Electrowetting

and
Digital Microfluidics
Lecture - 10

Different driving forces become pertinent in microscale systems in contrast

to their macroscale counterparts to drive fluids.

Surface tension force

Important in microscale domain owing to the fact that the surface to
volume ratio increases significantly in microscale.

Precise manipulation of droplets in the micrometer scale.

Four fundamental fluidic operations (creating, transporting, cutting, and

merging) with droplets are utilized to digitize droplet- based fluidic system
which has evolved into a new microfluidics paradigm called

Digital Microfluidics

Miniaturization results in a tremendous increase in the surface-to-volume ratio.

The control of surfaces and surface energies is one of the most important
challenges both in microtechnology in general as well as in microfluidics.

For liquid droplets of sub-millimetre dimensions, capillary forces dominate.

The control of interfacial energies has therefore become an important strategy

for manipulating droplets at surfaces.

Both liquidvapour and solidliquid interfaces have been influenced in order to

control droplets

Ways to influence the interfaces

Temperature gradients

Interface motion induced by a thermal gradient between two regions of the

surface. The interface motion propagates into the bulk due to viscous forces.

Gradients in the concentration of surfactants across droplets

Gives rise to gradients in interfacial energies, mainly at the liquidvapour

interface, and thus produce forces that can propel droplets making use of the
thermocapillary and Marangoni effects.

Chemical and topographical structuring of surfaces - local

wettability

The main disadvantage of chemical and topographical patterns is

their static nature, which prevents active control of the liquids.

16

Electrocapillarity, the basis of modern electrowetting, was first described in

detail in 1875 by Gabriel Lippmann.
the capillary depression of mercury in contact with electrolyte solutions
could be varied by applying a voltage between the mercury and electrolyte

Generic electrowetting set-up. Partially wetting liquid droplet at zero

voltage (dashed) and at high voltage (solid).

Electrowetting (EW) has proven to be very successful:

Contact angle variations of several tens of degrees are routinely
achieved.

Switching speeds are limited (typically to several milliseconds) by the

hydrodynamic response of the droplet rather than the actual switching of the
equilibrium value of the contact angle.

Excellent stability without noticeable degradation

Nowadays, droplets can be moved along freely programmable paths on

surfaces; they can be split, merged, and mixed with a high degree of flexibility.
However, electrolysis start within a few milli-volts to make EW difficult to use
for practical applications.

Electrowetting (EW)
In EW an electrical double layer (EDL) is formed between the
electrode and aqueous solution that is between 1 nm and 10 nm thick.
Applying a voltage difference may cause a hydrophobic surface to
behave like a hydrophilic one. The electric energy counterbalances the

free surface energy and lowers the surface tension sl.

Electrowetting-on-dielectric (EWOD)
Berge in the early 1990 introduced the idea of using a thin insulating layer to
separate the conductive liquid from the metallic electrode in order to eliminate
the problem of electrolysis - Electrowetting on dielectric (EWOD).
In EWOD there is no electric double layer, but the change in the energy
balance takes place in the hydrophobic dielectric layer; A Teflon layer, 0.8 m
thick was used as the dielecric. Lee, J., Moon, H., Fowler, J., Schoellhammer,
T., and Kim, C.-J. (2002). Electrowetting and electrowetting-on-dielectric for
microscale liquid handling. Sens. Actuators, A, 95:259268.

Digital microfluidics refers to describe two different technologies

- an open system - droplet position is controlled by actuating
electrodes arranged in a two-dimensional array
- confined system - droplets are manipulated inside microchannels.

These systems enable the miniaturization of reactions by compartmentalizing

reactions in droplets of nanoliter to microliter volumes.

Compartmentalization in droplets provides rapid mixing of reagents, control

of the timing of reactions, control of interfacial properties, and the ability to
synthesize and transport solid reagents and products.

Droplet-based microfluidics can help to enhance and accelerate chemical and

biochemical screening, protein crystallization, enzymatic kinetics, assays.

Electrowetting: basics to applications

Electrowetting has become one of the most widely used tools for manipulating
tiny amounts of liquids on surfaces.
Applications range from lab-on-a-chip devices to adjustable lenses and new
kinds of electronic displays.

Issues
Fundamental and applied aspects.
Basic electrowetting equation,

Origin of the electrostatic forces that induce both contact angle

reduction and the motion of entire droplets.

