Eutectic Gallium‐Indium (EGaIn): A Liquid Metal Alloy for the Formation of Stable Structures in Microchannels at Room Temperature

This paper describes the rheological behavior of the liquid metal eutectic gallium‐indium (EGaIn) as it is injected into microfluidic channels to form stable microstructures of liquid metal. EGaIn is well‐ ;suited for this application because of its rheological properties at room temperature: it behaves like an elastic material until it experiences a critical surface stress, at which point it yields and flows readily. These properties allow EGaIn to fill microchannels rapidly when sufficient pressure is applied to the inlet of the channels, yet maintain structural stability within the channels once ambient pressure is restored. Experiments conducted in microfluidic channels, and in a parallel‐plate rheometer, suggest that EGaIn's behavior is dictated by the properties of its surface (predominantly gallium oxide, as determined by Auger measurement s); these two experiments both yield approximately the same number for the critical surface stress required to induce EGaIn to flow (～0 .5 N/m). This analysis–which shows that the pressure that must be exceeded for EGaIn to flow through a microchannel is inversely proportional to the critical (i.e., smallest) dimension of the channel–is useful to guide future fabrication of microfluidic channels to mold EGaIn into functional microstructures.     

Ionic Current Rectification in Soft‐Matter Diodes with Liquid‐Metal Electrodes

A soft‐matter‐based diode composed of hydrogel and liquid metal (eutectic gallium indium, EGaIn) is presented. The ability to control the thickness, and thus resistivity, of an oxide skin on the metal enables rectification. First, a simple model system with liquid‐metal/electrolyte‐solution/Pt interfaces is characterized. The electrically insulating oxide skin on the EGaIn electrode is reduced or oxidized further depending on the direction of the bias, thereby allowing unidirectional ionic current. The forward current of the diode increases as the conductivity of the electrolyte increases, whereas backward current depends on the pH of the medium in contact with the insulating oxide layer on the EGaIn electrode. As a result, the diode shows a higher rectification ratio (defined as the ratio of forward to backward current measured at the same absolute bias) with more conductive electrolyte at neutral pH. Replacement of the liquid electrolyte solution with a hydrogel improves the structural stability of the soft diode. The rectification performance also improves due to the increased ionic conductivity by the gel. Finally, a diode composed entirely of soft materials by replacing the platinum electrode with a second liquid‐metal electrode is presented. Contacting each liquid metal with a polyelectrolyte gel featuring different pH values provided asymmetry in the device, which is necessary for rectification. A hydrogel layer infused with a strong basic polyelectrolyte removes the insulating oxide layer, allowing one interface with the EGaIn electrode to be conductive regardless of the direction of bias. Thus, the oxide layer at the other interface rectifies the current.     

Size‐Scalable and High‐Density Liquid‐Metal‐Based Soft Electronic Passive Components and Circuits Using Soft Lithography

The use of conducting liquids with high electrical conductivity, such as eutectic gallium–indium (EGaIn), has great potential in electronics applications requiring stretchability and deformability beyond conventional flexible electronics relying on solid conductors. An advanced liquid metal thin‐line patterning process based on soft lithography and a compatible vertical integration technique are presented that enable size‐scalable and high‐density EGaIn‐based, soft microelectronic components and circuits. The advanced liquid metal thin‐line patterning process based on poly(dimethylsiloxane) (PDMS) substrates and soft lithography techniques allows for simultaneous patterning of uniform and residue‐free EGaIn lines with line width from single micrometers to several millimeters at room temperature and under ambient pressure. Using this fabrication technique, passive electronic components and circuits are investigated under elastic deformations using numerical and experimental approaches. In addition, soft through‐PDMS vias with high aspect ratio are demonstrated for multilayer interconnections in 2.5D and 3D integration approaches. To highlight the system‐level potential of the patterning technique, a chemical sensor based on an integrated LC resonance circuit with a microfluidic‐tunable interdigitated capacitor and a planar spiral inductor is fabricated and characterized. Finally, to show the flexibility and stretchability of the resulting electronics, circuits with embedded light emitting diodes (LEDs) are investigated under bending, twisting, and stretching deformations.     

