphene/polymer nanocomposites[20], carbonized silk fabrics[21], electrospun nanotubes[6a,22] and commom cloth coated with carbonaceous materials[7b, 16b,23]

Despite this progress, a wholetextile-
based pressure sensor is still required. In addition, large area textile-based pressure-sensor arrays able to map pressure distributions are seldom reported by far.

Here, we demonstrate a facile and novel approach for fabricating all-textile-based pressure sensors and large-area sensor arrays.

构成：

底部为相互交叉的纺织电极，顶部为CNT沉积的棉纤维。

通过激光划线屏蔽和无电沉积共形的Ni，在常见的纺织品(比如涤纶， 尼龙等)上制备交叉电极。The interdigitated conductive electrodes on common textile (polyester, nylon, etc.) were fabricated by laserscribing masking and electroless deposition of conformal Ni coatings

Figure 1a,展示了基于纺织的制造过程。

商业涤纶纺织品，两面用Kapton胶带密封，然后使用激光划片，形成所需要的模板。所使用的激光强度控制在只能穿过上层的Kapton胶带而不损坏下层的纺织品。

使用【4a】描述的方法，使用ELD(electroless deposition)方法，在掩模上覆盖一层共形的Ni涂层。当移除Kapton掩模后，形成两个交叉梳妆的Ni电极。

接下来，将涂覆CNT的棉织物，放在中间交叉的电极上，之后再上面覆盖一层 3M VHB 9496(典型的 acrylate polymers 丙烯酸酯类聚合物)薄膜作为封装。

样品的图片显示：
采用掩模辅助的ELD涂层法，两个Ni指状电极之间有明显的间隙，原始织物的纺织特性得以保存(Fig 2b)。

在放大图像下观察，

在Fig1c中可以看到包裹涤纶纤维的Ni纳米颗粒，
Fig 1d,e, CNT涂覆的棉的SEM图像，CNT涂层均匀，每根棉纤维上都装饰有一层渗透CNT网络【the CNT coating is uniform and each individual cotton fiber is decorated with a
layer of percolated CNT networks 】

Ni和CNT涂层都很薄，最终的压力传感器保持着原始织物的机械柔性，Figure 1f。

对于底部电极，宽度为0.8mm，绝缘间隙为0.4mm（figure S2）

CNT纤维和Ni纳米颗粒涂覆的织物的层级多孔结构提供了大的表面积，足够粗糙度和柔性来感知施加压力时接触电阻的变化。【The hierarchical, porous nanostructure of both CNT fabric and nanoparticle-coated Ni textiles provides large surface area,
sufficient roughness and elasticity to “feel” the variation of contact
resistance when pressure is loaded】

施加外部压力会使得多孔结构变形，从而增加顶部CNT纤维和底部Ni电极之间的接触面积，接触面积的增大会导致在CNT和Ni泡沫之间更多的导电通路，增加压力时会电流会增加，Figure 1a.【Applying an external pressure would cause a small deformation of the porous structures and hence an increase in the contact area between the top CNT fabric bridge and the bottom Ni textile electrodes. Such an increase in the contact area will lead to more conductive pathways between CNTs and Ni film, so the current will increase when increasing the applied pressure, as schematically shown in Figure 1a.】

将0.2V的固定电压施加在Ni电极上，使得电流能通过Ni和CNT接触的每一个点，梳妆的每一个梳齿等效为并联的一个电阻（Figure S3 support information）【A constant voltage of 0.2 V is applied to the bottom Ni interdigitated fabric such that current will flow
through each contact tips between the CNTs and Ni coatings, with each tip equivalent to a resistor in the parallel circuit】

接触电阻的变化是织物对外部压力响应的主要表现形式[16b]【The variation in the contact resistance is majorly responsible for the textile sensor’s response to the applied external pressure.】

掩模辅助的ELD方法能在织物上打印各种导电图案，对于在织物上打印电路有巨大的潜力。【This mask-assisted ELD method is able to coat the wavy fabric with various conductive patterns, and could be promising for applications in textile circuits.】
为了展示，在涤纶织物上制作了一系列图案（Fig 1j）。

