Ionic Tactile Sensors for Emerging Human‐Interactive Technologies: A Review of Recent Progress

Ionic tactile sensors (ITS) represent a new class of deformable sensory platforms that mimic not only the tactile functions and topological structures but also the mechanotransduction mechanism across the biological ion channels in human skin, which can demonstrate a more advanced biological interface for targeting emerging human‐interactive technologies compared to conventional e‐skin devices. Recently, flexible and even stretchable ITS have been developed using novel structural designs and strategies in materials and devices. These skin‐like tactile sensors can effectively sense pressure, strain, shear, torsion, and other external stimuli with high sensitivity, high reliability, and rapid response beyond those of human perception. In this review, the recent developments of the ITS based on the novel concepts, structural designs, and strategies in materials innovation are entirely highlighted. In particular, biomimetic approaches have led to the development of the ITS that extend beyond the tactile sensory capabilities of human skin such as sensitivity, pressure detection range, and multimodality. Furthermore, the recent progress in self‐powered and self‐healable ITS, which should be strongly required to allow human‐interactive artificial sensory platforms is reviewed. The applications of ITS in human‐interactive technologies including artificial skin, wearable medical devices, and user‐interactive interfaces are highlighted. Last, perspectives on the current challenges and the future directions of this field are presented.     

Large‐Area Compliant,Low‐Cost,and Versatile Pressure‐Sensing Platform Based on Microcrack‐Designed Carbon Black@Polyurethane Sponge for Human–Machine Interfacing

It is a challenge to manufacture pressure‐sensing materials that possess flexibility, high sensitivity, large‐area compliance, and capability to detect both tiny and large motions for the development of artificial intelligence products. Herein, a very simple and low‐cost approach is proposed to fabricate versatile pressure sensors based on microcrack‐designed carbon black (CB)@polyurethane (PU) sponges via natural polymer‐mediated water‐based layer‐by‐layer assembly. These sensors are capable of satisfying the requirements of ultrasmall as well as large motion monitoring. The versatility of these sensors benefits from two aspects: microcrack junction sensing mechanism for tiny motion detecting (91 Pa pressure, 0.2% strain) inspired by the spider sensory system and compressive contact of CB@PU conductive backbones for large motion monitoring (16.4 kPa pressure, 60% strain). Furthermore, these sensors exhibit excellent flexibility, fast response times (<20 ms), as well as good reproducibility over 50 000 cycles. This study also demonstrates the versatility of these sensors for various applications, ranging from speech recognition, health monitoring, bodily motion detection to artificial electronic skin. The desirable comprehensive performance of our sensors, which is comparable to the recently reported pressure‐sensing devices, together with their significant advantages of low‐cost, easy fabrication, especially versatility, makes them attractive in the future of artificial intelligence.     

Bubble‐Decorated Honeycomb‐Like Graphene Film as Ultrahigh Sensitivity Pressure Sensors

Recently, macroporous graphene monoliths (MGMs), with ultralow density and good electrical conductivity, have been considered as excellent pressure sensors due to their excellent elasticity with a rapid rate of recovery. However, MGMs can only exhibit good sensitivity when the strain is higher than 20%, which is undesirable for touch‐type pressure sensors, such as artificial skin. Here, an innovative method for the fabrication of freestanding flexible graphene film with bubbles decorated on honeycomb‐like network is demonstrated. Due to the switching effect depended on “point‐to‐point” and “point‐to‐face” contact modes, the graphene pressure sensor has an ultrahigh sensitivity of 161.6 kPa^?1 at a strain less than 4%, several hundred times higher than most previously reported pressure sensors. Moreover, the graphene pressure sensor can monitor human motions such as finger bending and pulse with a very low operating voltage of 10 mV, which is sufficiently low to allow for powering by energy‐harvesting devices, such as triboelectric generators. Therefore, the high sensitivity, low operating voltage, long cycling life, and large‐scale fabrication of the pressure sensors make it a promising candidate for manufacturing low‐cost artificial skin.     

Nematic Anisotropic Liquid‐Crystal Gels—Self‐Assembled Nanocomposites with High Electromechanical Response

The uniqueness of liquid crystals (LCs) lies in the large anisotropies of their properties, which can be utilized to generate high electromechanical responses. In a properly oriented LC polymer system, an external electric field can induce reorientation of the mesogenic units possessing a dielectric anisotropy, which, when coupled with the shape anisotropy of the mesogenic units, can in turn produce large mechanical strain. Anisotropic LC gels, which can be obtained by in‐situ photopolymerization of the reactive LC molecules in the presence of non‐reactive LC molecules in an oriented state, are an example of such liquid‐crystal polymer systems. It is shown here that a homeotropically aligned LC gel in its nematic phase exhibits high electrically induced strain (> 2 %) with an elastic modulus of 100 MPa and a high electromechanical conversion efficiency (75 %) under an electric field of 25 MV/m. These anisotropic LC polymeric materials could provide a technologically compatible system for such applications as artificial muscles and as microelectromechanical devices.     