Liquid Metal Droplets Wrapped with Polysaccharide Microgel as Biocompatible Aqueous Ink for Flexible Conductive Devices

Nanometerization of liquid metal in organic systems can facilitate deposition of liquid metals onto substrates and then recover its conductivity through sintering. Although having broader potential applications, producing stable aqueous inks of liquid metals keeps challenging because of rapid oxidation of liquid metal when exposing to water and oxygen. Here, a biocompatible aqueous ink is produced by encapsulating alloy nanodroplets of gallium and indium (EGaIn) into microgels of marine polysaccharides. During sonicating bulk EGaIn in aqueous alginate solution, alginate not only facilitates the downsizing process via coordination of their carboxyl groups with Ga ions but also forms microgel shells around EGaIn droplets. Due to the deceasing oxygen‐permeability of microgel shells, aqueous ink of EGaIn nanodroplets can maintain colloidal and chemical stability for a period of >7 d. Crosslinked alginate‐gel with tunable thickness can retard the generation and release of toxic cations, thereby affording high biocompatibility. The soft alginate shells also enable to recover electric conductivity of EGaIn layers by “mechanical sintering” for applications in microcircuits, electric‐thermal actuators, and wearable sensors, offering huge potential for electronic tattoos, artificial limbs, electric skins, etc.     

Self‐Limiting Galvanic Growth of MnO2 Monolayers on a Liquid Metal—Applied to Photocatalysis

Liquid metals offer unprecedented chemistry. Here it is shown that they can facilitate self‐limiting oxidation processes on their surfaces, which enables the growth of metal oxides that are atomically thin. This claim is exemplified by creating atomically thin hydrated MnO₂ using a Galvanic replacement reaction between permanganate ions and a liquid gallium–indium alloy (EGaIn). The “liquid solution”–“liquid metal” process leads to the reduction of the permanganate ions, resulting in the formation of the oxide monolayer at the interface. It is presented that under mechanical agitation liquid metal droplets are established, and simultaneously, hydrated gallium oxides and manganese oxide sheets delaminate themselves from the interfacial boundaries. The produced nanosheets encapsulate a metallic core, which is found to consist of solid indium only, with the full migration of gallium out of the droplets. This process produces core/shell structures, where the shells are made of stacked atomically thin nanosheets. The obtained core/shell structures are found to be an efficient photocatalyst for the degradation of an organic dye under simulated solar irradiation. This study presents a new research direction toward the modification and functionalization of liquid metals through spontaneous interfacial redox reactions, which has implications for many applications beyond photocatalysis.     

Formation of Spherical and Non‐Spherical Eutectic Gallium‐Indium Liquid‐Metal Microdroplets in Microfluidic Channels at Room Temperature

Here, the formation of eutectic Gallium‐Indium (EGaIn) liquid‐metal microdroplets, both spherical and non‐spherical, in microfluidic devices at room temperature is reported. Monodisperse microdroplets were created in an aqueous polyethylene glycol (PEG) solution, in oxygenated and in deoxygenated silicone oil. The volume of the droplets depends on the channel dimensions and flow rates applied, varying between 0.5 and 4 nL. Non‐spherical droplets were formed in oxygenated silicone oil due to the instantaneous formation of an oxide layer. These metal “micro‐rice” droplets retained their shape and did not spontaneously reflow to form shapes of the lowest interfacial energy on egress from the channel, unlike in aqueous PEG solution and in deoxygenated silicone oil. Liquid‐metal droplets with such tunable morphology can potentially be used in MEMS devices for optical and electrical switches, valves and micropumps.     

