Exploring role of microbatteries in enhancing sustainability and functionality of implantable biosensors and bioelectronics.

Microbatteries are emerging as a sustainable, miniaturized power source, crucial for implantable biomedical devices. Their significance lies in offering high energy density, longevity, and rechargeability, facilitating uninterrupted health monitoring and treatment within the body. The review delves into the development of microbatteries, emphasizing their miniaturization and biocompatibility, crucial for long-term, safe in-vivo use. It examines cutting-edge manufacturing techniques like physical and chemical vapor deposition, and atomic layer deposition, essential for the precision manufacture of the microbatteries. The paper contrasts primary and secondary batteries, highlighting the advantages of zinc-ion and magnesium-ion batteries for enhanced stability and reduced reactivity. It also explores biodegradable batteries, potentially obviating the need for surgical extraction post-use. The integration of microbatteries into diagnostic and therapeutic devices is also discussed, illustrating how they enhance the efficacy and sustainability of implantable biosensors and bioelectronics.

Cobalt MOF-Based Porous Carbonaceous Spheres for Multimodal Soft Actuator Exhibiting Intricate Biomimetic Motions.

The advancement of active electrode materials is essential to meet the demand for multifaceted soft robotic interactions. In this study, a new type of porous carbonaceous sphere (PCS) for a multimodal soft actuator capable of both magnetoactive and electro-ionic responses is reported. The PCS, derived from the simultaneous oxidative and reductive breakdown of specially designed cobalt-based metal-organic frameworks (Co-MOFs) with varying metal-to-ligand ratios, exhibits a high specific surface area of 529 m2 g-1 and a saturated magnetization of 142.7 Am2 kg-1. The size of the PCS can be controlled through the Ostwald ripening mechanism, while the porous structure can be regulated by adjusting the metal-to-ligand mol ratio. Its exceptional compatibility with poly(3,4-ethylene-dioxythiophene)-poly(styrenesulfonate) enables the creation of uniform electrode, crucial for producing soft actuators that work in both magnetic and electrical fields. Operated at an ultralow voltage of 1 V, the PCS-based actuator generates a blocking force of 47.5 mN and exhibits significant bending deflection even at an oscillation frequency of 10 Hz. Employing this simultaneous multimodal actuation ensures the dynamic and complex motions of a balancing bird robot and a dynamic eagle robot. This advancement marks a significant step toward the realization of more dynamic and versatile soft robotic systems.

Influence of MXene Composition on Triboelectricity of MXene-Alginate Nanocomposites.

MXenes are highly versatile and conductive 2D materials that can significantly enhance the triboelectric properties of polymer nanocomposites. Despite the growing interest in the tunable chemistry of MXenes for energy applications, the effect of their chemical composition on triboelectric power generation has yet to be thoroughly studied. Here, we investigate the impact of the chemical composition of MXenes, specifically the Ti3CNTx carbonitride vs the most studied carbide, Ti3C2Tx, on their interactions with sodium alginate biopolymer and, ultimately, the performance of a triboelectric nanogenerator (TENG) device. Our results show that adding 2 wt % of Ti3CNTx to alginate produces a synergistic effect that generates a higher triboelectric output than the Ti3C2Tx system. Spectroscopic analyses suggest that a higher oxygen and fluorine content on the surface of Ti3CNTx enhances hydrogen bonding with the alginate matrix, thereby increasing the surface charge density of the alginate oxygen atoms. This was further supported by Kelvin probe force microscopy, which revealed a more negative surface potential on Ti3CNTx-alginate, facilitating high charge transfer between the TENG electrodes. The optimized Ti3CNTx-alginate nanogenerator delivered an output of 670 V, 15 µA, and 0.28 W/m2. Additionally, we demonstrate that plasma oxidation of the MXene surface further enhances triboelectric performance. Due to the diverse surface terminations of MXene, we show that Ti3CNTx-alginate can function as either tribopositive or tribonegative material, depending on the counter-contacting material. Our findings provide a deeper understanding of how MXene composition affects their interaction with biopolymers and resulting tunable triboelectrification behavior. This opens up new avenues for developing flexible and efficient MXene-based TENG devices.

