High-Performance Yet Sustainable Triboelectric Nanogenerator Based on Sulfur-Rich Polymer Composite with MXene Segregated Structure.

State-of-the-art triboelectric nanogenerators (TENGs) typically employ fluoropolymers, highly negative chargeable materials in triboelectric series. However, many researchers nowadays are concerned about environmental pollution caused by poly-and per-fluoroalkyl substances (PFAS) due to their critical immunotoxicity as fluoropolymers are likely to release PFAS into the ecosystem during their life cycle. Herein, a sulfur-rich polymer (SRP)/MXene composite, offering high-performance yet sustainable TENG is developed. Value-addition of sulfur into SRP-based TENG has huge advantages since sulfur is abundant waste from petroleum refining and possesses the highest electron affinity (-200 kJ mol-1) among polymerizable atoms. MXene segregated structure is introduced into SRP to achieve homogeneous distribution without electrical percolation by utilizing below 0.5 wt% of MXene, resulting in a significantly enhanced dielectric constant without a drastic increase of dielectric loss. Due to homogeneous MXene distribution, SRP/MXene composite-based TENG demonstrates 2.9 times and 19.5 times enhances peak voltage and peak current compared to previous SRP-based TENGs. Additionally, it exhibits reusability without critical reduction of modulus and TENG performance due to dynamically exchangeable disulfide bonds. Finally, after the corona discharging and scaling-up process to a 4-inch wafer size, SRP/MXene composite-based TENG exhibits an 8.4 times improvement in peak power density, reaching 3.80 W m-2 compared to previous SRP-based TENGs.

Prominent enhancement of stability under high current density of LiFePO4-based multidimensional nanocarbon composite as cathode for lithium-ion batteries.

A facile method for synthesizing carbon-coated lithium iron phosphate (LiFePO4, LFP) and an LFP-based multidimensional nanocarbon composite to enhance the electrochemical performance of lithium-ion batteries is presented herein. Three types of cathode materials are prepared: carbon-coated LFP (LC), carbon-coated LFP with carbon nanotubes (LC@C), and carbon-coated LFP with carbon nanotubes/graphene quantum dots (LC@CG). The electrochemical performances of the LC-nanocarbon composites are compared, and both LC@C and LC@CG show improved electrochemical performance than LC. Compared with both the LC and LC@C electrodes, the LC@CG electrode exhibits the highest specific capacity of 107.1 mA h g-1 under 20C of current density, as well as higher capacities and greater stability over all measured current densities. Moreover, after 300 charge-discharge cycles, the LC@CG electrode exhibits the best stability than the LC and LC@C electrodes. This is attributable to the graphene quantum dots, which enhance the morphological stability of the LC@CG electrode during electrochemical measurements. Our findings suggest that LFP-nanocarbon composites are promising as cathode materials and highlight the potential of graphene quantum dots for improving the stability of cathodes.

Recent Advances in Triboelectric Nanogenerators: From Technological Progress to Commercial Applications.

Serious climate changes and energy-related environmental problems are currently critical issues in the world. In order to reduce carbon emissions and save our environment, renewable energy harvesting technologies will serve as a key solution in the near future. Among them, triboelectric nanogenerators (TENGs), which is one of the most promising mechanical energy harvesters by means of contact electrification phenomenon, are explosively developing due to abundant wasting mechanical energy sources and a number of superior advantages in a wide availability and selection of materials, relatively simple device configurations, and low-cost processing. Significant experimental and theoretical efforts have been achieved toward understanding fundamental behaviors and a wide range of demonstrations since its report in 2012. As a result, considerable technological advancement has been exhibited and it advances the timeline of achievement in the proposed roadmap. Now, the technology has reached the stage of prototype development with verification of performance beyond the lab scale environment toward its commercialization. In this review, distinguished authors in the world worked together to summarize the state of the art in theory, materials, devices, systems, circuits, and applications in TENG fields. The great research achievements of researchers in this field around the world over the past decade are expected to play a major role in coming to fruition of unexpectedly accelerated technological advances over the next decade.

Laminating Structure for Interlayer Corona Discharge Treatment Toward Ion-Based Nanogenerators.