Reversibly Deformable and Mechanically Tunable Fluidic Antennas

This paper describes the fabrication and characterization of fluidic dipole antennas that are reconfigurable, reversibly deformable, and mechanically tunable. The antennas consist of a fluid metal alloy injected into microfluidic channels comprising a silicone elastomer. By employing soft lithographic, rapid prototyping methods, the fluidic antennas are easier to fabricate than conventional copper antennas. The fluidic dipole radiates with ≈90% efficiency over a broad frequency range (1910–1990 MHz), which is equivalent to the expected efficiency for a similar dipole with solid metallic elements such as copper. The metal, eutectic gallium indium (EGaIn), is a low‐viscosity liquid at room temperature and possesses a thin oxide skin that provides mechanical stability to the fluid within the elastomeric channels. Because the conductive element of the antenna is a fluid, the mechanical properties and shape of the antenna are defined by the elastomeric channels, which are composed of polydimethylsiloxane (PDMS). The antennas can withstand mechanical deformation (stretching, bending, rolling, and twisting) and return to their original state after removal of an applied stress. The ability of the fluid metal to flow during deformation of the PDMS ensures electrical continuity. The shape and thus, the function of the antenna, is reconfigurable. The resonant frequency can be tuned mechanically by elongating the antenna via stretching without any hysteresis during strain relaxation, and the measured resonant frequency as a function of strain shows excellent agreement (±0.1–0.3% error) with that predicted by theoretical finite element modeling. The antennas are therefore sensors of strain. The fluid metal also facilitates self‐healing in response to sharp cuts through the antenna.     

Sonication‐Assisted Synthesis of Gallium Oxide Suspensions Featuring Trap State Absorption: Test of Photochemistry

Gallium is a near room temperature liquid metal with extraordinary properties that partly originate from the self‐limiting oxide layer formed on its surface. Taking advantage of the surface gallium oxide (Ga₂O₃), this work introduces a novel technique to synthesize gallium oxide nanoflakes at high yield by harvesting the self‐limiting native surface oxide of gallium. The synthesis process follows a facile two‐step method comprising liquid gallium metal sonication in DI water and subsequent annealing. In order to explore the functionalities of the product, the obtained hexagonal α‐Ga₂O₃ nanoflakes are used as a photocatalytic material to decompose organic model dyes. Excellent photocatalytic activity is observed under solar light irradiation. To elucidate the origin of these enhanced catalytic properties, the electronic band structure of the synthesized α‐Ga₂O₃ is carefully assessed. Consequently, this excellent photocatalytic performance is associated with an energy bandgap reduction, due to the presence of trap states, which are located at ≈1.65 eV under the conduction band minimum. This work presents a novel route for synthesizing oxide nanostructures that can be extended to other low melting temperature metals and their alloys, with great prospects for scaling up and high yield synthesis.     

Creation of Liquid Metal 3D Microstructures Using Dielectrophoresis

Patterning customized arrays of microscale Galinstan or EGaIn liquid metals enables the creation of a variety of microfabricated systems. Current techniques for creating microsized 3D structures of liquid metals are limited by the large dimension or low aspect ratio of such structures, and time‐consuming processes. Here, a novel technique for creating 3D microstructures of Galinstan using dielectrophoresis is introduced. The presented technique enables the rapid creation of Galinstan microstructures with various dimensions and aspect ratios. Two series of proof‐of‐concept experiments are conducted to demonstrate the capabilities of this technique. First, the 3D Galinstan microstructures are utilized as 3D microelectrodes to enhance the trapping of tungsten trioxide (WO₃) nanoparticles flowing through a microfluidic channel. Second, the patterned Galinstan microstructures are utilized as microfins to improve the dissipation of heat within a microfluidic channel that is located onto a hot spot. The presented technique can be readily used for creating customized arrays of 3D Galinstan microstructures for a wide range of applications.     

