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From micro to nano reentrant structures: Hysteresis on superomniphobic

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Article  in  Colloid and Polymer Science · February 2013

DOI: 10.1007/s00396-012-2750-7

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Colloid Polym Sci
DOI 10.1007/s00396-012-2750-7
ORIGINAL CONTRIBUTION
From micro to nano reentrant structures: hysteresis
on superomniphobic surfaces
Renaud Dufour & Guillaume Perry & Maxime Harnois &
Yannick Coffinier & Vincent Thomy & Vincent Senez &
Rabah Boukherroub
Received: 20 July 2012 / Accepted: 28 July 2012
# Springer-Verlag 2012
Abstract The paper reports on the wetting characterization
of two surfaces presenting reentrant shapes at micro- and
nanoscale using low surface tension liquids (down to
28 mN/m). On the one hand, mushroom-like microstruc-
tures are fabricated by molding poly(dimethylsiloxane)
(PDMS) onto a patterned sacrificial photoresist bilayer. On
the other hand, zinc oxide nanostructures (ZnO NS) are
synthesized by easy and fast chemical bath deposition tech-
nique. The PDMS and ZnO NS surfaces are then chemically
modified with 1H,1H,2H,2H-perfluorodecyltrichlorosilane
in vapor phase. Both PDMS and ZnO NS surfaces exhibit
a large apparent contact angle (>150°) and contact angle
hysteresis varying from 50° to a quasi-null value. This large
discrepancy can be ascribed to the length scale and topogra-
phy of the structures, promoting either a vertical imbibition or
a lateral spreading within the roughness.
Keywords Wetting . Hysteresis . Superomniphobic
surfaces . PDMS . ZnO . BSA
Renaud Dufour and Guillaume Perry contributed equally to the article
and share first co-authorship.
This article is part of the Topical Collection on Contact Angle
Hysteresis
R. Dufour : G. Perry : M. Harnois : V. Thomy (*) : V. Senez
Institut d’Electronique, de Microélectronique et de
Nanotechnologie (IEMN, UMR CNRS 8520), Université Lille1,
Cité Scientifique, Avenue Poincaré, BP 60069,
59652 Villeneuve d’Ascq, France
e-mail: vincent.thomy@iemn.univ-lille1.fr
R. Dufour : G. Perry : Y. Coffinier : R. Boukherroub
Institut de Recherche Interdisciplinaire
(IRI, CNRS-USR 3078), Université Lille 1,
Parc de la Haute Borne, 50 Avenue de Halley,
BP 70478, 59658 Villeneuve d’Ascq, France
Introduction
The observation of nature has always been an inspiration to
mankind. In the field of surface engineering, the most famous
example is the Lotus leaf which exhibits amazing wetting
properties due to its multiscale roughness (from micro to
nanoscale). Barthlott and Neinhuis were the first to relate the
wetting properties of such leaves to their surface topography
by using scanning electron microscopy (SEM) [1]. On such
surface, roughness prevents liquid droplets from contacting
the solid surface completely by trapping air pockets at the
water–solid interface, which is usually referred to as Cassie or
fakir state [2]. Other plants exhibit similar behavior such as
bamboo (Fargesia murielae) whose micro-grooves lead to
anisotropic wetting properties: rain droplets roll off the leaf
down to parallel veins where they are pinned (Fig. 1a). SEM
images show that these leaves are made of parallel micro-hills
and valleys coated by nano-textured micro-bumps (Fig. 1b, c).
Thus, many works have been undertaken to replicate,
characterize, and understand the strategies developed by
nature [3]. The development of micro and nanotechnologies
has led to the emergence of a lot of results in the field of
microfluidics dealing with wetting properties of superhydro-
phobic surfaces [4–7]. As for nature, synthetic surfaces
combining both roughness and hydrophobic coating lead
to high static apparent contact angle (SACA) associated
with a more or less important contact angle hysteresis
(CAH). The latter is the one of the most important param-
eters of liquid-repellent surfaces since it is directly
connected to liquid adhesion [8, 9]. Up to now, water has
been the most intensively studied liquid, and two different
well-known states have been reported: (1) A Cassie config-
uration, for which the droplet stays at the top of the rough-
ness, leading to a high SACA (>150°) associated with a low
CAH (<10°) and (2) a Wenzel state, where the droplet is

Fig. 1 a Rain droplets on a bamboo leaf (F. murielae), b–c SEM
images of the bamboo leaf at ×99 and ×2,330 magnifications, respec-
tively, d Wetting states on a micro- or a nano-structured surface: 1–2
Classical micropillars enable high repellency of high surface tension
impaled inside the roughness, giving a lower SACA (>140°)
with a higher CAH (>30°). It should be noted that an
intermediate state (named semi-impaled or semi-Wenzel
state) has been described recently (SACA >140° with a
CAH comprises between 10 and 30°) [10–12].