One‐Pot Synthesis of Luminescent Polymer‐Nanoparticle Composites from Task‐Specific Ionic Liquids

A multifunctional polymerizable ionic liquid, diallyldimethylammonium tetrafluoroborate (DADMA BF₄), is used in a one‐pot synthesis of novel luminescent polymer‐nanoparticle composites. First, small monodisperse lanthanide fluoride nanoparticles are formed by microwave irradiation in the presence of Ln(OAc)₃·xH₂O (Ln = Gd, Eu, Tb; OAc = acetate) in the ionic liquid. The nanoparticles can be precipitated for structural characterization or kept in the solution, which yields after irradition by high intensity UV light colorless, processable polymer materials with good photophysical properties. Both green‐emitting Tb‐containing and red‐emitting Eu‐containing IL‐ polymers are described.     

Large‐Scale Fabrication of Three‐Dimensional Surface Patterns Using Template‐Defined Electrochemical Deposition

A new strategy to achieve large‐scale, three‐dimensional (3D) micro‐ and nanostructured surface patterns through selective electrochemical growth on monolayer colloidal crystal (MCC) templates is reported. This method can effectively create large‐area (>1 cm²), 3D surface patterns with well‐defined structures in a cost‐effective and time‐saving manner (<30 min). A variety of 3D surface patterns, including semishells, Janus particles, microcups, and mushroom‐like clusters, is generated. Most importantly, our method can be used to prepare surface patterns with prescribed compositions, such as metals, metal oxides, organic materials, or composites (e.g., metal/metal oxide, metal/polymer). The 3D surface patterns produced by our method can be valuable in a wide range of applications, such as biosensing, data storage, and plasmonics. In a proof‐of‐concept study, we investigated, both experimentally and theoretically, the surface‐enhanced Raman scattering (SERS) performance of the fabricated silver 3D semishell arrays.     

Ultrauniform Embedded Liquid Metal in Sulfur Polymers for Recyclable,Conductive, and Self‐Healable Materials

Liquid metals (LMs) are receiving growing interest in modern technologies for their various advantages. This work reports using elemental sulfur to achieve nanodispersed liquid metals in bulk polymers for multifunctional LM‐based materials. Ring‐opening polymerization and inverse vulcanization of elemental sulfur provide many polysulfide loops and thiol groups as effective binding ligands that enable extraordinarily uniform dispersion of liquid metals (≈1 µm) in bulk matrix and improve the mechanical performance of the materials. Interestingly, the liquid‐metal‐embedded sulfur polymer (LMESP) materials exhibit excellent thermal‐/solvent‐processability and recyclability. The uniform dispersion leads to phenomenal electrical conductivity of the LMESP at a low volume percentage of LM (30 vol%), overcoming the issue of nonconductivity typically seen in insulated LM–polymer blends. Additionally, the LMESP shows resistive sensitivity toward external pressure. Furthermore, the LMESP materials exhibit an excellent self‐healing ability under mild conditions via the dynamic bonds between polysulfide loops/thiol groups and liquid metals. This work clearly offers a new platform to design liquid metals and can push them for broad applications.     

A Self‐Healable,Highly Stretchable,and Solution Processable Conductive Polymer Composite for Ultrasensitive Strain and Pressure Sensing

Mimicking human skin's functions to develop electronic skins has inspired tremendous efforts in design and synthesis of novel soft materials with simplified fabrication methods. However, it still remains a great challenge to develop electronically conductive materials that are both stretchable and self‐healable. Here it is demonstrated that a ternary polymer composite comprised of polyaniline, polyacrylic acid, and phytic acid can exhibit high stretchability ( ≈ 500%) and excellent self‐healing properties. The polymer composite with optimized composition shows an electrical conductivity of 0.12 S cm^?1. On rupture, both electrical and mechanical properties can be restored with ≈ 99% efficiency in a 24 h period, which is enabled by the dynamic hydrogen bonding and electrostatic interactions. It is further shown that this composite is both strain and pressure sensitive, and therefore can be used for fabricating strain and pressure sensors to detect a variety of mechanical deformations with ultrahigh sensitivity. The sensitivity and sensing range are the highest among all of the reported self‐healable piezoresistive pressure sensors and even surpass most flexible mechanical sensors. Notably, this composite is prepared via a solution casting process, which potentially allows for large‐area, low‐cost fabrication electronic skins.     