由于金属薄膜的高导电率，Ni纺织品的表面电阻仅为0.7 Ohm $s{q}^{-1}$【Due to the high conductivity of metal film, the sheet resistance of the Ni textile was measured to be only about 0.7 Ohm sq−1.】

Ni导电电极可使用线性马达在曲率半径为20mm的情况下弯曲2000次，展示出机械柔性和耐性，并且导电性没有明显的降低(Figure S4)【The Ni-conductive electrode can be bent at curvature radius of 20 mm for 2000 cycles by a linear motor to confirm the mechanical flexibility and durability.The conductivity of the conductive fabrics shows no obvious degradation (see Figure S4, Supporting Information).】

LED粘附在Ni涂覆的纤维上，作为展示【LED和导电纤维链接细节在Figure S5中】，即使在打结或缠绕条件下，仍能使用DC电流点亮LED

在尼龙织物上成功地制备出各种具有明显空隙的花纹（Figure S6a），Figure S6b-h展示了粗糙织物基底上的线和空间图案。

我们的制造方法能实现线之间的间隙最小为300um，最小线宽为300um（Figure S6）

这些尺寸对于商用电极组件的链接已经足够小了[24],【These dimensions are sufficiently small for the attachment of commercial electronic components】

测量了器件在不同压力下的电流响应，【To explore the pressure responses of the presented sensor, we measured the current responses to different pressures applied on the device】
从不同压力下的I-V曲线可以看出，对于静态压力，器件的响应是稳定的，而且在每一个电压下，电阻是常量值【The I–V curves at different pressures indicate that the response of our device to static pressure is steady and the resistance (slope of I–V curves) under each applied pressure is constant (see Figure 2a)】

压力传感器灵敏度的定义：
$$S=\frac{\delta (\Delta I/I_0)}{\delta P}$$

P是施加的压力，$I_0$是未添加电压时的电流，$\Delta I$时施加压力时电流的改变值
【The sensitivity of the pressure sensor is defined as S = δ(ΔI/I0)/δP, where ΔI is the relative change in current, I0 is current without applied pressure, and P is the applied pressure】

浸涂15次后在低于3.5KPa时灵敏度为$14.4kP{a}^{-1}$, 3.5-15KPa，灵敏度为$7.8kP{a}^{-1}$(Figure 2b)【The sensitivities were obtained for the textile sensor with cotton fabrics with 15 cycles of CNTs coatings, i.e., 14.4 kPa−1 for pressure below 3.5 kPa and 7.8 kPa−1 for 3.5–15 kPa (see Figure 2b)】

Figure 2c 展示了在四个不同压力下的$\Delta I/I_0$的值，在2.9kPa的压力下，loading-unloading 约1000个周期后，电流$\Delta I/I_0$没有明显的下降（Figure 2d），证实了织物传感器在长期的使用中是稳定可靠的。【Figure 2c shows representative current profiles (ΔI/I0) of the textile sensor at four different pressures. After ≈1000 cycles of repeated loading–unloading under a pressure of 2.9 kPa, the current profiles show no obvious degradation (see Figure 2d), confirming that the performance of the textile sensor is stable for long-term service】

除此之外，在压力为1.6kPa下，压力波和电流响应有一个良好的匹配度（Figure S7）【In addition, the current responses and the input pressure waves matched well under a pressure of 1.6 kPa (see Figure S7, Supporting Information).】

由于传感器的各部分都基于柔软的织物，传感器的柔性程度很高，使用线性马达，以25mm的曲率半径弯曲900多次，传感器的压力响应仅产生很小的变化。(Figure 2e)【The textile sensor is also highly flexible since all the components are based on soft textiles. Furthermore, after repeated bending for over 900 cycles at 25 mm of curvature radius by a linear motor, the performance of the device shows negligible variation 】

Figure 2e内嵌的光学图像展示了固定在线性马达上的弯曲的织物压力传感器【The inset optical image in Figure 2e shows the bent textile pressure sensor fixed on a linear motor】

实例展示：

检测finger gesture，hand gesture 和acoustic vibration

Figure 3a 手指弯曲程度越大，电流增加越大。【The current can further increase with the enlargement of bending angles.】