A corona discharge treatment (CDT) is utilized to maximize the performance of triboelectric nanogenerators (TENGs) by injecting extra electrons into the negative tribomaterials. Increased performance of CDT TENGs, however, exhibits rapid degradation due to the electron dissipation by air moisture or thermal emission. To overcome such drawbacks and circumvent such dissipation, the source of charges should be replaced with ionic charges. This study reports a Ag nanowires (NWs)-embedded laminating structure (AeLS) with a unique fabrication procedure for ionic charge injection by CDT. The injection of ions is achieved by interlayer-CDT (i-CDT), in which positive charges are dissipated by Ag NWs, and the opposite negative ions can remain on the outmost surface. The AeLS TENGs with i-CDT exhibit high performance, long-term stability, and durability. It shows voltage, current, and maximum power outputs of 380 V, 15 µA, and 827 mW m-2 , respectively. As a practical demonstration, rotational TENG integrated with a direct discharge system is realized, and its current and voltage reach 7.4 mA and 7800 V, respectively. This work can pave the way for the design of ion-based TENGs with high performance and long-lasting retention of triboelectric charges.

Ultra-thin membrane filter with a uniformly arrayed nanopore structure for nanoscale separation of extracellular vesicles without cake formation.

Extracellular vesicles (EVs) have emerged as vehicles that mediate diverse cell-cell communication. However, in-depth understanding of these vesicles is hampered by a lack of a reliable isolation method to separate different types of EVs with high levels of integrity and purity. Here, we developed a nanoporous and ultra-thin membrane structure (NUTS) that warrants the size-based isolation of EVs without cake formation, minimizing the sample loss during the filtration process. By utilizing the micro-electro-mechanical systems (MEMS) technique, we could also control the pore size in nanoscale. We validated the performance of this membrane to separate EVs according to their size range.

Reversible electrical percolation in a stretchable and self-healable silver-gradient nanocomposite bilayer.

The reversibly stable formation and rupture processes of electrical percolative pathways in organic and inorganic insulating materials are essential prerequisites for operating non-volatile resistive memory devices. However, such resistive switching has not yet been reported for dynamically cross-linked polymers capable of intrinsic stretchability and self-healing. This is attributable to the uncontrollable interplay between the conducting filler and the polymer. Herein, we present the development of the self-healing, stretchable, and reconfigurable resistive random-access memory. The device was fabricated via the self-assembly of a silver-gradient nanocomposite bilayer which is capable of easily forming the metal-insulator-metal structure. To realize stable resistive switching in dynamic molecular networks, our device features the following properties: i) self-reconstruction of nanoscale conducting fillers in dynamic hydrogen bonding for self-healing and reconfiguration and ii) stronger interaction among the conducting fillers than with polymers for the formation of robust percolation paths. Based on these unique features, we successfully demonstrated stable data storage of cardiac signals, damage-reliable memory triggering system using a triboelectric energy-harvesting device, and touch sensing via pressure-induced resistive switching.

A Bioinspired Stretchable Sensory-Neuromorphic System.

Conventional stretchable electronics that adopt a wavy design, a neutral mechanical plane, and conformal contact between abiotic and biotic interfaces have exhibited diverse skin-interfaced applications. Despite such remarkable progress, the evolution of intelligent skin prosthetics is challenged by the absence of the monolithic integration of neuromorphic constituents into individual sensing and actuating components. Herein, a bioinspired stretchable sensory-neuromorphic system, comprising an artificial mechanoreceptor, artificial synapse, and epidermal photonic actuator is demonstrated; these three biomimetic functionalities correspond to a stretchable capacitive pressure sensor, a resistive random-access memory, and a quantum dot light-emitting diode, respectively. This system features a rigid-island structure interconnected with a sinter-free printable conductor, which is optimized by controlling the evaporation rate of solvent (≈160% stretchability and ≈18 550 S cm-1 conductivity). Devised design improves both areal density and structural reliability while avoiding the thermal degradation of heat-sensitive stretchable electronic components. Moreover, even in the skin deformation range, the system accurately recognizes various patterned stimuli via an artificial neural network with training/inferencing functions. Therefore, the new bioinspired system is expected to be an important step toward implementing intelligent wearable electronics.

Polarization- and Electrode-Optimized Polyvinylidene Fluoride Films for Harsh Environmental Piezoelectric Nanogenerator Applications.

