What Do We Need For A Superhydrophobic Surface? A Review On The Recent Progress in The Preparation of Superhydrophobic Surfaces

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CRITICAL REVIEW www.rsc.org/csr | Chemical Society Reviews
What do we need for a superhydrophobic surface? A review on the recent

progress in the preparation of superhydrophobic surfaces
Xue-Mei Li, David Reinhoudt* and Mercedes Crego-Calama*
Received 17th October 2006
First published as an Advance Article on the web 31st January 2007
Published on 31 January 2007. Downloaded by Louisiana State University on 10/22/2019 8:47:55 PM.
DOI: 10.1039/b602486f
Superhydrophobic surfaces have drawn a lot of interest both in academia and in industry because
of the self-cleaning properties. This critical review focuses on the recent progress (within the last
three years) in the preparation, theoretical modeling, and applications of superhydrophobic
surfaces. The preparation approaches are reviewed according to categorized approaches such as
bottom-up, top-down, and combination approaches. The advantages and limitations of each
strategy are summarized and compared. Progress in theoretical modeling of surface design and
wettability behavior focuses on the transition state of superhydrophobic surfaces and the role of
the roughness factor. Finally, the problems/obstacles related to applicability of superhydrophobic
surfaces in real life are addressed. This review should be of interest to students and scientists
interested specifically in superhydrophobic surfaces but also to scientists and industries focused in
material chemistry in general.
1 Introduction practical applications.5,6 A direct expression of the wettability

of a surface is the contact angle (CA) of a water droplet on
Wettability of a solid surface is an important property1–4 the surface. Surfaces with very high water contact angles
because controlling the surface wettability is crucial in many particularly larger than 150u are usually called superhydro-
phobic (SH) surfaces. These surfaces are of special interest,
because properties such as antisticking, anti-contamination,7,8
Laboratory of Supramolecular Chemistry and Technology group,
MESA+ Institute for Nanotechnology, University of Twente, and self-cleaning9–13 are expected. These properties are
P. O. Box 217, 7500AE, Enschede, The Netherlands desirable for many industrial and biological applications such
Dr. Xue-Mei Li was born in chemistry in 1969 with

China in 1971. She received her Professor H. C. Beijerman. In
Bachelor degree of Engineering the period 1970–1975 he
at Dalian University of worked at Shell where he
Technology in 1994. started the crown ether research
Thereafter, she was admitted program. In 1975 he was
by Dalian Institute of Chemical appointed as a part-time pro-
Physics, Chinese Academy of fessor (extraordinarius) at the
Sciences (CAS) and received University of Twente followed
her master degree in 1997. In by the appointment as a full
1 99 8, s he m ov ed t o t he professor in 1978. The major
Netherlands, and started to part of his research deals with
work at Prof. Reinhoudt’s supramolecular chemistry and
group for a short project. technology. Nanotechnology,
Xue-Mei Li Meanwhile, she was offered a David N. Reinhoudt molecular recognition, and
PhD candidateship. In 2003, non-covalent combinatorial
she obtained her PhD degree in nanofabrication. In 2004, she synthesis are the major fields. His interest is also on application
started her career at DSM Resins BV working at the Customer of supramolecular chemistry e.g. in ‘‘lab-on-a-chip’’, in the field of
Competence Center in Zwolle. One year later, she came back to electronic or optical sensor systems, catalysis, and molecular
University of Twente and joined Prof. Reinhoudt as a post- materials. Prof. Reinhoudt is the scientific director of the MESA+
doctoral researcher working on the development of superhydro- Research Institute. Since 2002 he is the chairman of the Board of
phobic surfaces for medical applications. Her PhD thesis was NanoNed, the Dutch Network for Nanotechnology. He is a
awarded the Backer prize in 2004. Her research interest member of the Royal Dutch Academy of Sciences, Fellow of the
encompasses nano/microfabrication, development of nano- American Association for the Advancement of Science, and Fellow
materials, and application of nanotechnology in medicine. of the Institute of Physics. He is the author of more than 800
scientific publications, patents, review articles, and books. He has
Professor David N. Reinhoudt was born in 1942 in The been honored with the Izatt–Christensen award (1995), the Simon
Netherlands. He studied Chemical Technology at the Delft Stevin Mastership (1998) and Knight of the Order of the Dutch
University of Technology and graduated (suma cum laude) in Lion (2002).
1350 | Chem. Soc. Rev., 2007, 36, 1350–1368 This journal is ß The Royal Society of Chemistry 2007
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as antibiofouling paints for boats,14,15 antisticking of snow for with special focus on the fabrication methodology, materials,
antennas and windows,16,17 self-cleaning windshields for and structures. The fourth section discusses the recent progress
automobiles,18 metal refining, stain resistant textiles, antisoil- in theoretical modeling, while the fifth section gives an
ing architectural coatings.19 The wettability of a surface is overview of the potential application of superhydrophobic
directly related to the surface energy. Materials with low surfaces. Finally a personal perspective of the principles of
surface energy, for example a surface with hexagonally packed fabrication of superhydrophobic surfaces is given.
–CF3 groups gives water contact angles as high as 120u.20,21
These surfaces are easy to clean, however, they do not have 2 Theoretical background and characteristics of
self-cleaning properties. In nature, many natural species natural species