While these superhydrophobic surfaces have been consid-
erably studied, only a few works have been reported on their
integration into microfluidic-based microsystems [13–15]. As
a matter of fact, water is not an issue for real applications in
BioMEMS where liquids containing high concentrations of
biomolecules, surfactants, alcohols, etc. need to be manipulat-
ed. In the latter case, the surface tension of the liquid is
dramatically reduced (from 72.6 mN/m for water down to
20–30 mN/m for alcohols). As a consequence, the wetting
properties are deeply modified since these low surface tension
liquids tend to wet most of the natural or artificial superhy-
drophobic surfaces. Indeed, despite their high water repellency,
plant leaves are not able to repel oil droplets, which spread into
the asperities of their micro/nano-structures. This case is rep-
resented schematically in 1–2 of Fig. 1d, which shows that a
superhydrophobic surface made for instance of classical micro-
pillars is able to sustain a stable fakir state with water, but fails
to repel an oil droplet. To overcome this limitation, theoretical
investigations suggested a specific design criterion preventing
liquid penetration between microstructures [16]. This criterion
involves geometries presenting reentrant curvatures (or over-
hangs), which enable contact line pinning to keep a composite
interface (i.e., air and solid) under the drop [17, 18]. In this
case, a metastable Cassie configuration can be achieved even
with low surface tension liquids (3–4 of Fig. 1d). Such surfaces
are thus called superomniphobic (SACA>140° for a wide
range of liquids). This concept has been demonstrated with
the so-called micro-mushrooms and nano-nails obtained by
Colloid Polym Sci
liquids such as water (i.e., Cassie state), whereas oil drops stay in a
fully wetted state (i.e., Wenzel configuration) [31]. 3–4 Addition of a
reentrant geometry confers a superomniphobic property to the surface
(Cassie state for both water and oil)
silicon etching processes [17] and also with inverted trapezoi-
dal structures in poly(dimethylsiloxane) (PDMS) involving a
diffusive photolithography technique [19]. Few other reports
deal with nanotextured surfaces exhibiting superomniphobic
character due to their double-scale roughness. They consist of
microstructured Ti surface covered by TiO2 nanotube arrays
[20], assembly of silica and porous polystyrene nanoparticles
[21], structured silicon surfaces, and cellulose nanocrystals
[22] or a double layer made of silicon nanowires grown by
the vapor–liquid–solid growth technique [23].
Whatever the involved roughness scale (from micro to
nano), the superomniphobic character was assigned to the
presence of a “reentrant” shape. In this paper, we compare
and contrast wetting properties of two surfaces presenting
micro- or nanoscaled reentrant structures. The wetting char-
acterization of PDMS-based microstructured [24] and zinc
oxide (ZnO) nanotextured surfaces [25] has been performed
with liquids of surface tension as low as 28 mN/m. In order
to explain the respective sticking and sliding properties of
low surface tension liquids, we use fluorescently labeled
biomolecules to relate contact angle hysteresis to liquid–
solid interaction. We show that depending on the length
scale and topography of the structures, variations in CAH
with liquid surface tension are different, and that each kind
of surface displays its own advantages and drawbacks.
Material and methods
Mushroom-like microstructured surfaces
Mushroom-like microstructured surfaces were fabricated by
molding PDMS onto a patterned sacrificial photoresist
Colloid Polym Sci
bilayer. For the mold, AZ9260 (MicroChem, MA, USA)
was used as a thick photoresist and PMGI SF11 (Micro-
Chem, MA, USA) as an undercut layer. Sylgard 184 PDMS
was purchased from Dow Corning (Midland, MI, USA),
mixed with curing agent at a weight ratio of 10:1, and
degassed for 30 min before spin-coating onto the mold.
