Surface Wrinkling for Flexible and Stretchable Sensors.

Recent advances in nanolithography, miniaturization, and material science, along with developments in wearable electronics, are pushing the frontiers of sensor technology into the large-scale fabrication of highly sensitive, flexible, stretchable, and multimodal detection systems. Various strategies, including surface engineering, have been developed to control the electrical and mechanical characteristics of sensors. In particular, surface wrinkling provides an effective alternative for improving both the sensing performance and mechanical deformability of flexible and stretchable sensors by releasing interfacial stress, preventing electrical failure, and enlarging surface areas. In this study, recent developments in the fabrication strategies of wrinkling structures for sensor applications are discussed. The fundamental mechanics, geometry control strategies, and various fabricating methods for wrinkling patterns are summarized. Furthermore, the current state of wrinkling approaches and their impacts on the development of various types of sensors, including strain, pressure, temperature, chemical, photodetectors, and multimodal sensors, are reviewed. Finally, existing wrinkling approaches, designs, and sensing strategies are extrapolated into future applications.

Crocodile-Skin-Inspired Omnidirectionally Stretchable Pressure Sensor.

Stretchable pressure sensors are important components of multimodal electronic skin needed for potentializing numerous Internet of Things applications. In particular, to use pressure sensors in various wearable/skin-attachable electronics, both high deformability and strain-independent sensitivity must be realized. However, previously reported stretchable pressure sensors cannot meet these standards because they exhibit limited stretchability and nonuniform sensitivity under deformation. Herein, inspired by the unique sensory organ of a crocodile, an omnidirectionally stretchable piezoresistive pressure sensor made of polydimethylsiloxane (PDMS)/silver nanowires (AgNWs) composites with microdomes and wrinkled surfaces is developed. The stretchable pressure sensor exhibits high sensitivity that changes negligibly even under uniaxial and biaxial tensile strains of 100% and 50%, respectively. This behavior is attributed to the microdomes responsible for detecting applied pressures being weakly affected by tensile strains, while the isotropic wrinkles between the microdomes deform to effectively reduce the external stress. In addition, because the device comprises all PDMS-based structures, it exhibits outstanding robustness under repeated mechanical stimuli. The device shows strong potential as a wearable pressure sensor and an artificial crocodile sensing organ, successfully detecting applied pressures in various scenarios. Therefore, the pressure sensor is expected to find applications in electronic skin for prosthetics and human-machine interface systems.

Integration of Vertical Graphene Onto a Tunnelling Cathode for Digital X-Ray Imaging.

As an alternative to thermionic X-ray generators, cold-cathode X-ray tubes are being developed for portable and multichannel tomography. Field emission propagating from needle structures such as carbon nanotubes or Si tips currently dominates related research and development, but various obstacles prevent the widespread of this technology. An old but simple electron emission design is the planar tunnelling cathode using a metal-oxide-semiconductor (MOS) structure, which achieves narrow beam dispersion and low supplying voltage. Directly grown vertical graphene (VG) is employed as the gate electrode of MOS and tests its potential as a new emission source. The emission efficiency of the device is initially ≈1% because of unavoidable fabrication damage during the patterning processes; it drastically improves to >40% after ozone treatment. The resulting emission current obeys the Fowler-Nordheim tunnelling model, and the enhanced emission is attributed to the effective gate thickness reduction by ozone treatment. As a proof-of-concept experiment, a clustered array of 2140 cells is integrated into a system that provides mA-class emission current for X-ray generation. With pulsed digital excitations, X-ray imaging of a chest phantom, demonstrating the feasibility of using a VG MOS electron emission source as a new and innovative X-ray generator is realized.

Mechanically Robust and Linearly Sensitive Soft Piezoresistive Pressure Sensor for a Wearable Human-Robot Interaction System.