exhibit water contact angle higher than 150u such as sacred
lotus leaves,4 water strider’s legs,22 cicada orni’s wings,23 etc. 2.1 Theoretical background
These surfaces are water repellent in that the water droplets
The wettability of a flat surface, expressed by contact angle
roll off the surface at a small tilt angle (sliding angle) and
(CA) h of a water droplet, is given by Young’s equation:
hereby removing contaminates from the surface (self-cleaning).
Recently, a great deal of research has been devoted to the cSV {cSL
cos h~ (1)
preparation and theoretical modeling of superhydrophobic cLV
surfaces as witnessed by the large number of publications and
diverse approaches.3,4,24–26 The major objective of this review where cSV, cSLand cLV refer to the interfacial surface tensions
with S, L, and V as solid, liquid, and gas, respectively. Young’s
is: (a) to discuss the superhydrophobic effect and self-cleaning
angle is a result of thermodynamic equilibrium of the free
mechanism; (b) to illustrate the most recent progress in the
energy at the solid–liquid–vapor interphase.
preparation methods in a systematic way; (c) to address the
potential application of superhydrophobic coatings, and (d) to Depending on the value of the contact angle, surface
review a series of theoretical models in order to provide properties are determined as hydrophobic (CA . 90u) or
guidelines for the preparation of superhydrophobic surfaces. hydrophilic (CA , 90u). In practice, two types of CA values
Because water repellency mechanisms, self-cleaning materials, are used: static and dynamic CAs. For a flat surface, static
and application potentials have been reviewed in a number of contact angle is close to Young’s angle. Dynamic contact
publications,3,4,26 here we only give an overview of the most angles are non-equilibrium CAs. Static CAs are obtained by
recent activities (the last three years) in this area. The major sessile drop measurements, where a drop is deposited on the
surface and the value is obtained by a goniometer. Dynamic
part of this review is organized in five sections. The first
CAs are measured during the growth (advancing CA, ha) and
section gives a brief introduction about the superhydrophobic
shrinkage (receding CA, hr) of a water droplet. The difference
effect. The second section briefly summarizes the basic
between ha and hr is defined as contact angle hysteresis (Dh).
guidelines for the preparation of superhydrophobic surfaces
The values of Dh can be as low as 10u for a self-assembled
and the characteristics of natural superhydrophobic surfaces.
monolayer on silicon, and many surfaces show much larger
The third section provides a comprehensive overview on the
hysteresis due to chemical heterogeneity and roughness.27,28
strategies for the preparation of superhydrophobic surfaces,
Surfaces with water CA higher than 150u are super-
hydrophobic or ultraphobic (with very little CA hysteresis).
Dr. Mercedes Crego Calama This very high CA is normally called apparent CA since this
was born in Salamanca, Spain value does not represent the ‘‘real’’ CA value of the
in 1967. Here, she received her corresponding flat surfaces. The superhydrophobic surfaces
Master degree (1991) and are usually covered with micro- or nanoscale asperities
her PhD (cum laude) in (rough). The behavior a water droplet on a rough surface is
Chemistry (1995) with J. R. schematically shown in Fig. 1. Water can either penetrate the
Moran. In 1995, she moved to asperities or suspend above the asperities. In either case, much
University of Pittsburgh, USA higher contact angles are observed than that obtained for the
(NATO fellowship) to colla-
corresponding flat surface. These two situations are named the
borate with A. D. Hamilton. In
1997 she was awarded with a Wenzel state (penetration) and the Cassie–Baxter state
Marie Curie European post- (suspension) after the corresponding theoretical models: the
doctoral fellowship and she Wenzel29 and Cassie–Baxter (CB)30 models. These models
moved to the University of
Mercedes Crego Calama Twente, The Netherlands
where she worked with D. N.
Reinhoudt on dynamic combinatorial libraries. In 2000, she
became Researcher of the Royal Dutch Academy of Sciences
(KNWA) working on combinatorial sensor fabrication.
Alongside her KNWA duties, she currently holds a tenured
position as Universiteit Docent in the University of Twente. Her
current research interests, besides in glass microarrays, are in Fig. 1 Behavior of a liquid drop on a rough surface. Left, liquid
the design and fabrication of nanostructures via self-assembly penetrates into the spikes (Wenzel state); right: liquid suspends on the
and self-organization. spikes (Cassie–Baxter state).
This journal is ß The Royal Society of Chemistry 2007 Chem. Soc. Rev., 2007, 36, 1350–1368 | 1351
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form the basic guidelines for the study of superhydrophobic surfaces behavior, which is critical in designing superhydro-
surfaces.11,31–36 phobic surfaces. Thus, many research interests have been
The basic assumption in Wenzel’s theory is that the liquid devoted to modeling superhydrophobic surfaces. The new
follows the roughness of the surface as shown in Fig. 1 (left). models for predicting surface wettability will be discussed in
At thermodynamic equilibrium, there is a linear relationship more detail in section 4.
between the apparent contact angle of the surface and the
roughness factor of the given surface: 2.2 Structures of natural superhydrophobic (SH) surfaces
Many plant surfaces39 and animal furs22 exhibit water

