High-Throughput Manufacturing of Multimodal Epidermal Mechanosensors with Superior Detectability Enabled by a Continuous Microcracking Strategy.

Non-invasive human-machine interactions (HMIs) are expected to be promoted by epidermal tactile receptive devices that can accurately perceive human activities. In reality, however, the HMI efficiency is limited by the unsatisfactory perception capability of mechanosensors and the complicated techniques for device fabrication and integration. Herein, a paradigm is presented for high-throughput fabrication of multimodal epidermal mechanosensors based on a sequential "femtosecond laser patterning-elastomer infiltration-physical transfer" process. The resilient mechanosensor features a unique hybrid sensing layer of rigid cellular graphitic flakes (CGF)-soft elastomer. The continuous microcracking of CGF under strain enables a sharp reduction in conductive pathways, while the soft elastomer within the framework sustains mechanical robustness of the structure. As a result, the mechanosensor achieves an ultrahigh sensitivity in a broad strain range (GF of 371.4 in the first linear range of 0-50%, and maximum GF of 8922.6 in the range of 61-70%), a low detection limit (0.01%), and a fast response/recovery behavior (2.6/2.1 ms). The device also exhibits excellent sensing performances to multimodal mechanical stimuli, enabling high-fidelity monitoring of full-range human motions. As proof-of-concept demonstrations, multi-pixel mechanosensor arrays are constructed and implemented in a robot hand controlling system and a security system, providing a platform toward efficient HMIs.

Generating an M2 × N2 spot array with a dual-period hybrid Dammann grating fabricated using maskless projection lithography.

The Dammann grating (DG), which redistributes a collimated laser beam into a spot array with a uniform intensity, is a widely adopted approach for profile measurement. Conventional DGs for dense spot projection are binary phase gratings with precisely designed groove structures, which suffer from low efficiency, poor uniformity, and a hard-to-fabricate fine feature size when utilized for a large field of view (FOV). Here, we propose a new, to the best of our knowledge, hybrid DG architecture consisting of two different grating periods which effectively generates an engineering M2 × N2 spot array with a non-complex structural design. As a proof-of-concept, a dual-period hybrid DG with a two-scale grating period ratio of 11.88 µm/95.04 µm (∼1/8) is designed and fabricated as a means to generate a dense 72 × 72 diffraction spot array with a FOV of 17° × 17°. In addition, the DG exhibits superior performance, with a high efficiency (>60%) and a low non-uniformity (<18%) at a wavelength of 532 nm. This kind of hybrid DG constructed from photoresist patterns with a minimum feature size of ∼1.2 µm can be perfectly fabricated by maskless projection lithography for large-scale and low-cost production. The proposed dual-period hybrid DG can pave the way for depth-perception-related applications such as face unlocking and motion sensing.

Ti3 C2 TX MXene Ink Direct Writing Flexible Sensors for Disposable Paper Toys.

Flexible electronics have gained great attention in recent years owing to their promising applications in biomedicine, sustainable energy, human-machine interaction, and toys for children. Paper mainly produced from cellulose fibers is attractive substrate for flexible electronics because it is biodegradable, foldable, tailorable, and light-weight. Inspired by daily handwriting, the rapid prototyping of sensing devices with arbitrary patterns can be achieved by directly drawing conductive inks on flat or curved paper surfaces; this provides huge freedom for children to design and integrate "do-it-yourself (DIY)" electronic toys. Herein, viscous and additive-free ink made from Ti3 C2 TX MXene sediment is employed to prepare disposable paper electronics through a simple ball pen drawing. The as-drawn paper sensors possess hierarchical microstructures with interweaving nanosheets, nanoflakes, and nanoparticles, therefore exhibiting superior mechanosensing performances to those based on single/fewer-layer MXene nanosheets. As proof-of-concept applications, several popular children's games are implemented by the MXene-based paper sensors, including "You say, I guess," "Emotional expression," "Rock-Paper-Scissors," "Arm wrestling," "Throwing game," "Carrot squat," and "Grab the cup," as well as a DIY smart whisker for a cartoon mouse. Moreover, MXene-based paper sensors are safe and disposable, free from producing any e-waste and hazard to the environment.