3D Visible-Light-Driven Plasmonic Oxide Frameworks Deviated from Liquid Metal Nanodroplets

Eutectic gallium-indium (EGaIn) liquid metal droplets have been considered as a suitable platform for producing customized 3D composites with functional nanomaterials owing to their soft and highly reductive surface. Herein, the synthesis of a 3D plasmonic oxide framework (POF) is reported by incorporating the ultra-thin angstrom-scale-porous hexagonal molybdenum oxide (h-MoO₃) onto the spherical EGaIn nanodroplets through ultrasonication. Simultaneously, a large number of oxygen vacancies form in h-MoO₃, boosting its free charge carrier concentration and therefore generating a broad surface plasmon resonance across the whole visible light spectrum. The plasmonic chemical sensing properties of the POF is investigated by the surface-enhanced Raman scattering detection of rhodamine 6G (R6G) at 532 nm, in which the minimum detectable concentration is 10⁻⁸ m and the enhancement factor reached up to 6.14 × 10⁶. The extended optical absorption of the POF also allowed the efficient degradation of the R6G dye under the excitation of ultraviolet-filtered simulated solar light. Furthermore, the POF exhibits remarkable photocurrent responses towards the entire visible light region with the maximum response of ≈ 1588 A W⁻¹ at 455 nm. This work demonstrates the great potential of the liquid metal-based POFs for high-performance sensing, catalytic, and optoelectronic devices.     

Soft Electronics Manufacturing Using Microcontact Printing

This work describes a microcontact printing (µCP) process for reproducible manufacturing of liquid gallium alloy–based soft and stretchable electronics. One of the leading approaches to create soft and stretchable electronics involves embedding liquid metals (LM) into an elastomer matrix. Although the advantages of liquid metal–based electronics have been well established, their mainstream adoption and commercialization necessitates development of precise and scalable manufacturing methods. To address this need, a scalable µCP process is presented that uses surface‐functionalized, reusable rigid, or deformable stamps to transfer eutectic gallium–indium (EGaIn) patterns onto elastomer substrates. A novel approach is developed to create the surface‐functionalized stamps, enabling selective transfer of LM to desired locations on a substrate without residues or electrical shorts. To address the critical needs of precise and reproducible positioning, alignment, and stamping force application, a high‐precision automated µCP system is designed. After describing the approach, the precision of stamps is evaluated and EGaIn features (as small as 15 µm line width), as well as electrical functionality of printed circuits with and without deformation, are fabricated. The presented process addresses many of the limitations associated with the alternative fabrication processes, and thus provides an effective approach for scalable fabrication of LM‐based soft and stretchable microelectronics.     

Inertial Microfluidics with Integrated Vortex Generators Using Liquid Metal Droplets as Fugitive Ink

This work demonstrates a simple method for fabricating nearly spherical dome structures on top of lithographically defined microfluidic channels using gallium‐based liquid metal droplets as fugitive ink. The droplets remain stable during the pouring and curing of polydimethylsiloxane and can be easily removed by applying a basic solution. This facilitates the formation of domes with diameters of a few hundred micrometers patterned on the desired locations of the channel. The expansion of the channel at the interface of the dome leads to formation of a large vortex inside the dome. Experiments using high‐speed imaging along with numerical simulations show the utility of the vortex‐induced flow rotation for orbiting of human monocytes and polystyrene microbeads inside the dome. The lateral displacement of liquids caused by the vortex is further utilized for creating controllable multiband flow/color profiles within a T‐mixer. The method enables the fabrication of customized, complex, and 3D microfluidic systems utilizing planar microfabricated structures.     

Miniature Soft Electromagnetic Actuators for Robotic Applications

Electromagnetic actuators (EMAs) serve the majority of motion control needs in fields ranging from industrial robotics to automotive systems and biomedical devices, due to their unmatched combination of speed, precision, force, and scalability. This paper describes the design and fabrication of miniature soft EMAs that operate based on the Lorentz force principle. The actuators are fabricated from silicone polymer, liquid metal (LM) alloy (eutectic gallium indium, EGaIn), and magnetic (NdFeB) powder. They are small, intrinsically deformable, and can be fabricated using simple techniques. The central elements of the actuators are fine, 3D helical coil conductors, which are used as electromagnetic inductors. The coils are formed from stretchable filaments that are filled with a LM alloy. To achieve high power densities, the filaments themselves may be fabricated from colloids of EGaIn microdroplets in a silicone polymer matrix, allowing them to dissipate heat and accommodate high currents, and thus high forces. Millimeter‐scale cylindrical actuators are demonstrated for linear high frequency motion and articulated devices for bending motion. These actuators are applied in a vibrotactile feedback display and in a miniature soft robotic gripper.     

