Particle-assisted formation of oil-in-liquid metal emulsions.

Gallium-based liquid metals (LMs) have surface tension an order of magnitude higher than water and break up into micro-droplets when mixed with other liquids. In contrast, silicone oil readily mixes into LM foams to create oil-in-LM emulsions with oil inclusions. Previously, the LM was foamed through rapid mixing in air for an extended duration (over 2 h). This process first results in the internalization of oxide flakes that form at the air-liquid interface. Once a critical fraction of these randomly shaped solid flakes is reached, air bubbles internalize into the LM to create foams that can internalize secondary liquids. Here, we introduce an alternative oil-in-LM emulsion fabrication method that relies on the prior addition of SiO2micro-particles into the LM before mixing it with the silicone oil. This particle-assisted emulsion formation process provides a higher control over the composition of the LM-particle mixture before oil addition, which we employ to systematically study the impact of particle characteristics and content on the emulsions' composition and properties. We demonstrate that the solid particle size (0.8µm to 5µm) and volume fraction (1%-10%) have a negligible impact on the internalization of the oil inclusions. The inclusions are mostly spherical with diameters of 20-100µm diameter and are internalized by forming new, rather than filling old, geometrical features. We also study the impact of the particle characteristics on the two key properties related to the functional application of the LM emulsions in the thermal management of microelectronics. In particular, we measure the impact of particles and silicone oil on the emulsion's thermal conductivity and its ability to prevent deleterious gallium-induced corrosion and embrittlement of contacting metal substrates.

A highly stretchable smart dressing for wound infection monitoring and treatment.

Smart dressings integrated with bioelectronics have attracted considerable attention and become promising solutions for skin wound management. However, due to the mechanical distinction between human body and the interface of electronics, previous smart dressings often suffered obvious degradation in electrical performance when attached to the soft and curvilinear wound sites. Here, we report a stretchable dressing integrated with temperature and pH sensor for wound status monitoring, as well as an electrically controlled drug delivery system for infection treatment. The wound dressing was featured with the deployment of liquid metal for seamless connection between rigid electrical components and gold particle-based electrodes, achieving a stretchable soft-hard interface. Stretching tests showed that both the sensing system and drug delivery system exhibited good stretchability and long-term stable conductivity with the resistance change rate less than 6 % under 50 % strain. Animal experiments demonstrated that the smart dressing was capable of detecting bacterial infection via the biomarkers of temperature and pH value and the infection factors of wound were significantly improved with therapy through electrically controlled antibiotics releasing. This proof-of-concept prototype has potential to significantly improve management of the wound, especially those with dynamic strain.

Highly stretchable, self-healing, antibacterial, conductive, and amylopectin-enhanced hydrogels with gallium droplets loading as strain sensors.

In this study, we address the challenge of developing highly conductive hydrogels with enhanced stretchability for use in wearable sensors, which are critical for the precise detection of human motion and subtle physiological strains. Our novel approach utilizes amylopectin, a biopolymer, for the uniform integration of liquid metal gallium into the hydrogel matrix. This integration results in a conductive hydrogel characterized by remarkable elasticity (up to 7100 % extensibility) and superior electrical conductance (Gauge Factor = 31.4), coupled with a minimal detection limit of less than 0.1 % and exceptional durability over 5000 cycles. The hydrogel demonstrates significant antibacterial activity, inhibiting microbial growth in moist environments, thus enhancing its applicability in medical settings. Employing a synthesis process that involves ambient condition polymerization of acrylic acid, facilitated by a hydrophobic associative framework, this hydrogel stands out for its rapid gelation and robust mechanical properties. The potential applications of this hydrogel extend beyond wearable sensors, promising advancements in human-computer interaction through technologies like wireless actuation of robotic systems. This study not only introduces a viable material for current wearable technologies but also sets a foundation for future innovations in bio-compatible sensors and interactive devices.

Electrically Driven Deterministic Plasmon Light Sources Based on Arrays of Molecular Tunnel Junctions.

