Polymer hetero-electrolyte enabled solid-state 2.4-V Zn/Li hybrid batteries.

The high redox potential of Zn0/2+ leads to low voltage of Zn batteries and therefore low energy density, plaguing deployment of Zn batteries in many energy-demanding applications. Though employing high-voltage cathode like spinel LiNi0.5Mn1.5O4 can increase the voltages of Zn batteries, Zn2+ ions will be immobilized in LiNi0.5Mn1.5O4 once intercalated, resulting in irreversibility. Here, we design a polymer hetero-electrolyte consisting of an anode layer with Zn2+ ions as charge carriers and a cathode layer that blocks the Zn2+ ion shuttle, which allows separated Zn and Li reversibility. As such, the Zn‖LNMO cell exhibits up to 2.4 V discharge voltage and 450 stable cycles with high reversible capacity, which are also attained in a scale-up pouch cell. The pouch cell shows a low self-discharge after resting for 28 days. The designed electrolyte paves the way to develop high-voltage Zn batteries based on reversible lithiated cathodes.

Modular Design of Functional Glucose Monomer and Block Co-Polymer toward Stable Zn Anodes.

Aqueous Zn batteries employing mildly acidic electrolytes have emerged as promising contenders for safe and cost-effective energy storage solutions. Nevertheless, the intrinsic reversibility of the Zn anode becomes a focal concern due to the involvement of acidic electrolyte, which triggers Zn corrosion and facilitates the deposition of insulating byproducts. Moreover, the unregulated growth of Zn over cycling amplifies the risk of internal short-circuiting, primarily induced by the formation of Zn dendrites. In this study, a class of glucose-derived monomers and a block copolymer are synthesized through a building-block assembly strategy, ultimately leading to uncover the optimal polymer structure that suppresses the Zn corrosion while allowing efficient ion conduction with a substantial contribution from cation transport. Leveraging these advancements, remarkable enhancements are achieved in the realm of Zn reversibility, exemplified by a spectrum of performance metrics, including robust cycling stability without voltage overshoot and short-circuiting during 3000 h of cycling, stable operation at a high depth of charge/discharge of 75% and a high current density, >95% Coulombic efficiency over 2000 cycles, successful translation of the anode improvement to full cell performance. These polymer designs offer a transformative path based on the modular synthesis of polymeric coatings toward highly reversible Zn anode.

Self-assembly of Co/Pt stripes with current-induced domain wall motion towards 3D racetrack devices.

Modification of the magnetic properties under the induced strain and curvature is a promising avenue to build three-dimensional magnetic devices, based on the domain wall motion. So far, most of the studies with 3D magnetic structures were performed in the helixes and nanowires, mainly with stationary domain walls. In this study, we demonstrate the impact of 3D geometry, strain and curvature on the current-induced domain wall motion and spin-orbital torque efficiency in the heterostructure, realized via a self-assembly rolling technique on a polymeric platform. We introduce a complete 3D memory unit with write, read and store functionality, all based on the field-free domain wall motion. Additionally, we conducted a comparative analysis between 2D and 3D structures, particularly addressing the influence of heat during the electric current pulse sequences. Finally, we demonstrated a remarkable increase of 30% in spin-torque efficiency in 3D configuration.

Bio-Inspired Dynamically Morphing Microelectronics toward High-Density Energy Applications and Intelligent Biomedical Implants.

Choreographing the adaptive shapes of patterned surfaces to exhibit designable mechanical interactions with their environment remains an intricate challenge. Here, a novel category of strain-engineered dynamic-shape materials, empowering diverse multi-dimensional shape modulations that are combined to form fine-grained adaptive microarchitectures is introduced. Using micro-origami tessellation technology, heterogeneous materials are provided with strategic creases featuring stimuli-responsive micro-hinges that morph precisely upon chemical and electrical cues. Freestanding multifaceted foldable packages, auxetic mesosurfaces, and morphable cages are three of the forms demonstrated herein of these complex 4-dimensional (4D) metamaterials. These systems are integrated in dual proof-of-concept bioelectronic demonstrations: a soft foldable supercapacitor enhancing its power density (≈108 mW cm-2), and a bio-adaptive device with a dynamic shape that may enable novel smart-implant technologies. This work demonstrates that intelligent material systems are now ready to support ultra-flexible 4D microelectronics, which can impart autonomy to devices culminating in the tangible realization of microelectronic morphogenesis.