也可以检测压力，扭曲和拉伸【In addition to bending forces, our pressure sensor can also be used to detect the pressing (Figure 3b), twisting (Figure 3c), and stretching (Figure S10b, Supporting Information) forces】

通常来说，加载/卸载过程中电信号的迟滞(hysteresis)是物理传感器的关键问题。基于导电橡胶的传感性能很容易受迟滞效应的限制[7a, 28a]【In general, hysteresis of the electrical signal during loading/ unloading is one of the critical issues for physical sensors. Sensing performance based on conductive rubber are easily limited by hysteresis effect】

通过切换加载和卸载状态，需要几百毫秒才能将器件从拉伸/弯曲状态恢复到初始状态(Figure S10, Supporting Information).【By switching the state of loading and unloading, few hundred milliseconds are needed to recover the device from stretching/bending state to initial state (Figure S10, Supporting Information).】

由于其高灵敏度，能检测声音振动。为了展示，将器件附着在薄膜上，并放在靠近扬声器的位置（Figure 3d）。【Thanks to the high sensitivity, our pressure sensor could be also applied to detect acoustic vibrations. To demonstrate such a capability, we attached our sensor to a thin film and positioned them close to a speaker】
当扬声器打开时，音乐中微小的振动力可以被精确地记录下来，当扬声器关闭时，电流会恢复到初始状态（Figure 3e）。
也能识别吉他的微小振动(Figure S11)【Interestingly, with the speaker turned on, the tiny vibrational forces from music could be accurately recorded. As the speaker turned off, the responding current gradually returned to the initial state (see Figure 3e). In addition, the sensor can be attached to a guitar for tiny vibration recognition (see Figure S11, Supporting
Information).】

Figure 3f，在颈部放置一个织物传感器来无创检测说话时的技能振动的差别，【Figure 3f shows that a textile sensor was attached onto skin of the neck to noninvasively monitor pressure difference of the muscle movement during speech.】
Figure 3g为结果显示，说话人分别出“Textile”、“Pressure sensor”、“Go”等不同的单词和短语时，该器件表现出较高的灵敏度和不同的电流曲线【As shown in Figure 3g, the device exhibited high sensitivity and distinct current curves when the speaker said different words
and phrases such as “Textile,” “Pressure sensor,” and “Go,” respectively】

有趣的是，当检测振动，声音信号，来自扬声器和乐器的信号时，电流降低；而当检测压力，弯曲，弯曲时，电流增加，这与之前的研究一致[19b,29]【Interestingly, the current decreased during the detection of vibration, vocal signals, and signals from speaker and musical instruments; while the output current signals increased from pressing, bending, twisting of the sensors, which is in accordance with the previous studies】

与压力/弯曲/扭曲的力相比，声音信号总是伴随着高频振动，这会使得顶部和底部电极分开，因为柔软的织物基底不能在高频振动下变形。电流由于少的接触面积而降低。而对于压力/弯曲/扭曲的施加压力频率很低，两个织物电极能即使的响应和恢复，从而电流增加。【In general, compared with the loading forces of pressing/bending/twisting, the acoustic and vocal signals always accompany with
high-frequency vibrating, which make a tendency to separate the top and bottom textile electrode with each other, as the soft textile substrates cannot deform at high frequency accordingly. The current signals decrease with less contact area between the two electrodes. As for dynamic mechanical force of pressing/
bending/twisting at low frequency, the two textile electrodes can respond and recover in time, leading to the current increase.】

Figure 3h显示手模型，四个指尖放置压力传感器，在单个基底上，使用ELD技术在指尖打印梳妆电路，在手掌上打印连接电路图案。

Fifure 3i中显示的，四个压力传感器能检测手的运动

人机交互的压力传感器件：通过LED灯亮度来提供压力大小的实时视觉反馈（Figure S12）【A user-interactive pressure-
sensor device which provides a real-time visual response through a LED cell adhered to the textile electrode is shown in Figure S12 (Supporting Information).】

迁建放置在食指上
Figure 3j显示了不同压力下握手的电流响应，当两只手接触时，发光亮度显示了压力的大小。【The device was attached
on the index finger with pressure sensing area on the fingertip. Figure 3j depicted current response to hand shaking with different pressures. The red LED cell is turned on instantaneous when the two hands touched, and the intensity of the luminescence faithfully indicates the magnitude of the applied pressure of hand shaking】

