Emerging applications of liquid metals featuring surface oxides.
ABSTRACT: Gallium and several of its alloys are liquid metals at or near room temperature. Gallium has low toxicity, essentially no vapor pressure, and a low viscosity. Despite these desirable properties, applications calling for liquid metal often use toxic mercury because gallium forms a thin oxide layer on its surface. The oxide interferes with electrochemical measurements, alters the physicochemical properties of the surface, and changes the fluid dynamic behavior of the metal in a way that has, until recently, been considered a nuisance. Here, we show that this solid oxide "skin" enables many new applications for liquid metals including soft electrodes and sensors, functional microcomponents for microfluidic devices, self-healing circuits, shape-reconfigurable conductors, and stretchable antennas, wires, and interconnects.
Project description:Liquid metals have attracted attention as functional components for moldable electronics, such as soft flexible connectors, wires or conductive ink. The relatively high surface tension (>?400 mN m<sup>-1</sup>) and the fact that liquid metals do not readily wet ceramic or oxide surfaces have led to devising unique techniques to spread the liquid and mold its shape. These techniques include surface modification, electrowetting and vacuum filling of channels. This work presents an injection technique based on pressurized fountain pen lithography with glass nanopipettes developed to directly pattern liquid metal on flat hard substrates. The liquid metals were eutectic alloys of Gallium, including Gallium-Indium (EGaIn), Gallium-Indium-Zinc and Gallium-Indium-Tin. The nanopipettes were coated internally with gold, acting as a sacrificial layer and facilitating the wetting of the pipette down to its pore, with an inner diameter of?~?100-300 nm. By applying hydrodynamic pressure to the connected end of the pipette, the metal was extruded through the pore, forming long continuous (>?3 mm) and narrow (~?1-15 µm) metal lines on silicon oxide and gold surfaces at room temperature and ambient conditions. With this robust platform, it is possible to pattern liquid metals on a variety of substrates and geometries down to the micron range.
Project description:Embedding liquid metals (LMs) into an elastomer is emerging as a promising strategy for stretchable conductors. Existing manufacturing techniques are struggling between spatial resolution and process complexity and are limited to chemically resistant substrates. Here, we report on a hybrid process combining stencil lithography and centrifugal force-assisted patterning of liquid metal for the development of LM-based stretchable conductors. The selective wetting behavior of oxide-removed eutectic gallium-indium (EGaIn) on metal patterns defined by stencil lithography enables micrometer scale LM patterns on an elastomeric substrate. Stencil lithography allows for defining metal regions without harsh chemical treatments, making it suitable for a wide range of substrates. Microscale LM patterns are achieved by efficiently removing the excess material by the centrifugal forces experienced from spinning the substrate. The proposed approach allows for the creation of LM patterns with a line width as small as 2 μm on a stretchable poly(dimethylsiloxane) (PDMS) substrate. The electrical measurement results show that the fabricated EGaIn devices can endure 40% mechanical strain over several thousands of cycles. Furthermore, a stencil design using microbridges is proposed to address the mechanical stability issue in stencil lithography. An EGaIn conductor with a serpentine structure and an interdigitated capacitor are fabricated and characterized. The results demonstrate that the patterned serpentine conductors retain their functionality with applied mechanical strain up to 80%. The performance of the interdigitated capacitors upon applied strain is in good agreement with the theoretical estimation. Finally, we demonstrate our approach also on poly(octamethylene maleate (anhydride) citrate) (POMaC) substrates to broaden the use of the proposed method to not only flexible and stretchable but also biodegradable substrates, opening a way for in vivo transient microsystem engineering. The work presented here provides a versatile and reliable approach for manufacturing stretchable conductors.