A Photolithographable Electrolyte for Deeply Rechargeable Zn Microbatteries in On-Chip Devices.

Zn batteries show promise for microscale applications due to their compatibility with air fabrication but face challenges like dendrite growth and chemical corrosion, especially at the microscale. Despite previous attempts in electrolyte engineering, achieving successful patterning of electrolyte microscale devices has remained challenging. Here, successful patterning using photolithography is enabled by incorporating caffeine into a UV-crosslinked polyacrylamide hydrogel electrolyte. Caffeine passivates the Zn anode, preventing chemical corrosion, while its coordination with Zn2+ ions forms a Zn2+-conducting complex that transforms into ZnCO3 and 2ZnCO3·3Zn(OH)2 over cycling. The resulting Zn-rich interphase product significantly enhances Zn reversibility. In on-chip microbatteries, the resulting solid-electrolyte interphase allows the Zn||MnO2 full cell to cycle for over 700 cycles with an 80% depth of discharge. Integrating the photolithographable electrolyte into multilayer microfabrication creates a microbattery with a 3D Swiss-roll structure that occupies a footprint of 0.136 mm2. This tiny microbattery retains 75% of its capacity (350 µAh cm-2) for 200 cycles at a remarkable 90% depth of discharge. The findings offer a promising solution for enhancing the performance of Zn microbatteries, particularly for on-chip microscale devices, and have significant implications for the advancement of autonomous microscale devices.

3D nanofabricated soft microrobots with super-compliant picoforce springs as onboard sensors and actuators.

Microscale organisms and specialized motile cells use protein-based spring-like responsive structures to sense, grasp and move. Rendering this biomechanical transduction functionality in an artificial micromachine for applications in single-cell manipulations is challenging due to the need for a bio-applicable nanoscale spring system with a large and programmable strain response to piconewton-scale forces. Here we present three-dimensional nanofabrication and monolithic integration, based on an acrylic elastomer photoresist, of a magnetic spring system with quantifiable compliance sensitive to 0.5 pN, constructed with customized elasticity and magnetization distributions at the nanoscale. We demonstrate the effective design programmability of these 'picospring' ensembles as energy transduction mechanisms for the integrated construction of customized soft micromachines, with onboard sensing and actuation functions at the single-cell scale for microrobotic grasping and locomotion. The integration of active soft springs into three-dimensional nanofabrication offers an avenue to create biocompatible soft microrobots for non-disruptive interactions with biological entities.

Magnetotactic Sperm Cells for Assisted Reproduction.

Biohybrid micromotors are active microscopic agents consisting of biological and synthetic components that are being developed as novel tools for biomedical applications. By capturing motile sperm cells within engineered microstructures, they can be controlled remotely while being propelled forward by the flagellar beat. This makes them an interesting tool for reproductive medicine that can enable minimally invasive sperm cell delivery to the oocyte in vivo, as a treatment for infertility. The generation of sperm-based micromotors in sufficiently large numbers, as they are required in biomedical applications has been challenging, either due to the employed fabrication techniques or the stability of the microstructure-sperm coupling. Here, biohybrid micromotors, which can be assembled in a fast and simple process using magnetic microparticles, are presented. These magnetotactic sperm cells show a high motility and swimming speed and can be transferred between different environments without large detrimental effects on sperm motility and membrane integrity. Furthermore, clusters of micromotors are assembled magnetically and visualized using dual ultrasound (US)/photoacoustic (PA) imaging. Finally, a protocol for the scaled-up assembly of micromotors and their purification for use in in vitro fertilization (IVF) is presented, bringing them closer to their biomedical implementation.

Microelectronic Morphogenesis: Smart Materials with Electronics Assembling into Artificial Organisms.