Surface plasmons excited via inelastic tunnelling have led to plasmon light sources with small footprints and ultrafast response speeds, which are favored by integrated optical circuits. Self-assembled monolayers of organic molecules function as highly tunable tunnel barriers with novel functions. However, limited by the low effective contact between the liquid metal electrode and the self-assembled monolayers, it is quite challenging to obtain molecular plasmon light sources with high density and uniform emission. Here, by combining lithographic patterning with a solvent treatment method, we have demonstrated electrically driven deterministic plasmon emission from arrays of molecular tunnel junctions. The solvent treatment could largely improve the effective contact from 9.6% to 48% and simultaneously allow the liquid metal to fill into lithographically patterned micropore structures toward deterministic plasmon emission with desired patterns. Our findings open up new possibilities for tunnel junction-based plasmon light sources, laying the foundation for electrically driven light-emitting metasurfaces.

Semi-liquid metal-based highly permeable and adhesive electronic skin inspired by spider web.

Soft and stretchable electronics have garnered significant attention in various fields, such as wearable electronics, electronic skins, and soft robotics. However, current wearable electronics made from materials like conductive elastomers, hydrogels, and liquid metals face limitations, including low permeability, poor adhesion, inadequate conductivity, and limited stretchability. These issues hinder their effectiveness in long-term healthcare monitoring and exercise monitoring. To address these challenges, we introduce a novel design of web-droplet-like electronics featuring a semi-liquid metal coating for wearable applications. This innovative design offers high permeability, excellent stretchability, strong adhesion, and good conductivity for the electronic skin. The unique structure, inspired by the architecture of a spider web, significantly enhances air permeability compared to commercial breathable patches. Furthermore, the distribution of polyborosiloxane mimics the adhesive properties of spider web mucus, while the use of semi-liquid metals in this design results in remarkable conductivity (9 × 106 S/m) and tensile performance (up to 850% strain). This advanced electronic skin technology enables long-term monitoring of various physiological parameters and supports machine learning recognition functions with unparalleled advantages. This web-droplet structure design strategy holds great promise for commercial applications in medical health monitoring and disease diagnosis.

Design and Dynamic In Vivo Validation of a Multi-Channel Stretchable Liquid Metal Coil Array.

Recent developments in the field of radiofrequency (RF) coils for magnetic resonance imaging (MRI) offer flexible and patient-friendly solutions. Previously, we demonstrated a proof-of-concept single-element stretchable coil design based on liquid metal and a self-tuning smart geometry. In this work, we numerically analyze and experimentally study a multi-channel stretchable coil array and demonstrate its application in dynamic knee imaging. We also compare our flexible coil array to a commonly used commercial rigid coil array. Our numerical analysis shows that the proposed coil array maintains its resonance frequency (<1% variation) and sensitivity (<6%) at various stretching configurations from 0% to 30%. We experimentally demonstrate that the signal-to-noise ratio (SNR) of the acquired MRI images is improved by up to four times with the stretchable coil array due to its conformal and therefore tight-fitting nature. This stretchable array allows for dynamic knee imaging at different flexion angles, infeasible with traditional, rigid coil arrays. These findings are significant as they address the limitations of current rigid coil technology, offering a solution that enhances patient comfort and image quality, particularly in applications requiring dynamic imaging.

Liquid Metal Interlayer for Ultrastable Solid-State Sodium Metal Battery.

Solid-state sodium metal batteries have attracted wide attention due to their high energy density, remarkable safety, and abundant sodium resources. However, the growth of Na dendrites and poor interfacial contact between Na metal anode and Na3Zr2Si2PO12 (NZSP) solid-state electrolytes severely limit their practical application. Herein, a wettable liquid metal (GaIn) interlayer significantly reduces the interfacial resistance and avoids the formation of voids at the Na/NZSP interface. Moreover, the Ga4Na and NaIn alloys at the interface caused by the spontaneous reaction of GaIn with Na metal enhance the bond of NZSP with Na anode, which provides a continuous Na+ diffusion pathway and homogeneous Na+ flux to suppress Na dendrite growth. The symmetric cell can cycle stably for over 6500 h at 0.05 mA cm-2 and over 3000 h at 0.1 mA cm-2, with a critical current density of 0.8 mA cm-2 at 25 °C, and the interfacial resistance is significantly reduced to 21.6 Ω from 1095.1 Ω. The full cell coupled with NaNi1/3Fe1/3Mn1/3O2 also shows outstanding cycling performance, maintaining 85.1% capacity after 100 cycles at 0.5 C. This work demonstrates that the liquid metal interlayer has a large potential for the practical application of solid-state metal batteries.

