Recent Advances in Electrowetting Microdroplet Technologies
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Chapter 4 Recent Advances in Electrowetting Microdroplet Technologies Robert W. Barber and David R. Emerson 4.1 Introduction The ability to handle small volumes of liquid, typically from a few picolitres (pL) to a few microlitres (mL), has the potential to improve the performance of complex chemical and biological assays [1–6]. The benefits of miniaturisation are well documented [7–9] and include smaller sample requirements, reduced reagent con- sumption, decreased analysis time, lower power consumption, lower costs per assay and higher levels of throughput and automation. In addition, miniaturisation may offer enhanced functionality that cannot be achieved in conventional macroscale devices, such as the ability to combine sample collection, analyte extraction, preconcentration, filtration and sample analysis onto a single microfluidic chip [10]. Microfluidics-based lab-on-a-chip devices have received considerable attention in recent years, and are expected to revolutionise clinical diagnostics, DNA and protein analysis and many other laboratory procedures involving molecular biology [11–13]. Currently, most lab-on-a-chip devices employ continuous fluid flow through closed microchannels. However, an alternative approach, which is rapidly gaining popularity, is to mani- pulate the liquid in the form of discrete, unit-sized microdroplets—an approach which is often referred to as digital microfluidics [14–18]. The use of droplet-based microfluidics offers many benefits over continuous flow systems; one of the main advantages is that the reaction or assay can be performed sequentially in a similar manner to traditional (macroscale) laboratory techniques. Consequently, a wide range of established chemical and biological protocols can be transferred to the micro-scale without the need to establish continuous flow protocols for the same reaction. In addition, droplet-based systems avoid many of the problems associated with single- phase microfluidics such as sample cross-contamination and diffusional dilution. R.W. Barber (*) • D.R. Emerson Centre for Microfluidics and Microsystems Modelling, STFC Daresbury Laboratory, Warrington WA4 4AD, UK e-mail: [email protected] P. Day et al. (eds.), Microdroplet Technology: Principles and Emerging 77 Applications in Biology and Chemistry, Integrated Analytical Systems, DOI 10.1007/978-1-4614-3265-4_4, # Springer Science+Business Media, LLC 2012 78 R.W. Barber and D.R. Emerson One of the most important consequences of miniaturisation is the increase in the surface-to-volume ratio of the fluid. For example, the surface-to-volume ratio for a device with a characteristic length of 1 m is of order 1 mÀ1 whilst the surface-to- volume ratio for a microfluidic device having a characteristic length of 1 mm will increase to 106 mÀ1. In other words, the surface-to-volume ratio of the fluid scales according to the inverse of the characteristic length [8]. Consequently, as devices are reduced in size, inertial forces will decrease while viscous effects and surface energies will become increasingly important. In the case of submillimetre- sized liquid droplets, capillary forces dominate the motion [19]. Under these circumstances, the control of the surface energy provides a useful tool for manipulating droplets [20–23]. Although chemical and topographical patterning of substrates has received considerable attention in recent years [24–26], the static nature of these surface treatments prevents the active control of droplets, as required in a fully-controllable digital microfluidic system. As a consequence, considerable work has been dedicated to the development of techniques that allow the wettability of the substrate to be varied both spatially and temporally. The most promising droplet actuation technique for digital microfluidic applications appears to be electrowetting [27–32], although other mechanisms have been demonstrated including dielectrophoresis [33–35], thermocapillary actuation [36–38] and optoelectrowetting [39–43]. In addition, other promising droplet handling techniques such as surface acoustic wave (SAW) actuation have been developed [44–47] although in this case, the droplet movement is achieved via the creation of acoustic waves rather than by changing the wettability of the surface. Furthermore, electrowetting can be combined with electrophoresis/dielectrophoresis, to provide a method for particle separation or sample enrichment [48–51], or can be used to collect or separate magnetic particles [52–54]. Over the last few years, electrowetting has become an increasingly important technology for droplet manipulation. Electrowetting can commonly achieve contact angle variations of more than 40 and the switching cycles can be performed hundreds of thousands of times without any detrimental effects to either the fluid or the chip. The switching response time for millimetre-sized droplets is relatively fast (typically several milliseconds) and is only limited by the inertia of the droplet rather than the switching time of the equilibrium contact angle [31]. Within just a few years, a rapidly expanding community of researchers has taken the concept of electrowetting from the initial research stage into fully-integrated digital microfluidic devices that are capable of complex chemical and biological assays [55–57]. 