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3D Printing of Free Standing Liquid Metal Microstructures

Collin Ladd, Ju-Hee So, John Muth, and Michael D. Dickey*
This paper describes a method to direct-write liquid metal microcomponents at room temperature. Three-dimensional (3D) printing is gaining popularity for rapid prototyping and patterning. Many 3D printers extrude molten polymer that quickly cools and solidies. The ability to pattern liquids into arbitrary shapes both in and out of plane is usually limited by interfacial tension. A classic example is the break-up of cylinders of liquid into droplets when the aspect ratio of the cylinder exceeds the Rayleigh stability limit of .[1] Here, we show it is possible to direct-write a low viscosity liquid metal at room temperature into a variety of stable free-standing 3D microstructures (cylinders with aspect ratios signicantly beyond the Rayleigh stability limit, 3D arrays of droplets, out of plane arches, wires). A thin (1 nm thick), passivating oxide skin forms rapidly on the surface of the liquid metal and stabilizes the microstructures despite the low viscosity and large surface energy of the liquid.[2] The ability to directly print metals with liquid-like properties is important for soft, stretchable, and shape recongurable analogs to wires, electrical interconnects, electrodes, antennas, meta-materials, and optical materials. In the absence of external elds, interfacial tension dictates the shape and the behavior of liquids at the sub-mm length scale. It can cause smaller droplets to coalesce, jets of liquid to break up, and thin lms of liquid to dewet.[3,4] Several techniques have been developed to stabilize the shape of uids into desirable shapes despite the destabilizing inuence of surface tension. The most prevalent approach is to convert a liquid into a solid to trap it in a non-equilibrium shape (e.g., polymer melt processing). Liquid droplets can be stabilized against coalescence by the inclusion of solid particles, macromolecules, or surfactants on their surface. However, these structures (e.g., liquid marbles, colloidosomes, and emulsions) typically adopt spherical shapes.[5,6] The ability to pattern materials into arbitrary 3D microstructures is important for electronics,[7] microuidic networks,[8,9] tissue engineering scaffolds,[10] photonic band gap structures,[11] and chemical synthesis.[12] There are several strategies to pattern 3D microstructures including lithography, laser writing, colloidal assembly and direct-write techniques.[11,1317] Direct-write techniques are appealing because they are additive processes, although most work has focused on the patterning
Mr. C. Ladd, Dr. J.-H. So, Prof. M. D. Dickey Department of Chemical and Biomolecular Engineering North Carolina State University Raleigh, NC 27695, USA E-mail: mddickey@ncsu.edu Prof. J. Muth Department of Electrical and Computer Engineering North Carolina State University Raleigh, NC 27695, USA

DOI: 10.1002/adma.201301400

of polymers. Recently, there has been great interest in new methods to direct write 3D conductive microstructures for antennas,[18] exible displays[19,20] and wire bonds.[21,22] One approach is to pattern composites of conductive additives in insulating materials (e.g. polymers), but these composites often have limited conductivity and mechanical properties. Recently, two new methods have been demonstrated for direct writing solid metal wires including extrusion of metal particles from a nozzle[21] or by electrodeposition from a conductive tip.[22] Here, we demonstrate that it is possible to direct write structures composed of a low-viscosity liquid with metallic conductivity at room temperature. The liquid metal is useful for soft, stretchable, or shape recongurable electronics. We focus on the binary eutectic alloy of gallium and indium (EGaIn, 75% Ga 25% In by weight), but any alloy of gallium will also work. EGaIn is liquid at room temperature (m.p. 15.7 C) with metallic conductivity.[23] The liquid metal exhibits a negligible vapor pressure and low toxicity. Upon exposure to air, the metal forms a thin (1 nm) passivating skin composed of gallium oxide.[2] Passivation occurs nearly instantaneously under atmospheric oxygen levels and electrical resistance remains largely unaffected because the skin is thin.[24] In addition, the liquid metal adheres to most surfaces and alloys with many metals to form ohmic contacts. Injection of liquid metal into microchannels is an established method to shape the metal for recongurable wires and antennas,[25,26] interconnects,[27,28] electrical components for microuidics,[29] and soft electrodes for electrical characterizations of thin lms.[30] The use of microuidics limits the ability to shape the metal because the channels are in a single plane, whereas many applications (e.g., interconnects, meta-materials, optical materials) require out of plane or 3D architectures. In addition, the necessity of inlet and outlet ports makes it difcult to pattern arrays of small, discrete structures of the metal via microuidic injection. A number of other methods for patterning liquid metal in 2D are beginning to emerge.[3134] Here, we present free standing liquid metal structures such as wires, bers, interconnects, and stacks and arrays of droplets using four separate yet related direct-write patterning methods. We elucidate the mechanism by which these structures form and present a working proof-of-concept exible circuit using liquid metal wire bonds. Fabrication of Free Standing Wires: Figure 1 depicts the general approach for printing liquid metal structures. Modest gauge pressure (<5 kPa) applied to a syringe needle extrudes the liquid metal wire onto a substrate controlled by a motorized translation stage (see Supporting Information and Video S1). The travel of the translation stage set an upper limit on the length of the wires, which can be several cm long when the wires span from the substrate to the tip of the syringe. The wires, however, can be terminated at any time by applying an appropriate amount of vacuum to the syringe (c.f., Figure 1).