Issues contd.
Limitations of the electrowetting equation
Failure of the electrowetting equation, namely the saturation of
the contact angle at high voltage,
The dynamics of electrowetting
Overview of commercial applications

Theoretical background
Basic aspects of wetting
In electrowetting, one is generically dealing with droplets (typical size of the
order of 1 mm or less) of partially wetting liquids (aqueous salt solutions) on
planar solid substrates.

Bond number Bo g R 2 / lv which measures the strength of gravity with

respect to surface tension, is smaller than unity.
Therefore gravity is neglected and the behavior of the droplets is determined
by surface tension alone.

The free energy F of a droplet is a function of the droplet shape.

The free energy F of a droplet is the

sum of the areas Ai of the interfaces
between three phases, weighted by the
respective interfacial energies i, i.e. sv,
sl , and lv :
Force balance at the contact line

F Fif Ai i V

(1)

is equal to the pressure drop p across the liquidvapour interface.

Minimization of Eq. (l) leads to the following condition that any equilibrium liquid
morphology has to fulfill Laplace Equation

Young Equation

1
1
P lv
r1 r 2

sv sl
cos Y
lv

lv

(3)

( 2)

relates Youngs equilibrium

contact angle to the
interfacial energies

Both equations are approximations intended for mesoscopic scales.

Electrowetting theory for homogeneous substrates

The thermodynamic and electrochemical approach - Lippmanns derivation
- direct metal electrolyte interfaces

Upon applying a voltage dU, an electric double layer builds up

spontaneously at the solidliquid interface consisting of charges on the metal
surface on one hand and of a cloud of oppositely charged counter-ions on the
liquid side of the interface.
Since the accumulation is a spontaneous process, it leads to a reduction of the
(effective) interfacial tension, eff

d sleff sl dU
sl sl (U )

(4)

is the surface charge density of the counter-ions, U = applied

voltage
The voltage dependence of eff is calculated by integrating this equation
sl

Simplifying assumption - the counter-ions are all located at a fixed distance

dH (of the order of a few nanometres) from the surface (Helmholtz model).

In this case, the double layer has a fixed capacitance per unit area,

cH
Where

o1

dH

is the dielectric constant of the liquid.

eff
sl

(U ) sl

C H U d U sl

U pzc

0 1
2d H

(U ) 2

(5)

Upzc is the potential (difference) of zero charge and approximated to zero.

Mercury surfaceslike those of most other materialsacquire a spontaneous charge when

immersed into electrolyte solutions at zero voltage. The voltage required to compensate for
this spontaneous charging is Upzc

This equation for

sleff

is inserted into Youngs equation.

For an electrolyte droplet placed directly on an electrode surface one can find
Upzc approximated to zero

0 1
cos cosY
U
2d H lv

(6)

For typical values of dH (2 nm), l (81), and lv (0.072 mJ m2) the ratio on
the rhs of equation is on the order of 1 V2.
The contact angle thus decreases rapidly upon the application of a voltage.

This equation is only applicable within a voltage range below the onset of
electrolytic processes, i.e. typically up to a few hundred millivolts.
Y - equilibrium contact angle at zero applied voltage, 0 - permittivity of free
space, d - dielectric constant of the insulating layer, lv -surface tension between
the liquid and the vapur, and U - voltage

Modern applications of electrowetting usually circumvent this problem by introducing a

thin dielectric film, which insulates the droplet from the electrode.

In this EWOD configuration, the electric double layer builds up at the insulatordroplet
interface.

Since the insulator thickness d is usually much larger than dH, the total capacitance of the
system is reduced tremendously.

The system may be described as two capacitors in series, namely the solidinsulator
interface (capacitance cH ) and the dielectric layer with

cd

0 d
d

d is the dielectric constant of the insulator.

Since

c d c H

, the total capacitance per unit area c cd.

With this approximation, the finite penetration of the electric field into the
liquid, is neglected (liquid treated as a perfect conductor) and the voltage drop
occurs within the dielectric layer.
Equation (5) is replaced by

eff
sl

(U ) sl

0 d
2d

U2

(7)

It is assumed that the surface of the insulating layer does not give rise to
spontaneous adsorption of charge in the absence of an applied voltage, i.e.
Upzc = 0.

