Silky Liquid Metal Electrodes for On-Skin Health Monitoring.

Next generation on-skin electrodes will require soft, flexible, and gentle materials to provide both high-fidelity sensing and wearer comfort. However, many commercially available on-skin electrodes lack these key properties due to their use of rigid hardware, harsh adhesives, uncomfortable support structures, and poor breathability. To address these challenges, this work presents a new device paradigm by joining biocompatible electrospun spider silk with printable liquid metal to yield an incredibly soft and scalable on-skin electrode that is strain-tolerant, conformable, and gentle on-skin. These electrodes, termed silky liquid metal (SLiM) electrodes, are found to be over five times more breathable than commercial wet electrodes, while the silk's intrinsic adhesion mechanism allows SLiM electrodes to avoid the use of harsh artificial adhesives, potentially decreasing skin irritation and inflammation over long-term use. Finally, the SLiM electrodes provide comparable impedances to traditional wet and other liquid metal electrodes, offering a high-fidelity sensing alternative with increased wearer comfort. Human subject testing confirmed the SLiM electrodes ability to sense electrophysiological signals with high fidelity and minimal irritation to the skin. The unique properties of the reported SLiM electrodes offer a comfortable electrophysiological sensing solution especially for patients with pre-existing skin conditions or surface wounds.

Mechanical integrated circuit materials.

Recent developments in autonomous engineered matter have introduced the ability for intelligent materials to process environmental stimuli and functionally adapt1-4. To formulate a foundation for such an engineered living material paradigm, researchers have introduced sensing5-11 and actuating12-16 functionalities in soft matter. Yet, information processing is the key functional element of autonomous engineered matter that has been recently explored through unconventional techniques with limited computing scalability17-20. Here we uncover a relation between Boolean mathematics and kinematically reconfigurable electrical circuits to realize all combinational logic operations in soft, conductive mechanical materials. We establish an analytical framework that minimizes the canonical functions of combinational logic by the Quine-McCluskey method, and governs the mechanical design of reconfigurable integrated circuit switching networks in soft matter. The resulting mechanical integrated circuit materials perform higher-level arithmetic, number comparison, and decode binary data to visual representations. We exemplify two methods to automate the design on the basis of canonical Boolean functions and individual gate-switching assemblies. We also increase the computational density of the materials by a monolithic layer-by-layer design approach. As the framework established here leverages mathematics and kinematics for system design, the proposed approach of mechanical integrated circuit materials can be realized on any length scale and in a wide variety of physics.

Textile-Integrated Liquid Metal Electrodes for Electrophysiological Monitoring.

Next generation textile-based wearable sensing systems will require flexibility and strength to maintain capabilities over a wide range of deformations. However, current material sets used for textile-based skin contacting electrodes lack these key properties, which hinder applications such as electrophysiological sensing. In this work, a facile spray coating approach to integrate liquid metal nanoparticle systems into textile form factors for conformal, flexible, and robust electrodes is presented. The liquid metal system employs functionalized liquid metal nanoparticles that provide a simple "peel-off to activate" means of imparting conductivity. The spray coating approach combined with the functionalized liquid metal system enables the creation of long-term reusable textile-integrated liquid metal electrodes (TILEs). Although the TILEs are dry electrodes by nature, they show equal skin-electrode impedances and sensing capabilities with improved wearability compared to commercial wet electrodes. Biocompatibility of TILEs in an in vivo skin environment is demonstrated, while providing improved sensing performance compared to previously reported textile-based dry electrodes. The "spray on dry-behave like wet" characteristics of TILEs opens opportunities for textile-based wearable health monitoring, haptics, and augmented/virtual reality applications that require the use of flexible and conformable dry electrodes.

3D-Printed Self-Healing Elastomers for Modular Soft Robotics.

Advances in materials, designs, and controls are propelling the field of soft robotics at an incredible rate; however, current methods for prototyping soft robots remain cumbersome and struggle to incorporate desirable geometric complexity. Herein, a vat photopolymerizable self-healing elastomer system capable of extreme elongations up to 1000% is presented. The material is formed from a combination of thiol/acrylate mixed chain/step-growth polymerizations and uses a combination of physical processes and dynamic-bond exchange via thioethers to achieve full self-healing capacity over multiple damage/healing cycles. These elastomers can be three dimensional (3D) printed with modular designs capable of healing together to form highly complex and large functional soft robots. Additionally, these materials show reprogrammable resting shapes and compatibility with self-healing liquid metal electronics. Using these capabilities, subcomponents with multiple internal channel systems were printed, healed together, and combined with functional liquid metals to form a high-wattage pneumatic switch and a humanoid-scale soft robotic gripper. The combination of 3D printing and self-healing elastomeric materials allows for facile production of support-free parts with extreme complexity, resulting in a paradigm shift for the construction of modular soft robotics.