cos hw = r cos h (2)
repellent properties, i.e. very high water CA. With the aid of
scanning electron microscopy (SEM), the microstructures of
where hw corresponds to the apparent contact angle, r
plant surfaces have revealed that water repellency is mainly
represents the roughness factor, and h refers to Young’s angle.
caused by epicuticular wax crystalloids that cover the cuticular
The roughness factor is defined by the actual surface area
surface in a regular microrelief of about 1–5 mm in height.40,41
divided by the projected surface area, therefore, for a rough
Lotus leaves are one of the most famous examples among
surface r . 1. Following Wenzel’s prediction, for a hydro-
naturally occurring superhydrophobic surfaces.7 The water
phobic surface hw . h . 90u and for a hydrophilic surface
CA of a lotus leaf is 161 ¡ 2.7u with CA hysteresis of 2u.4,42
hw , h , 90u. Roughness enhances both hydrophobicity and
Pictures of a lotus leaf and its microstructure image obtained
hydrophilicity depending on the nature of the corresponding
by Barthlott and Neihuis are shown in Fig. 2. The structure of
flat surface.24 In the Wenzel’s regime, the contact angle and its
a lotus leaf consists of a combination of a two scale roughness:
hysteresis increases as the roughness factor increases for a
one around 10 mm (rough structure) and one around 100 nm
hydrophobic surface. Nevertheless, it has been demonstrated
(fine structure). These surfaces are also referred as hierarchical
that the contact angle increases steadily with the roughness
micro- and nano-structures.4 The hydrophobicity of a lotus
factor until it exceeds 1.7 then contrary to the Wenzel’s
leaf arises from the epicuticular wax secreted by the leaf itself.7
prediction the contact angle hysteresis starts to decrease.37,38
The wax has a contact angle of 110u, not highly hydrophobic,
The decrease in the contact angle hysteresis is attributed to the
however, the lotus leaf still exhibits a superhydrophobic
switching from the Wenzel to the Cassie–Baxter state because
property. It is presumed that this combination of roughness
of the increased air fraction leading to the suspension of
and wax contribute to the superhydrophobicity of the lotus
water droplet on top of the asperities as shown in Fig. 1, right.
leaf4,42 The rolling off of water droplets and collecting the
The suspension of water droplet is also described as a
contaminants from the lotus leaf is dubbed as the ‘‘lotus
composite state.
effect’’. The lotus leaf therefore always exhibits a very low
As a result of the suspension of the water droplet on the
degree of contamination: self-cleaning.
asperities, in the Cassie–Baxter (CB) model,30 the apparent
The self-cleaning effect is evident for the lotus leaf. The
contact angle is the sum of all the contributions of the different
underlying mechanism has been thoroughly studied. At the
phases as described by eqn (3):
interface between a viscous fluid and a solid surface, usually, a
nonslip boundary condition dominates.43 Slip on the boundary
cos hc = f1 cos h1 + f2 cos h1 (3)
can occur on the scale of a few tens of nanometers, which is
not appreciated for macroscopic flow. However, when a drop
where hc is the apparent CA, f1 and f2 surface fraction of
moves down a tilted rough SH surface, due to the high contact
phase 1 and 2, respectively; h1 and h2 CA of phase 1 and
angle (minimized contact between the fluid and surface),
phase 2, respectively. For a rough surface containing only one
effective macroscopic slip occurs on scales consistent with the
type of asperities, given f is the solid fraction, then the air
characteristic size of the surface features. For a drop of water
fraction is (1 2 f). With h = 180u for air, the resulting CA can
rolling off a lotus leaf, the droplet behaves as an elastic ball
be calculated by the following equation:
cos hc = f(1 + cos h) 2 1 (4)
Thus, for the CB model, the apparent CA (hc) is a sole