Soft piezoresistive pressure sensors play an underpinning role in enabling a plethora of future Internet of Things (IoT) applications such as human-robot interaction (HRI) technologies, wearable devices, and metaverse ecosystems. Despite significant attempts to enhance the performance of these sensors, existing sensors still fall short of achieving high strain tolerance and linearity simultaneously. Herein, we present a low-cost, facile, and scalable approach to fabricating a highly strain-tolerant and linearly sensitive soft piezoresistive pressure sensor. Our design utilizes thin nanocracked gold films (NC-GFs) deposited on poly(dimethylsiloxane) (PDMS) as electrodes of the sensor. The large mismatch stress between gold (Au) and PDMS induces the formation of secondary wrinkles along the pyramidal-structured electrode under pressure; these wrinkles function as protuberances on the electrode and enable exceptional linear sensitivity of 4.2 kPa-1 over a wide pressure range. Additionally, our pressure sensor can maintain its performance even after severe mechanical deformations, including repeated stretching up to 30% strain, due to the outstanding strain tolerance of NC-GF. Our sensor's impressive sensing performance and mechanical robustness make it suitable for diverse IoT applications, as demonstrated by its use in wearable pulse monitoring devices and human-robot interaction systems.

Advances in Biodegradable Electronic Skin: Material Progress and Recent Applications in Sensing, Robotics, and Human-Machine Interfaces.

The rapid growth of the electronics industry and proliferation of electronic materials and telecommunications technologies has led to the release of a massive amount of untreated electronic waste (e-waste) into the environment. Consequently, catastrophic environmental damage at the microbiome level and serious human health diseases threaten the natural fate of the planet. Currently, the demand for wearable electronics for applications in personalized medicine, electronic skins (e-skins), and health monitoring is substantial and growing. Therefore, "green" characteristics such as biodegradability, self-healing, and biocompatibility ensure the future application of wearable electronics and e-skins in biomedical engineering and bioanalytical sciences. Leveraging the biodegradability, sustainability, and biocompatibility of natural materials will dramatically influence the fabrication of environmentally friendly e-skins and wearable electronics. Here, the molecular and structural characteristics of biological skins and artificial e-skins are discussed. The focus then turns to the biodegradable materials, including natural and synthetic-polymer-based materials, and their recent applications in the development of biodegradable e-skin in wearable sensors, robotics, and human-machine interfaces (HMIs). Finally, the main challenges and outlook regarding the preparation and application of biodegradable e-skins are critically discussed in a near-future scenario, which is expected to lead to the next generation of biodegradable e-skins.

Low-Temperature Alignment of Conjugated Polymers by Plasticizer-Aided Physical Rubbing.

Rubbing-induced alignment of conjugated polymers is systematically investigated in terms of intra- and inter-molecular interaction. Various polymer films with a broad range of polymer chain rigidity are rubbed, and the degree of polymer chain alignment is quantitatively characterized. The rubbing technique effectively aligns crystalline domains in conjugated polymer films when the temperature approaches the critical rubbing temperature ( T r c $T_{\mathrm{r}}^{\mathrm{c}}$ ), at which the rearrangement and the slip of polymer chains are possible. A polymer with significant intra-/inter-molecular interactions exhibits higher T r c $T_{\mathrm{r}}^{\mathrm{c}}$ , though quantitative analysis reveals an intermediately aligned state at temperature Tr ' lower than T r c $T_{\mathrm{r}}^{\mathrm{c}}$ . This state originates from polymer chain aggregation in an amorphous domain. The intermediately aligned state can be controlled by plasticizer, which enables low-temperature alignment of high-mobility polymer film by reducing Tr ' to near 100 °C, increases the crystallinity, and improves the alignment effect at this state comparable to that of the completely aligned state obtained at extremely high temperatures.

Abaxial leaf surface-mounted multimodal wearable sensor for continuous plant physiology monitoring.

