Michael D. Dickey

3D Printing of Free Standing Liquid Metal Microstructures

This paper describes a method to direct-write 3D liquid metal microcomponents at room temperature. The thin oxide layer on the surface of the metal allows the formation of mechanically stable structures strong enough to stand against gravity and the large surface tension of the liquid. The method is capable of printing wires, arrays of spheres, arches, and interconnects.

Self-folding of polymer sheets using local light absorption

This paper demonstrates experimentally and models computationally a novel and simple approach for self-folding of thin sheets of polymer using unfocused light. The sheets are made of optically transparent, pre-strained polystyrene (also known as Shrinky-Dinks) that shrink in-plane if heated uniformly. Black ink patterned on either side of the polymer sheet provides localized absorption of light, which heats the underlying polymer to temperatures above its glass transition. At these temperatures, the predefined inked regions (i.e., hinges) relax and shrink, and thereby cause the planar sheet to fold into a three-dimensional object. Self-folding is therefore achieved in a simple manner without the use of multiple fabrication steps and converts a uniform external stimulus (i.e., unfocused light) on an otherwise compositionally homogenous substrate into a hinging response. Modeling captures effectively the experimental folding trends as a function of the hinge width and support temperature and suggests that the hinged region must exceed the glass transition temperature of the sheet for folding to occur.

Light‐Powered Electrical Switch Based on Cargo‐Lifting Azobenzene Monolayers

Inspired by the complex molecular machines found in nature, chemists have developed much simpler molecular motors. Among them, several systems incorporating azobenzene have been proposed, which exploit the reversible trans–cis isomerization triggered by light or an electric field for applications such as optical data-storage devices, switchable supramolecular cavities, and sensors. Recently, it has been demonstrated that the photoisomerization process of individual polymer chains incorporating azobenzenes can express mechanical work. In light of these findings, one can foresee self-assembled monolayers (SAMs) of aromatic azobenzenes as molecular systems able to express forces of unprecedented magnitude by exploiting a collective subnanometer structural change. We recently designed a rigid and fully conjugated azobenzene exposing a thiol anchoring group, which was able to form a tightly packed SAM on Au(111) (SAMAZO). Scanning tunneling microscopy (STM) studies revealed that upon light irradiation of the chemisorbed SAMs, a collective isomerization of entire molecular-crystalline domains occurred with an outstandingly high directionality. Based on these results, a cooperative nature of the isomerization of adjacent AZO molecules has been proposed. Furthermore, the joint action of the molecules in the SAM provides an ideal system as a potential “cargo” lifter. Herein, we show that, upon irradiation, azobenzene SAMs incorporated in a junction between an Au(111) surface and a mercury drop are able to 1) lift the “heavy” Hg drop, and 2) reversibly photoswitch the current flowing through the junction (Figure 1). Current–voltage (I–V) characteristics averaged over more than 30 junctions incorporating AZO SAMs in the trans and the cis conformations are shown in Figure 2a. The SAMAZO in the cis conformation was obtained with extremely high yield (98%) upon irradiation by UV light of the SAMAZO initially formed by the trans conformer. The difference in the measured currents, which amounts to about 1.4 orders of magnitude, is in agreement with a through-bond tunneling mechanism described by Equation (1).

Self‐Healing Stretchable Wires for Reconfigurable Circuit Wiring and 3D Microfluidics

This article describes the fabrication of self-healing stretchable wires formed by embedding liquid metal wires in microchannels composed of self-healing polymer. These stretchable wires can be completely severed with scissors and rapidly self-heal both mechanically and electrically at ambient conditions. By cutting the channels strategically, the pieces can be re-assembled in a different order to form complex microfluidic networks in 2D or 3D space.

Emerging Applications of Liquid Metals Featuring Surface Oxides

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.