4.2 Theory of Electrowetting The phenomenon of electrocapillarity (or electrowetting) was first described by Lippmann [58] in 1875 when he showed that the capillary depression of mercury in contact with an electrolyte solution could be controlled by the application of a voltage. 4 Recent Advances in Electrowetting Microdroplet Technologies 79 As well as formulating the basic theory for electrocapillarity, he also proposed several practical devices that made use of the phenomenon, including a very sensitive electrometer which was later used to record the world’s first electrocardiogram (ECG). Unfortunately, the application of electrowetting to aqueous electrolytes is severely restricted due to the electrolytic decomposition of water beyond a few hundred millivolts. In the 1990s, however, Berge [59] and Vallet et al. [60]realised that the problem of electrolysis could be overcome by the introduction of a thin insulating layer to separate the conductive liquid from the metal electrode. This concept is nowadays referred to as electrowetting-on-dielectric (EWOD) [61]or electrowetting-on-insulator-coated-electrodes (EICE) [28] and involves applying a voltage to modify the wetting behaviour of a conductive liquid in contact with a hydrophobic, insulated electrode. Thorough descriptions of electrowetting have been published by Mugele and Baret [31], Berthier [62] and Berthier and Silberzan [63] whilst investigations into the types of liquids that can be transported by EWOD have been conducted by Pollack [64], Srinivasan [65] and Chatterjee et al. [66]. In most practical electrowetting applications, the droplets reside on a hori- zontal planar substrate and are usually composed of aqueous solutions with a typical droplet diameter of 1 mm or less. The medium surrounding the droplet can either be air or another immiscible liquid such as silicone oil. However, recent work by Brassard et al. [67] has shown that it is possible to use an alternative mode of operation where the aqueous droplet is enclosed in a thin layer of oil which in turn is surrounded by air; this technique is referred to as water-oil core-shell droplets. The relative importance of the gravitational force to the surface tension force can 2 be expressed by the Bond number [62], Bo ¼ DrgR =slv where Dr is the difference in density between the droplet and the surrounding medium, g is the acceleration due to gravity, R is the radius of curvature of the droplet, and slv is the liquid-vapour surface tension. (The Bond number is sometimes referred to as the Eotv€ os€ number, Eo.) In most electrowetting applications, the Bond number is usually less than unity [62], implying that gravitational forces are small in comparison to the surface tension force; it is therefore appropriate to ignore gravity in electrowetting applications [31]. In the absence of an external electric field, the shape of the droplet is determined solely by the surface tension, according to standard equilibrium theory (Young’s equation) [62]. As shown in Fig. 4.1a, a surface tension (a force per unit length or an energy per unit area) is associated with the interface between each of the three phases; the solid substrate (s), the liquid droplet (l) and the surrounding ambient phase, which for simplicity is often denoted as vapour (v). Each interface exerts a force on the three-phase contact line, and the balance between the interfacial surface tensions i.e. ssv (solid-vapour), ssl (solid–liquid) and slv (liquid-vapour) must be in equilibrium: ssv À ssl À slv cos yeq ¼ 0 (4.1) 80 R.W. Barber and D.R. Emerson Fig. 4.1 A schematic diagram of wetting and electrowetting. (a) In the absence of an external electric field, the sum of the forces along the three-phase contact line must balance, leading to an equilibrium contact angle, yeq.(b) Application of a potential difference between the liquid and the substrate creates a capacitance, C, at the solid–liquid interface which causes the solid–liquid interfacial surface tension to be reduced by CV2=2. This causes the droplet to spread and reduces the contact angle to yEW where yeq is the equilibrium (or Young’s) contact angle. Rearranging (4.1) yields the familiar form of Young’s equation: ssv À ssl cos yeq ¼ (4.2) slv It should be noted that the vertical component of the surface tension force is balanced by normal stresses within the solid substrate [31]. Applying a potential difference, V, between the liquid and the substrate will change the shape of the droplet, as shown schematically in Fig. 4.1b. This is due to the fact that the solid–liquid interface effectively behaves as a parallel-plate capacitor, with a capacitance per unit area, C. The energy stored in the capacitor is CV2=2 whilst the work done by the external supply voltage is À CV2 and therefore the free energy of the droplet per unit interfacial area is reduced by CV2=2.