Functionally antagonistic polyelectrolyte for electro-ionic soft actuator.

Electro-active ionic soft actuators have been intensively investigated as an artificial muscle for soft robotics due to their large bending deformations at low voltages, small electric power consumption, superior energy density, high safety and biomimetic self-sensing actuation. However, their slow responses, poor durability and low bandwidth, mainly resulting from improper distribution of ionic conducting phase in polyelectrolyte membranes, hinder practical applications to real fields. We report a procedure to synthesize efficient polyelectrolyte membranes that have continuous conducting network suitable for electro-ionic artificial muscles. This functionally antagonistic solvent procedure makes amphiphilic Nafion molecules to assemble into micelles with ionic surfaces enclosing non-conducting cores. Especially, the ionic surfaces of these micelles combine together during casting process and form a continuous ionic conducting phase needed for high ionic conductivity, which boosts the performance of electro-ionic soft actuators by 10-time faster response and 36-time higher bending displacement. Furthermore, the developed muscle shows exceptional durability over 40 days under continuous actuation and broad bandwidth below 10 Hz, and is successfully applied to demonstrate an inchworm-mimetic soft robot and a kinetic tensegrity system.

Role of a cyclopentadienyl ligand in a heteroleptic alkoxide precursor in atomic layer deposition.

Alkoxide precursors have been highlighted for depositing carbon-free films, but their use in Atomic Layer Deposition (ALD) often exhibits a non-saturated growth. This indicates no self-limiting growth due to the chain reaction of hydrolysis or ligand decomposition caused by ß-hydride elimination. In the previous study, we demonstrated that self-limiting growth of ALD can be achieved using our newly developed precursor, hafnium cyclopentadienyl tris(N-ethoxy-2,2-dimethyl propanamido) [HfCp(edpa)3]. To elucidate the growth mechanism and the role of cyclopentadienyl (Cp) ligand in a heteroleptic alkoxide precursor, herein, we compare homoleptic and heteroleptic Hf precursors consisting of N-ethoxy-2,2-dimethyl propanamido (edpa) ligands with and without cyclopentadienyl ligand-hafnium tetrakis(N-ethoxy-2,2-dimethyl propanamido) [Hf(edpa)4] and HfCp(edpa)3. We also investigate the role of a Cp ligand in growth characteristics. By substituting an alkoxide ligand with a Cp ligand, we could modify the surface reaction during ALD, preventing undesired reactions. The last remaining edpa after Hf(edpa)4 adsorption can undergo a hydride elimination reaction, resulting in surface O-H generation. In contrast, Cp remains after the HfCp(edpa)3 adsorption. Accordingly, we observe proper ALD growth with self-limiting properties. Thus, a comparative study of different ligands of the precursors can provide critical clues to the design of alkoxide precursors for obtaining typical ALD growth with a saturation behavior.

Janus CoMOF-SEBS Membrane for Bifunctional Dielectric Layer in Triboelectric Nanogenerators.

Considerable research has been conducted on the application of functional nano-fillers to enhance the power generation capabilities of triboelectric nanogenerators (TENGs). However, these additives often exhibit a decrease in output power at higher concentration. Here, a Janus cobalt metal-organic framework-SEBS (JCMS) membrane is reported as a dual-purpose dielectric layer capable of efficiently capturing and blocking charges for high-performance TENGs. The JCMS is produced asymmetrically through gravitational sedimentation, employing spherical CoMOFs within a diluted SEBS solution. Beyond its dual dielectric characteristics, the JCMS showcases exceptional mechanical durability, displaying notable stretchability of up to 475% and remarkable resilience when subjected to diverse mechanical pressures. Consequently, the JCMS-TENG produces a maximum peak-to-peak voltage of 936 V, a current of 42.8 µA, and a power density of 10.89 W m- 2 when exposed to an external force of 10 N at a 5 Hz frequency. This investigation highlights the potential of JCMS-TENGs with unique structures, known for their exceptional energy harvesting capabilities, mechanical strength, and flexibility. Additionally, the promising prospects of easily produced asymmetric structures is emphasized with bifunctionalities for developing efficient and flexible MOFs-based TENGs. These advancements are well-suited for self-powered wearables, rehabilitation devices, and energy harvesters.