这些展示表明，我们的器件柔性，可穿戴，在低压力下具有高灵敏度，在舒适智能织物中已与集成更多的感知器件[2c]。【These demonstrations suggest that our device is flexible, wearable, highly sensitive in the low-pressure range,
and facile for integration of more sensing components in a comfortable smart textile】

我们的全植物压力传感器是可穿戴的，能用于医疗检测。

附着于手腕上能试试检测脉冲物理信号(Figure 4a)
快速的响应时间(18-24ms)和压力传感器的高灵敏度提供了更高的分辨率来获得更精细的脉冲波。【The fast response time (18–24 ms) and high sensitivity of the pressure sensor provide high resolution to obtain the detailed pulse wave】

Figure 4b记录了桡动脉压力波的三部分：冲击波§、潮汐波(T)、舒张波(d).
【Figure 4b shows a record of radial artery pressure wave consist of three component waves: percussion wave, tidal wave, and diastolic wave.[31] Such data can be used to derive the radial augmentation index (AIr), defined as P2/P1 in Figure 4b, which is related to arterial stiffness (useful information for diagnosing vascular aging).[7a]】

在Figure 4cd中，分析了压力传感器的检测阈值和响应/弛豫时间。【The detection pressure limit and response/relaxation time of the pressure sensor were also analyzed in Figure 4c,d】

树叶的压力2Pa，在0.2V电压下响应时间为18ms，弛豫时间为24ms【The
pressure sensor immediately responded to a little leaf pressure of 2 Pa, with response time of 18 ms and a delay of 24 ms under a supplied voltage of 0.2 V.】

Figure S13中，最高响应压力为2.9kPa，响应时间24ms，弛豫时间30ms

低的检测阈值，快速响应和低能量消耗与之前的研究相比可比拟甚至更好，包括：

• Au-nanowire-coated tissue paper (13 Pa, 17 ms, and 1.5 V)
• micropyramidal conductive composite array (23 Pa, 200 ms, and 0.2 V)[9a, 26] (Table S1)
  【The low detection limit, short response time, and small energy consumption are remarkable better or comparable with several representative previous studies, including those using Au-nanowire-coated tissue paper (13 Pa, 17 ms, and 1.5 V), and micropyramidal conductive composite array (23 Pa, 200 ms, and 0.2 V)[9a,26]】

演示了摩尔斯电码 Figuer 4e【In addition, we inputted Morse code by touching the surface of the sensor device, and the curves of the current responses correspond to four characters, i.e., “BINN” (see Figure 4e).】

为测试对于智能织物的触觉感知的可行性，将我们的感知器组成感知阵列来对压力信息做一个空间映射。【To test the feasibility of tactile sensing for smart textiles, it is desirable to build our sensors into a textile sensing array to spatially map resolved pressure information】

Figure 5a描述了在粗糙织物基底上的4*4的感知阵列(每一个单元为 4.5 *4.5 $m{m}^2$)【Figure 5a schematically describes the 4 × 4 pixels sensing arrays (each is 4.5 × 4.5 mm2) on rugged textile substrate】

使用ELD方法打印底层交叉电极和相互连接的Ni线（see Figure S14），接下来在上放置CNT涂覆的纤维作为顶部电极，VHB薄膜作为封装【The mask-aided deposition method was used to pattern bottom electrodes with interdigitated geometry and interconnecting Ni wires (see details in Figure S14, Supporting Information).Next, we sandwiched CNT-coated fabric as top electrode and VHB thin film as encapsulation】

这个感知阵列柔软，能非常容易的缝在衣服上，能够弯曲和扭曲(Figure 5b)【This sensing array is flexible can be easily
sewed onto a cloth, and can be bent or twisted (see Figure 5b).】

Figure 5c展示了感知阵列能够完美的贴合到手腕上，并能检测到两个手指指压的接触点(Figure 5d)【Figure 5c shows that the sensing array can be conformally attached onto human wrist, and the contact points touched by two fingers were identified (see Figure 5d).】