In this equation the entire dielectric layer is considered part of one effective
solidliquid interface with a thickness of the order of d, typically O(1 m).

Combining Eq. (7) with Eq. (3), the basic equation for EWOD is obtained

cos cos Y

0 d 2

U
2 d lv

0 d 2
U cos Y
2 d lv

(8)

is the dimensionless electrowetting number which

measures the strength of the electrostatic energy
compared to surface tension.

The ratio in the middle of Eq. (8) is typically four to six orders of magnitude
0 1
smaller than that in Eq. (6),
depending on the properties of the
insulating layer.
2d H lv
Consequently, the voltage required to achieve a substantial contact angle
decrease in EWOD is much higher.

Contact angle versus applied voltage

for a glycerolsalt (NaCl) water
droplet.
Filled (open) symbols: increasing
(decreasing) voltage.
Solid line: parabolic fit according to
Eq. (8)
Equation (8) is found to hold as long as the voltage is not too high.

Beyond a certain system dependent threshold voltage, however, the contact

angle has always been found to become independent of the applied voltage - Contact angle saturation phenomenon

At high voltage, the contact angle has always been found to saturate.
In particular, no voltage-induced transition from partial to complete wetting
has ever been observed. (On the basis of equation (8), such a transition
would be expected to occur at

Uspread = (2lvd(1 cos Y)/(0d))(1/2) .

Instead, adopts a saturation value sat varying between 30 and 80 ,
depending on the system

Contact angle saturation is still not well understood.

Complex surfaces and droplet morphologies

Morphological transitions on structured surfaces
- e.g. hydrophobic surface (e.g. = 180 ) with a stripe of variable
wettability.
For moderate wettability contrasts, there is only one stable morphology,
which is a droplet slightly stretched along the stripe.
Patterned electrodes
- multilayer substrates with various patterned electrodes separated by
dielectric layers

Topographically patterned surfaces

- Superhydrophobicity and hydrophilicity are amongst the most spectacular
consequences of surface roughness

Lecture 12

Proof-of-concept experiment to test EWOD

Electrowetting-on-dielectric (EWOD) device with electric potential on

corresponding to a hydrophilic lower surface

A water droplet was placed on a Teflon-coated surface (hydrophobic), and it

was demonstrated that upon applying a voltage of about 100 V, the surface
switched to hydrophilic, causing spreading of the droplet.

DMF is typically implemented in one of two different configurations

The closed format (also known as the two-plate format), in which droplets are
sandwiched between two substrates patterned with electrodes (the substrates house
driving and ground electrodes, respectively).
The open format (also known as the single-plate format), in which droplets are
placed on top of a single substrate, housing both actuation and ground electrodes.

In both configurations, an insulating layer of a dielectric material is deposited on

top of the actuation electrodes, to limit current and prevent electrolysis.
Typically, the insulating layer is covered by an additional hydrophobic coating, which
reduces droplet-sticking to the surface.
Closed DMF devices are best suited for a wide range of droplet operations
dispensing, moving, splitting, and merging are all feasible.

Open DMF devices are typically not capable of splitting and dispensing; however,
the open format facilitates fast sample and reagent mixing, the capacity to move large
droplets, and better access to samples for external detectors.

Additionally, evaporation rates are higher in open-format devices, which may be

advantageous or inconvenient, depending on the application.

Liquid motion could only be achieved above some threshold voltage.

This observation is attributed to contact angle hysteresis: droplet motion can
only set in when the contact angle on the leading (trailing) edge of the droplet
exceeds (is smaller than) the local advancing (receding) contact angle.

Reynolds numbers of electrowetting-induced flows are rather low.

With typical velocities of the order of v 102101 m s1 and droplet sizes of
R 103 m or less, one obtains Re = vR/ 100 for water and even smaller
values for more viscous liquids. Hence, the flow is usually laminar.

Within the range of validity of the electrowetting equation EW-induced motion

is analogous to the motion of droplets on chemically heterogeneous substrates,

A droplet of polarizable and conductive liquid is sandwiched between two sets

of planar electrodes. The upper plate consists of a single continuous ground
electrode, while the bottom plate consists of an array of independently
addressable control electrodes. Both electrode surfaces are covered by a thin
layer of hydrophobic insulation.