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2

force by measuring the deection imposed by droplets of various sizes at the end of the cantilever and then measured the deection of the needle while stretching wires. Figure 2a plots the force as a function of minimum circumference of the wire. The slope of the tted line is 0.77 N/m, which is similar to the previously reported value of the critical surface yield stress of the oxide (0.5 N/m) measured in shear.[31] This value may also include the effects of surface tension associated with increasing the surface area of the liquid. Increasing the distance between the stage and the syringe generates the tensile force necessary to elongate the wire. For the wires (e.g., those shown in Figure 1) to form, three things seemingly must happen: the oxide skin must yield in tensile mode for the wire to elongate, the liquid metal must be under pressure to Figure 1. Direct write of free standing liquid metal wires. Sequential images in which a syringe prevent the liquid from collapsing during needle extrudes liquid metal to form a straight wire on a withdrawn substrate. The oxide skin on elongation, and the pressure inside the wire the surface of the metal stabilizes the liquid metal wire against gravity and surface tension. The cannot be too large otherwise the ber will diameter of the wire is 270 m. The length of the rightmost wire is 8 mm. In the last image, bulge radially. To determine the range of the wire was intentionally severed by applying vacuum to the syringe. pressures over which the metal necks, bulges, or forms stable wires, we formed numerous Once detached from the syringe, the wires maintain their wires while only varying the pressure of the metal. Figure 2b shape. The tallest freestanding wires were 1 cm tall with a demonstrates that the wires form at room temperature over a diameter of 200 m. The diameter of the nozzle dictates the range of pressures that are easy to control experimentally. As diameter of the wire; the narrowest wire had a diameter of 30 expected, at low pressures, the wires neck and at larger presm, which corresponds to the diameter of the smallest glass sures the wires bulge. The wires begin to bulge at pressures capillary we produced and is slightly smaller than a typical wire (5 kPa) in nearly perfect agreement with that predicted by the bond. The draw rate (2200 m/sec) of the wire has a negligible yield stress of the oxide skin for the radius of the fabricated effect on the diameter. wires. Figure 2b also suggests that formation of wires requires The wires in Figure 1 are remarkable and unexpected. The minimal positive pressure, which implies that the oxide skin process of forming the wires begins by forming a bead of the re-forms rapidly and stabilizes the wire against capillary forces. metal on the tip of the syringe. Although the metal is under Three Additional Approaches to Fabricate Freestanding Micropressure the entire time, it does not ow out of the syringe due structures: In addition to extruding wires, it is possible to to the stabilizing inuence of the oxide skin. Without increasing form free standing liquid metal microstructures using at least or decreasing the pressure in the syringe, wires form when the three additional methods: (1) Expelling rapidly the metal to metal contacts the substrate and the tip of the syringe withform a stable liquid metal lament, (2) Stacking droplets, and draws away from the substrate. Because the oxide skin spans (3) Injecting the metal into microchannels and subsequently from the nozzle of the syringe to the substrate, increasing the removing the channels chemically. distance between the nozzle and substrate generates a tensile The structures in Figures 3a and 3b rely on rapidly expelling force along the axis of the wire that yields the skin and allows the metal from the syringe using bursts of pressure (60 kPa the wire to elongate. The pressure of the liquid metal retards of pressure for tens of msec; Supporting Video S2). Fibers also any destabilizing capillary forces long enough for new skin to form at larger pressures, but rupture when they reach the subform and thereby mechanically stabilizes the wire. strate. The resulting structures are bers composed of liquid To investigate this mechanism, we measured the tensile force metal that are tens of micrometers in diameter. In Figure 3a, required to stretch the wire. We modeled an extruded straight the ber spans from a microsyringe to the substrate and in wire (c.f., Figure 1) as a cylinder coated with a thin, radially symFigure 3b, the resulting ber is strong enough to span across metric shell of oxide with uniform thickness. The tensile stress a large gap. The bers in Figure 3a naturally form a bead upon within the oxide shell can be approximated using the equation hitting the surface, which may be useful for forming contact (1), where F is the applied force, r is the minimum radius of the pads. Without optimization, these bers have a nearly uniform extruded wire, and is the tensile surface yield stress. diameter with some beading along the axis of the ber. The structure in Figure 3c forms in a manner identical to F = 2 r (1) those in Figure 1, but is bent into an arch using the motion of the stage. This process can fabricate 3D microstructures of the The deection of a calibrated cantilever (a 32 gauge needle) liquid metal such as wires, arches, and bridges. measured the tensile force of the wire. We rst calibrated the