当将一个Z形的亚克力板放在感知阵列上(Figure 5e),如在Figure 5f中看到的，输出电流强度能显示Z形，代表了接触区域。【When a Z-shaped acrylic plate was placed on the sensor arrays (Figure 5e), the output current intensity can literally represent the touching area, as shown in Figure 5f】

除此之外，也可以检测到运动轨迹，当食指在感知阵列表面移动式，能记录运动路径【Moreover, motion trajectory can be monitored using the pressure-sensing array. When an index finger moves along the surface of sensing array (Figure 5g–i), the motion paths could be clearly tracked (Figure 5j–l).】

总结

In summary, we have reported a versatile and facile approach to highly sensitive and flexible textile pressure sensors and sensing arrays

By the combination of mask-assisted Ni-coating and CNT fabric, our method allows for the fabrication of pressure sensors and multipixel arrays directly on cloth without the use of conventional wafer-based technologies

The resulting all-textile pressure sensors achieve high sensitivity (14.4 kPa−1), stable cycling performances (1000 cycles), a fast response time (≈24 ms), low power consumption (<6 μW), and mechanical
stability under harsh deformations

The devices can act as part of human skin or clothing to detect various external pressures, human activities, and even real-time monitoring of pulse wave

These remarkable features endow our device capabilities of facile integration with other functional devices (e.g., LED cells)
for human-readable user-interactive interfaces

based on the low-cost fabrication, high performance, flexibility, and humanfriendly
characteristics， we have presented a route to pressure sensors with great promise in smart textiles or wearable electronics.

实验章节

1. 在织物上柔性图案和电阻的制造

   • 首先将聚酯/尼龙织物分别在丙酮，酒精和去离子水中超声清洗【Polyester/nylon textile was first thoroughly cleaned by abundant acetone, alcohol, and deionized (DI) water with a bath sonicator, respectively.】
   • 接下来，在织物两边紧密覆盖一层商用的卡普顿胶带【Subsequently, both sides of the textile were covered with commercial Kapton tape tightly】
   • 使用商用的$C{O}_2$激光切割机在卡普顿胶带上刻印与设计图案，而不损坏下层的织物【A computer-controlled commercial CO2 laser cutter system was then used to scribe the Kapton into predesigned patterns without damaging the sandwiched textile】
   • Ni街来来通过化学沉积的方式沉积到织物基底上，利用【32】中采用的方法。【Ni was then deposited on the textile substrate with the aid of the mask via electroless plating similar to the previous report.[32]】

2. CNT涂覆的纤维和传感器制造

   • 将1.6mg/mL的单壁碳纳米管分散到10mg/mL的十二烷基苯磺酸钠水溶液中 ，超声处理1h[33]【The CNT ink was prepared by dispersing 1.6 mg mL−1 single-walled carbon nanotubes (SWNTs) in water with 10 mg mL−1 sodium dodecylbenzene sulfonat as surfactant by 1 h sonication.[33]】
   • 接着将棉纤维浸入到SWNT溶液中，然后干燥，重复15次，制成表面电阻为75.4k$\Omega s{q}^{-1}$的纤维。【Then a cotton textile was dipped into the black SWNT ink and dried for 15 cycles, leading to a piece of uniform black fabric with a sheet resistance of 75.4 kΩ sq−1】
   • 样本接下来在去离子水中清洗然后在真空干燥炉中干燥。【The sample was then washed with deionized (DI) water and dried in a vacuum oven】
   • 底层的Ni电极与CNT涂覆的纤维和VHB薄膜密封？How？【Then, the bottom Ni electrode was sealed with the CNT-coated fabric and VHB thin film】

3. 柔性多像素阵列的制作
   The CNT-coated fabric was cut by a computer-controlled commercial CO2 laser cutter system and then integrated in a 4 × 4 pixel arrays of interdigitated textile pixels and sandwiched between a VHB thin film, leading to large-area, patterned pressure sensors

Characterization:

The current intensity was measured by an
electrochemical work station (CHI 760E) and a Keithley electrometer
6514. A LabVIEW controlled digital source meter (Keithley 2450) was
used to measure the I–t curves in real-time. The SEM images were
collected using a Hitachi SU8200. A step motor (Linmot E1100) was
used to test the mechanical stability of the device.