Mechanisms for self-templating design of micro/nanostructures toward efficient energy storage.

The ever-growing demand in modern power systems calls for the innovation in electrochemical energy storage devices so as to achieve both supercapacitor-like high power density and battery-like high energy density. Rational design of the micro/nanostructures of energy storage materials offers a pathway to finely tailor their electrochemical properties thereby enabling significant improvements in device performances and enormous strategies have been developed for synthesizing hierarchically structured active materials. Among all strategies, the direct conversion of precursor templates into target micro/nanostructures through physical and/or chemical processes is facile, controllable, and scalable. Yet the mechanistic understanding of the self-templating method is lacking and the synthetic versatility for constructing complex architectures is inadequately demonstrated. This review starts with the introduction of five main self-templating synthetic mechanisms and the corresponding constructed hierarchical micro/nanostructures. Subsequently, the structural merits provided by the well-defined architectures for energy storage are elaborately discussed. At last, a summary of current challenges and future development of the self-templating method for synthesizing high-performance electrode materials is also presented.

Recent Advances in Molybdenum-Based Materials for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries as power supply systems possessing a theoretical energy density of as high as 2600 Wh kg-1 are considered promising alternatives toward the currently used lithium-ion batteries (LIBs). However, the insulation characteristic and huge volume change of sulfur, the generation of dissolvable lithium polysulfides (LiPSs) during charge/discharge, and the uncontrollable dendrite formation of Li metal anodes render Li-S batteries serious cycling issues with rapid capacity decay. To address these challenges, extensive efforts are devoted to designing cathode/anode hosts and/or modifying separators by incorporating functional materials with the features of improved conductivity, lithiophilic, physical/chemical capture ability toward LiPSs, and/or efficient catalytic conversion of LiPSs. Among all candidates, molybdenum-based (Mo-based) materials are highly preferred for their tunable crystal structure, adjustable composition, variable valence of Mo centers, and strong interactions with soluble LiPSs. Herein, the latest advances in design and application of Mo-based materials for Li-S batteries are comprehensively reviewed, covering molybdenum oxides, molybdenum dichalcogenides, molybdenum nitrides, molybdenum carbides, molybdenum phosphides, and molybdenum metal. In the end, the existing challenges in this research field are elaborately discussed.

Injection-seeded high-repetition-rate short-pulse micro-laser based on upconversion nanoparticles.

We demonstrate a high repetition-rate upconversion green pulsed micro-laser, which is prepared by the fast thermal quenching of lanthanide-doped upconversion nanoparticles (UCNPs) via femtosecond-laser direct writing. The outer rim of the prepared upconversion hemi-ellipsoidal microstructure works as a whispering-gallery-mode (WGM) optical resonator for the coherent photon build-up of third-harmonic ultra-short seed pulses. When near-infrared (NIR) femtosecond laser pulses of wavelength 1545 nm are focused onto the upconversion WGM resonator, the optical third-harmonic is generated at 515 nm together with the upconversion luminescence. The weak third-harmonic (TH) seed pulses are coherently amplified in the hemi-ellipsoidal upconversion resonator as a result of the resonant interaction between the incident femtosecond laser field, the TH, the upconversion luminescence and the WGM. This upconversion lasing preserves the original repetition rate of the NIR pump laser and the output polarization state is also coherently aligned to the pump laser polarization. Because of the isotropic nature of the upconversion micro-ellipsoids, the upconversion lasing shows maximum intensity with a linearly polarized pump beam and minimum intensity with a circularly polarized pump beam. Our scheme devised for realizing high-repetition-rate lasing at higher photon energies in a compact micro platform will open up new ways for on-chip optical information processing, high-throughput microfluidic sensing, and localized micro light sources for optical memories.

Mechanistic insight in site-selective and anisotropic etching of prussian blue analogues toward designable complex architectures for efficient energy storage.