Project description:A variety of deposition methods for two-dimensional crystals have been demonstrated; however, their wafer-scale deposition remains a challenge. Here we introduce a technique for depositing and patterning of wafer-scale two-dimensional metal chalcogenide compounds by transforming the native interfacial metal oxide layer of low melting point metal precursors (group III and IV) in liquid form. In an oxygen-containing atmosphere, these metals establish an atomically thin oxide layer in a self-limiting reaction. The layer increases the wettability of the liquid metal placed on oxygen-terminated substrates, leaving the thin oxide layer behind. In the case of liquid gallium, the oxide skin attaches exclusively to a substrate and is then sulfurized via a relatively low temperature process. By controlling the surface chemistry of the substrate, we produce large area two-dimensional semiconducting GaS of unit cell thickness (?1.5?nm). The presented deposition and patterning method offers great commercial potential for wafer-scale processes.
Project description:We report a versatile method to make liquid metal composites by vigorously mixing gallium (Ga) with non-metallic particles of graphene oxide (G-O), graphite, diamond, and silicon carbide that display either paste or putty-like behavior depending on the volume fraction. Unlike Ga, the putty-like mixtures can be kneaded and rolled on any surface without leaving residue. By changing temperature, these materials can be stiffened, softened, and, for the G-O-containing composite, even made porous. The gallium putty (GalP) containing reduced G-O (rG-O) has excellent electromagnetic interference shielding effectiveness. GalP with diamond filler has excellent thermal conductivity and heat transfer superior to a commercial liquid metal-based thermal paste. Composites can also be formed from eutectic alloys of Ga including Ga-In (EGaIn), Ga-Sn (EGaSn), and Ga-In-Sn (EGaInSn or Galinstan). The versatility of our approach allows a variety of fillers to be incorporated in liquid metals, potentially allowing filler-specific "fit for purpose" materials.
Project description:Structured metallic patterns are routinely used for a wide variety of applications, ranging from electronic circuits to plasmonics and metamaterials. Numerous techniques have been developed for the fabrication of these devices, in which the metal patterns are typically formed using conventional metals. While this approach has proven very successful, it does generally limit the ability to reconfigure the geometry of the overall device. Here, we demonstrate the ability to create artificially structured metallic devices using liquid metals, in which the configuration can be altered via the electrolysis of saline solutions or deionized water. We accomplish this using an elastomeric mold with two different sets of embedded microfluidic channels that are patterned and injected with EGaIn and water, respectively. The electrochemical reaction is then used to etch the thin oxide layer that forms on eutectic gallium indium (EGaIn) in a controlled reproducible manner. Once the oxide layer is dissolved locally, the underlying liquid metal retracts away from the original position to a position where a new stable oxide layer can reform, which is equivalent to erasing a section of the liquid metal. To allow for full reconfigurability, the entire device can be reset by refilling all of the microchannels with EGaIn.
Project description:Stable suspensions of eutectic gallium indium (EGaIn) liquid metal nanoparticles form by probe-sonicating the metal in an aqueous solution. Positively-charged molecular or macromolecular surfactants in the solution, such as cetrimonium bromide or lysozyme, respectively, stabilize the suspension by interacting with the negative charges of the surface oxide that forms on the metal. The liquid metal breaks up into nanospheres <i>via</i> sonication, yet can transform into rods of gallium oxide monohydroxide (GaOOH) <i>via</i> moderate heating in solution either during or after sonication. Whereas heating typically drives phase transitions from solid to liquid (<i>via</i> melting), here heating drives the transformation of particles from liquid to solid <i>via</i> oxidation. Interestingly, indium nanoparticles form during the process of shape transformation due to the selective removal of gallium. This dealloying provides a mechanism to create indium nanoparticles at temperatures well below the melting point of indium. To demonstrate the versatility, we show that it is possible to shape transform and dealloy other alloys of gallium including ternary liquid metal alloys. Scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDS) mapping, and X-ray diffraction (XRD) confirm the dealloying and transformation mechanism.