function of solid fraction for a given surface with CA h.
Therefore, to obtain a superhydrophobic surface, the con-
tribution of the solid part should be as small as possible or a
solid material with very high CA should be used. In practice,
the CB model cannot predict accurately the wetting behavior
of a predesigned surface. However, it is often used to compare
it with a practical result in order to confirm the presence of the
CB state.
In summary, both theories can predict the contact angle of a
rough surface only qualitatively. Furthermore, it is not evident Fig. 2 A microscopic SEM image of a lotus leaf showing the two-
which theory should be used and when. Therefore, it would be scale roughness. (Picture adapted from ref. 7 with kind permission of
very important to obtain some guidelines for predicting the Springer Science and Business Media.)
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3 Methods used for the preparation of

superhydrophobic surfaces
Both Wenzel and Cassie–Baxter theories have pointed out that
a rough surface is essential for enhancing hydrophobicity and
hydrophilicity. In practice, the approaches for superhydro-
phobic surface preparation can be basically categorized into
two directions: top-down and bottom-up approaches. Top-
down approaches encompass lithographic and template-based

techniques,43 and plasma treatment of the surfaces.32,34,36,44–51
Bottom-up approaches involve mostly self-assembly and self-
organization.43,52–60 Examples of bottom-up approaches
include chemical deposition,60–66 layer-by-layer (LBL) deposi-
Fig. 3 Slip of a water droplet from an inclined hydrophobic surface
tion,52,53,57,60,62 hydrogen bonding,67 and colloidal assem-
(left) where the water drop crawls over the dust particles and an
blies.35,43,59,68–70 There are also methods based on the
inclined superhydrophobic surface (right) where the dust particles are
collected and taken away: self-cleaning. (Pictures adapted from ref. 7, combination of both bottom-up and top-down approaches,
with kind permission of Springer Science and Business Media.) for example, casting of polymer solution and phase separa-
tion,71 and electrospinning.63,72–74 In the following section,
rather than a fluid (Fig. 3). In case of a normal hydrophobic different approaches are addressed in detail.
surface, because of the nonslip boundary condition, the water
drop falls across the dirt particles and the dirt particles are 3.1 Top-down approaches
mainly displaced to the sides of the droplet and re-deposited Top-down approach is a general term in microelectronics
behind the droplet. Especially hydrophobic particles tend to referring to the fabrication of materials and devices by carving,
remain on such surfaces (Fig. 3, left). In the case of water- molding, or machining bulk materials with tools and lasers.
repellent rough surfaces, the solid/water interface is minimized. For the generation of superhydrophobic surfaces, template75,76
Water forms a spherical droplet, and collects the particles from and lithographic approaches,10,33,77–80 micromachining,31 and
the surface (Fig. 3, right). The rolling off of water droplets and plasma treatments have been used. Templation often involves
collecting the contaminants from the lotus leaf is dubbed as the molding and replication steps. Thereafter, the template can be
‘‘lotus effect’’. The lotus leaf therefore always exhibits a very removed by lifting off75,76 or dissolution81 or even sublima-
low degree of contamination: self-cleaning. tion.82,83 In the lithographic approaches, light is irradiated
In animals, water repellent structures are also quite through a mask with desired features onto the substrates (often
common.23 Recently Jiang et al. have reported that a water silicon) with a photoresist. Subsequent etching steps yield the
strider’s leg contains hierarchical micro- and nanostructures.22 desired patterned surfaces. These surfaces are made hydro-
They ascribe the water strider’s capability of standing and phobic by silanization.10,33,77–80 In micromachining, surfaces
moving rapidly on water to numerous oriented, needle-shaped are diced into the desired texture.31 In the plasma treatments,
setae on the legs (Fig. 4). The setae are needle-shaped, with surfaces are etched anisotropically thus generating rough
diameters ranging from 3 microns down to several hundred surfaces. Examples includes plasma treatment of poly(ethylene
nanometers. Most setae are roughly 50 mm in length and terephthalate) (PET),49,50 poly(tetrafluoroethylene) (PTFE),84
arranged at an inclined angle about 20u from the surface of the and polyethylene (PE).44 Pulse-laser treatments of poly-
leg. Many elaborate, nanoscale grooves are evident on each (dimethylsiloxane) (PDMS) for the generation of superhydro-
microseta forming a unique hierarchical structure. The phobic surfaces have also been shown.85,86
maximal supporting force for a single leg is about 15 times
of the body weight of a water strider before it will pierce into 3.1.1 Templation. Templation involves the use of a master
the water as tested by using a cantilever made of a water with the desired features, replication of the features (Fig. 5) by
strider’ leg. This phenomenon is ascribed to super water molding and subsequent lifting off the replica or dissolution of
repellency of the hierarchical structures of the legs. the templates. Templation is useful for the preparation of
Fig. 4 Images of the non-wetting leg of a water strider. (a) a water droplet on a leg with a contact angle of 167.6 ¡ 4.4u; (b) and (c), scanning
electron microscope images of the leg showing numerous oriented spindly microsetae (b) and the fine nanoscale grooved structures on a seta (c).
Scale bars: (b) 20 mm, (c) 200 nm. (Reprinted with permission from Macmillan Publishers Ltd: [Nature].22 Copyright 2004.)
Published on 31 January 2007. Downloaded by Louisiana State University on 10/22/2019 8:47:55 PM. View Article Online
Fig. 5 Schematic illustration of nanocasting and SEM images of (a) a natural lotus leaf and (b) its positive PDMS replica. (Images reprinted with
permission from Sun et al.42 Copyright 2005, American Chemical Society.)
polymeric superhydrophobic coatings. Many materials can be

