3D printed microfluidic valve on PCB for flow control applications using liquid metal.

Direct 3D printing of active microfluidic elements on PCB substrates enables high-speed fabrication of stand-alone microdevices for a variety of health and energy applications. Microvalves are key components of microfluidic devices and liquid metal (LM) microvalves exhibit promising flow control in microsystems integrated with PCBs. In this paper, we demonstrate LM microvalves directly 3D printed on PCB using advanced digital light processing (DLP). Electrodes on PCB are coated by carbon ink to prevent alloying between gallium-based LM plug and copper electrodes. We used DLP 3D printers with in-house developed acrylic-based resins, Isobornyl Acrylate, and Diurethane Dimethacrylate (DUDMA) and functionalized PCB surface with acrylic-based resin for strong bonding. Valving seats are printed in a 3D caterpillar geometry with chamber diameter of 700 µm. We successfully printed channels and nozzles down to 90 µm. Aiming for microvalves for low-power applications, we applied square-wave voltage of 2 Vpp at a range of frequencies between 5 to 35 Hz. The results show precise control of the bistable valving mechanism based on electrochemical actuation of LMs.

Tungsten Oxide Coated Liquid Metal Electrodes via Galvanic Replacement as Heavy Metal Ion Sensors.

Gallium liquid metals (LMs) like Galinstan and eutectic Gallium-Indium (EGaIn) have seen increasing applications in heavy metal ion (HMI) sensing, because of their ability to amalgamate with HMIs like lead, their high hydrogen potential, and their stable electrochemical window. Furthermore, coating LM droplets with nanopowders of tungsten oxide (WO) has shown enhancement in HMI sensing owing to intense electrical fields at the nanopowder-liquid-metal interface. However, most LM HMI sensors are droplet based, which show limitations in scalability and the homogeneity of the surface. A scalable approach that can be extended to LM electrodes is therefore highly desirable. In this work, we present, for the first time, WO-Galinstan HMI sensors fabricated via photolithography of a negative cavity, Galinstan brushing inside the cavity, lift-off, and galvanic replacement (GR) in a tungsten salt solution. Successful GR of Galinstan was verified using optical microscopy, SEM, EDX, XPS, and surface roughness measurements of the Galinstan electrodes. The fabricated WO-Galinstan electrodes demonstrated enhanced sensitivity in comparison with electrodes structured from pure Galinstan and detected lead at concentrations down to 0.1 mmol·L-1. This work paves the way for a new class of HMI sensors using GR of WO-Galinstan electrodes, with applications in microfluidics and MEMS for a toxic-free environment.

Generation of precision microstructures based on reconfigurable photoresponsive hydrogels for high-resolution polymer replication and microoptics.

Microstructured molds are essential for fabricating various components ranging from precision optics and microstructured surfaces to microfluidics. However, conventional fabrication technology such as photolithography requires expensive equipment and a large number of processing steps. Here, we report a facile method to fabricate micromolds based on a reusable photoresponsive hydrogel: Uniform micropatterns are engraved into the hydrogel surface using photo masks under UV irradiation within a few minutes. Patterns are replicated using polydimethylsiloxane with minimum feature size of 40 µm and smoothness of Rq ~ 3.4 nm. After replication, the patterns can be fully erased by light thus allowing for reuse as a new mold without notable loss in performance. Utilizing greyscale lithography, patterns with different height levels can be produced within the same exposure step. We demonstrate the versatility of this method by fabricating diffractive optical elements devices and a microlens array and microfluidic device with 100 µm wide channels.

In Situ Actuators with Gallium Liquid Metal Alloys and Polypyrrole-Coated Electrodes.

Gallium liquid metal alloys (GLMAs) such as Galinstan and gallium-indium eutectic (EGaIn) are interesting materials due to their high surface tensions, low viscosities, and electrical conductivities comparable to classical solid metals. They have been used for applications in microelectromechanical systems (MEMS) and, more recently, liquid metal microfluidics (LMMF) for setting up devices like actuators. However, their high tendency to alloy with the most common metals used for electrodes such as gold (Au), platinum (Pt), titanium (Ti), nickel (Ni), and tungsten-titanium (WTi) is a major problem limiting the scaleup and applicability, e.g., liquid metal actuators. Stable electrodes are key elements for many applications and thus, the lack of an electrode material compatible with GLMAs is detrimental for many potential application scenarios. In this work, we study the effect of actuating Galinstan on various solid metal electrodes and present an electrode protection methodology that, first, prevents alloying and, second, prevents electrode corrosion. We demonstrate reproducible actuation of GLMA segments in LMMF, showcasing the stability of the proposed protective coating. We investigated a range of electrode materials including Au, Pt, Ti, Ni, and WTi, all in aqueous environments, and present the resulting corrosion/alloying effects by studying the interface morphology. Our proposed protective coating is based on a simple method to electrodeposit electrically conductive polypyrrole (PPy) on the electrodes to provide a conductive alloying-barrier layer for applications involving direct contact between GLMAs and electrodes. We demonstrate the versatility of this approach by direct three-dimensional (3D) printing of a 500 µm microfluidic chip on a set of electrodes onto which PPy is electrodeposited in situ for actuation of Galinstan plugs. The developed protection protocol will provide a generic, widely applicable strategy to protect a wide range of electrodes from alloying and corrosion and thus form a key element in future applications of GLMAs.