Trash into Treasure: Nano-coating of Catheter Utilizes Urine to Deprive H2S Against Persister and Rip Biofilm Matrix.

Bacteria-derived hydrogen sulfide (H2S) often contributes to the emergence of antibiotic-recalcitrant bacteria, especially persister (a sub-population of dormant bacteria), thus causing the treatment failure of Catheter-associated urinary tract infection (CAUTI). Here, an H2S harvester nanosystem to prevent the generation of persister bacteria and disrupt the dense biofilm matrix by the self-adaptive ability of shape-morphing is prepared. The nanosystem possesses a core-shell structure that is composed of liquid metal nanoparticle (LM NP), AgNPs, and immobilized urease. The nanosystem decomposes urea contained in urine to generate ammonia for eliminating bacteria-derived H2S. Depending on the oxidative layer of liquid metal, the nanosystem also constitutes a long-lasting reservoir for temporarily storing bacteria-derived H2S, when urease transiently overloads or in the absence of urine in a catheter. Depriving H2S can prevent the emergence of persistent bacteria, enhancing the bacteria-killing efficiency of Ga3+ and Ag+ ions. Even when the biofilm has formed, the urine flow provides heat to trigger shape morphing of the LM NP, tearing the biofilm matrix. Collectively, this strategy can turn trash (urea) into treasure (H2S scavengers and biofilm rippers), and provides a new direction for the antibacterial materials application in the medical field.

Electrophysiological Analysis of Retinal Organoid Development Using 3D Microelectrodes of Liquid Metals.

Despite of the substantial potential of human-derived retinal organoids, the degeneration of retinal ganglion cells (RGCs) during maturation limits their utility in assessing the functionality of later-born retinal cell subtypes. Additionally, conventional analyses primarily rely on fluorescent emissions, which limits the detection of actual cell functionality while risking damage to the 3D cytoarchitecture of organoids. Here, an electrophysiological analysis is presented to monitor RGC development in early to mid-stage retinal organoids, and compare distinct features with fully-mature mouse retina. This approach utilizes high-resolution 3D printing of liquid-metal microelectrodes, enabling precise targeting of specific inner retinal layers within organoids. The adaptable distribution and softness of these microelectrodes facilitate the spatiotemporal recording of inner retinal signals. This study not only demonstrates the functional properties of RGCs in retinal organoid development but also provides insights into their synaptic connectivity, reminiscent of fetal native retinas. Further comparison with fully-mature mouse retina in vivo verifies the organoid features, highlighting the potential of early-stage retinal organoids in biomedical research.

Gallium-Carbon: A Universal Composite for Sustainable 3D Printing of Integrated Sensor-Heater-Battery Systems in Wearable and Recyclable Electronics.

This study presents a novel three-dimensional (3D) printable gallium-carbon black-styrene isoprene styrene block copolymer (Ga-CB-SIS), offering a versatile solution for the rapid fabrication of stretchable and integrated sensor-heater-battery systems in wearable and recyclable electronics. The composite exhibits sinter-free characteristics, allowing for printing on various substrates, including heat-sensitive materials. Unlike traditional conductive inks, the Ga-CB-SIS composite, composed of gallium, carbon black, and styrene isoprene block copolymers, combines electrical conductivity, stretchability, and digital printability. By introducing carbon black as a filler material, the composite achieves promising electromechanical behavior, making it suitable for low-resistance heaters, batteries, and electrical interconnects. The fabrication process involves a simultaneous mixing and ball-milling technique, resulting in a homogeneous composition with a CB/Ga ratio of 4.3%. The Ga-CB-SIS composite showcases remarkable adaptability for digital printing on various substrates. Its self-healing property and efficient recycling technique using a deep eutectic solvent contribute to an environmentally conscious approach to electronic waste, with a high gallium recovery efficiency of ∼98%. The study's innovation extends to applications, presenting a fully digitally printed stretchable Ga-CB-SIS battery integrated with strain sensors and heaters, representing a significant leap in LM-based composites. This multifunctional and sustainable Ga-CB-SIS composite emerges as a key player in the future of wearable electronics, offering integrated circuits with sensing, heating, and energy storage elements.

