Simulation of hydrophobic surfaces: A case study
of ZnO thin film
Hajar Ghannaml, Zakaria Oulad EI hmaidil, Zineb
Yamlahi Alami\ Mohamed Addou\ and Adil
Chahboun1,2
lUniversity Abdelmalek Essaadi, FST Tangier
2University of New England, Tangier Campus
Tangier, Morocco
a.chahboun@fstt.ac.com
Abstract- Surface self-cleaning is observed in nature through
plant's leaf (lotus) or animal's skin. This extraordinary
behavior is related mainly to surface structure
roughness. In this work, Wenzel model have been used to predict
the hydrophobicity of ZnO thin film grown by Spray coating on
glass. The measured water drops contact angles over ZnO
surfaces were found within the theoretical predicted values.
Keywords- Self-cleaning; hydrophobic; contact
Simulation; Spray pyrolysis; ZnO
I. INTRODUCTION
Renewable energy plants are often located at remote desert
regions. They are a subject of lot of stress. The panels' surfaces
become covered by dusts and organic molecules, which
reduces their efficiency. Among, the proposed solution to this
issue is to cover their surfaces by hydrophobic thin films.
The wettability of solid surfaces is a very important
property. It is usually determined by measuring the contact
angle (CA) formed between liquid droplet and solid surface.
Wetting is defined as a phenomenon where the CA between the
liquid drop and the solid surface approaches zero; while non­
wetting means that the CA is greater than 90°. In this case the
surface is called hydrophobic.
Hydrophobic self-cleaning surface is inspired by nature.
The most famous example is lotus plant leaves [ I]. This
observed hydrophobicity is believed to be related to surface
roughness, which referred as hierarchical micro and
nanostructures [1-3]. Mimicking nature hydrophobic behavior
has attracted significant attention. This interest is driven by the
desire to fabricate such surfaces for many applications in daily
life as well as in many industrial processes [4]. Various types
of materials are exploited for this application. Among these
materials ZnO which is able to repel water due to its surfaces
textures such as nanowires [5], and nanorods [6]. In fact, ZnO
nanorods thin films have been demonstrated to be super­
hydrophobic (CA 2:150°) due to the combination of both
surface roughness and the low surface energy of the (001)
plane of the nanorods on the surface [7].
To describe the relationship between CA on a rough
surface, and that on a smooth one of the same surface, several
978-1-4799-7336-1/14/$31.00 ©2014 IEEE
Moez Salem and Mounir Gaidi
Research and Technology Center of Energy
Borj Cedria, Tunisia
mounirgaidi@yahoo.com
basic theoretical models have been reported. Thomas Young
proposed an equation which makes a correlation between the
and its CA and the interfaces energies. Young's angle is a result of
thermodynamic equilibrium of the free energy at the solid­
liquid-vapor interface, is applicable only to flat and smooth
surfaces and not to rough ones [8]. Wenzel modified Young's
equation and proposed a model describing the contact angle e'
at a rough surface by considering the increase of the practical
angle;
surface area [9]. According to this model, the roughness of the
surface plays a key role in determining the wetting behavior of
solid surfaces. Therefore, Cassie and Baxter (CB) developed
their model for hydrophobic surface [10], by assuming that
the surface is composed of solid and air like a porous material.
In such case, water does not wet or penetrate into the pores.
Johnson and Dettre simulated the CA on sinusoidal
hydrophobic surfaces [11-12], two regimes are revealed: the
first is when Wenzel mode is dominant, in this case the CA
increases as the roughness factor increases. The second regime
consisted of the transition state from Wenzel's to Cassie's
model due to the large roughness inducing the air fraction
between solid and water. Lundgen et al. [13] have described
different wetting properties of the top and the sides of the
pillars, which play a relevant role in determining the CA. We
can introduce this system in two regimes; the Wenzel regime
with low pillar heights (h) and the CB regime when increasing
the height. Bico et al. [14] analyzed a textured super­
hydrophobic surface with spikes, holes and stripes. These
surfaces have a specific roughness value and them all
showed contact angles that meet the CB prediction regardless
of their roughness factor. It is however important to point out
that for the surface with holes the static angle is 131° with a
huge hysteresis. This later was due to the water retained in the
holes at the retraction. It is therefore difficult to conclude that
the water droplet on the surface is in a composite state as
indicated by the authors. Patankar [15] modeled square post
surfaces. The drop forming process was based on a minimized
energy and the recommendation of using high pillars at given
pillar size which leads to a high roughness factor unlike Bico's
conclusion. Tested with the data of Bico et al. brought very
good agreements.
The most reported papers [11-15] have studied the
wettability on regular surfaces. In this work, we used Wenzel
model to predict the wettability of irregular surfaces. The IV. RESULTS AND DISCUSSION
obtained CAs were compared with experimental data
obtained on thin ZnO films. A. Experimental results
The morphology of ZnO thin films was studied by AFM
II. EXPERIMENTL SECTION microscopy. Fig. 2 shows a typical picture of a surface of
A solution of ZnO was prepared by dissolved Zn (N03)Z, 4f.!m2• The surface is polycrystalline and granular characterized
6H20 in distilled water. The resulting solution was sprayed for by a roughness varying between 5 and 50 nm.
10min at a rate of 2ml/in on glass substrates heated to a
01 gi t.l tnst"VMent� N"nQSc:ope

temperature of 500°C. Three samples prepared by spray Sca" size 2.000 �

.... ",....".,.
5(:;ln ".�e 1.001 H:t

... ..
,.uorb of 512

pyrolysis, presenting different molar concentrations of zinc ..