While piezoelectric nanogenerators have demonstrated the effective conversion of tiny mechanical vibrations to electricity, their performances are rarely examined under harsh environmental conditions. Here, a multilayered polyvinylidene fluoride (PVDF) film-based piezoelectric nanogenerator (ML-PENG) is demonstrated to generate considerable and stable power outputs even at extremely low temperatures and pressures, and under strong UV. Up-/down-polarized PVDF films are alternately stacked, and Ag electrodes are intercalated between the two adjacent films. At -266 °C and 10-5  Torr, the ML-PENG generates an open-circuit voltage of 1.1 V, a short-circuit current density of 8 nA cm-2 , and a power density of 4.4 nW cm-2 . The piezoelectric outputs are quite stable against prolonged illumination of UV, large temperature- and pressure-variations, and excessive mechanical vibrations. The piezoelectric power density is greatly enhanced above the freezing and glass transition temperatures of PVDF and recorded to be 10, 105, and 282 nW cm-2 at -73, 0, and 77 °C, respectively. The ML-PENG generates sufficient power to operate five light-emitting diodes by harvesting biomechanical energy under simulated Martian conditions. This work suggests that polarization- and electrode-optimized ML-PENG can serve as a reliable and economic power source in harsh and inaccessible environments like polar areas of Earth and extraterrestrial Mars.

Large-Scale Assembly of Peptide-Based Hierarchical Nanostructures and Their Antiferroelectric Properties.

An effective strategy is developed to create peptide-based hierarchical nanostructures through the meniscus-driven self-assembly in a large area and fabricate antiferroelectric devices based on these nanostructures for the first time. The diphenylalanine hierarchical nanostructures (FF-HNs) are self-assembled by vertically pulling a substrate from a diphenylalanine (FF) solution dissolved in a miscible solvent under precisely controlled conditions. Owing to the unique structural properties of FF nanostructures, including high crystallinity and α-helix structures, FF-HNs possess a net electrical dipole moment, which can be switched in an external electric field. The mass production of antiferroelectric devices based on FF-HNs can be successfully achieved by means of this biomimetic assembly technique. The devices show an evident antiferroelectric to ferroelectric transition under dark conditions, while the ferroelectricity is found to be tunable by light. Notably, it is discovered that the modulation of antiferroelectric behaviors of FF-HNs under glutaraldehyde exposure is due to the FF molecules that are transformed into cyclophenylalanine by glutaraldehyde. This work provides a stepping stone toward the mass production of self-assembled hierarchical nanostructures based on biomolecules as well as the mass fabrication of electronic devices based on biomolecular nanostructures for practical applications.

Attachable piezoelectric nanogenerators using collision-induced strain of vertically grown hollow MoS2 nanoflakes.

Piezoelectric materials convert external mechanical force into electrical energy, due to the breaking of the centrosymmetry of the atomic structure. Piezoelectricity-based nano-generators (PNGs) based on two-dimensional transition metal dichalcogenides (TMDs) can generate electrical energy stably by the piezoelectric effect at their nanoscale thickness. However, the commercialization of TMD-based PNGs is limited by their poor piezoelectric performance and microscale energy harvesting. Here, we present the first centimeter-scale PNGs based on molybdenum disulfide (MoS2) nanosheets with vertically grown hollow MoS2 nanoflakes (v-MoS2 NFs) obtained by chemical vapor deposition for energy harvesting from human motions. The collision of v-MoS2 NFs with a preferred odd-atomic-layer number and their 2H antiparallel phase leads to efficient electrical energy generation during the bending movement. Further, basal MoS2 films with v-MoS2 NFs are transferred onto flexible substrates via conventional polymer-assisted methods for the fabrication of attachable and wearable piezoelectric power generators.

Nanogap Engineering for Enhanced Transmission of Wire Grid Polarizers in Mid-Wavelength Infrared Region.