Bulge-Free and Homogeneous Metal Line Jet Printing with StarJet Technology.

The technology to jet print metal lines with precise shape fidelity on diverse substrates is gaining higher interest across multiple research fields. It finds applications in additively manufactured flexible electronics, environmentally friendly and sustainable electronics, sensor devices for medical applications, and fabricating electrodes for solar cells. This paper provides an experimental investigation to deepen insights into the non-contact printing of solder lines using StarJet technology, eliminating the need for surface activation, substrate heating, curing, or post-processing. Moreover, it employs bulk metal instead of conventional inks or pastes, leading to cost-effective production and enhanced conductivity. The effect of molten metal temperature, substrate temperature, standoff distance, and printing velocity was investigated on polymer foils (i.e., PET sheets). Robust printing parameters were derived to print uniform, bulge-free, bulk metal lines suitable for additive manufacturing applications. The applicability of the derived parameters was extended to 3D-printed PLA, TPU, PA-GF, and PETG substrates having a much higher surface roughness. Additionally, a high aspect ratio of approx. 16:1 wall structure has been demonstrated by printing multiple metal lines on top of each other. While challenges persist, this study contributes to advancing additively manufactured electronic devices, highlighting the capabilities of StarJet metal jet-printing technology.

Liquid-metal-based microfluidic nanoplasmonic platform for point-of-care naked-eye antibody detection.

Despite high sensitivity of nanoparticle-on-mirror cavities, a crucial branch of plasmonic nanomaterials, complex preparation and readout processes limit their extensive application in biosensing. Alternatively, liquid metals (LMs) combining fluidity and excellent plasmonic characteristics have become potential candidates for constructing plasmonic nanostructures. Herein, we propose a microfluidic-integration strategy to construct LM-based immunoassay platform, enabling LM-based nanoplasmonic sensors to be used for point-of-care (POC) clinical biomarker detection. Flowable LM is introduced onto protein-coated Au nanoparticle monolayer to form a "mirror-on-nanoparticle" nanostructure, simplifying the fabrication process in the conventional nanoparticle-on-mirror cavities. When antibodies were captured by antigens coated on the Au nanoparticle monolayer, devices respond both thickness and refractive index change of biomolecular layers, outputting naked-eye readable signals with high sensitivity (limit of detection: ∼ 604 fM) and a broad dynamic range (6 orders). This new assay, which generates quantitative results in 30 min, allows for high-throughput, smartphone-based detection of SARS-CoV-2 antibodies against multiple variants in clinical serum or blood samples. These results establish an advanced avenue for POC testing with LM materials, and demonstrate its potential to facilitate diagnostics, surveillance and prevalence studies for various infectious diseases.

Microconfined Assembly of High-Resolution and Mechanically Robust EGaIn Liquid Metal Stretchable Electrodes for Wearable Electronic Systems.

Stretchable electrodes based on liquid metals (LM) are widely used in human-machine interfacing, wearable bioelectronics, and other emerging technologies. However, realizing the high-precision patterning and mechanical stability remains challenging due to the poor wettability of LM. Herein, a method is reported to fabricate LM-based multilayer solid-liquid electrodes (m-SLE) utilizing electrohydrodynamic (EHD) printed confinement template. In these electrodes, LM self-assembled onto these high-resolution templates, assisted by selective wetting on the electrodeposited Cu layer. This study shows that a m-SLE composed of PDMS/Ag/Cu/EGaIn exhibits line width of ≈20 µm, stretchability of ≈100%, mechanical stability ≈10 000 times (stretch/relaxation cycles), and recyclability. The multi-layer structure of m-SLE enables the adjustability of strain sensing, in which the strain-sensitive Ag part can be used for non-distributed detection in human health monitoring and the strain-insensitive EGaIn part can be used as interconnects. In addition, this study demonstrates that near field communication (NFC) devices and multilayer displays integrated by m-SLEs exhibit stable wireless signal transmission capability and stretchability, suggesting its applicability in creating highly-integrated, large-scale commercial, and recyclable wearable electronics.