used as a template ranging from natural lotus leaves,42 a
master prepared by lithographic processes, to commercial
inorganic membranes.
Sun et al.42 have used a lotus leaf as the template, where the
replication process was denoted nanocasting. After casting and
lifting off PDMS, a negative replication of the lotus leaf
structure was obtained (Fig. 5). This negative template was
used further as a master for preparation of a positive replica of
the lotus leaf. The positive replica has almost the same surface Fig. 6 Direct observation of a composite drop and a wetted situation
morphology on both the micro- and nanoscale as the natural on the surface depending on how the drop is deposited on the surface.
Left, gentle deposition (suspension); right, water drop deposited from
lotus leaf. The SEM images of the positive replica showed
a distance (collapsed). (Images reprinted with permission from He
small papillae hills with an average distance of 6 microns. Even
et al.76 Copyright 2003, American Chemical Society.)
the intricate nanotextures between the hills and in the valleys
were clearly replicated (Fig. 5, SEM images). The positive
membranes were prepared and used as replication templates.
replica exhibits the same superhydrobic property as the natural
Polystyrene (PS) polymer substrates were applied in the
lotus leaf with an advancing contact angle of 160u. On the
nanoimprinting process. After cooling down to room tem-
other hand the negative replica of the lotus leaf has a contact
perature and pressure release, the replication template was
angle of 110u.
removed from the polymer substrate by dissolution of Al with
In a similar replication process He et al.76 have fabricated
saturated HgCl2 solution to give the large area, nanostructured
PDMS structures with features of relatively big size (squared
PS surface. The diameters of PS nanofibers were controlled
posts of 25 microns in width, 30 microns in depth, at varied
by using the AAO replication templates with different pore
distances from 8 to 80 microns). The replication process was
based on a master prepared by macromachining. A water drop
can both be suspended on top of the posts and wet the posts
depending on how the water drop is deposited. In case of
gentle deposition, a composite form is formed, and the
observed contact angles are close to the CB theory prediction.
When the water is dropped from some height, the gaps
between the posts were wetted and the measured apparent
contact angle follows the Wenzel theory (Fig. 6).
Nanoimprint lithography is also a pattern replication
process, however, the pattern replication is accomplished by
heat- and pressure-driven process where a hard master is
pressed onto a thermoplastic polymer layer above the glass
transition temperature of the polymer.87 After cooling and
removing the master a negative replica of the template is
obtained. Nanoimprint lithography is capable of making very
small features down to a few nanometers depending on the
Fig. 7 Schematic outline of the heat- and pressure-driven nano-
master design.
imprint pattern transfer process for nanofabricating the surface of the
Lee et al.23 have demonstrated the use of nanoimprint thick polymer substrate with (a) aligned nanoemboss, (b) nanopost
lithography for the preparation of polystyrene substrates array with embossed base, and (c) aligned nanofibers. (Images
with different nanostructures as shown in Fig. 7. Textured reprinted with permission from Lee et al.23 Copyright 2004,