Project description:Liquid metals show unparalleled advantages in printable circuits, flexible wear, drug carriers, and electromagnetic shielding. However, the efficient and large-scale preparation of liquid metal nanodroplets (LM NDs) remains a significant challenge. Here, we propose a simple and efficient method for the large-scale preparation of stable eutectic gallium indium nanodroplets (EGaIn NDs). We compared different preparation methods and found that droplets with smaller particle sizes could quickly be produced using a shaking technique. The size of EGaIn NDs produced using this technique can reach 200 nm in 30 min and 100 nm in 240 min. Benefiting from the simple method, various surfactants can directly modify the surface of the EGaIn NDs to stabilize the prepared droplets. In addition, we discovered that shaking in an ice bath produced spherical nanodroplets, and after shaking for 30 min in a non-ice bath, rod-shaped gallium oxide hydroxide (GaOOH) appeared. Furthermore, the EGaIn NDs we produced have excellent stability-after storage at room temperature for 30 days, the particle size and morphology change little. The excellent stability of the produced EGaIn NDs provides a wider application of liquid metals in the fields of drug delivery, electromagnetic shielding, conductive inks, printed circuits, etc.
Project description:In this paper, a gravity-triggered liquid metal microstrip patch antenna with reconfigurable frequency is proposed with experimental verification. In this work, the substrate of the antenna is quickly obtained through three-dimensional (3D) printing technology. Non-toxic EGaIn alloy is filled into the resin substrate as a radiation patch, and the NaOH solution is used to remove the oxide film of EGaIn. In this configuration, the liquid metal inside the antenna can be flexibly flowed and deformed with different rotation angles due to the gravity to realize different working states. To validate the conception, the reflection coefficients and radiation patterns of the prototyped antenna are then measured, from which it can be observed that the measured results closely follow the simulations. The antenna can obtain a wide operating bandwidth of 3.69-4.95 GHz, which coverage over a range of frequencies suitable for various channels of the 5th generation (5G) mobile networks. The principle of gravitational driving can be applied to the design of reconfigurable antennas for other types of liquid metals.
Project description:Gallium-based liquid metal alloys have been attracting attention from both industry and academia as soft, deformable, reconfigurable and multifunctional materials in microfluidic, electronic and electromagnetic devices. Although various technologies have been explored to control the morphology of liquid metals, there is still a lack of methods that can achieve precise morphological control over a free-standing liquid metal droplet without the use of mechanical confinement. Electrochemical manipulation can be relatively easy to apply to liquid metals, but there is a need for techniques that can enable automatic and precise control. Here, we investigate the use of an electrochemical technique combined with a feedback control system to automatically and precisely control the morphology of a free-standing liquid metal droplet in a sodium hydroxide solution. We establish a proof-of-concept platform controlled by a microcontroller to demonstrate the reconfiguration of a liquid metal droplet to desired patterns. We expect that this method will be further developed to realize future reconfigurable liquid metal-enabled soft robots.
Project description:Micro- to nanosized droplets of liquid metals, such as eutectic gallium indium (EGaIn) and Galinstan, have been used for developing a variety of applications in flexible electronics, sensors, catalysts, and drug delivery systems. Currently used methods for producing micro- to nanosized droplets of such liquid metals possess one or several drawbacks, including the lack in ability to control the size of the produced droplets, mass produce droplets, produce smaller droplet sizes, and miniaturize the system. Here, a novel method is introduced using acoustic wave-induced forces for on-chip production of EGaIn liquid-metal microdroplets with controllable size. The size distribution of liquid metal microdroplets is tuned by controlling the interfacial tension of the metal using either electrochemistry or electrocapillarity in the acoustic field. The developed platform is then used for heavy metal ion detection utilizing the produced liquid metal microdroplets as the working electrode. It is also demonstrated that a significant enhancement of the sensing performance is achieved by introducing acoustic streaming during the electrochemical experiments. The demonstrated technique can be used for developing liquid-metal-based systems for a wide range of applications.