Engineering coordination compounds, e.g., prussian blue (PB) and its analogues (PBAs), with designable complex nanostructures via chemical etching holds great opportunities for improving energy storage performances by adjusting topological geometry, selectively exposing active sites, tuning electronic properties and enhancing accessible surface area. Unfortunately, it remains ambiguous particularly on site-selective and anisotropic etching behaviors. Herein, for the first time, we propose that two distinct regions are formed inside NiCo PBA (NCP) cubes due to the competition between classical ion-by-ion crystallization and non-classical crystallization based on aggregation. Such a unique structure ultimately determines not only the etching position but also the anisotropic pathway by selectively exposing unprotected Ni sites. According to this principle, complex PBA architectures, including nanocages, open nanocubes (constructed by six cones sharing the same apex), nanocones, and chamfer nanocubes can be intentionally obtained. After thermal annealing, NCP nanocones are converted to morning glory-like porous architectures composed of NiO/NiCo2O4 heterostructures with a mean particle size of 5 nm, which show improved rate performance and cycling stability.

Microstructure Design of Carbonaceous Fibers: A Promising Strategy toward High-Performance Weaveable/Wearable Supercapacitors.

Fiber-based supercapacitors (FSCs) possess great potential as an ideal type of power source for future weaveable/wearable electronics and electronic-textiles. The performance of FSCs is, without doubt, primarily determined by the properties of fibrous electrodes. Carbonaceous fibers, e.g., commercial carbon fibers, newly developed graphene fibers, and carbon nanotube fibers, are deemed as promising materials for weaveable/wearable supercapacitors owing to their exotic properties including high tensile strength and robustness, excellent electrical conductivity, good flexibility, and environmental stability. Nevertheless, bare carbonaceous fiber normally exhibits low capacitance originating from electric double-layer capacitance, which remains unsatisfactory for efficiently powering wearable and portable devices. Numerous efforts have been devoted to tailoring fiber properties by hybridizing pseudocapacitive materials, and impressive progress has been achieved thus far. Herein, the microstructures of pristine carbonaceous fibers are introduced in detail, and the recent advances in rational nano/microstructure design of their hybrids, which provides the feasibility to achieve the synergistic interaction between conductive agents and pseudocapacitive nanomaterials but are normally overlooked, are comprehensively reviewed. Besides, the challenges in developing high-performance fibrous electrodes are also elaborately discussed.

Solution-Processed Sensing Textiles with Adjustable Sensitivity and Linear Detection Range Enabled by Twisting Structure.

Wearable strain sensors are emerging rapidly for their promising applications in human motion detection for diagnosis, healthcare, training instruction, and rehabilitation exercise assessment. However, it remains a bottleneck in gaining comfortable and breathable devices with the features of high sensitivity, linear response, and tunable detection range. Textiles possess fascinating advantages of good breathability, aesthetic property, tailorability, and excellent mechanical compliance to conformably attach to human body. As the meandering loops in a textile can be extended in different directions, it provides plenty of room for exploring ideal sensors by tuning a twisting structure with rationally selected yarn materials. Herein, textile sensors with twisting architecture are designed via a solution-based process by using a stable water-based conductive ink that is composed of polypyrrole/polyvinyl alcohol nanoparticles with a mean diameter of 50 nm. Depending on the predesigned twisting models, the thus-fabricated textile sensors show adjustable performances, exhibiting a high sensitivity of 38.9 with good linearity and a broad detection range of 200%. Such sensors can be integrated into fabrics and conformably attached to skin for monitoring subtle (facial expressions, breathing, and speaking) and large (stretching, jumping, running and jogging, and sign language) human motions. As a proof-of-concept application, by integrating with a wireless transmitter, the signals detected by our sensors during exercise (e.g., running) can be remotely received and displayed on a smartphone. It is believed that the integration of our textile sensors with selected twisting models into a cloth promises full-range motion detection for wearable electronics and human-machine interfaces.

Ultrasensitive Anti-Interference Voice Recognition by Bio-Inspired Skin-Attachable Self-Cleaning Acoustic Sensors.