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Figure 2. (a) Tensile force increases as a function of the minimum circumference of the extruded wire. The slope of the best t line (0.77 N/m) represents the tensile stress required to elongate the metal wire along the long axis. (b) The mechanical stability of the liquid metal wires as a function of the applied pressure (circles: necking, rectangles: stable wires, triangles: bulging). The inset shows images of a glass capillary forming wires that necked, stabilized, and bulged.

Figures 3d, 3e and 3f are 3D microstructures composed of sequentially stacked droplets of liquid metal (Supporting Video S3). The droplets form using short bursts of pressure (2060 kPa for 12 msec) and remain suspended from the tip of the syringe until they contact another droplet. When the droplets touch each other, they merge to form a physical and electrical contact without coalescing into one bigger droplet. Figure 3d and 3e show stacks of droplets and Figure 3f shows a wire arch crossing over another wire composed of metal droplets. Chemically etching the microuidic molds after injection of the liquid metal offers another way of fabricating free standing conductive microstructures. After injecting the liquid metal into a 10-turn, coil-shaped polydimethylsiloxane (PDMS) microchannel that is 200 m wide and tall, a solution of 1.0 M tetrabutylammonium uoride (TBAF)/ dimethylformamide (DMF) removed the PDMS via chemical etching (Figure 3g). The patterned metal lines maintain mechanical stability due to the oxide skin even after removing completely the polymer casing. Encasing the free standing liquid metal structures with other materials such as polymers, elastomers and ceramics may be desirable. Since the metal is liquid, the encasing material dictates the mechanical properties of the resulting devices. To demonstrate an application of liquid metal wires for stretchable electronics (i.e., electronics that function while being elongated), we embedded the wires in PDMS (Figure 4). A micrograph of the wire in PDMS (Figure 4a, inset) shows a wire bond composed of liquid metal droplets connecting two surface mounted LEDs separated by 5 mm. The liquid metal bridge connecting the LEDs functioned up to the strain limit of PDMS (Figure 4b, 35% strain) and while being exed (Figure 4c, d) without losing its electrical continuity. In summary, we describe four different methods to direct write 3D, free standing, liquid metal microstructures by extruding the liquid metal through a capillary. The thin oxide layer on the surface of the metal allows for the formation of mechanically stable structures strong enough to stand against gravity and the large surface tension of the liquid. We described the mechanics of wire formation, created wires with aspect

Figure 3. Direct writing of liquid metal 3D structures. Photographs of the diverse free standing, liquid metal microstructures that can be direct printed at room temperature. (a) Liquid metal ejected rapidly from a glass capillary forms a thin wire. (b) These bers are strong enough to suspend over a gap despite being composed of liquid. (c) A free standing liquid metal arch. (d) A tower of liquid metal droplets. (e) A 3D cubic array of stacked droplets. (f) A metal wire and an arch composed of liquid metal droplets. (g) An array of in-plane lines of free standing liquid metal fabricated by lling a microchannel with the metal and dissolving away the mold. Scale bars represent 500 m.

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Figure 4. Stretchable interconnects formed by direct-write. (a) A prototype device composed of two LEDs connected by a stretchable wire bond and embedded in PDMS (Inset: Microscopy image of the liquid metal wire bonds). (bd) The uidic property of the metal wire in the elastomer allows elasticity (b) and exibility (c, d) of the device and keeps its electrical continuity.

ratios more than 100 times the Rayleigh stability limit, and demonstrated stretchable wire bonds in which the uidic properties of the metal facilitate deformation without losing electrical continuity. The smallest components we fabricated were 10 m, but there may be opportunities to create smaller structures through, for example, the use of smaller nozzles. We expect that other types of encasing materials such as castable plastics, ceramics, resins and gels could provide new functionalities with the liquid metal microstructures. This work demonstrates new methods for 3D patterning and suggests that skin forming liquids may be used to direct-write liquids into shapes previously prohibited by the destabilizing effects of surface tension.

Acknowledgements
This work has been funded by National Science Foundation (CAREER Award CMMI-0954321) and the NSF ASSIST ERC (EEC-1160483). Authors C.L. and J.-H.S. contributed equally to this work. Received: March 27, 2013 Revised: Published online:

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