Microelectronic morphogenesis is the creation and maintenance of complex functional structures by microelectronic information within shape-changing materials. Only recently has in-built information technology begun to be used to reshape materials and their functions in three dimensions to form smart microdevices and microrobots. Electronic information that controls morphology is inheritable like its biological counterpart, genetic information, and is set to open new vistas of technology leading to artificial organisms when coupled with modular design and self-assembly that can make reversible microscopic electrical connections. Three core capabilities of cells in organisms, self-maintenance (homeostatic metabolism utilizing free energy), self-containment (distinguishing self from nonself), and self-reproduction (cell division with inherited properties), once well out of reach for technology, are now within the grasp of information-directed materials. Construction-aware electronics can be used to proof-read and initiate game-changing error correction in microelectronic self-assembly. Furthermore, noncontact communication and electronically supported learning enable one to implement guided self-assembly and enhance functionality. Here, the fundamental breakthroughs that have opened the pathway to this prospective path are reviewed, the extent and way in which the core properties of life can be addressed are analyzed, and the potential and indeed necessity of such technology for sustainable high technology in society is discussed.

Fast-Response Micro-Phototransistor Based on MoS2/Organic Molecule Heterojunction.

Over the past years, molybdenum disulfide (MoS2) has been the most extensively studied two-dimensional (2D) semiconductormaterial. With unique electrical and optical properties, 2DMoS2 is considered to be a promising candidate for future nanoscale electronic and optoelectronic devices. However, charge trapping leads to a persistent photoconductance (PPC), hindering its use for optoelectronic applications. To overcome these drawbacks and improve the optoelectronic performance, organic semiconductors (OSCs) are selected to passivate surface defects, tune the optical characteristics, and modify the doping polarity of 2D MoS2. Here, we demonstrate a fast photoresponse in multilayer (ML) MoS2 by addressing a heterojunction interface with vanadylphthalocyanine (VOPc) molecules. The MoS2/VOPc van der Waals interaction that has been established encourages the PPC effect in MoS2 by rapidly segregating photo-generated holes, which move away from the traps of MoS2 toward the VOPc molecules. The MoS2/VOPc phototransistor exhibits a fast photo response of less than 15 ms for decay and rise, which is enhanced by 3ordersof magnitude in comparison to that of a pristine MoS2-based phototransistor (seconds to tens of seconds). This work offers a means to realize high-performance transition metal dichalcogenide (TMD)-based photodetection with a fast response speed.

Zn Microbatteries Explore Ways for Integrations in Intelligent Systems.

As intelligent microsystems develop, many revolutionary applications, such as the swallowing surgeon proposed by Richard Feynman, are about to evolve. Nonetheless, integrable energy storage satisfying the demand for autonomous operations has emerged as a major obstacle to the deployment of intelligent microsystems. A reason for the lagging development of integrable batteries is the challenge of miniaturization through microfabrication procedures. Lithium batteries, generated by the most successful battery chemistry, are not stable in the air, thus creating major manufacturing challenges. Other cations (Na+ , Mg2+ , Al3+ , K+ ) are still in the early stages of development. In contrast, the superior stability of zinc batteries in the air brings high compatibility to microfabrication protocols and has already demonstrated excellent practicability in full-sized devices. To obtain energy-dense and high-power zinc microbatteries within square-millimeter or smaller footprints, sandwich, pillar, and Swiss-roll configurations are developed. Thin interdigital and fiber microbatteries find their applications being integrated into wearable devices and electronic skin. It is foreseeable that zinc microbatteries will find their way into highly integrated microsystems unlocking their full potential for autonomous operation. This review summarizes the material development, configuration innovation, and application-oriented integration of zinc microbatteries.

Ultra-dense plasmonic nanogap arrays for reorientable molecular fluorescence enhancement and spectrum reshaping.

Understanding interactions between molecular transition and intense electromagnetic fields confined by plasmon nanostructures is of great significance due to their huge potential in fundamental cavity quantum electrodynamics and practical applications. Here, we report reorientable plasmon-enhanced fluorescence leveraging the flexibilities in densely-packed gold nanogap arrays by template-assisted depositions. By finely adjusting the symmetry of the unit structure, arrays of nanogaps along two nearly-orthogonal axes can be tailored collectively with spacing down to sub-10 nm on a single chip, facilitating distinct "inter-cell" and "intra-cell" plasmon couplings. Through engineering two sets of nanogaps, the varying hybridization-induced plasmonic bonding modes lead to adjustable splitting of the fluorescence emission peak with a width up to 81 nm and narrowing of linewidths up to a factor of 3. Besides, polarization anisotropy with a ratio up to 63% is obtained on the basis of spectrally separated local hotspots with discrepant oscillation directions. The developed plasmonic nanogap array is envisaged to provide a promising chip-scale, cost-effective platform for advancing fluorescence-based detection and emission technologies in both classical and quantum regimes.