Polysulfonated covalent organic framework as active electrode host for mobile cation guests in electrochemical soft actuator.

Tailoring transfer dynamics of mobile cations across solid-state electrolyte-electrode interfaces is crucial for high-performance electrochemical soft actuators. In general, actuation performance is directly proportional to the affinity of cations and anions in the electrolyte for the opposite electrode surfaces under an applied field. Herein, to maximize electrochemical actuation, we report an electronically conjugated polysulfonated covalent organic framework (pS-COF) used as a common electrolyte-electrode host for 1-ethyl-3-methylimidazolium cation embedded into a Nafion membrane. The pS-COF-based electrochemical actuator exhibits remarkable bending deflection at near-zero voltage (~0.01 V) and previously unattainable blocking force, which is 34 times higher than its own weight. The ultrafast step response shows a very short rising time of 1.59 seconds without back-relaxation, and substantial ultralow-voltage actuation at higher frequencies up to 5.0 hertz demonstrates good application prospects of common electrolyte-electrode hosts. A soft fluidic switch is constructed using the proposed soft actuator as a potential engineering application.

Effective Approach for Fabricating Highly Precise High-Curvature Structural Patterns via Air-Bubble Induction.

Developing a new master mold-based patterning technology that can be used to accurately, precisely, and uniformly create large-area micropatterns while controlling the micropatterns of curved structures is essential for promoting innovative developments in various application fields. This study develops a new top-down lithographic process that can effectively produce structural patterns with high curvatures by growing isolated microbubbles in the master pattern holes. The isolated air-pocket lithography (IAL) we developed is based on the controlled behavior of micrometer-sized air pockets trapped between the grooves of the master pattern and the curable polymer. We successfully fabricated a concave array polydimethylsiloxane (PDMS) film and a convex array polymer film. In addition, the IAL mechanism was proven by confirming the expansion process of micrometer-sized air pockets trapped between the deep groove of the silicon master pattern and the PDMS coating film by using optical microscopy images. We successfully obtained complex three-dimensional structural patterns containing both 3D hollow spherical concave and ring-shaped two-dimensional convex patterns. This simple, fast, and effective high-curvature patterning technique is expected to provide innovative solutions for future applications such as nanoelectronics, optical devices, displays, and photovoltaics.

Area-Selective Atomic Layer Deposition for Resistive Random-Access Memory Devices.

Resistive random-access memory (RRAM) is a promising technology for data storage and neuromorphic computing; however, cycle-to-cycle and device-to-device variability limits its widespread adoption and high-volume manufacturability. Improving the structural accuracy of RRAM devices during fabrication can reduce these variabilities by minimizing the filamentary randomness within a device. Here, we studied area-selective atomic layer deposition (AS-ALD) of the HfO2 dielectric for the fabrication of RRAM devices with higher reliability and accuracy. Without requiring photolithography, first we demonstrated ALD of HfO2 patterns uniformly and selectively on Pt bottom electrodes for RRAM but not on the underlying SiO2/Si substrate. RRAM devices fabricated using AS-ALD showed significantly narrower operating voltage range (2.6 × improvement) and resistance states than control devices without AS-ALD, improving the overall reliability of RRAM. Irrespective of device size (1 × 1, 2 × 2, and 5 × 5 µm2), we observed similar improvement, which is an inherent outcome of the AS-ALD technique. Our demonstration of AS-ALD for improved RRAM devices could further encourage the adoption of such techniques for other data storage technologies, including phase-change, magnetic, and ferroelectric RAM.

Easy-To-Wear Auxetic SMA Knot-Architecture for Spatiotemporal and Multimodal Haptic Feedbacks.