The fabrication steps are shown in Fig. 2. First, a gold layer
was sputtered on a 3-in. silicon wafer, forming a low adhe-
sion surface for the PDMS. Then, PMGI and AZ9260 resists
were spin-coated to thicknesses which define structure
dimensions (Fig. 2a). A single photolithography step of
the thick resist defines center-to-center spacing and pillar
base diameter (Fig. 2b). Cap diameter was obtained by
etching of the undercut PMGI layer (Fig. 2c). To achieve a
good homogeneity and reproducibility of PMGI etching, it
is important to keep exactly the same protocol (same beaker
and developer volume, no agitation). Next, a PDMS layer
was spin-coated and degassed for 15 min to ensure that it
entirely filled the cavities (Fig. 2d). Polymer was cured at
60 °C for 3 h, avoiding stress or mold deformation. Before
demolding, a narrow strip of PDMS must be cut and peeled
off around the wafer to allow solvent to access the mold.
Resists were then dissolved for 10 h in Microposit Remover
1165 (Shipley, MA, USA). A second bake step of PDMS
(110 °C, 1 h in an oven) enables solvent evaporation and
improves polymer bulk strength. An example of structured
PDMS surface is shown in Fig. 3a.
ZnO nanostructures
ZnO nanostructures (NS) deposited on silicon substrate were
prepared through a chemical bath deposition method devel-
oped by Kokotov and Hodes [26]. All the chemicals used
were obtained from Sigma-Aldrich, MI, USA. The process is
fast, simple, and takes place at low temperature. Firstly, silicon
samples were cleaned successively in ultrasonic baths of
acetone and isopropyl alcohol. A surface pretreatment was
performed in PTFE vials filled with 20 mL of deionized water
Fig. 2 Fabrication process for mushroom-like PDMS microstructures:
a PMGI and AZ9260 spin-coating, b photolithography of AZ9260, c
etching of PMGI, d molding and curing of PDMS, e release and PFTS
coating
(DW), 12.7 mM of potassium permanganate aqueous solution
containing 50 μL of tert-butanol. The vials were closed and
placed in an oil bath at 84 °C for 20 min. This pretreatment is a
very important step because it allows good adhesion of ZnO
NS to the substrate. The resulting surfaces were intensively
rinsed with DW and sonicated for 10 min. Then, the samples
were dipped in 50 mM of zinc nitrate aqueous solution
(17.5 mL of DW) containing 2 mL of triethanolamine and
500 μL of ammonium hydroxide. The closed vials were
placed in an oil bath at 96 °C for 40 min. After deposition,
the samples were rinsed with DW and dried in an oven at 100 °
C for 1 h. The ZnO nanoparticles uniformly covered the
surface with a maximum thickness of about 10 μm. Further-
more, Fig. 3b shows that ZnO NP substrate clearly exhibits a
reentrant structure, considering the lower half part of the
nanoparticles.
Surface functionalization
All the resulting surfaces were modified through silanization
with 1H,1H,2H,2H-perfluorodecyltrichlorosilane (PFTS,
ABCR GmbH, Germany). The silanization reaction was
performed in gas phase. Vapor phase silanization was
achieved by evaporation of 50 μL of PFTS on the surfaces
in a desiccator under vacuum for 4 h.
Characterization
Scanning electron microscopy
SEM images were obtained using an electron microscope
ULTRA 55 (Zeiss, NY, USA) equipped with a thermal field
emission emitter and three different detectors (EsB detector
with filter grid, high-efficiency In-lens SE detector, and
Everhart-Thornley secondary electron detector).