Room‐Temperature Self‐Healing and Recyclable Tough Polymer Composites Using Nitrogen‐Coordinated Boroxines

In this paper, nitrogen‐coordinated boroxines are exploited for the fabrication of self‐healing and recyclable polymer composites with enhanced mechanical properties. The 3D polymer networks cross‐linked with nitrogen‐coordinated boroxines are first synthesized through the trimerization of ortho‐aminomethyl‐phenylboronic acid groups at the terminals of poly(propylene glycol) (PPG) chains, and subsequently, the mechanically robust polymer composites are fabricated by utilizing the complexation of nitrogen‐coordinated boroxine‐containing PPG (N‐boroxine‐PPG) with poly(acrylic acid) (PAA) and hydrogen‐bonding interactions between them. The N‐boroxine‐PPG is soft with a tensile strength of 0.19 MPa, whereas the tensile strengths of N‐boroxine‐PPG/PAA composites can be tailored to range from 1.7 to 12.7 MPa by increasing the PAA contents in the polymer composites. It is revealed that the amine ligands can facilitate the formation and dissociation of nitrogen‐coordinated boroxines at room temperature. Moreover, the reversibility of nitrogen‐coordinated boroxines and hydrogen‐bonding interactions enable multiple cycles of healing and recycling of the damaged N‐boroxine‐PPG/PAA composites. The healed and recycled N‐boroxine‐PPG/PAA polymer composites regain most of their mechanical strength.     

Auxetic Foam‐Based Contact‐Mode Triboelectric Nanogenerator with Highly Sensitive Self‐Powered Strain Sensing Capabilities to Monitor Human Body Movement

The first contact‐mode triboelectric self‐powered strain sensor using an auxetic polyurethane foam, conductive fabric, and polytetrafluroethylene (PTFE) is fabricated. Utilizing the auxetic properties of the polyurethane foam, the auxetic polyurethane foam would expand into the PTFE when the foam is stretched, causing contact electrification. Due to a larger contact area between the PTFE and the foam as the foam is stretched, this device can serve effectively as a strain sensor. The sensitivity of this method is explored, and this sensor has the highest sensitivity in all triboelectric nanogenerator devices that are used previously as a strain sensor. Different applications of this strain sensor are shown, and this sensor can be used as a human body monitoring system, self‐powered scale to measure weight, and a seat belt to measure body movements inside a car seat.     

Liquid‐Filled Valence Tautomeric Microcapsules: A Solid Material with Solution‐Like Behavior

The integration of stimuli‐responsive valence tautomeric (VT) molecular systems into solid materials without compromising their functionality is a major bottleneck for the use of these compounds in high‐added value applications. In this work, an innovative, simple, and universal approach is described to tackle this challenge based on the confinement of the active species into liquid‐filled polymeric capsules. A microstructured solid with optimized solution‐like behavior is obtained in this way, whose VT properties can be rationally tuned upon variation of the encapsulated solvent. Incorporation of the resulting capsules into thin films or other matrices of interest allows successful transfer of valence tautomerism from the liquid phase to solid materials, thus paving the way to the fabrication of functional devices based on spin transition compounds.     

Multiaxial and Transparent Strain Sensors Based on Synergetically Reinforced and Orthogonally Cracked Hetero‐Nanocrystal Solids

Wearable strain sensors are widely researched as core components in electronic skin. However, their limited capability of detecting only a single axial strain, and their low sensitivity, stability, opacity, and high production costs hinder their use in advanced applications. Herein, multiaxially highly sensitive, optically transparent, chemically stable, and solution‐processed strain sensors are demonstrated. Transparent indium tin oxide and zinc oxide nanocrystals serve as metallic and insulating components in a metal–insulator matrix and as active materials for strain gauges. Synergetic sensitivity‐ and stability‐reinforcing agents are developed using a transparent SU‐8 polymer to enhance the sensitivity and encapsulate the devices, elevating the gauge factor up to over 3000 by blocking the reconnection of cracks caused by the Poisson effect. Cross‐shaped patterns with an orthogonal crack strategy are developed to detect a complex multiaxial strain, efficiently distinguishing strains applied in various directions with high sensitivity and selectivity. Finally, all‐transparent wearable strain sensors with Ag nanowire electrodes are fabricated using an all‐solution process, which effectively measure not only the human motion or emotion, but also the multiaxial strains occurring during human motion in real time. The strategies can provide a pathway to realize cost‐effective and high‐performance wearable sensors for advanced applications such as bio‐integrated devices.     