Charge Transport and Rectification in Arrays of SAM-Based Tunneling Junctions

This paper describes a method of fabrication that generates small arrays of tunneling junctions based on self-assembled monolayers (SAMs); these junctions have liquid-metal top-electrodes stabilized in microchannels and ultraflat (template-stripped) bottom-electrodes. The yield of junctions generated using this method is high (70-90%). The junctions examined incorporated SAMs of alkanethiolates having ferrocene termini (11-(ferrocenyl)-1-undecanethiol, SC(11)Fc); these junctions rectify currents with large rectification ratios (R), the majority of which fall within the range of 90-180. These values are larger than expected (theory predicts R <or= 20) and are larger than previous experimental measurements. SAMs of n-alkanethiolates without the Fc groups (SC(n-1)CH(3), with n = 12, 14, 16, or 18) do not rectify (R ranged from 1.0 to 5.0). These arrays enable the measurement of the electrical characteristics of the junctions as a function of chemical structure, voltage, and temperature over the range of 110-293 K, with statistically large numbers of data (N = 300-800). The mechanism of rectification with Fc-terminated SAMs seems to be charge transport processes that change with the polarity of bias: from tunneling (at one bias) to hopping combined with tunneling (at the opposite bias).

Flexible Liquid Metal Alloy (EGaIn) Microstrip Patch Antenna

This paper describes a flexible microstrip patch antenna that incorporates a novel multi-layer construction consisting of a liquid metal (eutectic gallium indium) encased in an elastomer. The combined properties of the fluid and the elastomeric substrate result in a flexible and durable antenna that is well suited for conformal antenna applications. Injecting the metal into microfluidic channels provides a simple way to define the shape of the liquid, which is stabilized mechanically by a thin oxide skin that forms spontaneously on its surface. This approach has proven sufficient for forming simple, single layer antenna geometries, such as dipoles. More complex fluidic antennas, particularly those featuring large, co-planar sheet-like geometries, require additional design considerations to achieve the desired shape of the metal. Here, a multi-layer patch antenna is fabricated using specially designed serpentine channels that take advantage of the unique rheological properties of the liquid metal alloy. The flexibility of the resulting antennas is demonstrated and the antenna parameters are characterized through simulation and measurement in both the relaxed and flexed states.

A technique to transfer metallic nanoscale patterns to small and non-planar surfaces.

Conventional lithographic methods (e.g., electron-beam lithography, photolithography) are capable of producing high-resolution structures over large areas but are generally limited to large (>1 cm(2)) planar substrates. Incorporation of these features on unconventional substrates (i.e., small (<1 mm(2)) and/or non-planar substrates) would open possibilities for many applications, including remote fiber-based sensing, nanoscale optical lithography, three-dimensional fabrication, and integration of compact optical elements on fiber and semiconductor lasers. Here we introduce a simple method in which a thin thiol-ene film strips arbitrary nanoscale metallic features from one substrate and is then transferred, along with the attached features, to a substrate that would be difficult or impossible to pattern with conventional lithographic techniques. An oxygen plasma removes the sacrificial film, leaving behind the metallic features. The transfer of dense and sparse patterns of isolated and connected gold features ranging from 30 nm to 1 mum, to both an optical fiber facet and a silica microsphere, demonstrates the versatility of the method. A distinguishing feature of this technique is the use of a thin, sacrificial film to strip and transfer metallic nanopatterns and its ability to directly transfer metallic structures produced by conventional lithography.

Towards All‐Soft Matter Circuits: Prototypes of Quasi‐Liquid Devices with Memristor Characteristics