Wearable plant sensors hold tremendous potential for smart agriculture. We report a lower leaf surface-attached multimodal wearable sensor for continuous monitoring of plant physiology by tracking both biochemical and biophysical signals of the plant and its microenvironment. Sensors for detecting volatile organic compounds (VOCs), temperature, and humidity are integrated into a single platform. The abaxial leaf attachment position is selected on the basis of the stomata density to improve the sensor signal strength. This versatile platform enables various stress monitoring applications, ranging from tracking plant water loss to early detection of plant pathogens. A machine learning model was also developed to analyze multichannel sensor data for quantitative detection of tomato spotted wilt virus as early as 4 days after inoculation. The model also evaluates different sensor combinations for early disease detection and predicts that minimally three sensors are required including the VOC sensors.

Integrating charge mobility, stability and stretchability within conjugated polymer films for stretchable multifunctional sensors.

Conjugated polymers (CPs) are promising semiconductors for intrinsically stretchable electronic devices. Ideally, such CPs should exhibit high charge mobility, excellent stability, and high stretchability. However, converging all these desirable properties in CPs has not been achieved via molecular design and/or device engineering. This work details the design, synthesis and characterization of a random polythiophene (RP-T50) containing ~50 mol% of thiophene units with a thermocleavable tertiary ester side chain and ~50 mol% of unsubstituted thiophene units, which, upon thermocleavage of alkyl chains, shows significant improvement of charge mobility and stability. Thermal annealing a RP-T50 film coated on a stretchable polydimethylsiloxane substrate spontaneously generates wrinkling in the polymer film, which effectively enhances the stretchability of the polymer film. The wrinkled RP-T50-based stretchable sensors can effectively detect humidity, ethanol, temperature and light even under 50% uniaxial and 30% biaxial strains. Our discoveries offer new design rationale of strategically applying CPs to intrinsically stretchable electronic systems.

Tailored Uniaxial Alignment of Nanowires Based on Off-Center Spin-Coating for Flexible and Transparent Field-Effect Transistors.

The alignment of nanowires (NWs) has been actively pursued for the production of electrical devices with high-operating performances. Among the generally available alignment processes, spin-coating is the simplest and fastest method for uniformly patterning the NWs. During spinning, the morphology of the aligned NWs is sensitively influenced by the resultant external drag and inertial forces. Herein, the assembly of highly and uniaxially aligned silicon nanowires (Si NWs) is achieved by introducing an off-center spin-coating method in which the applied external forces are modulated by positioning the target substrate away from the center of rotation. In addition, various influencing factors, such as the type of solvent, the spin acceleration time, the distance between the substrate and the center of rotation, and the surface energy of the substrate, are adjusted in order to optimize the alignment of the NWs. Next, a field-effect transistor (FET) incorporating the highly aligned Si NWs exhibits a high effective mobility of up to 85.7 cm2 V-1 s-1, and an on-current of 0.58 µA. Finally, the single device is enlarged and developed in order to obtain an ultrathin and flexible Si NW FET array. The resulting device has the potential to be widely expanded into applications such as wearable electronics and robotic systems.

Cactus-Spine-Inspired Sweat-Collecting Patch for Fast and Continuous Monitoring of Sweat.

A sweat sensor is expected to be the most appropriate wearable device for noninvasive healthcare monitoring. However, the practical use of sweat sensors is impeded by irregular and low sweat secretion rates. Here, a sweat-collecting patch that can collect sweat efficiently for fast and continuous healthcare monitoring is demonstrated. The patch uses cactus-spine-inspired wedge-shaped wettability-patterned channels on a hierarchical microstructured/nanostructured surface. The channel shape, in combination with the superhydrophobic/superhydrophilic surface materials, induces a unidirectional Laplace pressure that transports the sweat to the sensing area spontaneously even when the patch is aligned vertically. The patch demonstrates superior sweat-collecting efficiency and reduces the time required to fill the sensing area by transporting sweat almost without leaving it inside the channel. Therefore, a sensor based on the patch responds quickly to biochemicals in sweat, and the patch enables the continuous monitoring of changes in sweat biochemicals according to their changes in the wearer's blood.

