Droplet manipulation with electric fields

CLL 798 Term Paper | Semester I 2020-21

Vipul (2021CHE2571)
Parth Singhal (2018CH10231)
Raunaq Saraswat (2018CH10139)

15th November 2021

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 Abstract
A fluid droplet is, generally speaking, a micro-sized spherical mass, containing the surface
energy associated with the formation of a droplet from fluid material. Motion of a droplet
can be observed under various circumstances – the following paper describes the use of electric
fields to move (manipulate) the droplet. The mathematical modelling of the said phenomenon of
Electrowetting is discussed, along with a brief overview of the various techniques and applications
of the same.

1 Introduction
Droplet manipulation via electric fields, or Electrowetting (EW) as it is more commonly known, is
the movement of a fluid droplet due to electric field of any kind. The motion can further result
in splitting or coalescing of droplet(s) and finds its use in varied real life systems, ranging from
the domains of electronics to medical sciences. The essential relevance of droplet manipulation in
microfluidics and numerous applications, such as diagnostic chips, organic synthesis, microreactors,
and so on, has piqued researchers’ curiosity. Mechanical vibration., electrostatic forces, nanoparticle
suspensions, and electrowetting are examples of demonstrated droplet manipulation technologies
(EW). The apparent benefits of EW, such as the lack of mechanically moving components, quick
reaction, low power consumption, and operation at a low voltage ( 10 volts), have sparked extensive
attention.

Electrowetting, in general, is a result of the repulsive force(s) between two like charges situated
at either side of the fluid interface. The equation governing the phenomenon is a commutative sum
of the electric energy and the cosine of the Young’s value, found to be equal to the cosine of the
apparent contact angle. The same can be mathematically expressed as follows:

cV 2
cosθY + = cosθapp
2

By raising the electric field, EW improves the wettability of a conductive droplet settling on a
substrate and lowers its CA. Direct EW on bare electrodes, on the other hand, induces electrolysis.
Berge [1] offered the concept of putting dielectric films on plate electrodes to alleviate this difficulty,
resulting in the well-known configuration: "EW on a dielectric (EWOD)." In EWOD, the coefficient
c is written as ϵϵo , where, ϵ, ϵo , γ, and d represent the relative permittivity of the insulating
layer, dielectric permittivity in vacuum, insulating layer thickness, and liquid/vapor interface surface
tension, respectively. EWOD’s droplet manipulation is stabler than its counterparts. The applied
voltage range is larger, and the droplet reacts quickly to the electric field. The droplet may be
carried, divided, combined, and distributed in a constrained region by modifying the patterns of
the embedded electrode. EW has so far found its usage in microfluidics applications like as digital
cameras, inkjet/soft printing, liquid lenses, quick response displays, and so on.

The electric potential needed to mobilize the droplet can be generated using a variety of means.

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 Figure 1: A schematic of the droplet manipulation caused by electric fields

Recent advancements in the field suggest that it is now feasible to shape electrode surfaces to
generate spatial changes in the electric potential because to developments in micro/nano-fabrication
methods. Large voltage dips too have been seen along thin and long wire electrodes. Bader et al.
describe a technique for fabricating electrodes that generates a spatial potential distribution, which
was used to separate microparticles when paired with a time-varying applied potential. Patterning
a thin nonuniform dielectric layer thickness may also produce spatial differences in the potential. In
a similar way to the electronic field-effect transistor, spatial changes in the local effective electro-
kinetic (zeta-) potential of the substrate may be obtained by exploiting capacitance effects coming
from implanted shielding electrodes. Alternatively, we see the ability to make thin (both in thickness
and breadth) dielectric layer strips.

It has also become feasible to produce a discrete spatial permittivity (and hence potential) distribution
by carefully choosing the dielectric material of each neighbouring layer depending on their permittivities.
It would thus be feasible to produce a continuous distribution in the limit of indefinitely narrow
widths. Another method for obtaining spatial potential distributions is to use shear horizontal
surface acoustic waves generated by fabricating thin interdigitated transducers on a polished piezoelectric
substrate; this is commonly used in interdigital dielectrometry for various sensing applications to
generate spatially periodic electrical potentials on the surface of substrates.

The subsequent sections of this term paper detail the methodologies that may be used to manipulate
a droplet, the underlying mathematical frameworks that dictate them, and a few industrial applications
of Electrowetting.

