Programmable Self‐Assembling 3D Architectures Generated by Patterning of Swellable MOF‐Based Composite Films

The integration of swellable metal–organic frameworks (MOFs) into polymeric composite films is a straightforward strategy to develop soft materials that undergo reversible shape transformations derived from the intrinsic flexibility of MOF crystals. However, a crucial step toward their practical application relies on the ability to attain specific and programmable actuation, which enables the design of self‐shaping objects on demand. Herein, a chemical etching method is demonstrated for the fabrication of patterned composite films showing tunable self‐folding response, predictable and reversible 2D‐to‐3D shape transformations triggered by water adsorption/desorption. These films are fabricated by selective removal of swellable MOF crystals allowing control over their spatial distribution within the polymeric film. Upon exposure to moisture, various programmable 3D architectures, which include a mechanical gripper, a lift, and a unidirectional walking device, are generated. Remarkably, these 2D‐to‐3D shape transformations can be reversed by light‐induced desorption. The reported strategy offers a platform for fabricating flexible MOF‐based autonomous soft mechanical devices with functionalities for micromanipulation, automation, and robotics.     

Self‐Healing of Polarizing Films via the Synergy between Gold Nanorods and Vitrimer

Conventional self‐healing is about the recovery of shape and mechanical properties. In contrast, recovery of functional properties is still a great challenge, especially for optical functional materials, as the known self‐healing methods are incompatible with optical properties. By utilizing the synergistic effect between Au nanorods and vitrimer, the alignment of Au nanorods can be achieved in the crosslinked polymer. The optical properties of the resulting polarizing film, such as light transmittance and polarization degree, can be fully recovered without an external repair agent. With simple laser irradiation to induce the photothermal effect of Au nanorods, the shape‐memory effect of vitrimer returns the Au nanorods to their initial orientation, and the plasticity achieves in situ self‐healing of the cutting area. The self‐healing of polarizing film provides a new research direction and reference for the application of self‐healing systems in functional materials.     

Colorless,Transparent, Robust,and Fast Scratch‐Self‐Healing Elastomers via a Phase‐Locked Dynamic Bonds Design

Robust self‐healing thermoplastic elastomers are expected to have repeated healing capability, remarkable mechanical properties, transparency, and superior toughness. The phase‐locked design in this work provides excellent tensile mechanical properties and efficient healability at a moderate temperature due to the dynamic disulfide bonds embedded in the hard segments and mainly being locked in the viscoelastic hard microphase region. The self‐healing elastomers exhibit a maximum tensile stress of 25 MPa and a fracture strain of over 1600%, which are quite prominent compared to previous reports. The nanoscale domains of the elastomer are smaller than the wavelength of visible light by microphase separation control resulting in colorless, nearly 100% transparency, and are as good as quartz glasses. The high dynamics of the phase‐locked disulfide bonds renders a high healing efficiency of scratches on the surface within 60 s at 70 °C. The rapid scratch healing and complete transparency recovery of the elastomers provide new avenues in the highly transparent surface or protective films which finds potential applications for precision optical lenses, flexible display screens, and automobile or aircraft lighting finishes.     

Self‐Regulating Iris Based on Light‐Actuated Liquid Crystal Elastomer

The iris, found in many animal species, is a biological tissue that can change the aperture (pupil) size to regulate light transmission into the eye in response to varying illumination conditions. The self‐regulation of the eye lies behind its autofocusing ability and large dynamic range, rendering it the ultimate “imaging device” and a continuous source of inspiration in science. In optical imaging devices, adjustable apertures play a vital role as they control the light exposure, the depth of field, and optical aberrations of the systems. Tunable irises demonstrated to date require external control through mechanical actuation, and are not capable of autonomous action in response to changing light intensity without control circuitry. A self‐regulating artificial iris would offer new opportunities for device automation and stabilization. Here, this paper reports the first iris‐like, liquid crystal elastomer device that can perform automatic shape‐adjustment by reacting to the incident light power density. Similar to natural iris, the device closes under increasing light intensity, and upon reaching the minimum pupil size, reduces the light transmission by a factor of seven. The light‐responsive materials design, together with photoalignment‐based control over the molecular orientation, provides a new approach to automatic, self‐regulating optical systems based on soft smart materials.     