1 ge Oil U He I Qh'!:
o ,\;. s<:.l. 200.0 ...
Eng""e )< Pos -1978).4 um
nitrate 0.05M, O.lM, 0.15M respectively. This gives rise to engage Y PO,", -,,21S1..] um

different ZnO grain size and then roughness. The prepared

samples were named v I (0.05M), v2 (O. IM), and v3 (0.15M).
The sample's roughness was estimated using Nanoscope III ,,1_ .nQle

atomic force microscopy (AFM). To measure the CA of a -¢- lloht ."Qle

water drop on ZnO surfaces we took pictures of the drops using

a digital camera.

III. MODELING THE HYDROPHOBIC SURFACES

)( 0.500 ....
/div

Wenzel model was used to predict the nature of the Z 200.000 nm/dlv

wettability of the rough surfaces while solid / liquid interface

exactly follows the solid roughness [16] . I t consists of
defining the apparent contact angle e* of a liquid on a rough
surface (Fig.1) There is a linear relationship between the
apparent contact angle of a surface and the roughness factor of
the given surface [9].
cos e * = r cos ee (1)
ee is the contact angle of a drop of water in
equilibrium with a smooth and flat ZnO surface. r is the
roughness factor, dimensionless number, defined as the ratio
of the actual surface area over the apparent surface area. The
real surface takes into account the roughness of the surface,
while the apparent surface is the corresponding geometric
Figure 2. AFM picture of sample v3
AFM images revealed that the grain size of ZnO films
increases with the molar concentration of the ZnO solution.
However, in some surfaces there is a formation of clusters that
influences the roughness factors r, as illustrated in fig. 4 for
sample v I.
Fig. 3 illustrates a cross section of the roughness of the
three samples. It is clearly observed a height roughness for
sample v1 corresponding to the formation of clusters.
CROSS SEcno OF THE CENTERLINE OF SAMPLES
80

flat surface. According to the literature, the contact angle ee

�Vl -v2
for flat bulk ZnO surface is about 96 ° ± 5 ° [17]. Due the -
v3
linear relationship in equation (1), Wenzel model amplifies
both the hydrophobicity of hydrophobic surface and the
hydrophilicity of hydrophilic ones.

%L-� __ -L__-L__�__L
I __�__�__L-�__�

x (flm)

Figure 3. Evolution of the roughness of samples vI,v2 and v3

Figure I. Wetting state: Wenzel model To measure the contact angle of the prepared surfaces, we
used a very sample method. In fact, we filed a small drop of
water on the surfaces and then we took photos of these drops to
measures apparent contact angles. The CA measured on a drop
deposited on samples is shown below. The CA is about 105°
for sample v I, 94.5° for sample v2 and 96° for v3 (FigA).
 data it was determined roughness factor and quality of
wetting of ZnO surface through the Wenzel equation.
From the AFM images, it is found that the roughness
factor varied between 2.99 and 2.66, which corresponds
to CA of IOS0 and 94.S0 respectively, as illustrated by table
I.

TABLET. THE THEORETICAL AND EXPERIMENTALRESULTS

Results
samples
r 9* theoretical 0* experimental

vi 2.99 108° 105°

v2 2.66 106.14° 94.5°

v3 2.83 107.22° 96°

A previous study realized by Dettre and Johnson [11-12]

where they introduces a sinusoidal surface model which looks
similar to our surface model and they have estimated a limit
value of roughness underneath from which the apparition of air
pockets is inexistence. This critical roughness is given by the
following equation:
r* = I + (tan 2 ee)/4 (2)

There are two possible states where a water drop can be

formed on a sinusoidal surface, one that follow the Cassie
Baxter model (Fig. Sa)) and one following Wenzel model
(Fig.S b)).

a) b)

Figure 5. Wetting state a) Cassie-Baxter model b) Wenzel model

For ZnO, ee present a value of 96°±So which gives an r*

equal to 23.63 this values is higher than the r value obtained
Figure 4. 2D AFM topographical images accompany of water CA of from our simulation (Table I). This justifies our use of Wenzel
samples vi, v2 and v3. model to predict the surface wettability meaning that the solid
Iliquid interface follows exactly the solid roughness and not
Cassie- Baxter which is used to predict the wettability on
composite surfaces constituted of air and solid (Fig. S).
B. Simulation results

The factor r was obtained from AFM pictures converting C. Discusion

those pictures into numerical values to determine the
different coordinates (x, y, z). AFM image magnified to
demonstrate pixel values to be used for the roughness
factors. Knowing that image is characterized by a number of
pixels and a change in the value of pixels, through these two
The following figure illustrates the evolution of the
calculated apparent CA with r for ee equal to 96°±So (water CA
on smooth surface of ZnO).
According to the Table I and the Fig. 6, the experimental
results obtained for all samples are in a relatively good
agreement with the calculated results obtained by simulation.
Noting that, the experimental results (presented by v I, v2 and
v3 crosses) are well within the theoretical limits. The properties
of the wettability does not only consider the morphology of
the surface (roughness) but also other factors explaining the
small difference between calculated CA and measured ones
could come from, the model that takes only mechanical
factors, the speed of taking pictures, and the purity of the water
drop.
WENZEL MODEL
140
-CA:96-5'
-CA:96'
0
1"\
towards the improvement of CSP reflectors for less intensive
maintenance both in term of labor and water"
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In this work, we implemented a very simple tool to
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demonstrated the possibility to predict the hydrophobic
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predictions.
ACKNOWLEDGMET
This work was partially funded by IRESEN through the
project InnoTherm 1&11 "Nanocoating and testing; a step
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Triggered Wetting Transition of Water Droplets upon hydrophobic