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2 Method
Digital microfluidics (DMF) is a potential method for manipulating biological targets such as DNA,
proteins, and cells in extremely tiny liquid volumes. The use of fewer, more expensive chemicals,
improved biochemical reaction efficiency, and shorter operating durations are all benefits of such
systems. DMF, which is based on EWOD, is a rapidly evolving technology. In such microsystems,
fundamental drop manipulations may be accomplished. Open systems, in which the sessile droplet
sits freely on a horizontal solid substrate, and covered systems, in which the droplet is contained
between two plates, are the two kinds of EWOD-based microsystems that have been established.
Each system has its own set of benefits. In covered EWOD systems, drop dispense, motion, and
splitting are simpler, but mixing and evaporation (for species concentration) are best done in the
open format. These two forms of EWOD are interfaced in certain hybrid systems, allowing droplet
migration between a covered and an open zone under electrowetting actuation.

Figure 2: An example of Open (A) and Closed (B) EWOD System

3 Discussion

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Here, we are considering a conducting, incompressible, Newtonian liquid drop of equilibrium thickness
on a non-conducting dielectric. When a direct or alternating electric potential is applied across the drop
and dielectric, the electric charges gather at the interface of conducting (droplet) and non-conducting
(dielectric) material. The induced electric forces are especially strong on liquid gas interface, because
electric fields become very large at sharp wedges near the triple contact line. This in turns lowers the
surface energy of interface and leads to spreading of drop over dielectric. The physics describing the
electric forces on interfaces of conducting liquids and on triple contact lines is called “electrowetting.”
Now, we will provide brief detail about governing equations encapsulating the physics of electrowetting
phenomenon using thermodynamic approach:
Assumptions: a) Potential difference is small enough so that no electric charge is flowing inside droplet.
b) All the voltage drop is across the electric double layer, c) Drop is spherical in shape. d) bond number
is much smaller than 1, so that gravitational effect can be neglected. E0 temp and pressure is constant
throughout the process.
Gibb’s interface thermodynamics relates normal force density to gradient in interfacial tension.
𝑒𝑓𝑓
𝑑ɤ𝑆𝐿 = −ρ𝑆𝐿 𝑑𝑉
𝑒𝑓𝑓
Here, ɤ𝑆𝐿 denotes the effective surface tension at the liquid solid interface, ρ𝑆𝐿 is the field-induced
surface charge density in counterions, and V is the electric potential,
𝑉
𝑒𝑓𝑓
ɤ𝑆𝐿 (𝑉) = ɤ𝑆𝐿 − ∫ ρ𝑆𝐿 dV
𝑉𝑖𝑛

ρ𝑆𝐿 = 𝐶𝑉
Here, C is the total capacitance of dielectric and metal placed in parallel,
1 1 1
= +
𝐶 𝐶𝑀 𝐶𝐷
Neglecting Double layer capacitance C ≈ CD,
𝜺0 𝛆𝐷
𝐶=
𝑑
Here, 𝜺0 is the permittivity of free space, 𝛆𝐷 is permittivity of vacuum and d is the width of electric
double layer,
𝑉
𝑒𝑓𝑓 𝜺0 𝛆𝐷
ɤ𝑆𝐿 (𝑉) = ɤ𝑆𝐿 − ∫ . V. dV
𝑉𝑖𝑛 𝑑

𝑒𝑓𝑓 𝜺0 𝛆𝐷 2
ɤ𝑆𝐿 (𝑉) = ɤ𝑆𝐿 − .𝑉
2𝑑
Above equation is also called Lippmann’s law for EWOD.
𝜺0 𝛆𝐷 2
cos 𝜃 = cos 𝜃0 + .𝑉
2ɤ𝐿𝐺
This equation is called Lippmann-Young’s law for EWOD.
Fig 1(A, B). Lippmann-Young’s relation between contact angle and applied voltage: (A) contact angle
θ versus V and (B) (cos θ - cos θ0) versus V.
Saturation of Electrowetting effect.
The validity of the Lippmann-Young’s equation is limited to small and medium electric potentials. If
we keep on increasing the voltage across the electric double layer, then after a certain voltage the contact
angle does not decrease any more with increasing voltage. Hence there is an upper limit to
electrowetting force.
When the voltage becomes sufficiently large, the electric charge gets trapped into the insulator. The
trapping of charge reduces the density of charge near solid liquid interface which weakens the
electrowetting effect and a saturation is reached.
For higher voltages, we have to use modified Lippmann-Young’s equation to determine the change in
contact angle with voltage.
cos θ − cos θ0 𝐶𝑉 2
= 𝐿( )
cos θ𝑠 = cos θ0 2ɤ(cos θ𝑠 − cos θ0 )
Here, L is Langevin function which is given by L(x)= 𝑐𝑜𝑡ℎ(𝑥) – 1/3(x) and θs is the contact angle at
start of saturation potential.