Lead‐Free Perovskite Nanowire‐Employed Piezopolymer for Highly Efficient Flexible Nanocomposite Energy Harvester

In the past two decades, mechanical energy harvesting technologies have been developed in various ways to support or power small‐scale electronics. Nevertheless, the strategy for enhancing current and charge performance of flexible piezoelectric energy harvesters using a simple and cost‐effective process is still a challenging issue. Herein, a 1D–3D (1‐3) fully piezoelectric nanocomposite is developed using perovskite BaTiO₃ (BT) nanowire (NW)‐employed poly(vinylidene fluoride‐co‐trifluoroethylene) (P(VDF‐TrFE)) for a high‐performance hybrid nanocomposite generator (hNCG) device. The harvested output of the flexible hNCG reaches up to ≈14 V and ≈4 µA, which is higher than the current levels of even previous piezoceramic film‐based flexible energy harvesters. Finite element analysis method simulations study that the outstanding performance of hNCG devices attributes to not only the piezoelectric synergy of well‐controlled BT NWs and within P(VDF‐TrFE) matrix, but also the effective stress transferability of piezopolymer. As a proof of concept, the flexible hNCG is directly attached to a hand to scavenge energy using a human motion in various biomechanical frequencies for self‐powered wearable patch device applications. This research can pave the way for a new approach to high‐performance wearable and biocompatible self‐sufficient electronics.     

Microtopography‐Guided Conductive Patterns of Liquid‐Driven Graphene Nanoplatelet Networks for Stretchable and Skin‐Conformal Sensor Array

Flexible thin‐film sensors have been developed for practical uses in invasive or noninvasive cost‐effective healthcare devices, which requires high sensitivity, stretchability, biocompatibility, skin/organ‐conformity, and often transparency. Graphene nanoplatelets can be spontaneously assembled into transparent and conductive ultrathin coatings on micropatterned surfaces or planar substrates via a convective Marangoni force in a highly controlled manner. Based on this versatile graphene assembled film preparation, a thin, stretchable and skin‐conformal sensor array (144 pixels) is fabricated having microtopography‐guided, graphene‐based, conductive patterns embedded without any complicated processes. The electrically controlled sensor array for mapping spatial distributions (144 pixels) shows high sensitivity (maximum gauge factor ≈1697), skin‐like stretchability (<48%), high cyclic stability or durability (over 10⁵ cycles), and the signal amplification (≈5.25 times) via structure‐assisted intimate‐contacts between the device and rough skin. Furthermore, given the thin‐film programmable architecture and mechanical deformability of the sensor, a human skin‐conformal sensor is demonstrated with a wireless transmitter for expeditious diagnosis of cardiovascular and cardiac illnesses, which is capable of monitoring various amplified pulse‐waveforms and evolved into a mechanical/thermal‐sensitive electric rubber‐balloon and an electronic blood‐vessel. The microtopography‐guided and self‐assembled conductive patterns offer highly promising methodology and tool for next‐generation biomedical devices and various flexible/stretchable (wearable) devices.     

High‐Performance Piezoelectric Nanogenerators with Imprinted P(VDF‐TrFE)/BaTiO3 Nanocomposite Micropillars for Self‐Powered Flexible Sensors

Piezoelectric nanogenerators with large output, high sensitivity, and good flexibility have attracted extensive interest in wearable electronics and personal healthcare. In this paper, the authors propose a high‐performance flexible piezoelectric nanogenerator based on piezoelectrically enhanced nanocomposite micropillar array of polyvinylidene fluoride‐trifluoroethylene (P(VDF‐TrFE))/barium titanate (BaTiO₃) for energy harvesting and highly sensitive self‐powered sensing. By a reliable and scalable nanoimprinting process, the piezoelectrically enhanced vertically aligned P(VDF‐TrFE)/BaTiO₃ nanocomposite micropillar arrays are fabricated. The piezoelectric device exhibits enhanced voltage of 13.2 V and a current density of 0.33 µA cm^?2, which an enhancement by a factor of 7.3 relatives to the pristine P(VDF‐TrFE) bulk film. The mechanisms of high performance are mainly attributed to the enhanced piezoelectricity of the P(VDF‐TrFE)/BaTiO₃ nanocomposite materials and the improved mechanical flexibility of the micropillar array. Under mechanical impact, stable electricity is stably generated from the nanogenerator and used to drive various electronic devices to work continuously, implying its significance in the field of consumer electronic devices. Furthermore, it can be applied as self‐powered flexible sensor work in a noncontact mode for detecting air pressure and wearable sensors for detecting some human vital signs including different modes of breath and heartbeat pulse, which shows its potential applications in flexible electronics and medical sciences.     