A Novel Strategy for Preparing Stretchable and Reliable Biphasic Liquid Metal

Low‐melting liquid metal is a hugely promising material for flexible conductive patterns due to its excellent conductivity and supercompliance, especially low‐cost and environmental liquid processing technology. However, the ever‐present fluidity characteristic greatly limits the stable shape and reliability of prepared liquid metal conductive electronics. Herein, a novel solidification strategy of liquid GaIn alloys by Ni doping and heat treatment is first reported, which can efficiently create a solid phase in the liquid metal and provide an effective solution for practical applications. Particularly, the liquid characteristic is preserved for conveniently fabricating different flexible electronic circuits, and then the solidification is carried out on prepared conductive patterns by heat treatment. The solidification mechanism is revealed by the interface chemical reaction between Ni and GaIn, creating the solid phase of intermetallic compound (Ga₄Ni₃ and InNi₃) during heat treatment. Moreover, a biphasic GaInNi can be obtained by regulating the atomic ratio of gallium, indium, and nickel. As a result, the obtained GaInNi possesses extremely low sheet resistance (15 ± 4.5 to 135 ± 2.5 mΩ sq^?1) and the variation of ΔR/R₀ exhibits low level (0–2) when strained up to 100%, which offers a promising strategy to prepare stretchable and reliable liquid metal electronics.     

Direct Writing of Gallium‐Indium Alloy for Stretchable Electronics

In this paper, a direct writing method for gallium‐indium alloys is presented. The relationships between nozzle inner diameter, standoff distance, flow rate, and the resulting trace geometry are demonstrated. The interaction between the gallium oxide layer and the substrate is critically important in understanding the printing behavior of the liquid metal. The difference between receding and advancing contact angles demonstrates that the adhesion of the oxide layer to the substrate surface is stronger than the wetting of the surface by the gallium‐indium alloy. This further demonstrates why free‐standing structures such as the traces described herein can be realized. In addition to the basic characterization of the direct writing process, a design algorithm that is generalizable to a range of trace geometries is developed. This method is applied to the fabrication of an elastomer‐encapsulated strain gauge that displays an approximately linear behavior through 50% strain with a gauge factor of 1.5.     

Surface Textured Polymer Fibers for Microfluidics

This article introduces surface textured polymer fibers as a new platform for the fabrication of affordable microfluidic devices. Fibers are produced tens of meters‐long at a time and comprise 20 continuous and ordered channels (equilateral triangle grooves with side lengths as small as 30 micrometers) on their surfaces. Extreme anisotropic spreading behavior due to capillary action along the grooves of fibers is observed after surface modification with polydopamine (PDA). These flexible fibers can be fixed on any surface—independent of its material and shape—to form three‐dimensional arrays, which spontaneously spread liquid on predefined paths without the need for external pumps or actuators. Surface textured fibers offer high‐throughput fabrication of complex open microfluidic channel geometries, which is challenging to achieve using current photolithography‐based techniques. Several microfluidic systems are designed and prepared on either planar or 3D surfaces to demonstrate outstanding capability of the fiber arrays in control of fluid flow in both vertical and lateral directions. Surface textured fibers are well suited to the fabrication of flexible, robust, lightweight, and affordable microfluidic devices, which expand the role of microfluidics in a scope of fields including drug discovery, medical diagnostics, and monitoring food and water quality.     