The system geometry and droplet volume are controlled such that the
footprint of the droplet overlaps at least two adjacent control electrodes while
also making contact to the upper ground electrode.

Initially all electrodes are grounded and the contact angle everywhere is the
equilibrium contact angle of the droplet.

When an electrical potential is applied to a control electrode underneath the

droplet, a layer of charge builds up at the interface between the droplet and
the energized electrode resulting in a local reduction of the interfacial energy.

Since the solid insulator controls the capacitance between the droplet and the
electrode the effect does not depend on the electrolytes specific space-charge
effects as did uninsulated electrode implementations.

If a portion of the droplet also overlaps a grounded electrode, the droplet

meniscus is deformed asymmetrically and a pressure gradient is established
between the ends of the droplet which results in bulk flow towards the
energized electrode.

Dynamic aspects of electrowetting

For many practical applications, the dynamic response of the liquid is of interest
The contact angle assumes a
time and speed dependent value
which is determined by local
dissipative processes and flow
fields in the vicinity of the TCL.

On the other hand, the entire

droplet also responds on a global
scale, e.g. by a translation of its
centre of mass,

Top view of a droplet partially overlapping

with an activated (right) and a deactivated (left)
electrode. Arrows indicate the force acting on
the contact line.

Side view of imbalanced droplets partially overlapping with a deactivated

(left) and with an activated (right) electrode. (a) Droplet dominated by
contact line friction; (b) droplet dominated by bulk viscous dissipation.
There are several contributions to the net force which oppose the motion.
If the dissipation is dominated by contact line friction, the pressure within the
droplet equilibrates quickly and the droplet retains its spherical cap shape but
with a time dependent dynamic contact angle d
If bulk viscous effects dominate, the contact angle assumes its local
equilibrium angle everywhere along the contact line. As a result, the drop shape
is non-spherical and a hydrodynamic pressure gradient arises and drives fluid
flow within the droplet.
In most practical situations, an intermediate behaviour is expected.

By considering the static mechanical equilibrium, the bubble driving force

produced by electrowetting actuation may be approximated as follows:

R L
FDriving 2 w sin
( cos R cos L )
2
where is the interfacial tension between the liquid and the bubble, and w
is the width of the bubble base that linearly scales with the radius R of the
bubble.
Here, the contact angle R of the bubble is modulated by electrowetting
actuation and decreases from the equilibrium contact angle e with a large
span (generally ~40).

 L
FDriving 2 w sin R
( cos R cos L )
2

Therefore, the sine term can be roughly approximated to the sine of the
equilibrium contact angle e, whereas the difference in the cosines increases
as the contact angle R for the bubble is decreased by electrowetting
modulation.

Based on these relationships, it can be concluded that the maximum driving

force can be achieved when the equilibrium contact angle is close to 90 and
the contact angle modulation is maximized by electrowetting actuation.

This force can be in the micro Newton range.

Digital Revolution In Microfluidics

In digital microfluidics (DMF), discrete droplets are manipulated by applying
electrical fields to an array of electrodes.
In contrast to microchannels, in DMF each sample and reagent is individually
addressable, which facilitates exquisite control over chemical reactions.

The DMF paradigm. a) Schematic and b) pictures from a movie depicting the
four principle DMF processes: dispensing, moving, splitting, and merging.

Secondly, droplets serve as discrete microvessels, in which reactions can be

carried out without cross-talk between samples or reagents.
DMF is inherently an array-based technique, good match for array-based
biochemical applications.
DMF devices are straightforward to use, and are reconfigurable for any desired
combination of droplet operations.

d) Picture of an ATDA (all-terrain droplet actuation) device, capable of manipulating

droplets on flexible substrates. e) Picture of a DMF device powered by a cross
reference electrode array.

DMF devices are typically fabricated in a clean-room facility using

conventional techniques, such as photolithography and etching.
Electrodes are formed from substrates common to such facilities (e.g.,
chromium, gold, indium-tin oxide (ITO), and doped polysilicon).
The insulating dielectric layer - vapor deposition (parylene, amorphous
fluoropolymers, and silicon nitride), thermal growth (silicon oxide), or spincoating (PDMS or SU-8).
The hydrophobic coating - spin-coating a thin layer of Teflon-AF.
Series of pictures
from a video
(left-to-right)
depicting droplet
dispensing on an
optically driven
DMF device.