Bioinspired Flexible Volatile Organic Compounds Sensor Based on Dynamic Surface Wrinkling with Dual‐Signal Response

Living systems can respond to external stimuli by dynamic interface changes. Moreover, natural wrinkle structures allow the surface to switch dynamically and reversibly from flat to rough in response to specific stimuli. Artificial wrinkle structures have been developed for applications such as optical devices, mechanical sensors, and microfluidic devices. However, chemical molecule‐triggered flexible sensors based on dynamic surface wrinkling have not been demonstrated. Inspired by human skin wrinkling, herein, a volatile organic compound (VOC)‐responsive flexible sensor with a switchable dual‐signal response (transparency and resistance) is achieved based on a multilayered Ag nanowire (AgNW)/SiO_x/polydimethylsiloxane (PDMS) film. Wrinkle structures can form dynamically in response to VOC vapors (such as ethanol, toluene, acetone, formaldehyde, and methanol) due to the instability of the multilayer induced by their different swelling capabilities. By controlling the modulus of PDMS and the thickness of the SiO_x layer, tunable sensitivities in resistance and transparency of the device are achieved. Additionally, the proximity mechanism of the solubility parameter is proposed, which explains the high selectivity of the device toward ethanol vapor compared with that of other VOCs well. This stimuli‐responsive sensor exhibits the dynamic visual feedback and the quantitative electrical signal, which provide a novel approach for developing smart flexible electronics.     

A Flexible Stretchable Hydrogel Electrolyte for Healable All‐in‐One Configured Supercapacitors

The development of integrated high‐performance supercapacitors with all‐in‐one configuration, excellent flexibility and autonomously intrinsic self‐healability, and without the extra healable film layers, is still tremendously challenging. Compared to the sandwich‐like laminated structures of supercapacitors with augmented interfacial contact resistance, the flexible healable integrated supercapacitor with all‐in‐one structure could theoretically improve their interfacial contact resistance and energy densities, simplify the tedious device assembly process, prolong the lifetime, and avoid the displacement and delamination of multilayered configurations under deformations. Herein, a flexible healable all‐in‐one configured supercapacitor with excellent flexibility and reliable self‐healing ability by avoiding the extra healable film substrates and the postassembled sandwich‐like laminated structures is developed. The healable all‐in‐one configured supercapacitor is prepared from in situ polymerization and deposition of nanocomposites electrode materials onto the two‐sided faces of the self‐healing hydrogel electrolyte separator. The self‐healing hydrogel film is obtained from the physically crosslinked hydrogel with enormous hydrogen bonds, which can endow the healable capability through dynamic hydrogen bonding. The assembled all‐in‐one configured supercapacitor exhibits enhanced capacitive performance, good cycling stability, reliable self‐healing capability, and excellent flexibility. It holds broad prospects for obtaining various flexible healable all‐in‐one configured supercapacitors for working as portable energy storage devices in wearable electronics.     

Nitrogen‐Doped Carbon Encapsulated Mesoporous Vanadium Nitride Nanowires as Self‐Supported Electrodes for Flexible All‐Solid‐State Supercapacitors

Flexible 3D nanoarchitectures have received tremendous interest recently because of their potential applications in flexible/wearable energy storage devices. Herein, 3D intertwined nitrogen‐doped carbon encapsulated mesoporous vanadium nitride nanowires (MVN@NC NWs) are investigated as thin, lightweight, and self‐supported electrodes for flexible supercapacitors (SCs). The MVN NWs have abundant active sites accessible to charge storage, and the N‐doped carbon shell suppresses electrochemical dissolution of the inner MVN NWs in an alkaline electrolyte, leading to excellent capacitive properties. The flexible MVN@NC NWs film electrode delivers a high areal capacitance of 282 mF cm⁻² and exhibits excellent long‐term stability with 91.8% capacitance retention after 12 000 cycles in a KOH electrolyte. All‐solid‐state flexible SCs assembled by sandwiching two flexible MVN@NC NWs film electrodes with alkaline poly(vinyl alcohol) (PVA), sodium polyacrylate, and KOH gel electrolyte boast a high volumetric capacitance of 10.9 F cm⁻³, an energy density of 0.97 mWh cm⁻³, and a power density of 2.72 W cm⁻³ at a current density of 0.051 A cm⁻³ based on the entire cell. By virtue of the excellent mechanical flexibility, high capacitance, and large energy/power density, the self‐supported MVN@NC NWs paper‐like electrodes have large potential applications in portable and wearable flexible electronics.     