Molecular Electronics: Creating and Bridging Molecular Junctions and Promoting Its Commercialization.

Molecular electronics is driven by the dream of expanding Moore's law to the molecular level for next-generation electronics through incorporating individual or ensemble molecules into electronic circuits. For nearly 50 years, numerous efforts have been made to explore the intrinsic properties of molecules and develop diverse fascinating molecular electronic devices with the desired functionalities. The flourishing of molecular electronics is inseparable from the development of various elegant methodologies for creating nanogap electrodes and bridging the nanogap with molecules. This review first focuses on the techniques for making lateral and vertical nanogap electrodes by breaking, narrowing, and fixed modes, and highlights their capabilities, applications, merits, and shortcomings. After summarizing the approaches of growing single molecules or molecular layers on the electrodes, the methods of constructing a complete molecular circuit are comprehensively grouped into three categories: 1) directly bridging one-molecule-electrode component with another electrode, 2) physically bridging two-molecule-electrode components, and 3) chemically bridging two-molecule-electrode components. Finally, the current state of molecular circuit integration and commercialization is discussed and perspectives are provided, hoping to encourage the community to accelerate the realization of fully scalable molecular electronics for a new era of integrated microsystems and applications.

Nanomaterial-decorated micromotors for enhanced photoacoustic imaging.

Micro-and nanorobots have the potential to perform non-invasive drug delivery, sensing, and surgery in living organisms, with the aid of diverse medical imaging techniques. To perform such actions, microrobots require high spatiotemporal resolution tracking with real-time closed-loop feedback. To that end,  photoacoustic imaging has appeared as a promising technique for imaging microrobots in deep tissue with higher molecular specificity and contrast. Here, we present different strategies to track magnetically-driven micromotors with improved contrast and specificity using dedicated contrast agents (Au nanorods and nanostars). Furthermore, we discuss the possibility of improving the light absorption properties of the employed nanomaterials considering possible light scattering and coupling to the underlying metal-oxide layers on the micromotor's surface. For that, 2D COMSOL simulation and experimental results were correlated, confirming that an increased spacing between the Au-nanostructures and the increase of thickness of the underlying oxide layer lead to enhanced light absorption and preservation of the characteristic absorption peak. These characteristics are important when visualizing the micromotors in a complex in vivo environment, to distinguish them from the light absorption properties of the surrounding natural chromophores. Supplementary Information: The online version contains supplementary material available at 10.1007/s12213-023-00156-7.

Single "Swiss-roll" microelectrode elucidates the critical role of iron substitution in conversion-type oxides.

Advancing the lithium-ion battery technology requires the understanding of electrochemical processes in electrode materials with high resolution, accuracy, and sensitivity. However, most techniques today are limited by their inability to separate the complex signals from slurry-coated composite electrodes. Here, we use a three-dimensional "Swiss-roll" microtubular electrode that is incorporated into a micrometer-sized lithium battery. This on-chip platform combines various in situ characterization techniques and precisely probes the intrinsic electrochemical properties of each active material due to the removal of unnecessary binders and additives. As an example, it helps elucidate the critical role of Fe substitution in a conversion-type NiO electrode by monitoring the evolution of Fe2O3 and solid electrolyte interphase layer. The markedly enhanced electrode performances are therefore explained. Our approach exposes a hitherto unexplored route to tracking the phase, morphology, and electrochemical evolution of electrodes in real time, allowing us to reveal information that is not accessible with bulk-level characterization techniques.

Microbatteries with twin-Swiss-rolls redefine performance limits in the sub-square millimeter range.