Long-Term Corrosion of Eutectic Gallium, Indium, and Tin (EGaInSn) Interfacing with Diamond.

Thermal transport is of grave importance in many high-value applications. Heat dissipation can be improved by utilizing liquid metals as thermal interface materials. Yet, liquid metals exhibit corrosivity towards many metals used for heat sinks, such as aluminum, and other electrical devices (i.e., copper). The compatibility of the liquid metal with the heat sink or device material as well as its long-term stability are important performance variables for thermal management systems. Herein, the compatibility of the liquid metal Galinstan, a eutectic alloy of gallium, indium, and tin, with diamond coatings and the stability of the liquid metal in this environment are scrutinized. The liquid metal did not penetrate the diamond coating nor corrode it. However, the liquid metal solidified with the progression of time, starting from the second year. After 4 years of aging, the liquid metal on all samples solidified, which cannot be explained by the dissolution of aluminum from the titanium alloy. In contrast, the solidification arose from oxidation by oxygen, followed by hydrolysis to GaOOH due to the humidity in the air. The hydrolysis led to dealloying, where In and Sn remained an alloy while Ga separated as GaOOH. This hydrolysis has implications for many devices based on gallium alloys and should be considered during the design phase of liquid metal-enabled products.

High-Entropy Alloy Array via Liquid Metal Nanoreactor.

High-entropy alloy (HEA) nanostructures arranged into well-defined configurations hold great potential for accelerating the development of electronics, photonics, catalysis, and device integration. However, the random nucleation induced by the disparity in physicochemical properties of multiple elements makes it challenging to achieve single-particle synthesis at the patterned preset sites in the high-entropy scenario. Herein, the liquid metal nanoreactor strategy is proposed to realize the construction of HEA arrays. The coalescence of the liquid metal driven by the tendency to decrease surface energy provides a restricted environment for the nucleation and growth to form single HEA particles at the preset locations, which can be regarded as a self-confinement reaction. Liquid metal endowing a low diffusion energy barrier on the substrate and a high diffusivity of the alloy system can dynamically promote the aggregation process. As a result, the HEA array is prepared with elements up to eleven and possesses uniform periodicity, which exhibits excellent holography response in a broad spectrum. This work injects new vitality into the construction of HEA nanopatterns and provides an excellent platform for propelling their fundamental research and applications.

Van der Waals Encapsulation by Ultra-thin Oxide for Air-Sensitive 2D Materials.

The ambient stability is one of the focal points for applications of 2D materials, especially for those well-known air-sensitive ones such as black phosphorus (BP) and transitional metal telluride. Traditional methods of encapsulation, such as atomic layer deposition of oxides and heterogeneous integration of hexagonal boron nitride, can hardly avoid removal of encapsulation layer when the 2D materials are encapsulated for further device fabrication, which causes complexity and damage during the procedure. Here, a van der Waals encapsulation method that allows direct device fabrication without removal of encapsulation layer is introduced using Ga2O3 from liquid gallium. Taking advantage of the robust isolation ability against ambient environment of the dense native oxide of gallium, hundreds of times longer retention time of (opto)electronic properties of encapsulated BP and MoTe2 devices is realized than unencapsulated devices. Due to the ultra-thin high-κ properties of Ga2O3, top-gated devices are directly fabricated with the encapsulation layer, simultaneously as a dielectric layer. This direct device fabrication is realized by selective etching of Ga2O3, leaving the encapsulated materials intact. Encapsulated 1T' MoTe2 exhibits high conductivity even after 150 days in ambient environment. This method is therefore highlighted as a promising and distinctive one compared with traditional passivation approaches. This article is protected by copyright. All rights reserved.

Fabrication of Poly(ionic liquid) Hydrogels Incorporating Liquid Metal Microgels for Enhanced Synergistic Antifouling Applications.