Digital logic gates in soft, conductive mechanical metamaterials.

Integrated circuits utilize networked logic gates to compute Boolean logic operations that are the foundation of modern computation and electronics. With the emergence of flexible electronic materials and devices, an opportunity exists to formulate digital logic from compliant, conductive materials. Here, we introduce a general method of leveraging cellular, mechanical metamaterials composed of conductive polymers to realize all digital logic gates and gate assemblies. We establish a method for applying conductive polymer networks to metamaterial constituents and correlate mechanical buckling modes with network connectivity. With this foundation, each of the conventional logic gates is realized in an equivalent mechanical metamaterial, leading to soft, conductive matter that thinks about applied mechanical stress. These findings may advance the growing fields of soft robotics and smart mechanical matter, and may be leveraged across length scales and physics.

Gallium-indium nanoparticles as phase change material additives for tunable thermal fluids.

One of the most critical limitations for high-power electronics today is thermal management and routing thermal energy efficiently away from thermally sensitive components. A potential solution to this problem is the integration of cooling channels in close proximity to thermally sensitive materials for increased heat removal efficiency. These channels typically use single phase fluids (liquid), dual phase fluids (vapor-liquid), or suspended organic/polymer phase change material particles in a fluid (PCM slurry). Expanding upon the latter, this work demonstrates the use of inorganic Ga-In alloy nanoparticles (NPs) suspended in a traditional thermal transport fluid to simultaneously (1) increase the overall thermal diffusivity of the fluid and (2) serve as a cyclable solid-liquid PCM slurry which provides a thermal sink that is definable over a wide range of relevant temperatures for power electronics. Herein, the relationship between particle size, composition, and volume fraction are explored as they relate to the PCM slurry optimum working temperature, total energy absorption, and rheological properties. A mere 0.10 volume fraction of Ga-In NPs is reported to increase the overall thermal conductivity by nearly 50% and can be optimized to melt at temperatures as low as -46 °C. Based on thermal measurements, it was observed that these nanoparticle systems lack the preference to form αGa and have a large thermal hysteresis due to exhibiting extreme undercooling, with crystallization temperatures near -130 °C, enabling opportunities within extreme environments such as space applications or low temperature imaging systems.

Oxidation of Gallium-based Liquid Metal Alloys by Water.

Gallium alloys with other low melting point metals, such as indium or tin, to form room-temperature liquid eutectic systems. The gallium in the alloys rapidly forms a thin surface oxide when exposed to ambient oxygen. This surface oxide has been previously exploited for self-stabilization of liquid metal nanoparticles, retention of metastable shapes, and imparting stimuli-responsive behavior to the alloy surface. In this work, we study the effect of water as an oxidant and its role in defining the alloy surface chemistry. We identify several pathways that can lead to the formation of gallium oxide hydroxide (GaOOH) crystallites, which may be undesirable in many applications. Furthermore, we find that some crystallite formation pathways can be reinforced by typical top-down particle synthesis techniques like sonication. This improved understanding of interfacial interactions provides critical insight for process design and implementation of advanced devices that utilize the unique coupling of flexibility and conductivity offered by these gallium-based liquid metal alloys.

Graphene-based encapsulation of liquid metal particles.

Liquid metals are a promising functional material due to their unique combination of metallic properties and fluidity at room temperature. They are of interest in wide-ranging fields including stretchable and flexible electronics, reconfigurable devices, microfluidics, biomedicine, material synthesis, and catalysis. Transformation of bulk liquid metal into particles has enabled further advances by allowing access to a broader palette of fabrication techniques for device manufacture or by increasing area available for surface-based applications. For gallium-based liquid metal alloys, particle stabilization is typically achieved by the oxide that forms spontaneously on the surface, even when only trace amounts of oxygen are present. The utility of the particles formed is governed by the chemical, electrical, and mechanical properties of this oxide. To overcome some of the intrinsic limitations of the native oxide, it is demonstrated here for the first time that 2D graphene-based materials can encapsulate liquid metal particles during fabrication and imbue them with previously unattainable properties. This outer encapsulation layer is used to physically stabilize particles in a broad range of pH environments, modify the particles' mechanical behavior, and control the electrical behavior of resulting films. This demonstration of graphene-based encapsulation of liquid metal particles represents a first foray into the creation of a suite of hybridized 2D material coated liquid metal particles.

Chemically modifying the mechanical properties of core-shell liquid metal nanoparticles.