One of the substrates contains the patterned electrodes for liquid actuation.

The other substrate consists of a homogeneous electrode that provides electrical

contact to the droplet(s) independently of its (their) position.
- transparent ITO layer on a glass substrate, covered with a thin
hydrophobic layer that gives rise to a large contact angle and weak contact
angle hysteresis but does not prevent electrical contact.

Droplet actuation- droplet edges must overlap with at least two adjacent electrodes.

With substrate separations of 100500m and electrode sizes of the order of 1 mm,
this means typical droplet volumes of 0.11 l.

Routine tasks e.g., moving, merging, mixing, and splitting of droplets

JOURNAL OF MICROELECTROMECHANICAL
SYSTEMS, VOL. 12, NO. 1, FEBRUARY 2003

Sequential images of successful cutting and merging of droplets at 25 V

(gap size d = 70 m, electrode is 1.4 mm x 1.4 mm, volume is 0.2 l).

While many DMF devices are used to actuate droplets in air, another common
technique uses droplets suspended in oil, which prevents evaporation and
reduces the voltages required for droplet actuation.

Fouling by a variety of bio-fluids containing high concentrations of potential

surface-fouling molecules, including blood, serum, plasma, urine, saliva, sweat,
and tear could be minimized by suspending droplets in an immiscible oil.

Oil-immersed systems have drawbacks,

- requirement of gaskets or other structures to contain the oil bath,
- liquidliquid extraction of analytes into the surrounding oil,
- the incompatibility with oil-miscible liquids (e.g, organic solvents),
- the incompatibility with assays requiring drying droplets onto the
device surface.

Biological Applications of Digital Microfluidics

DNA Extraction, Repair, and Amplification- Handling, purifying, detecting,

and characterizing samples of DNA - genome research
Proteomics and Enzyme Assays - drug development, prepare peptide and
protein samples for matrix assisted laser desorption/ionization mass
spectrometry
Cell Assays Cell-based assays have been a popular target for miniaturization,
as the reagents and other materials are often prohibitively expensive.
Immunoassays to detect analytes in biological samples with high selectivity.

Optical applications
Microlenses - Liquid lenses are flexible. Their curvature and hence their focal length
can be tuned by adjusting their shape. This can be achieved by changing the contact
angle of sessile droplets via electrowetting. This allows for the design of optical systems
with variable focal length that can be addressed purely electrically,
Fibre optics Display technology - electrowetting-based reflective display

Paricle Synthesis

Particles being synthesized using DMF.

Conductive
gold/SU-8
particles
(1),
semiconducting polypyrrole particles (2),
eyeball microbeads (3), and
cups, formed by drying water droplets
that were originally encapsulated in latex (4).
Scale bars: 1 mm.

DMF Based Cooling

Infrared image of a laptop bottom skin during operation

Electronics Cooling
Microchannels have been applied to electronics cooling, and have been shown
to be capable of achieving cooling rates as high as 100W/cm2 may not be
sufficient to cool local hot spots on integrated circuits (300W/cm2).
DMF seems well suited for this application, as droplets can be moved directly to
hot spots, by-passing the regions not requiring cooling.

Pictures depicting the use of DMF to cool an artificial hot spot (an imbedded
microheater). The top half of each frame shows an infrared image of the hot
spot (white - hot); the temperature drops significantly during and after the
droplet passes over it.

DMF IIT KGP VIDEO

Temperature distributions at and around the hot spot (represented by the

circular region) (a) in absence of droplet (b) by placing a droplet

Electrically Induced Droplet Oscillation

DC pulse input function

Oscillation video 1
300V, 200 ms

Oscillation video 2
300V, 25 ms

EWOD Partially Wetting

Interferometric images of equilibrium/steady state meniscus subjected

to different heat inputs and applied voltages

Contact Line Displacement and Evaporation

Q1= 0.12 W
Q2 = 0.24 W

For Q1 and Q2 - EWOD completely

nullifies retraction due to heat.
For Q3 - EWOD only partially
successful

Q3 = 0.33 W.