Wearable haptic interfaces prioritize user comfort, but also value the ability to provide diverse feedback patterns for immersive interactions with the virtual or augmented reality. Here, to provide both comfort and diverse tactile feedback, an easy-to-wear and multimodal wearable haptic auxetic fabric (WHAF) is prepared by knotting shape-memory alloy wires into an auxetic-structured fabric. This unique meta-design allows the WHAF to completely expand and contract in 3D, providing superior size-fitting and shape-fitting capabilities. Additionally, a microscale thin layer of Parylene is coated on the surface to create electrically separated zones within the WHAF, featuring zone-specified actuation for conveying diverse spatiotemporal information to users with using the WHAF alone. Depending on the body part it is worn on, the WHAF conveys either cutaneous or kinesthetic feedback, thus, working as a multimodal wearable haptic interface. As a result, when worn on the forearm, the WHAF intuitively provides spatiotemporal information to users during hands-free navigation and teleoperation in virtual reality, and when worn on the elbow, the WHAF guides users to reach the desired elbow flexion, like a personal exercise advisor.

Physicochemically Interlocked Sulfur Covalent Triazine Framework for Lithium-Sulfur Batteries with Exceptional Longevity.

An electronically conjugated functional triazine framework is used to synthesize a physicochemically interlocked sulfur cathode that delivers high energy density coupled with exceptional cycle life in lithium-sulfur batteries. Conventional melt-diffusion strategies to impregnate sulfur in the cathode offer poor cycle life due to physical mixing with weak interactions. By contrast, in this approach, sulfur is physicochemically entrapped within a nanoporous and heteroatom doped high surface area covalent triazine framework, resulting in outstanding electrochemical performance (≈89% capacity retention after 1000 cycles, the energy density of ≈2,022 Wh kg-1 sulfur and high-rate capability up to 12 C). The overall structural characteristics and interactions of sulfur with the covalent triazine framework are explored in detail to explain the intriguing properties of the sulfur cathode.

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.

Magnetically and Electrically Responsive Soft Actuator Derived from Ferromagnetic Bimetallic Organic Framework.

The advancement in smart devices and soft robotics necessitates the use of multiresponsive soft actuators with high actuation stroke and stable reversibility for their use in real-world applications. Here, this work reports a magnetically and electrically dual responsive soft actuator based on neodymium and iron bimetallic organic frameworks (NdFeMOFs@700). The ferromagnetic NdFeMOFs@700 exhibits a porous carbon structure with excellent magnetization saturation (166.96 emu g-1 ) which allows its application to a dual functional material in both magnetoactive and electro-ionic actuations. The electro-ionic soft actuator, which is fabricated using NdFeMOFs@700 and PEDOT-PSS, demonstrates 4.5 times higher ionic charge storage capacity (68.21 mF cm-2 ) and has excellent cycle stability compared with the PEDOT-PSS based actuator. Under a low sinusoidal input voltage of 1 V, the dual-responsive actuator displays bending displacement of 15.46 mm and also generates deflection of 10 mm at 50 mT. Present results show that the ferromagnetic bimetallic organic frameworks can open a new way to make dual responsive soft actuators due to the hierarchically porous structures with its high redox activity, superior magnetic properties, and larger electrochemical capacitance. With the NdFeMOFs@700 based soft actuators, walking movement of a starfish robot is demonstrated by applying both the magnetic and electric fields.

Unveiling the Effect of Superlattice Interfaces and Intermixing on Phase Change Memory Performance.

Superlattice (SL) phase change materials have shown promise to reduce the switching current and resistance drift of phase change memory (PCM). However, the effects of internal SL interfaces and intermixing on PCM performance remain unexplored, although these are essential to understand and ensure reliable memory operation. Here, using nanometer-thin layers of Ge2Sb2Te5 and Sb2Te3 in SL-PCM, we uncover that both switching current density (Jreset) and resistance drift coefficient (v) decrease as the SL period thickness is reduced (i.e., higher interface density); however, interface intermixing within the SL increases both. The signatures of distinct versus intermixed interfaces also show up in transmission electron microscopy, X-ray diffraction, and thermal conductivity measurements of our SL films. Combining the lessons learned, we simultaneously achieve low Jreset ≈ 3-4 MA/cm2 and ultralow v ≈ 0.002 in mushroom-cell SL-PCM with ∼110 nm bottom contact diameter, thus advancing SL-PCM technology for high-density storage and neuromorphic applications.