Large‐Area Ultrathin Graphene Films by Single‐Step Marangoni Self‐Assembly for Highly Sensitive Strain Sensing Application

Promoted by the demand for wearable devices, graphene has been proved to be a promising material for potential applications in flexible and highly sensitive strain sensors. However, low sensitivity and complex processing of graphene retard the development toward the practical applications. Here, an environment‐friendly and cost‐effective method to fabricate large‐area ultrathin graphene films is proposed for highly sensitive flexible strain sensor. The assembled graphene films are derived rapidly at the liquid/air interface by Marangoni effect and the area can be scaled up. These graphene‐based strain sensors exhibit extremely high sensitivity with gauge factor of 1037 at 2% strain, which represents the highest value for graphene platelets at this small deformation so far. This simple fabrication for strain sensors with highly sensitive performance of strain sensor makes it a novel approach to applications in electronic skin, wearable sensors, and health monitoring platforms.     

Stretchable Energy‐Harvesting Tactile Interactive Interface with Liquid‐Metal‐Nanoparticle‐Based Electrodes

Energy‐harvesting electronic skin (E‐skin) is highly promising for sustainable and self‐powered interactive systems, wearable human health monitors, and intelligent robotics. Flexible/stretchable electrodes and robust energy‐harvesting components are critical in constructing soft, wearable, and energy‐autonomous E‐skin systems. A stretchable energy‐harvesting tactile interactive interface is demonstrated using liquid metal nanoparticles (LM‐NPs)‐based electrodes. This stretchable energy‐harvesting tactile interface relies on triboelectric nanogenerator composed of a galinstan LM‐NP‐based stretchable electrode and patterned elastic polymer friction and encapsulation layer. It provides stable and high open‐circuit voltage (268 V), short‐circuit current (12.06 µA), and transferred charges (103.59 nC), which are sufficient to drive commercial portable electronics. As a self‐powered tactile sensor, it presents satisfactory and repeatable sensitivity of 2.52 V·kPa^?1 and is capable of working as a touch interactive keyboard. The demonstrated stretchable and robust energy‐harvesting E‐skin using LM‐NP‐based electrodes is of great significance in sustainable human–machine interactive system, intelligent robotic skin, security tactile switches, etc.     

Hierarchical Porosity in Self‐Assembled Polymers: Post‐Modification of Block Copolymer–Phenolic Resin Complexes by Pyrolysis Allows the Control of Micro‐ and Mesoporosity

It is shown that self‐assembled hierarchical porosity in organic polymers can be obtained in a facile manner based on pyrolyzed block‐copolymer–phenolic resin nanocomposites and that a given starting composition can be post‐modified in a wide range from monomodal mesoporous materials to hierarchical micro‐mesoporous materials with a high density of pores and large surface area per volume unit (up to 500–600 m² g^–1). For that purpose, self‐assembled cured composites are used where phenolic resin is templated by a diblock copolymer poly(4‐vinylpyridine)‐block‐polystyrene (P4VP‐b‐PS). Mild pyrolysis conditions lead only to monomodal mesoscale porosity, as essentially only the PS block is removed (length scale of tens of nanometers), whereas during more severe conditions under prolonged isothermal pyrolysis at 420 °C the P4VP chains within the phenolic matrix are also removed, leading to additional microporosity (sub‐nanometer length scale). The porosity is analyzed using transmission electron microscopy (TEM), small‐angle X‐ray scattering, electron microscopy tomography (3D‐TEM), positron annihilation lifetime spectroscopy (PALS), and surface‐area Brunauer–Emmett–Teller (BET) measurements. Furthermore, the relative amount of micro‐ and mesopores can be tuned in situ by post modification. As controlled pyrolysis leaves phenolic hydroxyl groups at the pore walls and the thermoset resin‐based materials can be easily molded into a desired shape, it is expected that such materials could be useful for sensors, separation materials, filters, and templates for catalysis.     

Strain‐Responsive Polyurethane/PEDOT:PSS Elastomeric Composite Fibers with High Electrical Conductivity

It is a challenge to retain the high stretchability of an elastomer when used in polymer composites. Likewise, the high conductivity of organic conductors is typically compromised when used as filler in composite systems. Here, it is possible to achieve elastomeric fiber composites with high electrical conductivity at relatively low loading of the conductor and, more importantly, to attain mechanical properties that are useful in strain‐sensing applications. The preparation of homogenous composite formulations from poly­urethane (PU) and poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) that are also processable by fiber wet‐spinning techniques are systematically evaluated. With increasing PEDOT:PSS loading in the fiber composites, the Young's modulus increases exponentially and the yield stress increases linearly. A model describing the effects of the reversible and irreversible deformations as a result of the re‐arrangement of PEDOT:PSS filler networks within PU and how this relates to the electromechanical properties of the fibers during the tensile and cyclic stretching is presented.     