3D‐Structured Stretchable Strain Sensors for Out‐of‐Plane Force Detection

Stretchable strain sensors, as the soft mechanical interface, provide the key mechanical information of the systems for healthcare monitoring, rehabilitation assistance, soft exoskeletal devices, and soft robotics. Stretchable strain sensors based on 2D flat film have been widely developed to monitor the in‐plane force applied within the plane where the sensor is placed. However, to comprehensively obtain the mechanical feedback, the capability to detect the out‐of‐plane force, caused by the interaction outside of the plane where the senor is located, is needed. Herein, a 3D‐structured stretchable strain sensor is reported to monitor the out‐of‐plane force by employing 3D printing in conjunction with out‐of‐plane capillary force‐assisted self‐pinning of carbon nanotubes. The 3D‐structured sensor possesses large stretchability, multistrain detection, and strain‐direction recognition by one single sensor. It is demonstrated that out‐of‐plane forces induced by the air/fluid flow are reliably monitored and intricate flow details are clearly recorded. The development opens up for the exploration of next‐generation 3D stretchable sensors for electronic skin and soft robotics.     

Tough Supramolecular Polymer Networks with Extreme Stretchability and Fast Room‐Temperature Self‐Healing

Recent progress on highly tough and stretchable polymer networks has highlighted the potential of wearable electronic devices and structural biomaterials such as cartilage. For some given applications, a combination of desirable mechanical properties including stiffness, strength, toughness, damping, fatigue resistance, and self‐healing ability is required. However, integrating such a rigorous set of requirements imposes substantial complexity and difficulty in the design and fabrication of these polymer networks, and has rarely been realized. Here, we describe the construction of supramolecular polymer networks through an in situ copolymerization of acrylamide and functional monomers, which are dynamically complexed with the host molecule cucurbit[8]uril (CB[8]). High molecular weight, thus sufficient chain entanglement, combined with a small‐amount dynamic CB[8]‐mediated non‐covalent crosslinking (2.5 mol%), yields extremely stretchable and tough supramolecular polymer networks, exhibiting remarkable self‐healing capability at room temperature. These supramolecular polymer networks can be stretched more than 100× their original length and are able to lift objects 2000× their weight. The reversible association/dissociation of the host–guest complexes bestows the networks with remarkable energy dissipation capability, but also facile complete self‐healing at room temperature. In addition to their outstanding mechanical properties, the networks are ionically conductive and transparent. The CB[8]‐based supramolecular networks are synthetically accessible in large scale and exhibit outstanding mechanical properties. They could readily lead to the promising use as wearable and self‐healable electronic devices, sensors and structural biomaterials.     

Highly Stretchable,Adaptable, and Durable Strain Sensing Based on a Bioinspired Dynamically Cross‐Linked Graphene/Polymer Composite

Flexible strain sensors can detect physical signals (e.g., temperature, humidity, and flow) by sensing electrical deviation under dynamic deformation, and they have been used in diverse fields such as human motion detection, medical care, speech recognition, and robotics. Existing sensing materials have relatively low adaptability and durability and are not stretchable and flexible enough for complex tasks in motion detection. In this work, a highly flexible self‐healing conductive polymer composite consisting of graphene, poly(acrylic acid) and amorphous calcium carbonate is prepared via a biomineralization‐inspired process. The polymer composite shows good editability and processability and can be fabricated into stretchable strain sensors of various structures (sandwich structures, fibrous structures, self‐supporting structures, etc.). The developed sensors can be attached on different types of surfaces (e.g., flat, cambered) and work well both in air and under water in detecting various biosignals, including crawling, undulatory locomotion, and human body motion.     