Contact angle measurements
Contact angle measurements were performed using a drop
shape analysis system (DSA100, Krüss GmbH, Germany)
including automated dosing unit and tilting table, CCD
camera (50 fps), and analysis software. Static apparent con-
tact angle (SACA), θ
0 was measured just after drop deposi-
tion. Advancing and receding apparent contact angles,
respectively θ*A and θ*R, were measured using the tilting plate
method: tilting table was rotated from 0° to 90° (in steps of
1° per second), and drop deformation and displacement
were recorded (50 fps, ten computations per second). Ad-
vancing/receding apparent contact angles were calculated
just before advancing/receding contact line depinning, re-
spectively. CAH was calculated as the difference between
θ*A and θ*R. The test liquids were mixtures of deionized water
 Colloid Polym Sci

Fig. 3 SEM images of a

mushroom-like PDMS micro-
structures and b ZnO nanopar-
ticles’ structured surface. Scale
bar equals 10 μm

and ethanol. Volume proportions along with corresponding
surface tensions γ are reported in Table 1. The use of such
mixtures enables easy tuning of γ while avoiding large
variations in viscosity η and density ρ. The drop volume
was fixed at 8 μL for all experiments. This ensures easy
droplet sliding upon tilting while keeping drop radius
(≈1 mm) slightly below the capillary length
qffiffiffiffiffi
ρ:g
( 1:8mm  k 1 ¼ g  2:7mm depending on ethanol con-
centration). For apparent contact angle computation, part of
the drop profile which lies near the contact line is adapted to
fit a polynomial function. Apparent contact angles are then
determined from the slope at the triple point. This method
avoids measurement errors due to drop shape deformation
under gravity [27, 28]. For each surface–liquid set, apparent
contact angles were averaged over five measurements. Stan-
dard deviation was also calculated.
It is to be noted that the only drawback when using water/
ethanol mixtures is the eventual surface tension variation
during droplet evaporation. Since ethanol is more volatile
than water, it tends to evaporate first; consequently, liquid
surface tension increases as ethanol concentration decreases.
This is the reason why it is important to prepare solutions
just before use and to keep them in a hermetic container.
Moreover, apparent contact angle measurements were per-
formed within approximately 30 s following drop deposition
in order to avoid influence of evaporation phenomenon.
Table 1 Surface tensions of DI water/ethanol (Eth.) mixtures measured
using the pendant drop method (averaged over five measurements)
Liquid γ (mN/m)
DI water 100 (%) 72.6
DI water+Eth. 95/5 (%) 58.7
DI water+Eth. 90/10 (%) 52.0
DI water+Eth. 85/15 (%) 46.0
DI water+Eth. 80/20 (%) 42.9
DI water+Eth. 75/25 (%) 40.0
DI water+Eth. 70/30 (%) 35.0
DI water+Eth. 60/40 (%) 31.1
DI Water+Eth. 50/50 (%) 29.2
DI water+Eth. 40/60 (%) 27.9
Finally, the fraction of solid surface contacting the liquid
(ФS), on mushroom-like PDMS surfaces, is fixed by the
mushroom geometry. We obtain ΦS ffi p:r
2
l 2 , where r and
l correspond, respectively, to the cap radius and inter-post
spacing. On nanotextured surfaces, ФS was estimated by
measuring quantities of adsorbed fluorescent proteins onto
the surfaces. A solution of rhodamine-tagged BSA proteins
(3 μg/μL) in water was mixed with different concentrations
of isopropanol in order to tune the surface tension. Drops
were deposited onto the surface, and after 1 min, they were
allowed to slide down the surface (Fig. 4a, b). The quantities
of adsorbed proteins were measured a posteriori in order to
get an estimation of liquid–solid contacting surface
(Fig. 4c). Fluorescent images were recorded using a micro-
scope (Olympus IX71, Japan). Using ImageJ software, the
fluorescent images were translated into black and white
binary images. Then, the fraction of solid surface is obtained
from the ratio between black and white pixel numbers.
Results and discussion
The wetting characterization of the surfaces presenting re-
entrant shapes at micro- and nanoscale was done using low
surface tension liquids. The wetting properties of a flat
PFTS-coated silicon surface were determined first (Fig. 5).
The measured SACA corresponds to the Young angle de-
creasing quite linearly with the liquid surface tension, from
110° down to 70°. The boundary between wetting and non-
wetting (i.e., SACA090°) states corresponds to γC ≈46 mN/
m. CAH hardly varies and remains between 25° and 35°.
Wetting characterization of rough surfaces was then stud-
ied on PDMS-based micro-mushroom surface. This surface
is able to support a metastable Cassie state with a SACA
between 145° and 150° whatever the liquid surface tension
(from 72.2 to 27.9 mN/m, Fig. 6a). It is to be noted that in
the case of micro-scale structures, light diffraction below the
drop gives rise to visible air pockets and insures a clear
distinction between Cassie and Wenzel wetting states.