Eutectic gallium-indium (EGaIn) is a room temperature liquid metal that can be readily fabricated into nanoparticles which naturally form a thin, passivating gallium oxide shell. These core-shell nanoparticles are of interest for a variety of stimuli-responsive applications, which often utilize physical deformation of the particles to release the molten, conductive payload from within the gallium oxide shell. In the present work, we introduce a variety of chemical strategies to produce EGaIn nanoparticles which exhibit a wide range of gallium oxide shell thicknesses. These chemically modified oxide thicknesses are then correlated to the core-shell liquid nanoparticles' mechanical properties by subjecting the particles to orthogonal characterization techniques; XPS for measurement of the gallium oxide shell thickness and nanoindentation for measurement of particle stiffness and elastic modulus. Additionally, nanoindentation is used to determine the onset of particle rupture and resultant conductivity. Ultimately, quantification of the relationships between chemical treatment and derivative mechanical properties in liquid metal nanoparticles will enable advanced applications of these colloids, such as in tailored self-healing and responsive electronic devices.

Mechanoresponsive Polymerized Liquid Metal Networks.

Room-temperature liquid metals, such as nontoxic gallium alloys, show enormous promise to revolutionize stretchable electronics for next-generation soft robotic, e-skin, and wearable technologies. Core-shell particles of liquid metal with surface-bound acrylate ligands are synthesized and polymerized together to create cross-linked particle networks comprising >99.9% liquid metal by weight. When stretched, particles within these polymerized liquid metal networks (Poly-LMNs) rupture and release their liquid metal payload, resulting in a rapid 108 -fold increase in the network's conductivity. These networks autonomously form hierarchical structures that mitigate the deleterious effects of strain on electronic performance and give rise to emergent properties. Notable characteristics include nearly constant resistances over large strains, electronic strain memory, and increasing volumetric conductivity with strain to over 20 000 S cm-1 at >700% elongation. Furthermore, these Poly-LMNs exhibit exceptional performance as stretchable heaters, retaining 96% of their areal power across relevant physiological strains. Remarkable electromechanical properties, responsive behaviors, and facile processing make Poly-LMNs ideal for stretchable power delivery, sensing, and circuitry.

Patterning and Reversible Actuation of Liquid Gallium Alloys by Preventing Adhesion on Rough Surfaces.

This work reports a simple approach to form, study, and utilize rough coatings that prevent the adhesion of gallium-based liquid metal alloys. Typically, liquids with large interfacial tension do not wet nonreactive surfaces, regardless of surface topography. However, these alloys form a surface oxide "skin" that adheres to many substrates, even those with low surface energy. This work reports a simple approach to render closed channels and surfaces, including soft materials, to be "oxide-phobic" via spray-coating (NeverWet, which is commercially available and inexpensive). Surface spectroscopic techniques and metrology tools elucidate the coatings to comprise silica nanoparticles grafted with silicones that exhibit dual length scales of roughness. Although prior work shows the importance of surface roughness in preventing adhesion, the present work confirms that both hydrophobic and hydrophilic rough surfaces prevent oxide adhesion. Furthermore, the coating enables reversible actuation through submillimeter closed channels to form a reconfigurable antenna in the gigahertz range without the need for corrosive acids or bases that remove the oxide. In addition, the coating enables open surface patterning of conductive traces of liquid metal. This shows it is possible to actuate liquid metals in air without leaving neither metal nor oxide residue on surfaces to enable reconfigurable electronics, microfluidics, and soft electrodes.

Control of Gallium Oxide Growth on Liquid Metal Eutectic Gallium/Indium Nanoparticles via Thiolation.

Eutectic gallium-indium alloy (EGaIn, a room-temperature liquid metal) nanoparticles are of interest for their unique potential uses in self-healing and flexible electronic devices. One reason for their interest is due to a passivating oxide skin that develops spontaneously on exposure to ambient atmosphere which resists deformation and rupture of the resultant liquid particles. It is then of interest to develop methods for control of this oxide growth process. It is hypothesized here that functionalization of EGaIn nanoparticles with thiolated molecules could moderate oxide growth based on insights from the Cabrera-Mott oxidation model. To test this, the oxidation dynamics of several thiolated nanoparticle systems were tracked over time with X-ray photoelectron spectroscopy. These results demonstrate the ability to suppress gallium oxide growth by up to 30%. The oxide progressively matures over a 28 day period, terminating in different final thicknesses as a function of thiol selection. These results indicate not only that thiols moderate gallium oxide growth via competition with oxygen for surface sites but also that different thiols alter the thermodynamics of oxide growth through modification of the EGaIn work function.

Oxide-Free Actuation of Gallium Liquid Metal Alloys Enabled by Novel Acidified Siloxane Oils.