Desktop‐Stereolithography 3D‐Printing of a Poly(dimethylsiloxane)‐Based Material with Sylgard‐184 Properties

The advantageous physiochemical properties of poly(dimethylsiloxane) (PDMS) have made it an extremely useful material for prototyping in various technological, scientific, and clinical areas. However, PDMS molding is a manual procedure and requires tedious assembly steps, especially for 3D designs, thereby limiting its access and usability. On the other hand, automated digital manufacturing processes such as stereolithography (SL) enable true 3D design and fabrication. Here the formulation, characterization, and SL application of a 3D‐printable PDMS resin (3DP‐PDMS) based on commercially available PDMS‐methacrylate macromers, a high‐efficiency photoinitiator and a high‐absorbance photosensitizer, is reported. Using a desktop SL‐printer, optically transparent submillimeter structures and microfluidic channels are demonstrated. An optimized blend of PDMS‐methacrylate macromers is also used to SL‐print structures with mechanical properties similar to conventional thermally cured PDMS (Sylgard‐184). Furthermore, it is shown that SL‐printed 3DP‐PDMS substrates can be rendered suitable for mammalian cell culture. The 3DP‐PDMS resin enables assembly‐free, automated, digital manufacturing of PDMS, which should facilitate the prototyping of devices for microfluidics, organ‐on‐chip platforms, soft robotics, flexible electronics, and sensors, among others.     

Multiresponsive Graphene‐Aerogel‐Directed Phase‐Change Smart Fibers

Wearable devices and systems demand multifunctional units with intelligent and integrative functions. Smart fibers with response to external stimuli, such as electrical, thermal, and photonic signals, etc., as well as offering energy storage/conversion are essential units for wearable electronics, but still remain great challenges. Herein, flexible, strong, and self‐cleaning graphene‐aerogel composite fibers, with tunable functions of thermal conversion and storage under multistimuli, are fabricated. The fibers made from porous graphene aerogel/organic phase‐change materials coated with hydrophobic fluorocarbon resin render a wide range of phase transition temperature and enthalpy (0–186 J g^?1). The strong and compliant fibers are twisted into yarn and woven into fabrics, showing a self‐clean superhydrophobic surface and excellent multiple responsive properties to external stimuli (electron/photon/thermal) together with reversible energy storage and conversion. Such aerogel‐directed smart fibers promise for broad applications in the next‐generation of wearable systems.     

Spatially Probed Plasmonic Photothermic Nanoheater Enhanced Hybrid Polymeric–Metallic PVDF‐Ag Nanogenerator

Surface plasmon‐based photonics offers exciting opportunities to enable fine control of the site, span, and extent of mechanical harvesting. However, the interaction between plasmonic photothermic and piezoresponse still remains underexplored. Here, spatially localized and controllable piezoresponse of a hybrid self‐polarized polymeric‐metallic system that correlates to plasmonic light‐to‐heat modulation of the local strain is demonstrated. The piezoresponse is associated to the localized plasmons that serve as efficient nanoheaters leading to self‐regulated strain via thermal expansion of the electroactive polymer. Moreover, the finite‐difference time‐domain simulation and linear thermal model also deduce the local strain to the surface plasmon heat absorption. The distinct plasmonic photothermic–piezoelectric phenomenon mediates not only localized external stimulus light response but also enhances dynamic piezoelectric energy harvesting. The present work highlights a promising surface plasmon coordinated piezoelectric response which underpins energy localization and transfer for diversified design of unique photothermic–piezotronic technology.     

Highly Transparent,Stretchable, and Self‐Healing Ionic‐Skin Triboelectric Nanogenerators for Energy Harvesting and Touch Applications

Recently developed triboelectric nanogenerators (TENGs) act as a promising power source for self‐powered electronic devices. However, the majority of TENGs are fabricated using metallic electrodes and cannot achieve high stretchability and transparency, simultaneously. Here, slime‐based ionic conductors are used as transparent current‐collecting layers of TENG, thus significantly enhancing their energy generation, stretchability, transparency, and instilling self‐healing characteristics. This is the first demonstration of using an ionic conductor as the current collector in a mechanical energy harvester. The resulting ionic‐skin TENG (IS‐TENG) has a transparency of 92% transmittance, and its energy‐harvesting performance is 12 times higher than that of the silver‐based electronic current collectors. In addition, they are capable of enduring a uniaxial strain up to 700%, giving the highest performance compared to all other transparent and stretchable mechanical‐energy harvesters. Additionally, this is the first demonstration of an autonomously self‐healing TENG that can recover its performance even after 300 times of complete bifurcation. The IS‐TENG represents the first prototype of a highly deformable and transparent power source that is able to autonomously self‐heal quickly and repeatedly at room temperature, and thus can be used as a power supply for digital watches, touch sensors, artificial intelligence, and biointegrated electronics.     