Moreover, a composite interface can be obtained with low
surface tension liquids such as ethanol (γ021.7 mN/m).
However, in this case, the Cassie configuration is highly
unstable, and the pressure induced during drop deposition
Colloid Polym Sci
Fig. 4 Method for estimation of liquid–solid contacting surface: a A mixture of fluorescently tagged BSA and isopropanol is deposited onto the
surface, b proteins adsorb on micro/nano structures, c a microscope is used to measure the fraction of surface covered by proteins
from the syringe tip is sufficient to cause transition to the
Wenzel state [27]. Consequently, we limited wetting char-
acterization to γ≥27.9 mN/m. The results are plotted in
Fig. 6a. For all tested liquids, a large SACA is observed
along with a large CAH, which monotonously increases
(from 22° to 45°) as surface tension decreases. This phe-
nomenon is related to the fraction of solid surface contacting
the liquid (ΦS), which is relatively important (ΦS 00.16) and
causes strong contact line pinning at the trailing edge of the
drop [29]. Actually, ΦS cannot be reduced by increasing the
inter-post spacing l since this would dramatically impact
surface robustness (i.e., stability of the Cassie state). As a
consequence and as far as hysteresis is concerned, the per-
formance of such micro-structured superomniphobic surfa-
ces is limited by their length scale. In order to obtain both
low ΦS and low spacing l, it seems thus necessary to study
nanostructured surfaces.
On ZnO nanotextured surface, a different behavior was
observed. On the one hand, the SACA remains constant
around 150° for liquid surface tension down to 40 mN/m
and then decreases to 145° for a liquid with a surface tension
of 35 mN/m (Fig. 6b). Consequently, this surface can be
qualified as superomniphobic since large apparent contact
angles are achieved for liquids wetting the initial smooth
surface. For γ <35 mN/m, the surface cannot sustain a
Cassie state, and liquid spontaneously spreads into the
Fig. 5 Wetting properties of the different water–ethanol mixtures
(SACA and CAH) on a smooth PFTS-coated silicon surface. Transi-
tion from wetting to non-wetting is found for γ≈46 mN/m
nanostructures (Wenzel configuration). Thus, robustness of
the non-wetting state is slightly lower compared to
mushroom-like microstructures. On the other hand, CAH
is almost zero for liquids with surface tensions above
46 mN/m (i.e., initially non-wetting on smooth PFTS). It
then linearly increases up to 30° for liquids of lower surface
tension (γ<46 mN/m, i.e., liquids wetting the smooth PFTS
surface).
In order to understand this non-linear variation of hyster-
esis on ZnO nanostructures, it is necessary to gain a deeper
insight into the liquid–solid interaction below the drop. To
this end, other liquids were used. A 20-μL droplet suspen-
sion of fluorescently tagged BSA proteins (3 μg/μL) solu-
tion was mixed with isopropanol in volume proportions of
100/0, 70/30, and 50/50, leading to surface tensions of 60,
35, and 29 mN/m, respectively. The resulting fluorescent
images are depicted in Fig. 7.
In the first case (100 % BSA, Fig. 7a), the liquid–solid
contacting surface ΦS appears to be extremely low, between
1 and 5 %. This explains the almost zero hysteresis observed
for high surface tension liquids: the drop stays in a Cassie
state, and rolling-ball effect is achieved along with low
surface contamination (on the right of Fig. 7a; as for
Fig. 7b, c, a drag can be seen revealing the 20-μL drop
sliding). For a surface tension below the γC (critical surface
tension wetting, i.e., surface tension delimiting wetting from
non-wetting on the smooth surface), the area fraction is
strongly increased and lies between 20 and 30 %. This
observation corresponds to a partial impalement configura-
tion: liquid partially fills some cavities between nanostruc-
tures, but it does not completely stay in a Wenzel state. This
corresponds to a hysteresis around 20° (Fig. 6b). Finally, for
a high isopropanol concentration (Fig. 7c, γ029 mN/m), ΦS
almost equals 100 %, meaning that the liquid completely
fills the asperities (this case is not represented in Fig. 6b
since the 8-μL droplet does not slide upon surface tilting).