Human voice recognition systems (VRSs) are a prerequisite for voice-controlled human-machine interfaces (HMIs). In order to avoid interference from unexpected background noises, skin-attachable VRSs are proposed to directly detect physiological mechanoacoustic signals based on the vibrations of vocal cords. However, the sensitivity and response time of existing VRSs are bottlenecks for efficient HMIs. In addition, water-based contaminants in our daily lives, such as skin moisture and raindrops, normally result in performance degradation or even functional failure of VRSs. Herein, we present a skin-attachable self-cleaning ultrasensitive and ultrafast acoustic sensor based on a reduced graphene oxide/polydimethylsiloxane composite film with bioinspired microcracks and hierarchical surface textures. Benefitting from the synergetic effect of the spider-slit-organ-like multiscale jagged microcracks and the lotus-leaf-like hierarchical structures, our superhydrophobic VRS exhibits an ultrahigh sensitivity (gauge factor, GF = 8699), an ultralow detection limit (ε = 0.000 064%), an ultrafast response/recovery behavior, an excellent device durability (>10 000 cycles), and reliable detection of acoustic vibrations over the audible frequency range (20-20 000 Hz) with high signal-to-noise ratios. These superb performances endow our skin-attachable VRS with anti-interference perception of human voices with high precision even in noisy environments, which will expedite the voice-controlled HMIs.

Polarity-assisted formation of hollow-frame sheathed nitrogen-doped nanofibrous carbon for supercapacitors.

Heteroatom-doped carbon nanostructures with uniform size and morphology, well-designed architectures, and minimized interfacial resistance have been recognized as promising electrode materials for energy storage, but remain a crucial challenge. Herein, we develop a general approach of polarity-induced decoration of a monolayer sheath of metal-organic framework (MOF) particles with excellent uniformity in size and morphology on electrospun polymer nanofibers. These hybrid nanofibers are facilely converted into nitrogen-doped nanofibrous carbon (denoted as N-NFC) during pyrolysis. The thus-obtained N-NFC features (1) a one-dimensional nanofibrous structure with a highly conductive core, (2) a monolayer sheath of hollow carbon-frames with uniform size and morphology, (3) plenty of micro/mesopores with a highly accessible surface area, and (4) a high N-doping level, all of which guarantee its good electrochemical performance with a high capacitance of 387.3 F g-1 at 1 A g-1. In a solid-state supercapacitor, it delivers excellent rate capability (78.0 F g-1 at 0.2 A g-1 and 64.0 F g-1 at 1 A g-1), an enhanced energy density of 7.9 W h kg-1 at a power density of 219 W kg-1, and outstanding cycling stability with 90% capacity retained over 10 000 cycles at 1 A g-1.

Wearable Bandage-Based Strain Sensor for Home Healthcare: Combining 3D Aerosol Jet Printing and Laser Sintering.

Flexible and stretchable strain sensors are in great demand for many applications like wearables and home health. This work reports a strain sensor fabricated using aerosol jet printing technology on a commercially available bandage to be used as a low-cost wearable. Laser light is explored to sinter the silver nanoparticle ink on a low-temperature bandage substrate. The laser parameters, their effects on the microstructure of the film, and the resulting sensor performance are systematically investigated. The results showed that the sensor is stretchable and has good sensitivity and stability for 700 cycles of repeated bending.

Single-Step Selective Laser Writing of Flexible Photodetectors for Wearable Optoelectronics.

The increasing demand for wearable optoelectronics in biomedicine, prosthetics, and soft robotics calls for innovative and transformative technologies that permit facile fabrication of compact and flexible photodetectors with high performance. Herein, by developing a single-step selective laser writing strategy that can finely tailor material properties through incident photon density control and lead to the formation of hierarchical hybrid nanocomposites, e.g., reduced graphene oxide (rGO)-zinc oxide (ZnO), a highly flexible and all rGO-ZnO hybrid-based photodetector is successfully constructed. The device features 3D ultraporous hybrid films with high photoresponsivity as the active detection layer, and hybrid nanoflakes with superior electrical conductivity as interdigitated electrodes. Benefitting from enhanced photocarrier generation because of the ultraporous film morphology, efficient separation of electron-hole pairs at rGO-ZnO heterojunctions, and fast electron transport by highly conductive rGO nanosheets, the photodetector exhibits high, linear, and reproducible responsivities to a wide range of ultraviolet (UV) intensities. Furthermore, the excellent mechanical flexibility and robustness enable the photodetector to be conformally attached to skin, thus intimately monitoring the exposure dosage of human body to UV light for skin disease prevention. This study advances the fabrication of flexible optoelectronic devices with reduced complexity, facilitating the integration of wearable optoelectronics and epidermal systems.