An On-Chip Liquid Metal Plug Generator.

Gallium-based liquid metal nonspherical droplets (plugs) have seen increasing demand recently mainly because their high aspect ratios make them beneficial for a wide range of applications, including microelectromechanical systems (MEMS), microfluidics, sensor technology, radio-frequency devices, actuators, and switches. However, reproducibility of the generation of such plugs, as well as precise control over their size, is yet challenging. In this work, a simple on-chip liquid metal plug generator using a commercially available 3D microprinter is presented and the plug generator in poly(dimethylsiloxane) is replicated via soft lithography. Liquid metal plugs are generated via a combination of electrochemical oxidation, design of well-defined constrictions based on Laplace pressure, and the application of modulated voltage control signals. It is shown that plugs of various aspect ratios can be generated reproducibly for channel widths of 0.5, 0.8, and 1.5 mm with constriction widths of 0.1 mm at 6 V. Laplace-pressure-controlled plugs in constricted channels are compared to modulated-voltage-generated plugs in straight channels showing that this technique provides significantly enhanced reproducibility and control over the size and spacing between the plugs. This work paves the way to sub-millimeter liquid metal plugs generated directly on-chip for on-demand MEMS and microfluidic applications.

On-Chip Chemical Synthesis Using One-Step 3D Printed Polyperfluoropolyether.

Three-dimensional (3D) printing has already shown its high relevance for the fabrication of microfluidic devices in terms of precision manufacturing cycles and a wider range of materials. 3D-printable transparent fluoropolymers are highly sought after due to their high chemical and thermal resistance. Here, we present a simple one-step fabrication process via stereolithography of perfluoropolyether dimethacrylate. We demonstrate successfully printed microfluidic mixers with 800 µm circular channels for chemistry-on-chip applications. The printed chips show chemical, mechanical, and thermal resistance up to 200 °C, as well as high optical transparency. Aqueous and organic reactions are presented to demonstrate the wide potential of perfluoropolyether dimethacrylate for chemical synthesis.

Application of Micro/Nanoporous Fluoropolymers with Reduced Bioadhesion in Digital Microfluidics.

Digital microfluidics (DMF) is a versatile platform for conducting a variety of biological and chemical assays. The most commonly used set-up for the actuation of microliter droplets is electrowetting on dielectric (EWOD), where the liquid is moved by an electrostatic force on a dielectric layer. Superhydrophobic materials are promising materials for dielectric layers, especially since the minimum contact between droplet and surface is key for low adhesion of biomolecules, as it causes droplet pinning and cross contamination. However, superhydrophobic surfaces show limitations, such as full wetting transition between Cassie and Wenzel under applied voltage, expensive and complex fabrication and difficult integration into already existing devices. Here we present Fluoropor, a superhydrophobic fluorinated polymer foam with pores on the micro/nanoscale as a dielectric layer in DMF. Fluoropor shows stable wetting properties with no significant changes in the wetting behavior, or full wetting transition, until potentials of 400 V. Furthermore, Fluoropor shows low attachment of biomolecules to the surface upon droplet movement. Due to its simple fabrication process, its resistance to adhesion of biomolecules and the fact it is capable of being integrated and exchanged as thin films into commercial DMF devices, Fluoropor is a promising material for wide application in DMF.

High Resolution Patterning of an Organic-Inorganic Photoresin for the Fabrication of Platinum Microstructures.

Platinum (Pt) is an interesting material for many applications due to its high chemical resilience, outstanding catalytic activity, high electrical conductivity, and high melting point. However, microstructuring and especially 3D microstructuring of platinum is a complex process, based on expensive and specialized equipment often suffering from very slow processing speeds. In this work, organic-inorganic photoresins, which can be structured using direct optical lithography as well as two-photon lithography (TPL) with submicrometer resolution and high-throughput is presented. The printed structures are subsequently converted to high-purity platinum using thermal debinding of the binder and reduction of the salt. With this technique, complex 3D structures with a 3D resolution of 300 nm were fabricated. At a layer thickness of 35 nm, the patterns reach a high conductivity of 67% compared to bulk platinum. Microheaters, thermocouple sensors as well as a Lab-on-a-Chip system are presented as exemplary applications. This technology will enable a broad range of application from electronics, sensing and heating elements to 3D photonics and metamaterials.