16

Physics of Droplet Formation and Motion

Lecture 13
Drops on Non-homogeneous Surfaces
Corrections needed to Youngs Law

The Shape of Micro-drops

Comparison of the shape between micro-drops and macro-drops

The two pressures are of the same order when

l is called the capillary length. A drop of dimension smaller than the

capillary length has a shape resembling that of a spherical cap. A drop
larger than the capillary length is flattened by gravity.

Bond Number

R is of the order of the drop radius. If Bo < 1, the drop is spherical

(microscopic drops), or else the gravitational force flattens the drop on the
solid surface (large drops).
The capillary length is of the order of 2 mm for most liquids, even for
mercury.
These equations are valid for a perfectly flat surface.

Topographically patterned surfaces

Droplets wetting rough surfaces (a)Wenzel state with enhanced solidliquid

interfacial area (b) CassieBaxter state with entrapped air underneath the droplet.
In Fig. (a), roughness increases the actual solidliquid interfacial area Asl with
respect to the apparent, projected one Asl,p.
Wenzels law, cos = r cos Y with r = Asl /Asl,p.
Quantitatively, the validity of this picture turns out to be limited to a range of
C < Y < 90 , with C depending on the surface roughness .
As a result, the contact angle on a rough surface will be increased or (decreased)
as compared to the contact angle on a smooth surface of the same material,
depending on whether Y > 90 or (Y < 90 ), respectively.

For Y > 90 , a completely different liquid morphology is possible (Fig. b).

Asl is dramatically reduced and much of the apparent solidliquid interface is in
fact a liquidvapor interface.
This reduction in Asl gives rise to a very high mobility with extremely small
contact angle hysteresis.
In this state the contact angle is given by the CassieBaxter equation,
cos = 1 + f (1 + cos Y), where f is the fractional surface area of the
pillar tops.
The range of stability for both morphologies depends on the aspect ratio, the
spacing between the pillars, and the contact angle

Contact AngleYoungs Law

Schematic of forces at the contact line

At equilibrium, the resultant of the forces must be zero.

LG cos = SG SL
Work of Adhesion - YoungDupre Equation

Wa = (1 + cos )
For a super-hydrophobic contact, = ; Wa = 0: no work to separate a superhydrophobic liquid from a solid. The more hydrophobic is the contact
between a liquid and a solid, the smaller is the work of adhesion.

Drops on Inhomogeneous Surfaces

Youngs law should be corrected to take into account the imperfections of the
surface.
Roughness amplifies the hydrophilic or hydrophobic character of the contact.
is the angle with the surface with roughness and the angle with the
smooth surface.
The size of the roughness is
very small, so that the
molecules of the liquid are
macroscopically
interacting
with a plane surface but
microscopically with a rough
surface.

For a very small displacement of the contact line the work of the different
forces acting on the contact line is given by

where r is the roughness (rdx is the real distance on the solid surface when
the contact line is displaced by dx). Therefore, by definition, r > 1.
Thus the change in energy is

The drop finds its equilibrium state after the small perturbation dx, it
finally stops at a position where its energy is minimum, so

Therefore,

Youngs law for a smooth surface

Substitution gives Wenzels Law

As r > 1, this relation implies that

If is larger than 90 (hydrophobic contact), then > and the contact is

still more hydrophobic due to the roughness.
If is smaller than 90 (hydrophilic contact), then < and the contact is
still more hydrophilic.

Surface roughness increases the wetting character.

CassieBaxter Law
Chemically
inhomogeneous
solid surfaces.

Small size heterogeneities

compared to interaction size
between the liquid and the
solid wall.

A solid wall constituted by microscopic inclusions of two different materials.

1 and 2 are the contact angles for each material at a macroscopic size, and f1 and
f2 are the surface fractions of the two materials.

The energy to move the interface by dx is

Minimizing dE

Using Youngs Law

Casey-Baxter Relaion

The CassieBaxter law explains some unexpected experimental results.

Sometimes during micro-fabricationa microfabricated surface may present

chemical inhomogeneity and the wetting properties are not those that were
intended.
For example, if a uniform layer of Teflon is deposited on a rough substrate,
the surface should become hydrophobic.
However, if the layer is too thin, the Teflon layer may be porous and the
coating inhomogeneous; the wetting properties are then modified according
to the CassieBaxter law and the gain in hydrophobicity may not be as large
as expected.
The scale of change of the different chemical materials of the solid surface is
very small compared to that of the drop

Fabricated Surfaces: The Transition Between the Wenzel and Cassie Laws
PDMS, Teflon, SU8, glass, silicon, gold. Plastics are generally hydrophobic
whereas glass and metals are hydrophilic and silicon neutral.