Hydrogels are ideal for antifouling materials due to their high hydrophilicity and low adhesion properties. Herein, poly(ionic liquid) hydrogels integrated with zwitterionic copolymer-functionalized gallium-based liquid metal (PMPC-GLM) microgels were successfully prepared by a one-pot reaction. Poly(ionic liquid) hydrogels (IL-Gel) were obtained by chemical cross-linking the copolymer of ionic liquid, acrylic acid, and acrylamide, and the introduction of ionic liquid (IL) significantly increased the cross-linking density; this approach consequently enhanced the mechanical and antiswelling properties of the hydrogels. The swelling ratio of IL-Gel decreased eight times compared to the original hydrogels. PMPC-GLM microgels were prepared through grafting the zwitterionic polymer PMPC onto the GLM nanodroplet surface, which exhibited efficient antifouling performance attributed to the bactericidal effect of Ga3+ and the antibacterial effect of the zwitterionic polymer layer PMPC. Based on the synergistic effect of PMPC-GLM microgels and IL, the composite hydrogels PMPC-GLM@IL-Gel not only exhibited excellent mechanical and antiswelling properties but also showed outstanding antibacterial and antifouling properties. Consequently, PMPC-GLM@IL-Gel hydrogels achieved inhibition rates of over 90% against bacteria and more than 85% against microalgae.

Humidity-Responsive Liquid Metal Core-Shell Materials for Enduring Heat Retention and Insulation.

High humidity in extremely cold weather can undermine the insulation capability of the clothing, imposing serious life risks. Current clothing insulation technologies have inherent deficiencies in terms of insulation efficiency and humidity adaptability. Here, we report humidity-stimulated self-heating clothing using aluminum core-liquid metal shell microparticles (Al@LM-MPs) as the filler. Al@LM-MPs exhibit a distinctive capability to react to water molecules in the air to generate heat, exhibiting remarkable sensitivity across a broad temperature range. This ability leads to the creation of intelligent clothing capable of autonomously responding to extreme cold and wet weather conditions, providing both enduring heat retention and insulation capabilities. This article is protected by copyright. All rights reserved.

Needle-Like Multifunctional Biphasic Microfiber for Minimally Invasive Implantable Bioelectronics.

Implantable bioelectronics has attracted significant attention in electroceuticals and clinical medicine for precise diagnosis and efficient treatment of target diseases. However, conventional rigid implantable devices face challenges such as poor tissue-device interface and unavoidable tissue damage during surgical implantation. Despite continuous efforts to utilize various soft materials to address such issues, their practical applications remain limited. Here, a needle-like stretchable microfiber composed of a phase-convertible liquid metal (LM) core and a multifunctional nanocomposite shell for minimally invasive soft bioelectronics is reported. The sharp tapered microfiber can be stiffened by freezing akin to a conventional needle to penetrate soft tissue with minimal incision. Once implanted in vivo where the LM melts, unlike conventional stiff needles, it regains soft mechanical properties, which facilitate a seamless tissue-device interface. The nanocomposite incorporating with functional nanomaterials exhibits both low impedance and the ability to detect physiological pH, providing biosensing and stimulation capabilities. The fluidic LM embedded in the nanocomposite shell enables high stretchability and strain-insensitive electrical properties. This multifunctional biphasic microfiber conforms to the surfaces of the stomach, muscle, and heart, offering a promising approach for electrophysiological recording, pH sensing, electrical stimulation, and radiofrequency ablation in vivo.

Harmonizing Elastic Modulus and Dielectric Constant of Elastomers for Improved Pressure Sensing Performance.

Enhancing the sensitivity of capacitive pressure sensors through microstructure design may compromise the reliability of the device and rely on intricate manufacturing processes. It is an effective way to solve this issue by balancing the intrinsic properties (elastic modulus and dielectric constant) of the dielectric layer materials. Here, we introduce a liquid metal (LM) hybrid elastomer prepared by a chain-extension-free polyurethane (PU) and LM. The synergistic strategies of extender-free and LM doping effectively reduce the elastic modulus (7.6 ± 0.2-2.1 ± 0.3 MPa) and enhance the dielectric constant (5.12-8.17 @1 kHz) of LM hybrid elastomers. Interestingly, the LM hybrid elastomer combines reprocessability, recyclability, and photothermal conversion. The obtained flexible pressure sensor can be used for detecting hand and throat muscle movements, and high-precision speech recognition of seven words has been using a convolutional neural network (CNN) in deep learning. This work provides an idea for designing and manufacturing wearable, recyclable, and intelligent control pressure sensors.