The use of liquid metals based on gallium for soft and stretchable electronics is discussed. This emerging class of electronics is motivated, in part, by the new opportunities that arise from devices that have mechanical properties similar to those encountered in the human experience, such as skin, tissue, textiles, and clothing. These types of electronics (e.g., wearable or implantable electronics, sensors for soft robotics, e-skin) must operate during deformation. Liquid metals are compelling materials for these applications because, in principle, they are infinitely deformable while retaining metallic conductivity. Liquid metals have been used for stretchable wires and interconnects, reconfigurable antennas, soft sensors, self-healing circuits, and conformal electrodes. In contrast to Hg, liquid metals based on gallium have low toxicity and essentially no vapor pressure and are therefore considered safe to handle. Whereas most liquids bead up to minimize surface energy, the presence of a surface oxide on these metals makes it possible to pattern them into useful shapes using a variety of techniques, including fluidic injection and 3D printing. In addition to forming excellent conductors, these metals can be used actively to form memory devices, sensors, and diodes that are completely built from soft materials. The properties of these materials, their applications within soft and stretchable electronics, and future opportunities and challenges are considered.

Stretchable and Soft Electronics using Liquid Metals.

Post-transition elements, together with zinc-group metals and their alloys belong to an emerging class of materials with fascinating characteristics originating from their simultaneous metallic and liquid natures. These metals and alloys are characterised by having low melting points (i.e. between room temperature and 300 °C), making their liquid state accessible to practical applications in various fields of physical chemistry and synthesis. These materials can offer extraordinary capabilities in the synthesis of new materials, catalysis and can also enable novel applications including microfluidics, flexible electronics and drug delivery. However, surprisingly liquid metals have been somewhat neglected by the wider research community. In this review, we provide a comprehensive overview of the fundamentals underlying liquid metal research, including liquid metal synthesis, surface functionalisation and liquid metal enabled chemistry. Furthermore, we discuss phenomena that warrant further investigations in relevant fields and outline how liquid metals can contribute to exciting future applications.

Liquid metals: fundamentals and applications in chemistry

Several gallium-based liquid metal alloys are liquid at room temperature. As 'liquid', such alloys have a low viscosity and a high surface tension while as 'metal', they have high thermal and electrical conductivities, similar to mercury. However, unlike mercury, these liquid metal alloys have low toxicity and a negligible vapor pressure, rendering them much safer. In comparison to mercury, the distinguishing feature of these alloys is the rapid formation of a self-limiting atomically thin layer of gallium oxide over their surface when exposed to oxygen. This oxide layer changes many physical and chemical properties of gallium alloys, including their interfacial and rheological properties, which can be employed and modulated for various applications in microfluidics. Injecting liquid metal into microfluidic structures has been extensively used to pattern and encapsulate highly deformable and reconfigurable electronic devices including electrodes, sensors, antennas, and interconnects. Likewise, the unique features of liquid metals have been employed for fabricating miniaturized microfluidic components including pumps, valves, heaters, and electrodes. In this review, we discuss liquid metal enabled microfluidic components, and highlight their desirable attributes including simple fabrication, facile integration, stretchability, reconfigurability, and low power consumption, with promising applications for highly integrated microfluidic systems.

Liquid metal enabled microfluidics

Binary mixtures of liquid metal (LM) or low-melting-point alloy (LMPA) in an elastomeric or fluidic carrier medium can exhibit unique combinations of electrical, thermal, and mechanical properties. This emerging class of soft multifunctional composites have potential applications in wearable computing, bio-inspired robotics, and shape-programmable architectures. The dispersion phase can range from dilute droplets to connected networks that support electrical conductivity. In contrast to deterministically patterned LM microfluidics, LMPA- and LM-embedded elastomer (LMEE) composites are statistically homogenous and exhibit effective bulk properties. Eutectic Ga-In (EGaIn) and Ga-In-Sn (Galinstan) alloys are typically used due to their high conductivity, low viscosity, negligible nontoxicity, and ability to wet to nonmetallic materials. Because they are liquid-phase, these alloys can alter the electrical and thermal properties of the composite while preserving the mechanics of the surrounding medium. For composites with LMPA inclusions (e.g., Field's metal, Pb-based solder), mechanical rigidity can be actively tuned with external heating or electrical activation. This progress report, reviews recent experimental and theoretical studies of this emerging class of soft material architectures and identifies current technical challenges and opportunities for further advancement.

Soft Multifunctional Composites and Emulsions with Liquid Metals

This highlight describes emerging methods to pattern metals that are liquid at room temperature. The ability to pattern liquid metals is important for fabricating metallic components that are soft, stretchable, conformal, and in some cases, shape-reconfigurable. Applications include electrodes, antennas, micro-mirrors, plasmonic structures, sensors, switches, and interconnects. Gallium (Ga) and its liquid metal alloys are attractive alternatives to toxic mercury. This family of alloys spontaneously forms a surface oxide that dominates the rheological and wetting properties of the metal. These properties pose challenges using conventional fabrication methods, but present new opportunities for patterning innovations. For example, Ga-based liquid metals may be injected, imprinted, or 3D printed on either soft or hard substrates. The use of a liquid metal also enables rapid and facile room temperature processing. The patterning techniques organize into four categories: (i) patterning enabled by lithography, (ii) injection, (iii) subtractive techniques, and (iv) additive techniques. Although many of these approaches take advantage of the surface oxide that forms on Ga and its alloys, some of the approaches may also be suitable for patterning other soft-conductors (e.g., conductive inks, pastes, elastomeric composites).

Methods to pattern liquid metals

A nontoxic liquid metal, such as eutectic gallium-indium (EGaIn) alloy, has been used to develop tunable radio frequency (RF) components, such as antennas, inductors, or capacitors, for enabling large tunable range, better linearity, and low loss, using fluidic displacement of the liquid metal. However, EGaIn residue, due to its fast oxidation, limits multiple movement of the EGaIn in the reconfigurable RF components. This paper focuses on the use of surfactants, carrier liquids, and microchannel coating materials that minimize EGaIn fragmentation and EGaIn residues on poly(dimethylsiloxane) (PDMS)-based microfluidic channels during repeated actuation of an EGaIn plug. Using a combination of carrier liquids and microchannel coating materials to minimize EGaIn from leaving residues on the PDMS microfluidic channel, a microstrip transmission line switch as a proof-of-concept reconfigurable RF application using the EGaIn plug is demonstrated. It is switched ON<4 dB and OFF with a loss of <18 dB over the frequency range between 4 and 15 GHz. [2014-0228]

Hannah E. Fitzgerald

Papers

Manipulating Liquid Metal Droplets in Microfluidic Channels With Minimized Skin Residues Toward Tunable RF Applications