A Solid-State Fibriform Supercapacitor Boosted by Host-Guest Hybridization between the Carbon Nanotube Scaffold and MXene Nanosheets.

Fiber-shaped supercapacitors with improved specific capacitance and high rate capability are a promising candidate as power supply for smart textiles. However, the synergistic interaction between conductive filaments and active nanomaterials remains a crucial challenge, especially when hydrothermal or electrochemical deposition is used to produce a core (fiber)-shell (active materials) fibrous structure. On the other hand, although 2D pseudocapacitive materials, e.g., Ti3 C2 T x (MXene), have demonstrated high volumetric capacitance, high electrical conductivity, and hydrophilic characteristics, MXene-based electrodes normally suffer from poor rate capability owing to the sheet restacking especially when the loading level is high and solid-state gel is used as electrolyte. Herein, by hosting MXene nanosheets (Ti3 C2 T x ) in the corridor of a scrolled carbon nanotube (CNT) scaffold, a MXene/CNT fiber with helical structure is successfully fabricated. These features offer open spaces for rapid ion diffusion and guarantee fast electron transport. The solid-state supercapacitor based on such hybrid fibers with gel electrolyte coating exhibits a volumetric capacitance of 22.7 F cm-3 at 0.1 A cm-3 with capacitance retention of 84% at current density of 1.0 A cm-3 (19.1 F cm-3 ), improved volumetric energy density of 2.55 mWh cm-3 at the power density of 45.9 mW cm-3 , and excellent mechanical robustness.

Holey nickel hydroxide nanosheets for wearable solid-state fiber-supercapacitors.

Holey nickel hydroxide (Ni(OH)2) nanosheets with a mean thickness of 2 nm are facilely synthesized, and then embedded in carbon nanotube (CNT) scaffolds to construct a hybrid fiber electrode, which shows a high volumetric capacitance of 335.9 F cm-3 at 0.8 A cm-3 and superior rate performance. The hybrid supercapacitor made from the Ni(OH)2/CNT fiber can deliver a high specific capacitance of 24.8 F cm-3 and an energy density of 5.8 mW h cm-3 with outstanding mechanical stability under repeated bending conditions.

All-Graphene-Based Highly Flexible Noncontact Electronic Skin.

Noncontact electronic skin (e-skin), which possesses superior long-range and high-spatial-resolution sensory properties, is becoming indispensable in fulfilling the emulation of human sensation via prosthetics. Here, we present an advanced design and fabrication of all-graphene-based highly flexible noncontact e-skins by virtue of femtosecond laser direct writing (FsLDW). The photoreduced graphene oxide patterns function as the conductive electrodes, whereas the pristine graphene oxide thin film serves as the sensing layer. The as-fabricated e-skins exhibit high sensitivity, fast response-recovery behavior, good long-term stability, and excellent mechanical robustness. In-depth analysis reveals that the sensing mechanism is attributed to proton and ionic conductivity in the low and high humidity conditions, respectively. By taking the merits of the FsLDW, a 4 × 4 sensing matrix is facilely integrated in a single-step, eco-friendly, and green process. The light-weight and in-plane matrix shows high-spatial-resolution sensing capabilities over a long detection range in a noncontact mode. This study will open up an avenue to innovations in the noncontact e-skins and hold a promise for applications in wearable human-machine interfaces, robotics, and bioelectronics.

Design of a wearable and shape-memory fibriform sensor for the detection of multimodal deformation.