aluminium sheets and anodic aluminium oxide (AAO) American Chemical Society.)
Fig. 8 Schematic illustration of the capillary lithography, tilted SEM images for various PEG copolymer nanostructures with a negative PUA
mold, and the corresponding contact angles of water with time at t = 0 and 60 s.75 (a) the bare PEG; (b), (c), (d) and (e) with a pillar height of 170,
310, 440 and 500 nm, respectively. (Images reprinted with permission from Suh et al.75 Copyright 2005. American Chemical Society.)
diameters; the pore diameter was adjusted to the desired initial contact angle was less than 80u and the water droplet
dimension by wet-chemical etching. On the other hand, the easily invaded the surface grooves, leading to a reduced
length of PS nanofibers could be controlled by appropriately contact angle at equilibrium (Wenzel state). At relatively
varying the thickness of the AAO template. The resultant higher heights (.400 nm) on the other hand, the nanostruc-
surfaces showed water CA between 155.8 (1.1u) and 147.6 tured PEG surface showed a hydrophobic nature and no
(1.9u). A water drop placed on the surface rolls easily on the significant change in contact angle was observed with time
horizontal surface upon slight tilting, reflecting the high degree (Cassie–Baxter state). However, due to the hydrophilic nature
of water-repellent surface property. of PEG, the obtained CAs were relatively low (95u), the
Unlike imprint nanolithography, capillary force lithography contact angle might be further improved by changing the
involves a patterned elastomeric mold instead of a hard polymer material or optimizing the geometry of the mold.
master, where the mold is directly laid onto a spin coated A similar capillary lithographic approach was demonstrated
polymer film on a substrate (Fig. 8). The negative replica of the by Jin et al.81 An alumina membrane was used as the mold for
mold is formed by raising the temperature above the polymer’s the preparation of aligned polystyrene (PS) nanotubes. The PS
glass transition temperature after solvent evaporation (tem- solution was cast on glass and the membrane was then brought
perature-induced capillarity) or by direct molding prior to into contact with the PS cast. After capillary molding, the
solvent evaporation (solvent induced capillarity). membrane was dissolved in NaOH and aligned PS nanotubes
Suh and Jon75 have demonstrated the use of capillary were obtained. The PS nanotubes showed a contact angle of
lithography for the preparation of poly(ethylene glycol) (PEG) 162 ¡ 1.7u. The authors concluded that the water droplet was
structures with controllable wettability by changing the
geometry of the nanostructures. PEG nanostructures were
prepared by the use of an ultraviolet (UV) curable mold Table 1 Contact angle of PEG after capillary force lithography75
consisting of functionalized polyurethane with acrylate group. Sample 1 2 3 4
Two distinct wetting states were observed depending on the
d/nm 150 150 150 150
height of the nanostructures. The feature size, initial contact h/nm 170 310 500 440
angles, and equilibrium contact angles of the surfaces are h/d 1.13 2.07 3.33 2.93
shown in Table 1. A flat PEG surface is relatively hydrophilic s/nm 500 500 500 500
with an initial water contact angle of 61u. At relatively lower r 1.3 1.58 1.90 1.79
CA (adv./rec.) 75/46 81/56 95/90 88/81
heights (,300 nm for 150 nm pillars with 500 nm spacing), the
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photolithography are easy to characterize and they are often