Functional Coatings on High‐Performance Polymer Fibers for Smart Sensing

Above a critical temperature, high‐performance fibers may lose their mechanical properties resulting in catastrophic events of damage when, e.g., used as load‐carrying ropes. Here, a method to functionalize polymer fibers with thermochromic optical coatings that enable signaling of damaging thermal history is introduced. These smart coatings are comprised of an index‐tunable anti‐reflection coating based on chalcogenide phase change materials (PCM). It is demonstrated that the insulator?metal phase transition of these materials can be aligned with the critical deterioration temperature of both polyethylene terephthalate (PET) monofilaments and liquid‐crystal polyester (LCP) yarns by composition tuning. The carefully designed optical system amplifies the change in optical properties of its constituents upon phase change. The thermal and mechanical degradation of these fibers can thus be monitored and displayed by eye.     

Foam‐Like Behavior in Compliant,Continuously Reinforced Nanocomposites

In the pursuit of advanced polymer composites, nanoscale fillers have long been championed as promising candidates for structural reinforcement. Despite progress, questions remain as to how these diminutive fillers influence the distribution of stresses within the matrix and, in turn, influence bulk mechanical properties. The dynamic mechanical behavior of elastomer‐impregnated forests of carbon nanotubes (CNTs) has revealed distinct orientation‐dependent behavior that sheds light on these complicated interactions. When compressed along the axis of the fillers, the composite will mimic open‐cell foams and exhibit strain softening for increasing amplitudes due to the collective Euler buckling of the slender nanotubes. In contrast, the same material will behave similarly to the neat polymer when compressed orthogonal to the alignment direction of the nanotubes. However, in this orientation the material is incapable of achieving the same ultimate compressive strain due to the role that the embedded nanotubes play in augmenting the effective cross‐link density of the polymer network. Both of these responses are recoverable, robust, and show little dependency on the diameter and wall‐number of the included CNTs. Such observations give insight into the mechanics of polymer/nanoparticle interactions in nanocomposite structures under strain, and the thoughtful control of such coordinated buckling behavior opens the possibility for the development of foam‐like materials with large Poisson ratios.     

Self‐Powered Tactile Sensor Array Systems Based on the Triboelectric Effect

With the arrival of intelligent terminals, tactile sensors which are capable of sensing various external physical stimuli are considered among the most vital devices for the next generation of smart electronics. To create a self‐powered tactile sensor system that can function sustainably and continuously without an external power source is of crucial significance. An overview of the development in self‐powered tactile sensor array system based on the triboelectric effect is systematically presented. The combination of multi‐functionalization and high performance of tactile sensors aimed at achieving highly comprehensive performance is presented. For the tactile sensor unit, a development is summarized based on the two primary modes which are vertical contact–separation and single‐electrode. For the pressure mapping array, the resolution is significantly enhanced by the novel cross‐type configuration based on the single‐electrode mode. Integrated with other mechanisms, the performance will be further elevated by broadening of the detect range and realizing of visualization of pressure imaging. Then, two main applications of human–machine interaction (HMI) and trajectory monitoring are comprehensively summarized. Finally, the future perspectives of self‐powered tactile sensor system based on triboelectric effect are discussed.     

Swelling‐Agent‐Free Synthesis of Siliceous and Functional Mesocellular Foam‐Like Mesophases by Using a Carboxy‐Terminated Triblock Copolymer

Swelling‐agent‐free synthesis of mesocellular foam (MCF)‐like silica mesophases by a pH‐dependent structural transformation using carboxy‐terminated triblock copolymer Pluronic P123 has been discovered. The structural properties of the MCF‐like silica materials can be modulated by controlled calcination or post‐synthesis treatment with sulfuric acid, and either closed‐cell or open‐cell mesostructures have been prepared. The MCF‐like silica mesophases have also been applied as hard templates to prepare MCF‐like carbon materials via a nanocasting route. Furthermore, the swelling‐agent‐free synthesis has been found to be less sensitive to the presence of organosilanes, and the cocondensation syntheses of functional MCF‐like materials with carboxyethyl, iodopropyl, or mercaptopropyl groups have also been demonstrated.