IO N We present a new class of electrically functional devices composed entirely of soft, liquid-based materials that display memristor-like characteristics. A memristor, or a “memory resistor”, is an electronic device that changes its resistive state depending on the current or voltage history through the device. Memristors may become the core of next generation memory devices because of their low energy consumption and high data density and performance. [ 1–3 ] Since the concept of memristors was theorized in 1971, [ 4 ] resistive switching memories have been fabricated from a variety of materials operating on magnetic, [ 5 ] thermal, [ 6 ] photonic, [ 7 ] electronic and ionic mechanisms. [ 3 , 8 , 9 ] Conventional memristive devices typically include metalinsulator-metal (M-I-M) junctions composed of rigid stacks of fi lms fabricated by multiple vacuum-deposition steps, often at high temperature. The most common “insulator” materials in M-I-M memristor junctions are inorganic metal oxides such as TiO 2 [ 10 ] and NiO. [ 11 ] Conducting pathways can form by current through such layers. Solid electrolytes between metal electrodes can also be used to create resistance switches (e.g., Ag/ Ag 2 S/Pt), in which conductive metal fi laments that bridge the two electrodes can be formed or annihilated on demand. [ 3 , 9 ] Memristive circuits composed of organic materials have some advantages over conventional metal oxides due to their ease of processing, light weight, and low cost. A variety of organic materials such as homogeneous polymers, small-molecule or nanoparticle doped polymers, and organic donor-acceptor complexes have been evaluated as components in memory switching devices. [ 12 ] We report new controllably bi-stable memristor-like devices fabricated entirely from liquid-based materials. These soft and fl exible devices are built from liquid metal and hydrogels that are used routinely in laboratories for hosting biological molecules and supporting cell growth. Hydrogels are soft, moldable and bio-compatible media similar to biological systems with high ion mobility due to the high water content ( > 90% water). [ 13 , 14 ] The ionic properties of the gels can be tuned by inclusion of polyelectrolytes that are immobilized via entanglement within the gel network. Hydrogels doped with polyelectrolytes have been utilized for fabricating electronic devices such as diodes and photovoltaic cells. [ 13 , 15 , 16 ] The electrodes of these devices, however, are rigid metals such as platinum and

Nanoskiving: A New Method To Produce Arrays of Nanostructures

This Account reviews nanoskiving--a new technique that combines thin-film deposition of metal on a topographically contoured substrate with sectioning using an ultramicrotome--as a method of fabricating nanostructures that could replace conventional top-down techniques in selected applications. Photolithography and scanning beam lithography, conventional top-down techniques to generate nanoscale structures and nanostructured materials, are useful, versatile, and highly developed, but they also have limitations: high capital and operating costs, limited availability of the facilities required to use them, an inability to fabricate structures on nonplanar surfaces, and restrictions on certain classes of materials. Nanoscience and nanotechnology would benefit from new, low-cost techniques to fabricate electrically and optically functional structures with dimensions of tens of nanometers, even if (or perhaps especially if) these techniques have a different range of application than does photolithography or scanning beam lithography. Nanoskiving provides a simple and convenient procedure to produce arrays of structures with cross-sectional dimensions in the 30-nm regime. The dimensions of the structures are determined by (i) the thickness of the deposited thin film (tens of nanometers), (ii) the topography (submicrometer, using soft lithography) of the surface onto which the thin film is deposited, and (iii) the thickness of the section cut by the microtome (> or =30 nm by ultramicrotomy). The ability to control the dimensions of nanostructures, combined with the ability to manipulate and position them, enables the fabrication of nanostructures with geometries that are difficult to prepare by other methods. The nanostructures produced by nanoskiving are embedded in a thin epoxy matrix. These epoxy slabs, although fragile, have sufficient mechanical strength to be manipulated and positioned; this mechanical integrity allows the nanostructures to be stacked in layers, draped over curved surfaces, and suspended across gaps, while retaining the in-plane geometry of the nanostructures embedded in the epoxy. After removal of the polymer matrix by plasma oxidation, these structures generate suspended and draped nanostructures and nanostructures on curved surfaces. Two classes of applications, in optics and in electronics, demonstrate the utility of nanostructures fabricated by nanoskiving. This technique will be of primary interest to researchers who wish to generate simple nanostructures, singly or in arrays, more simply and quickly than can be accomplished in the clean-room. It is easily accessible to those not trained in top-down procedures for fabrication and those with limited or no access to the equipment and facilities needed for photolithography or scanning-beam fabrication. This Account discusses a new fabrication method (nanoskiving) that produces arrays of metal nanostructures. The defining process in nanoskiving is cutting slabs from a polymeric matrix containing embedded, more extended metal structures.