Electrowetting and electrocapillarity of liquid metals have a long history, and a recent explosion of renewed interest. Liquid metals have electromagnetic properties and surface tensions (>500 mN/m) that enable new forms of reconfigurable devices. However, the only nontoxic option, gallium alloys, suffer from immediate formation of a semirigid surface oxide. Although acids or electrochemical reduction can remove this oxide, these approaches surround the gallium alloy in a fluid that is also electrically conducting, diminishing electromagnetic effectiveness and precluding electrowetting actuation. Reported here are acidified siloxanes that remove and prevent oxide formation. Importantly, the siloxane oil associatively incorporates hydrochloric or hydrobromic acids, is electrically insulating, is chemically stable, removes etching byproducts (including water), and allows robust electrowetting. This work opens up new opportunities for liquid metal reconfiguration, and is of fundamental interest due to the unexpected chemical stability of the acidified siloxanes and their application to other materials and surfaces.

Pronounced effects of anisotropy on plasmonic properties of nanorings fabricated by electron beam lithography.

Gold nanoring dimers were fabricated via EBL with dimensions of 127.6 ± 2.5 and 57.8 ± 2.3 nm for the outer and inner diameters, respectively, with interparticle separations ranging from 17.8 ± 3.4 to 239.2 ± 3.7 nm. The coupling between the inner and outer surfaces of a single nanoring renders it very sensitive to any anisotropy. We found that anisotropy in the particle geometry and anisotropy introduced by the substrate combine to create very unique spectral features in this system.

Effect of orientation on plasmonic coupling between gold nanorods.

Radiative coupling of induced plasmonic fields in metal nanoparticles has drawn increasing attention in the recent literature due to a combination of improved experimental methods to study such phenomena and numerous potential applications, such as plasmonic nanoparticle rulers and plasmonic circuitry. Many groups, including ours, have used a near-exponential fit to express the size scaling of plasmonic coupling. First, we show experimental agreement between previously simulated nanorod coupling and plasmonic coupling in electron beam lithography (EBL) fabricated nanorods using the near-exponential expression. Next, we study the effect of nanoparticle orientation on plasmonic coupling using EBL and DDA simulations. We develop a mathematical relationship that is consistent with our findings and quantitatively describes plasmonic coupling between nanorods as a function of orientation, separation, induced dipole strength, and the dielectric constant of the medium. For applications utilizing plasmonic coupling to become viable with particle shapes that do not have spherical symmetry, such as nanoprisms and nanorods, comparison of the experimental and theoretical results of how particle orientation affects plasmonic coupling is essential.

On the use of plasmonic nanoparticle pairs as a plasmon ruler: the dependence of the near-field dipole plasmon coupling on nanoparticle size and shape.

The localized surface plasmon resonance (LSPR) spectral band of a gold or silver nanoparticle is observed to shift as a result of the near-field plasmonic field of another nanoparticle. The dependence of the observed shift on the interparticle distance is used as a ruler in biological systems and gave rise to a plasmonic ruler equation in which the fractional shift in the dipole resonance is found to decrease near exponentially with the interparticle separation in units of the particle size. The exponential decay length constant was observed to be consistent among a small range of nanoparticle sizes, shapes, and types of metal. The equation was derived from the observed results on disks and spherical nanoparticles and confirmed using results on a DNA conjugated nanosphere system. The aim of the present paper is to use electron beam lithography and DDA calculations to examine the constancy of the exponential decay length value in the plasmonic ruler equation on particle size and shape of a number of particles including nanoparticles of different symmetry and orientations. The results suggest that the exponent is almost independent of the size of the nanoparticle but very sensitive to the shape. A discussion of the nanoparticles most suitable for different applications in biological systems and a comparison of the plasmonic ruler with Forster resonance energy transfer (FRET) is mentioned.

A new catalytically active colloidal platinum nanocatalyst: the multiarmed nanostar single crystal.

Nanocatalysts that possess large amounts of atoms on sharp corners and edges and high indexed sites are known to be more catalytically active. We report here on a novel yet simple method to synthesize in large yields a very active platinum nanocatalyst; the multiarmed nanostar single crystal. We utilize a seed mediated method using tetrahedral nanoparticles that are also synthesized by a new and simple technique. High-resolution TEM shows that the nanostar has many arms, varying from a few to over 30, whereby even the largest ones are found to have single-crystal structures. This strongly suggests that they are formed by a growth mechanism of the seed crystals and not by the aggregation of seed crystals, which should produce twinning planes. Due to the reduction reaction of ferrricyanide by thiosulfate, the nanostars are found to have an activation energy, which is nearly 60% of that of the tetrahedral seeds themselves, both having the same PVP capping agent. This is undoubtedly due to the multiarms with edges, corners, and the presence of high indexed facets in the nanostar catalyst.