used for the surface modeling.
Furstner et al.10 created silicon wafers with regular patterns
of spikes by X-ray lithography. The wafer was hydro-
phobicized by sputtering a layer of gold and subsequent
immersion in a hexadecanethiol solution. The spikes have a
width (d) of 1 or 2 microns, the distance between the spikes (a)
were varied from 1 to 5 microns, and the height of the spikes
(h) was also varied from 1 to 4 microns. CA of the surfaces

varied from 113 to 161u depending on the pillar size, the
clearance and the height of the spikes. The self-cleaning
property of the specimen was addressed by the application of
an artificial fog. A best cleaning surface was found with d/a = 2
and h/d = 4.
Martines et al.80 have created nanopillars and nanopits on
silicon by e-beam lithography (Fig. 10). The center to center
pitch is kept constant at 300 nm. The diameter (d) and height
Fig. 9 SEM images of PS nanotubes ((a) top view, (b) magnified (h) of the pillars and pits are varied from sample to sample.
image of (a), and (c) side view) and the contact angle behavior (d). The specifications of the samples are shown in Table 2. The
(Images reprinted with permission from Jin et al.81 Copyright 2005, hydrophobic nanopatterns were obtained by silanization of the
John Wiley–VCH.) hydrophilic surfaces with octadecyltrichlorosilane (OTS). All
surfaces exhibit enhanced hydrophobicity as compared to the
in a composite state (the Cassie–Baxter regime). However, it flat control surface. For samples with nanopits, the contact
was found that the water droplet does not roll off the surface angle behavior falls in the Wenzel regime. For samples with
even at 180u tilt (Fig. 9), indicating that the surface is pillars, both Wenzel and Cassie–Baxter states were discovered
very sticky, although superhydrophobic. The authors which was ascribed to the differences in aspect ratio (h/d). They
have attributed this super sticky effect to the van der Waals’ disclosed that at given spacing, increasing aspect ratio can
forces between the water molecules and the high density dramatically stabilize the Cassie–Baxter regimes as shown by a
nanotubes generating a strong adhesion just like the gecko’s comparison of the wetting behavior of P22, P21, P13 and P12.
mechanism.88 The authors have applied such a sticky surface
as a mechanical hand to transfer a water droplet.
Fabrication of superhydrophobic PVA nanofibers were
accomplished through extrusion with AAO membranes.89
The AAO membranes have pores of average diameter of
68.7 nm. Although PVA is a hydrophilic material, the resulting
nanofibers showed superhydrophobicity with water contact
angle of 171u. The authors attribute this superhydrophobicity
to the orientation of the PVA molecules that results in
hydrophobic backbones exposed to the surface as confirmed
by angle dependent XPS study.
As shown above, templation is a useful technique for the
preparation of superhydrophobic surfaces. Depending on
the type of templates, many features can be fabricated
with tunable surface morphology. Furthermore, templation
is versatile in view of the diverse polymeric materials
available. The limitations of the templation approaches
are that the attainable geometry is limited by the available
templates and not every material is suitable for the templation
approach.
3.1.2 Photolithography. In photolithographic approaches,

light is irradiated through a mask with desired features to the
substrates (often silicon) with a photoresist. Subsequent
Fig. 10 SEM images of (a) P22 before hydrophobization; (b) P22
developing and etching steps yield the desired patterned
after hydrophobization; (c) profile of P22; (d) sample H83 after
surfaces. Depending on the light source (radiation, electrons), hydrophobization, the inset shows its profile; (e) P12 after hydro-
photolithography can be divided into X-ray lithography and phobization; (f) profile of P21. The profiles were imaged with a 90u tilt,
e-beam lithography. For the preparation of superhydrophobic the other images were taken at 45u, scale bar 500 nm (a–f) and 200 nm
surfaces, an extra surface treatment step is needed to (inset in (d)), respectively. (Reprinted with permission from Martines
render the surfaces hydrophobic. Structures prepared by et al.80 Copyright 2005, American Chemical Society.)
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Table 2 Sample specifications and contact angle results of the

nanopillars and nanopits80
Sample H90 H83 P22 P21 P13 P12
d/nm 105 138 157 156 124 117

h/nm 116 141 239 239 268 792
l/nm 300 300 300 300 300 300
h/d 1.10 1.02 1.52 1.53 2.16 6.77
hadv/hrec 125/92 129/89 155/0 159/140 161/150 164/163
a
H indicates pits, and P indicates pillars. d: diameter of the pits or
pillars; h: depth or height of feature; l: center to center pitch.
3.1.3 Plasma treatment of surfaces. Plasma treatment of