Wire-grid polarizers (WGPs) have been widely used in various fields, such as polarimetry, imaging, display, spectroscopy, and optical isolation. However, conventional WGPs used in diverse mid-wavelength infrared (MWIR) applications show high reflection losses, which intrinsically arise from high refractive indices of their IR-transmitting substrates, such as silicon (Si) and germanium (Ge). This study demonstrated the enhanced transmittance of a transverse magnetic (TM) wave that surpassed ~80% over the entire MWIR range from 3000 to 5000 nm in a narrow air gap of a WGP, where aluminum (Al) was selectively deposited on a nanopatterned Si substrate using an oblique angle deposition method. Moreover, a higher TM wave transmittance was achieved by reducing the air gaps of the WGPs in the nanopatterns, which were distinctly different from the traditional WGPs comprising metal wires patterned directly on a flat substrate. A finite-difference time-domain simulation was performed to investigate optical properties of the proposed WGPs, which showed that the electric field in the air nanogap was remarkably enhanced. The characteristic performances were further investigated using a combination of an effective medium approximation and an admittance diagram, revealing that the broadband transmission enhancement could be attributed to a combined effect of a strong electric field and a better admittance matching. The approach and results described in this paper hold promise for the design and the fabrication of high-quality WGPs, as well as their numerous applications.

Dominant Role of Young's Modulus for Electric Power Generation in PVDF⁻BaTiO3 Composite-Based Piezoelectric Nanogenerator.

The electric power output of a piezoelectric nanogenerator (PENG) depends on the various physical parameters of the constituent materials, including the piezoelectric coefficient, Young's modulus, and dielectric constant. Herein, we report the mechanical and electrical properties of a poly(vinylidene fluoride)⁻BaTiO3 (PVDF⁻BTO) composite-based PENG. Variation of the BTO nanoparticle (NP) content enabled the systematic tuning of the physical parameters that are related to power generation in the composite. The Young's modulus of the PVDF⁻BTO composite initially increased, and then eventually decreased, with the increasing BTO content, which was probably due to the clustering effect of the high modulus BTO NPs. The dielectric constant of the composite continuously increased as the BaTiO3 content increased. The piezoelectric outputs were greatly enhanced at 10 wt% of BTO, where the Young's modulus was the highest. These results indicate that the Young's modulus plays an important role in the piezoelectric power generation of the composite-based PENGs.

Improving Morphological Quality and Uniformity of Hydrothermally Grown ZnO Nanowires by Surface Activation of Catalyst Layer.

This paper presents a study about the dependence of the hydrothermal growth of ZnO nanowires (NWs) with the passivation level of the active surface of the Au catalyst layer. The hydrothermal method has many potential applications because of its low processing temperature, feasibility, and low cost. However, when a gold thin film is utilized as the seed material, the grown NWs often lack morphological homogeneity; their distribution is not uniform and the reproducibility of the growth is low. We hypothesize that the state or condition of the active surface of the Au catalyst layer has a critical effect on the uniformity of the NWs. Inspired by traditional electrochemistry experiments, in which Au electrodes are typically activated before the measurements, we demonstrate that such activation is a simple way to effectively assist and enhance NW growth. In addition, several cleaning processes are examined to find one that yields NWs with optimal quality, density, and vertical alignment. We find cyclic voltammetry measurements to be a reliable indicator of the seed-layer quality for subsequent NW growth. Therefore, we propose the use of this technique as a standard procedure prior to the hydrothermal synthesis of ZnO NWs to control the growth reproducibility and to allow high-yield wafer-level processing.

Colloidal Synthesis of Uniform-Sized Molybdenum Disulfide Nanosheets for Wafer-Scale Flexible Nonvolatile Memory.

Large-scale colloidal synthesis and integration of uniform-sized molybdenum disulfide (MoS2 ) nanosheets for a flexible resistive random access memory (RRAM) array are presented. RRAM using MoS2 nanosheets shows a ≈10 000 times higher on/off ratio than that based on exfoliated MoS2 . The good uniformity of the MoS2 nanosheets allows wafer-scale system integration of the RRAM array with pressure sensors and quantum-dot light-emitting diodes.

Nanogenerators consisting of direct-grown piezoelectrics on multi-walled carbon nanotubes using flexoelectric effects.

We report the first attempt to prepare a flexoelectric nanogenerator consisting of direct-grown piezoelectrics on multi-walled carbon nanotubes (mwCNT). Direct-grown piezoelectrics on mwCNTs are formed by a stirring and heating method using a Pb(Zr0.52Ti0.48)O3 (PZT)-mwCNT precursor solution. We studied the unit cell mismatch and strain distribution of epitaxial PZT nanoparticles, and found that lattice strain is relaxed along the growth direction. A PZT-mwCNT nanogenerator was found to produce a peak output voltage of 8.6 V and an output current of 47 nA when a force of 20 N is applied. Direct-grown piezoelectric nanogenerators generate a higher voltage and current than simple mixtures of PZT and CNTs resulting from the stronger connection between PZT crystals and mwCNTs and an enhanced flexoelectric effect caused by the strain gradient. These experiments represent a significant step toward the application of nanogenerators using piezoelectric nanocomposite materials.