Towards Sub‐Microscale Liquid Metal Patterns: Cascade Phase Change Mediated Pick‐n‐Place Transfer of Liquid Metals Printed and Stretched over a Flexible Substrate

Eutectic gallium indium (EGaIn) is actively investigated toward wearable and stretchable electronic devices due to the high fluidity, high electrical conductivity, and low toxicity. However, high surface tension along with spontaneous oxidation makes fine patterning below ≈10 µm challenging. In this paper, a novel manufacturing technique that enables EGaIn patterns of single‐digit micrometer widths on planar elastomeric substrates is presented. First, a custom direct printing setup is constructed for continuous and uniform printing of EGaIn by feedback control of the distance between the dispensing needle and the substrate. With this setup, a 120 µm wide linear pattern is printed on the Ecoflex, a stretchable elastomer. Then, the initial printed line is stretched, frozen with deionized water, and transferred to an unstretched Ecoflex substrate. Upon gentle heating after the pick‐n‐place of the EGaIn line frozen with deionized water, only the stretched EGaIn line is left on the new Ecoflex substrate. The aforementioned pick‐n‐place transfer of the stretched EGaIn frozen with water is cascaded multiple times until a target width is obtained. Finally, a 2 µm wide linear pattern, 60‐fold reduction with respect to the initial dimension, is acquired. For practical applications, strain and tactile sensors are demonstrated by width‐reduced EGaIn patterns.     

Liquid Metal Based Island‐Bridge Architectures for All Printed Stretchable Electrochemical Devices

The adoption of epidermal electronics into everyday life requires new design and fabrication paradigms, transitioning away from traditional rigid, bulky electronics towards soft devices that adapt with high intimacy to the human body. Here, a new strategy is reported for fabricating achieving highly stretchable “island‐bridge” (IB) electrochemical devices based on thick‐film printing process involving merging the deterministic IB architecture with stress‐enduring composite silver (Ag) inks based on eutectic gallium‐indium particles (EGaInPs) as dynamic electrical anchors within the inside the percolated network. The fabrication of free‐standing soft Ag‐EGaInPs‐based serpentine “bridges” enables the printed microstructures to maintain mechanical and electrical properties under an extreme (≈800%) strain. Coupling these highly stretchable “bridges” with rigid multifunctional “island” electrodes allows the realization of electrochemical devices that can sustain high mechanical deformation while displaying an extremely attractive and stable electrochemical performance. The advantages and practical utility of the new printed Ag‐liquid metal‐based island‐bridge designs are discussed and illustrated using a wearable biofuel cell. Such new scalable and tunable fabrication strategy will allow to incorporate a wide range of materials into a single device towards a wide range of applications in wearable electronics.     

On the transient response of organic electrochemical transistors

We present a universal model for the transient drain current response in organic electrochemical transistors (OECTs). Using equivalent circuits and charge injection physics, we are able to predict the drain current in OECT devices upon application of a gate voltage input. The model is applicable to both plain and membrane-functionalized devices, and allows us to extract useful physical quantities such as resistances and capacitances, which are related to functional properties of the system. We are also able to use the model to reconstruct the magnitude and shape in time of an applied voltage source based on the observed drain current response. This was experimentally demonstrated for drain current measurements under an applied action potential.     

Effects of Moisture on the Switching Characteristics of Oxide‐Based,Gapless‐Type Atomic Switches

Resistive switching memories based on the formation and dissolution of a metal filament in a simple metal/oxide/metal structure are attractive because of their potential high scalability, low‐power consumption, and ease of operation. From the standpoint of the operation mechanism, these types of memory devices are referred to as gapless‐type atomic switches or electrochemical metallization cells. It is well known that oxide materials can absorb moisture from the ambient air, which causes shifts in the characteristics of metal‐oxide‐semiconductor devices. However, the role of ambient moisture on the operation of oxide‐based atomic switches has not yet been clarified. In this work, current–voltage measurements were performed as a function of ambient water vapor pressure and temperature to reveal the effect of moisture on the switching behavior of Cu/oxide/Pt atomic switches using different oxide materials. The main findings are: i) the ionization of Cu at the anode interface is likely to be attributed to chemical oxidation via residual water in the oxide layer, ii) Cu ions migrate along grain boundaries in the oxide layer, where a hydrogen‐bond network might be formed by moisture absorption, and iii) the stability of residual water has an impact on the ionization and migration processes and plays a major role in determining the operation voltages. These findings will be important in the microscopic understanding of the switching behavior of oxide‐based atomic switches and electrochemical metallization cells.