Fig 2. At low voltages, all curves

collapse on the same straight line
defined by its slope C/2. At high
voltages, the curves separate to
merge with their asymptote
ɤLG(cos θsat 2 cos θ0). Continuous
lines correspond to the modified
Lippmann-Young’s law and dots
to experimental observations.
Force analysis on a drop and minimum actuation potential.

When we turn on/off the electric potential across the electric double layer, the contact angle of the drop
changes accordingly. If we turn the electric potential the drop spreads and the contact angle then is an
advancing contact angle and conversely if we turn off the electric potential the drop regains its original
shape and the contact angle then will be called receding contact angle. This process is called
electrowetting hysteresis.
Force on drop is given by:

𝐶𝑉 2
𝐹𝐸𝑊𝑂𝐷 = ɤ(cos θ − cos θ0 ) =
2
Here, θ is actuated contact angle and θ0 is the nano actuated contact angle.
If we take advancing and receding angle into account, then
𝐹𝑎𝑑𝑣 = ɤ cos( θ + 𝑎)
𝐹𝑟𝑒𝑐 = − ɤ cos( 𝜃0 − 𝑎)
Here, θ + 𝑎 and 𝜃0 − 𝑎 are static advancing and static receding contact angles.
Assuming small value of the above 2 equations can be re arranged in:
𝐹𝑎𝑑𝑣 = ɤ(cos θ − 𝑎(cos θ + sin θ))
𝐹𝑟𝑒𝑐 = − ɤ(cos θ0 − 𝑎(cos θ0 − sin θ0 ))
𝐹𝑡𝑜𝑡𝑎𝑙 = 𝐹𝑎𝑑𝑣 + 𝐹𝑟𝑒𝑐 = ɤ(cos θ − cos θ0 ) − ɤ𝑎(cos θ + sin θ − cos θ0 + sin θ0 )
For drop to move under electric field Ftotal must be greater than zero,
𝐶𝑉 2
𝐹𝑡𝑜𝑡𝑎𝑙 = 2
− ɤ𝑎(cos θ + sin θ − cos θ0 + sin θ0 ) >0

Which gives,

𝑉𝑚𝑖𝑛 > 2√(𝑎ɤ sin θ0 )/𝐶

This is the minimum electric potential which needs to be applied in order to move the droplet.
4 Conclusion
In this paper we have discussed the physical behaviour of micro-droplets under the applied electric
field. here we have used the thermodynamic approach to derive the Lippmann’s law i.e., the
dependency of contact angle on applied voltage. With the help of graphs (Fig 1) and Lippmann-
Young’s law it can be inferred that if we increase the voltage across the electric double layer the
contact angle keeps on decreasing, however at very high voltage the contact angle does not change
anymore with increase in applied voltage, which is called saturation voltage. Fig2. Suggests that
we cannot use Lippmann-Young’s equation at very high voltages hence we have to use modified
Lippmann-Young’s equation. We also did force analysis on drop to find the minimum actuation
voltage required to move drop from one point to another on our EWOD device.

References
1. Berge, B. Electrocapillarite et mouillage de films isolants par l’eau. Comptes rendus de
l’Academie des sciences, Se rie 2, Me canique, Physique, Chimie, Sciences de l’univers,
Sciences de la Terr, 1993; Vol. 317, pp 157163.
2. L.Y. Yeo , R.V. Craster , O.K. Matar, Drop manipulation and surgery using electric fields,
Journal of Colloid and Interface Science 306 (2007) 368–378
3. Electrowetting, Fundamental Principles and Practical Applications, Frieder Mugele and
Jason Heikenfeld
4. Micro-Drops and Digital Microfluidics, Second Edition, Jean Berthier