Chemical deposition of a hydrophobic/hydrophilic coating on top of the substrate.

A flat gold plate with CF4H2He plasma deposition becomes very hydrophobic.
(a) A water droplet bounces back from the surface treated with CF4H2He
plasma deposition, (b) whereas it spreads on the original gold surface

Microfabricated Substrate - Case of Hydrophobic Contact

Contact angle of a sessile drop sitting on microfabricated pillars

If the drop penetrates between the pillars, one can write the Wenzel angle as

cos W = r cos
If the drop stays on top of the pillars, one can write the Cassie law

cos C = f cos + (1 f) cos 0

C is the Cassie contact angle, 0 the contact angle with the layer of air, and f
the ratio of the contact surface (top of the pillars) to the total horizontal surface.

Sketch of a Cassie drop (fakir effect). The interface between the pillars
is roughly horizontal.

If the pillars are not too far from each other, the value of 0 is roughly 0 =

cos C = 1 + f (1 + cos )

Plot the Wenzel and

Cassie Laws

cos W = r cos
cos C = 1 +
f (1 + cos )

Plot of the Wenzel and Cassie laws for a

sessile droplet sitting on a surface textured
with micro-pillars.

The two lines intersect at a Young contact angle i

defined by C = W , so that

In the diagram, for a given Young angle,

there are two contact angles

cos W = r cos

From
energy
considerationsfor
example by using Laplaces lawit can
be deduced that the real contact angle is
the smaller one.
cos C = 1 + f (1 + cos )

So when the Young contact angle is not very hydrophobic ( < i ), the
contact corresponds to a Wenzel regime and the drop wets the whole surface.
When the Young contact angle is more hydrophobic ( > i), the drop is in a
Cassie regime and sits on top of the pillars.
General rule, exceptions are common, droplets are sometimes at metastable
regimes.

Drops Moving by Capillarity

At the microscopic scale there are other forces to move fluids that are not
efficient at the macroscopic scale. These forces are electro-osmosis and
capillarity. In particular capillarity is widely used for actuating droplets.
1. Drop Moving Over a Transition of Wettability

Resulting force
directed towards the
hydrophilic region

If L1 and L2 are the contact lines in the

hydrophilic and hydrophobic planes,
and 1 and 2 the contact angles, the
force acting on the drop is

Droplet at equilibrium

2. Drop Moving Uphill

Capillary forces may be sufficient to make micro-drops move upwards on
an inclined plane.
M.K. Chaudhury and G.M. Whitesides, How to make
water run uphill, Science, Vol. 256, pp. 15391541, 1992.

The required gradient in surface

free energy was generated on a
polished silicon wafer by
exposing it to the diffusing
front
of
a
vapor
of
decyltrichlorosilane,

An oil drop moves uphill towards the more hydrophilic

region.

The average velocity is

approximately 1 to 2 mm/s

3. Drop Moving up a Step

A micro-drop of water is initially located on a step at the boundary of a
hydrophilic region (on top of the step) and a hydrophobic region (at the
base of the step). The drop progressively moves towards the hydrophilic
region, even if this region is located at a higher level (simulation result)

Motion of a drop up a step towards the hydrophilic plane

(simulation)

4. Drop Moving Over a Gradient of Surface Concentration of Surfactant

Chemical reactions between the liquid of the droplet and the substrate can create
droplet motion. A droplet of n-alkanes containing silane molecules is placed on a
hydrophilic surface. Silane molecules form dense grafted monolayers on silicon
or glass, rendering the surface hydrophobic.
If such a droplet is deposited on a glass surface and pushed with a pipette, then
the droplet continues to move on the substrate. It moves in nearly linear segments
and changes its direction each time it encounters a hydrophobic barrier. The
droplet cannot cross its own tracks.

The advancing contact line has a hydrophilic

Young contact angle. Molecules of silane
concentrate at the vicinity of the receding contact
line and form a hydrophobic layer.

Pictures of a microbelt conveyer system

based on DMF;

A lady bug carried on a silicon

wafer supported by four droplets.
Sens. Actuators A 2006, 130131,
537.