Comparing micro and nanostructures, we can clearly
distinguish two different behaviors. First, on mushroom-
like PDMS surfaces, since the contact line is always
pinned around the cap contour, variation of ΦS with the
liquid surface tension is negligible. Consequently, CAH
is relatively large even for water, and variations are
smooth and related to γ only (Fig. 6a). These micro-
structures are able to sustain a composite interface with

Fig. 6 Static apparent contact angle (SACA) and contact angle hysteresis (CAH) versus surface tension for a PDMS-based micro-mushroom
surface and b ZnO nanotextured surface
liquid of surface tension down to 27.9 mN/m, but as
soon as this fakir state becomes unstable, the drop
completely spreads into the lattice. The transition from
Cassie to Wenzel state is discontinuous, and there is no
intermediate metastable configuration (partial impale-
ment). Thus, the superomniphobic property of PDMS
microstructures is exclusively attributed to their ability
to prevent locally the Cassie–Wenzel transition since
they cannot prevent lateral spreading once the compos-
ite interface disappears [30]. On the other hand, nano-
structured ZnO surfaces exhibit a more complex
variation of CAH due to the nonlinear relation between
ΦS and γ. As long as the liquid does not wet the
smooth PFTS surface (γ > γ c), ΦS remains very low
(<1 %), and zero hysteresis is achieved. However, as
soon as γ<γc, it seems that the reentrant geometry does
not totally prevent liquid penetration. Thereby, some
cavities are partially filled with liquid, resulting in an
increase of ΦS with γ (Fig. 7). The drop thus stays in
an intermediate wetting state, and CAH increases more
sharply compared to mushroom structures because (1)
Φ S increases and (2) γ decreases. Consequently, it
appears that the superomniphobic character of ZnO
nanostructures is more likely related to their ability to
prevent lateral spreading of liquid than to their ability to
prevent a local Cassie–Wenzel transition.
Fig. 7 Fluorescent images of
adsorbed BSA protein on a ZnO
nanotextured surface for
different fractions of solid
surface contacting the liquid
(ΦS) a 100 % BSA solution (γ0
60 mN/m), b 70 % BSA
solution with 30 % isopropanol
(γ035 mN/m), and c 50 % BSA
solution with 50 % isopropanol
(γ029 mN/m)
Colloid Polym Sci
Conclusion
We have presented in this paper characterizations of static
apparent contact angle and contact angle hysteresis of water/
ethanol mixtures on microstructured and nanotextured super-
omniphobic surfaces. While the measured apparent contact
angles are around 150° whatever the surface and the surface
tension of the test liquid, contact angle hysteresis exhibits
different behaviors. On the PDMS-based micro-mushroom
surfaces, despite a CAH of about 35°, a Cassie state is ob-
served for surface tensions as low as 27.9 mN/m. This prop-
erty is ascribed to large liquid–solid contacting surface ΦS. On
the ZnO reentrant nanotextured surface, the CAH is quasi-null
for liquids of surface tensions higher than 46 mN/m. Below
this critical value, the liquid stays in a semi-impalement state
characterized by a moderate CAH. In the latter case, fluores-
cence characterization shows that nanoscale cavities are filled
in due to lateral spreading of the liquid. Searching for super-
omniphobic surfaces presenting low hysteresis even for low
surface tension liquids may thus prevent both lateral spreading
and vertical transition of liquids inside the rough structures. In
order to do so, two strategies have to be pursued (the realiza-
tion of either micro/nano multiscaled surfaces micro or nano-
scaled micro mushroom-based surfaces). Therefore, these
superomniphobic surfaces would pave the way to the use of
low surface tension liquids for lab-on-chip applications.
Colloid Polym Sci
Acknowledgments We acknowledge the European Regional Devel-
opment Fund for financial support under the INTERREG IVa FW1.1.9
"PLASMOBIO" project and the European Community Seventh Frame-
work Programme (FP7/20072013) under grant agreement no. 22724.
This work was supported by Nord-Pas-de-Calais Region through the
2008-2013 CIA State Region Planning contract and by the Ministry of
Defense. The authors thank Mr. Christophe Boyaval for SEM imaging.
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