Elucidating the Reaction Mechanism of Atomic Layer Deposition of Al2O3 with a Series of Al(CH3)xCl3-x and Al(CyH2y+1)3 Precursors.

The adsorption of metalorganic and metal halide precursors on the SiO2 surface plays an essential role in thin-film deposition processes such as atomic layer deposition (ALD). In the case of aluminum oxide (Al2O3) films, the growth characteristics are influenced by the precursor structure, which controls both chemical reactivity and the geometrical constraints during deposition. In this work, a systematic study using a series of Al(CH3)xCl3-x (x = 0, 1, 2, and 3) and Al(CyH2y+1)3 (y = 1, 2, and 3) precursors is carried out using a combination of experimental spectroscopic techniques together with density functional theory calculations and Monte Carlo simulations to analyze differences across precursor molecules. Results show that reactivity and steric hindrance mutually influence the ALD surface reaction. The increase in the number of chlorine ligands in the precursor shifts the deposition temperature higher, an effect attributed to more favorable binding of the intermediate species due to higher Lewis acidity, while differences between precursors in film growth per cycle are shown to originate from variations in adsorption activation barriers and size-dependent saturation coverage. Comparison between the theoretical and experimental results indicates that the Al(CyH2y+1)3 precursors are favored to undergo two ligand exchange reactions upon adsorption at the surface, whereas only a single Cl-ligand exchange reaction is energetically favorable upon adsorption by the AlCl3 precursor. By pursuing the first-principles design of ALD precursors combined with experimental analysis of thin-film growth, this work enables a robust understanding of the effect of precursor chemistry on ALD processes.

A Dual-Responsive Magnetoactive and Electro-Ionic Soft Actuator Derived from a Nickel-Based Metal-Organic Framework.

There is growing demand for multiresponsive soft actuators for the realization of natural, safe, and complex motions in robotic interactions. In particular, soft actuators simultaneously stimulated by electrical and magnetic fields are always under development owing to their simple controllability and reliability during operation. Herein, magnetically and electrically driven dual-responsive soft actuators (MESAs) derived from novel nickel-based metal-organic frameworks (Ni-MOFs-700C), are reported. Nanoscale Ni-MOFs-700C has excellent electrochemical and magnetic properties that allow it to be used as a multifunctional material under both magnetoactive and electro-ionic actuations. The dual-responsive MESA exhibits a bending displacement of 30 mm and an ultrafast rising time of 1.5 s under a very low input voltage of 1 V and also exerts a bending deflection of 12.5 mm at 50 mT under a high excitation frequency of 5 Hz. By utilizing a dual-responsive MESA, the hovering motion of a hummingbird robot is demonstrated under magnetic and electrical stimuli.

Spherical Micro/Nano Hierarchical Structures for Energy and Water Harvesting Devices.

Three-dimensional (3D) hierarchical structures have been explored for various applications owing to the synergistic effects of micro- and nanostructures. However, the development of spherical micro/nano hierarchical structures (S-HSs), which can be used as energy/water harvesting systems and sensing devices, remains challenging owing to the trade-off between structural complexity and fabrication difficulty. This paper presents a new strategy for facile, scalable S-HS fabrication using a thermal expansion of microspheres and nanopatterned structures. When a specific temperature is applied to a composite film of microspheres and elastomers with nanopatterned surfaces, microspheres are expanded and 3D spherical microstructures are generated. Various nanopatterns and densities of spherical microstructures can thereby be quantitatively controlled. The fabricated S-HSs have been used in renewable electrical energy harvesting and sustainable water management applications. Compared to a triboelectric nanogenerator (TENG) with bare film, the S-HS-based TENG exhibited 4.48 times higher triboelectric performance with high mechanical durability. Furthermore, an S-HS is used as a water harvesting device to capture water in a fog environment. The water collection rate is dramatically enhanced by the increased surface area and locally concentrated vapor diffusion flux due to the spherical microstructures.