To maintain the downscaling of microelectronic devices with footprints less than one square millimeter, next-generation microbatteries should occupy the same area and deliver adequate energy for running a new generation of multi-functional microautonomous systems. However, the current microbattery technology fails in accomplishing this task because the micrometer-sized electrodes are not compatible with on-chip integration protocols and technologies. To tackle this critical challenge, an on-chip Swiss-roll microelectrode architecture is employed that exploits the self-assembly of thin films into ultra-compact device architectures. A twin-Swiss-roll microelectrode on a chip occupies a footprint of 0.045 mm2 and delivers an energy density up to 458 µW h cm-2. After packaging, the footprint of a full cell increases to 0.11 mm2 with a high energy density of 181 µW h cm-2. The volumetric energy density excluding the chip thickness is 16.3 mW h cm-3. These results open opportunities for deploying microbatteries as energy and power sources to drive smart dust microelectronics and microautonomous systems.

Multifunctional 4D-Printed Sperm-Hybrid Microcarriers for Assisted Reproduction.

Remotely controllable microrobots are appealing for various biomedical in vivo applications. In particular, in recent years, our group has focused on developing sperm-microcarriers to assist sperm cells with motion deficiencies or low sperm count (two of the most prominent male infertility problems) to reach the oocyte toward in-vivo-assisted fertilization. Different sperm carriers, considering their motion in realistic media and confined environments, have been optimized. However, the already-reported sperm carriers have been mainly designed to transport single sperm cell, with limited functionality. Thus, to take a step forward, here, the development of a 4D-printed multifunctional microcarrier containing soft and smart materials is reported. These microcarriers can not only transport and deliver multiple motile sperm cells, but also release heparin and mediate local enzymatic reactions by hyaluronidase-loaded polymersomes (HYAL-Psomes). These multifunctional facets enable in situ sperm capacitation/hyperactivation, and the local degradation of the cumulus complex that surrounds the oocyte, both to facilitate the sperm-oocyte interaction for the ultimate goal of in vivo assisted fertilization.

Direct imaging of nanoscale field-driven domain wall oscillations in Landau structures.

Linear oscillatory motion of domain walls (DWs) in the kHz and MHz regime is crucial when realizing precise magnetic field sensors such as giant magnetoimpedance devices. Numerous magnetically active defects lead to pinning of the DWs during their motion, affecting the overall behavior. Thus, the direct monitoring of the domain wall's oscillatory behavior is an important step to comprehend the underlying micromagnetic processes and to improve the magnetoresistive performance of these devices. Here, we report an imaging approach to investigate such DW dynamics with nanoscale spatial resolution employing conventional table-top microscopy techniques. Time-averaged magnetic force microscopy and Kerr imaging methods are applied to quantify the DW oscillations in Ni81Fe19 rectangular structures with Landau domain configuration and are complemented by numeric micromagnetic simulations. We study the oscillation amplitude as a function of external magnetic field strength, frequency, magnetic structure size, thickness and anisotropy and understand the excited DW behavior as a forced damped harmonic oscillator with restoring force being influenced by the geometry, thickness, and anisotropy of the Ni81Fe19 structure. This approach offers new possibilities for the analysis of DW motion at elevated frequencies and at a spatial resolution of well below 100 nm in various branches of nanomagnetism.

Collective Coupling of 3D Confined Optical Modes in Monolithic Twin Microtube Cavities Formed by Nanomembrane Origami.

We report the monolithic fabrication of twin microtube cavities by a nanomembrane origami method for achieving collective coupling of 3D confined optical modes. Owing to the well-aligned twin geometries, two sets of 3D confined optical modes in twin microtubes are spectrally and spatially matched, by which both the fundamental and higher-order axial modes are respectively coupled with each other. Multiple groups of the coupling modes provide multiple effective channels for energy exchange between coupled microcavities illustrated by the measured spatial optical field distributions. The spectral anticrossing and changing-over features of each group of coupled modes are revealed in experiments and calculations, indicating the occurrence of strong coupling. In addition, the simulated 3D mode profiles of twin microcavities confirm the collective strong coupling behavior, which shows good agreement with experiments. The collective coupling of 3D confined resonant modes promises broad applications in multichannel optical signal processing, nanophotonics, and 3D non-Hermitian systems.