A wearable multiplexed silicon nonvolatile memory array using nanocrystal charge confinement.

Strategies for efficient charge confinement in nanocrystal floating gates to realize high-performance memory devices have been investigated intensively. However, few studies have reported nanoscale experimental validations of charge confinement in closely packed uniform nanocrystals and related device performance characterization. Furthermore, the system-level integration of the resulting devices with wearable silicon electronics has not yet been realized. We introduce a wearable, fully multiplexed silicon nonvolatile memory array with nanocrystal floating gates. The nanocrystal monolayer is assembled over a large area using the Langmuir-Blodgett method. Efficient particle-level charge confinement is verified with the modified atomic force microscopy technique. Uniform nanocrystal charge traps evidently improve the memory window margin and retention performance. Furthermore, the multiplexing of memory devices in conjunction with the amplification of sensor signals based on ultrathin silicon nanomembrane circuits in stretchable layouts enables wearable healthcare applications such as long-term data storage of monitored heart rates.

Wearable Fall Detector using Integrated Sensors and Energy Devices.

Wearable devices have attracted great attentions as next-generation electronic devices. For the comfortable, portable, and easy-to-use system platform in wearable electronics, a key requirement is to replace conventional bulky and rigid energy devices into thin and deformable ones accompanying the capability of long-term energy supply. Here, we demonstrate a wearable fall detection system composed of a wristband-type deformable triboelectric generator and lithium ion battery in conjunction with integrated sensors, controllers, and wireless units. A stretchable conductive nylon is used as electrodes of the triboelectric generator and the interconnection between battery cells. Ethoxylated polyethylenimine, coated on the surface of the conductive nylon electrode, tunes the work function of a triboelectric generator and maximizes its performance. The electrical energy harvested from the triboelectric generator through human body motions continuously recharges the stretchable battery and prolongs hours of its use. The integrated energy supply system runs the 3-axis accelerometer and related electronics that record human body motions and send the data wirelessly. Upon the unexpected fall occurring, a custom-made software discriminates the fall signal and an emergency alert is immediately sent to an external mobile device. This wearable fall detection system would provide new opportunities in the mobile electronics and wearable healthcare.

Stretchable carbon nanotube charge-trap floating-gate memory and logic devices for wearable electronics.

Electronics for wearable applications require soft, flexible, and stretchable materials and designs to overcome the mechanical mismatch between the human body and devices. A key requirement for such wearable electronics is reliable operation with high performance and robustness during various deformations induced by motions. Here, we present materials and device design strategies for the core elements of wearable electronics, such as transistors, charge-trap floating-gate memory units, and various logic gates, with stretchable form factors. The use of semiconducting carbon nanotube networks designed for integration with charge traps and ultrathin dielectric layers meets the performance requirements as well as reliability, proven by detailed material and electrical characterizations using statistics. Serpentine interconnections and neutral mechanical plane layouts further enhance the deformability required for skin-based systems. Repetitive stretching tests and studies in mechanics corroborate the validity of the current approaches.

Oxide nanomembrane hybrids with enhanced mechano- and thermo-sensitivity for semitransparent epidermal electronics.

Oxide nanomembrane hybrids with enhanced mechano- and thermo-sensitivity for semitransparent epidermal electronics are developed. The use of nanomaterials (single wall nanotubes and silver nanoparticles) embedded in the oxide nanomembranes significantly enhances mechanical and thermal sensitivities. These mechanical and thermal sensors are utilized in wheelchair control and hypothermia detection, which are useful for patients with strokes.

Fabric-based integrated energy devices for wearable activity monitors.

A wearable fabric-based integrated power-supply system that generates energy triboelectrically using human activity and stores the generated energy in an integrated supercapacitor is developed. This system can be utilized as either a self-powered activity monitor or as a power supply for external wearable sensors. These demonstrations give new insights for the research of wearable electronics.