Antagonistically Functionalized Diatom Biosilica for Bio-Triboelectric Generators.

Although biomaterial-based triboelectric nanogenerators (Bio-TENGs) for use in wearable electronics and implantable sensors have been developed, power generation is not suitable for satisfying the basic requirements for practical applications. Here, to greatly enhance output performances of Bio-TENG devices, an antagonistic approach of diatom frustules (DFs) with amine and fluorine chemical functionalizations is reported. The DFs are treated with piranha solution to increase the density of hydroxyl groups and tribo-positive and tribo-negative composite films are designed with antagonistically functionalized DFs. The tribo-positive composites having electron donating functionality consist of aminated DFs and cellulose nanocrystals (CNCs), while the tribo-negative composite is composed of fluorinated DFs and polydimethylsiloxane (PDMS). An antagonistically and chemically functionalized TENG (ACF TENG) with an efficient contact area of 9.6 cm2 under a force of 8 N and a frequency of 5 Hz exhibits an output voltage of 248 V, a short-circuit current of 16.4 µA, and a power density of 2.01 W m-2 , which is 16.6 times higher than a reference (CNC:PDMS) TENG. This study shows a simple antagonistic approach for chemical functionalization as an efficient method to manipulate the tribo-polarity of bio-additives for enhancing power generation of Bio-TENGs.

Electro-Active and Photo-Active Vanadium Oxide Nanowire Thermo-Hygroscopic Actuators for Kirigami Pop-up.

Emerging technologies such as soft robotics, active biomedical devices, wearable electronics, haptic feedback systems, and healthcare systems require high-fidelity soft actuators showing reliable responses under multi-stimuli. In this study, the authors report an electro-active and photo-active soft actuator based on a vanadium oxide nanowire (VONW) hybrid film with greatly improved actuation performances. The VONWs directly grown on a cellulose fiber network increase the surface area up to 30-fold and boost the hydrophilicity owing to the presence of oxygen-rich functional groups in the nanowire surfaces. Taking advantage of the high surface area and hydrophilicity of VONWs, a soft thermo-hygroscopic VONW actuator capable of being controlled by both light and electric sources shows greatly enhanced actuation deformation by almost 70% and increased actuation speed over 3 times during natural convection cooling. Most importantly, the proposed VONW actuator exhibits a remarkably improved blocking force of up to 200% compared with a bare paper actuator under light stimulation, allowing them to realize a complex kirigami pop-up and to accomplish repeatable shape transformation from a 2D planar surface to a 3D configuration.

Boosting Oxygen Evolution Reaction on Metallocene-based Transition Metal Sulfides Integrated with N-doped Carbon Nanostructures.

In this study, utilizing metallocene and organosulfur chelating agent, an innovative synthetic route was developed towards electrochemically activated transition metal sulfides entrapped in pyridinic nitrogen-incorporated carbon nanostructures for superior oxygen evolution reaction (OER). Most importantly, the preferential electrochemical activation process, which consisted of both anodic and cathodic pre-treatment steps, strikingly enhanced OER and long-lasting cyclic stability. The substantial increase in OER electrocatalytic activity of Ni9 S8 /Ni3 S2 -NC and Co9 S8 -NC during the activation process was mainly attributed to the increase of faradaic active site density on the catalytic layer resulting from the reconstruction of catalytic interfaces. It was also found that Fe-based metallocene [ferrocene (Fc)]-incorporation in the Co9 S8 -NC and Ni9 S8 /Ni3 S2 -NC nanostructures significantly boosted the OER activity. Thus, the combined effects of Fc-incorporation and the electrochemical activation process reduced the overpotential to about 115 and 95 mV on the Ni9 S8 /Ni3 S2 -NC and Co9 S8 -NC nanostructures to derive a current density of 10 mA cm-2 , respectively. Notably, Fc-Ni9 S8 /Ni3 S2 -NC electrocatalysts required very small overpotentials of around 222, 244, and 280 mV to acquire the current densities of 10, 20, and 50 mA cm-2 , respectively. This work opens up a new avenue for superior OER electrocatalysts by the utilization of metallocene and the preferential electrochemical activation process.