A wearable and shape-memory strain sensor with a coaxial configuration is designed, comprising a thermoplastic polyurethane fiber as the core support, well-aligned and interconnected carbon nanotubes (CNTs) as conductive filaments, and polypyrrole (PPy) coating as the cladding layer. In this design, the stress relaxation between CNTs is well confined by the outer PPy cladding layer, which endows the fibriform sensor with good reliability and repeatability. The microcracks generated when the coaxial fiber is under strain guarantee the superior sensitivity of this fibriform sensor with a gauge factor of 12 at 0.1% strain, a wide detectable range (from 0.1% to 50% tensile strain), and the ability to detect multimodal deformation (tension, bending, and torsion) and human motions (finger bending, breathing, and phonation). In addition, due to its shape-memory characteristic, the sensing performance of the fibriform sensor is well retained after its shape recovers from 50% deformation and the fabric woven from the shape-memory coaxial fibers can be worn on the elbow joints in a reversible manner (original-enlarged-recovered) and fitted tightly. Thus, this sensor shows promising applications in wearable electronics.

Paper/Carbon Nanotube-Based Wearable Pressure Sensor for Physiological Signal Acquisition and Soft Robotic Skin.

A wearable and flexible pressure sensor is essential to the realization of personalized medicine through continuously monitoring an individual's state of health and also the development of a highly intelligent robot. A flexible, wearable pressure sensor is fabricated based on novel single-wall carbon nanotube /tissue paper through a low-cost and scalable approach. The flexible, wearable sensor showed superior performance with concurrence of several merits, including high sensitivity for a broad pressure range and an ultralow energy consumption level of 10-6 W. Benefited from the excellent performance and the ultraconformal contact of the sensor with an uneven surface, vital human physiological signals (such as radial arterial pulse and muscle activity at various positions) can be monitored in real time and in situ. In addition, the pressure sensors could also be integrated onto robots as the artificial skin that could sense the force/pressure and also the distribution of force/pressure on the artificial skin.

Femtosecond-Laser-Based 3D Printing for Tissue Engineering and Cell Biology Applications.

Fabrication of 3D cell scaffolds has gained tremendous attention in recent years because of its applications in tissue engineering and cell biology applications. The success of tissue engineering or cell interactions mainly depends on the fabrication of well-defined microstructures, which ought to be biocompatible for cell proliferation. Femtosecond-laser-based 3D printing is one of the solution candidates that can be used to manufacture 3D tissue scaffolds through computer-aided design (CAD) which can be efficiently engineered to mimic the microenvironment of tissues. UV-based lithography has also been used for constructing the cellular scaffolds but the toxicity of UV light to the cells has prevented its application to the direct patterning of the cells in the scaffold. Although the mask-based lithography has provided a high resolution, it has only enabled 2D patterning not arbitrary 3D printing with design flexibility. Femtosecond-laser-based 3D printing is trending in the area of tissue engineering and cell biology applications due to the formation of well-defined micro- and submicrometer structures via visible and near-infrared (NIR) femtosecond laser pulses, followed by the fabrication of cell scaffold microstructures with a high precision. Laser direct writing and multiphoton polymerization are being used for fabricating the cell scaffolds, The implication of spatial light modulators in the interference lithography to generate the digital hologram will be the future prospective of mask-based lithography. Polyethylene glycol diacrylate (PEG-DA), ormocomp, pentaerythritol tetraacrylate (PETTA) have been fabricated through TPP to generate the cell scaffolds, whereas SU-8 was used to fabricate the microrobots for targeted drug delivery. Well-designed and precisely fabricated 3D cell scaffolds manufactured by femtosecond-laser-based 3D printing can be potentially used for studying cell migration, matrix invasion and nuclear stiffness to determine stage of cancer and will open broader horizons in the future in tissue engineering and biology applications.

Inkjet-printed optoelectronics.

Inkjet printing is a powerful and cost-effective technique for deposition of liquid inks with high accuracy, which is not only of great significance for graphic applications but also has enormous potential for the direct printing of optoelectronic devices. This review highlights a comprehensive overview of the progress that has been made in optoelectronics fabrication by the inkjet printing technique. The first part briefly covers the droplet-generation process in the nozzles of printheads and the physical properties affecting droplet formation and the profiles of the printed patterns. The second section outlines the recent activities related to applications of inkjet printing in optoelectronics fabrication including solar cells, light-emitting diodes, photodetectors and transparent electrodes. In each application field, the challenges with the inkjet printing process and the possible solutions are discussed before a few remarks. In the last section, a brief summary on the progress of inkjet printing fabrication of optoelectronics and an outlook for future research effort are presented.