Fingerpad-Inspired Multimodal Electronic Skin for Material Discrimination and Texture Recognition.

Human skin plays a critical role in a person communicating with his or her environment through diverse activities such as touching or deforming an object. Various electronic skin (E-skin) devices have been developed that show functional or geometrical superiority to human skin. However, research into stretchable E-skin that can simultaneously distinguish materials and textures has not been established yet. Here, the first approach to achieving a stretchable multimodal device is reported, that operates on the basis of various electrical properties of piezoelectricity, triboelectricity, and piezoresistivity and that exceeds the capabilities of human tactile perception. The prepared E-skin is composed of a wrinkle-patterned silicon elastomer, hybrid nanomaterials of silver nanowires and zinc oxide nanowires, and a thin elastomeric dielectric layer covering the hybrid nanomaterials, where the dielectric layer exhibits high surface roughness mimicking human fingerprints. This versatile device can identify and distinguish not only mechanical stress from a single stimulus such as pressure, tensile strain, or vibration but also that from a combination of multiple stimuli. With simultaneous sensing and analysis of the integrated stimuli, the approach enables material discrimination and texture recognition for a biomimetic prosthesis when the multifunctional E-skin is applied to a robotic hand.

User-Interactive Thermotherapeutic Electronic Skin Based on Stretchable Thermochromic Strain Sensor.

User-interactive electronic skin (e-skin) with a distinguishable output has enormous potential for human-machine interfaces and healthcare applications. Despite advances in user-interactive e-skins, advances in visual user-interactive therapeutic e-skins remain rare. Here, a user-interactive thermotherapeutic device is reported that is fabricated by combining thermochromic composites and stretchable strain sensors consisting of strain-responsive silver nanowire networks on surface energy-patterned microwrinkles. Both the color and heat of the device are easily controlled through electrical resistance variation induced by applied mechanical strain. The resulting monolithic device exhibits substantial changes in optical reflectance and temperature with durability, rapid response, high stretchability, and linear sensitivity. The approach enables a low-expertise route to fabricating dynamic interactive thermotherapeutic e-skins that can be used to effectively rehabilitate injured connective tissues as well as to prevent skin burns by simultaneously accommodating stretching, providing heat, and exhibiting a color change.

Pressure/Temperature Sensing Bimodal Electronic Skin with Stimulus Discriminability and Linear Sensitivity.

Human skin imperfectly discriminates between pressure and temperature stimuli under mixed stimulation, and exhibits nonlinear sensitivity to each stimulus. Despite great advances in the field of electronic skin (E-skin), the limitations of human skin have not previously been overcome. For the first time, the development of a stimulus-discriminating and linearly sensitive bimodal E-skin that can simultaneously detect and discriminate pressure and temperature stimuli in real time is reported. By introducing a novel device design and using a temperature-independent material, near-perfect stimulus discriminability is realized. In addition, the hierarchical contact behavior of the surface-wrinkled microstructure and the optimally reduced graphene oxide in the E-skin contribute to linear sensitivity to applied pressure/temperature stimuli over wide intensity range. The E-skin exhibits a linear and high pressure sensitivity of 0.7 kPa-1 up to 25 kPa. Its operation is also robust and exhibits fast response to pressure stimulus within 50 ms. In the case of temperature stimulus, the E-skin shows a linear and reproducible temperature coefficient of resistance of 0.83% K-1 in the temperature range 22-70 °C and fast response to temperature change within 100 ms. In addition, two types of stimuli are simultaneously detected and discriminated in real time by only impedance measurements.

Linearly and Highly Pressure-Sensitive Electronic Skin Based on a Bioinspired Hierarchical Structural Array.

Pressure-sensitive electronic skin composed of a hierarchical structural array exhibits outstanding linear and high sensitivity in the pressure range exerted by gentle touch. By virtue of monolayer graphene acting as electrode material, this device can be operated with low voltage. Especially, its high transparency enables an accurate placement of the device on the target position when it is used for health monitoring.