Dislocation‐Free and Atomically Flat GaN Hexagonal Microprisms for Device Applications

III‐nitrides are considered the material of choice for light‐emitting diodes (LEDs) and lasers in the visible to ultraviolet spectral range. The development is hampered by lattice and thermal mismatch between the nitride layers and the growth substrate leading to high dislocation densities. In order to overcome the issue, efforts have gone into selected area growth of nanowires (NWs), using their small footprint in the substrate to grow virtually dislocation‐free material. Their geometry is defined by six tall side‐facets and a pointed tip which limits the design of optoelectronic devices. Growth of dislocation‐free and atomically smooth 3D hexagonal GaN micro‐prisms with a flat, micrometer‐sized top‐surface is presented. These self‐forming structures are suitable for optical devices such as low‐loss optical cavities for high‐efficiency LEDs. The structures are made by annealing GaN NWs with a thick radial shell, reforming them into hexagonal flat‐top prisms with six equivalents either m‐ or s‐facets depending on the initial heights of the top pyramid and m‐facets of the NWs. This shape is kinetically controlled and the reformation can be explained with a phenomenological model based on Wulff construction that have been developed. It is expected that the results will inspire further research into micron‐sized III‐nitride‐based devices.     

Self‐Folded Gripper‐Like Architectures from Stimuli‐Responsive Bilayers

Self‐folding microgrippers are an emerging class of smart structures that have widespread applications in medicine and micro/nanomanipulation. To achieve their functionalities, these architectures rely on spatially patterned hinges to transform into 3D configurations in response to an external stimulus. Incorporating hinges into the devices requires the processing of multiple layers which eventually increases the fabrication costs and actuation complexities. The goal of this work is to demonstrate that it is possible to achieve gripper‐like configurations in an on‐demand manner from simple planar bilayers that do not require hinges for their actuation. Finite element modeling of bilayers is performed to understand the mechanics behind their stimuli‐responsive shape transformation behavior. The model predictions are then experimentally validated and axisymmetric gripper‐like shapes are realized using millimeter‐scale poly(dimethylsiloxane) bilayers that undergo differential swelling in organic solvents. Owing to the nature of the computational scheme which is independent of length scales and material properties, the guidelines reported here would be applicable to a diverse array of gripping systems and functional devices. Thus, this work not only demonstrates a simple route to fabricate functional microgrippers but also contributes to self‐assembly in general.     

Stretchable All‐Gel‐State Fiber‐Shaped Supercapacitors Enabled by Macromolecularly Interconnected 3D Graphene/Nanostructured Conductive Polymer Hydrogels

Nanostructured conductive polymer hydrogels (CPHs) have been extensively applied in energy storage owing to their advantageous features, such as excellent electrochemical activity and relatively high electrical conductivity, yet the fabrication of self‐standing and flexible electrode‐based CPHs is still hampered by their limited mechanical properties. Herein, macromolecularly interconnected 3D graphene/nanostructured CPH is synthesized via self‐assembly of CPHs and graphene oxide macrostructures. The 3D hybrid hydrogel shows uniform interconnectivity and enhanced mechanical properties due to the strong macromolecular interaction between the CPHs and graphene, thus greatly reducing aggregation in the fiber‐shaping process. A proof‐of‐concept all‐gel‐state fibrous supercapacitor based on the 3D polyaniline/graphene hydrogel is fabricated to demonstrate the outstanding flexibility and mouldability, as well as superior electrochemical properties enabled by this 3D hybrid hydrogel design. The proposed device can achieve a large strain (up to ≈40%), and deliver a remarkable volumetric energy density of 8.80 mWh cm^?3 (at power density of 30.77 mW cm^?3), outperforming many fiber‐shaped supercapacitors reported previously. The all‐hydrogel design opens up opportunities in the fabrication of next‐generation wearable and portable electronics.