surfaces always involves plasma etching. Plasma etching is a
dry etch technique in which reactive atoms or ions (such as
oxygen, chlorine, fluorine) are generated in a gas discharge.
Reactive ion etching makes use of the fact that ions are
accelerated in the boundary layer between plasma and
substrate with high directivity and are thus able to create deep
grooves with steep walls. Plasma treatment of surfaces can
cause a considerable change in the surface structure because of
the anisotropic etching of the surface layers.
Fresnais et al.44 have used treated low-density polyethylene
(LDPE) with plasma etching. Sequential treatment of LDPE
with oxygen and CF4 plasma yielded a surface with CA of 170u
and low hysteresis (,5u).44 The roughness of the resulting
surfaces was within the range of 20 to 400 nm.
Minko et al.84 have reported plasma treatment of PTFE for
the fabrication of self-adaptive surfaces (Fig. 11). Oxygen
plasma etched PTFE showed water CA about 160u without
CA hysteresis. The superhydrophobic PTFE surfaces were Fig. 11 Scanning electron micrographs of PTFE foils: untreated (a);
further treated with ammonia plasma for the incorporation treated with oxygen plasma for 60 s (b), 120 s (c), 5 min (d) or 10 min
of amino groups in the substrates. These amino modified (e); and treated with oxygen plasma for 10 min + NH3 for 1 min (f).
substrates were then grafted with a mixed polymer brush (Reprinted with permission from Minko et al.84 Copyright 2003,
American Chemical Society.)
consisting of two carboxyl terminated incompatible polymers:
carboxyl-terminated poly(styrene-co-2,3,4,5,6-pentafluoro-
tetrafluomethane, ammonia, argon or oxygen, different
styrene) (PSF-COOH) and carboxyl-terminated poly(2-vinyl-
elements can be easily introduced in the surface, providing
pyridine) (PVP-COOH). The grafted surface exhibits
additional functions.
switchable wettability upon soaking in different solvents which
was ascribed to the enrichment of favored component at the
3.2 Bottom up approaches
top of the film and the other component collapsing into
dimples in the interior of the polymer film (Fig. 12). Contrary to the top-down approach, bottom-up methods
There are many more examples using the plasma method for involve the building (or designing) larger, more complex
the preparation of superhydrophobic surfaces.49–51,90–92 As objects by integration of smaller building blocks or compo-
mentioned above, plasma treatment is a dry etching technique, nents. The bottom-up approach in nanofabrication involves
thus rough surfaces are easily obtained after the plasma often self-assembly and self-organization. Self-assembly is
treatment. Furthermore, depending on the type of gas, an integration method where components spontaneously
Fig. 12 Photograph of a water drop deposited onto the self-adaptive surface: the image shows that a water drop jumps and rolls on the
ultrahydrophobic surface obtained after exposure of the sample to toluene (a). In contrast, exposure to acidic water switches the sample to a
hydrophilic state and the water drop spreads on the substrate. (Reprinted with permission from Minko et al.84 Copyright 2003, American Chemical
Society.)
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assemble in solution or the gas phase until a stable structure of Wu et al.107 also used CBD for the preparation of
minimum energy is reached. Bottom-up approaches that have superhydrophobic surfaces of zinc oxide (ZnO) nanorods on
been applied for the preparation of superhydrophobic surfaces glass slides starting from a solution mixture of Zn(NO3)2,
include chemical deposition methods such as chemical NH4Cl, urea, and ammonia. ZnO nanorods with diameters
bath deposition (CBD),51,63,64,66 chemical vapor deposition ranging from 400 to 600 nm form a uniform and dense film on
(CVD),63,64 and electrochemical deposition,60,62,65 layer-by- the substrates. The surfaces were then modified with SAMs of
layer (LBL) deposition via electrostatic assembly,52,57 colloidal alkanoic acids of different chain length. All the SAM modified
assembly,59,68,70 sol–gel methods,35,57,70,93–104 hydrogen bond- surfaces showed high advancing contact angle (.150u), the
ing,67 and chemical synthesis.105 In the following paragraphs, receding angles of the surfaces depends strongly on the chain
some important examples will be given and discussed in detail. length of the alkanoic acids.
Huang et al.108 have prepared aligned carbon nanotubes by
3.2.1 Chemical deposition. Chemical deposition takes place chemical vapor deposition on a Fe–N coated silicon substrates.
in a chemical reaction, where the product self-assembles After the deposition a ZnO layer, the substrates showed water
and deposits on a suitable substrate. Chemical deposition is CA of 159u. The surface, however, became hydrophilic after
commonly used for generating thin films of crystalline prolonged exposure to UV illumination. The hydrophobicity
inorganic materials, such as ZnS, CuSe, InS, CdS etc. of the surface can be restored after storage in the darkness.
Depending on the deposition conditions, several terms have This tunable wettability is interesting in microfluidic devices.
been used such as chemical bath deposition (CBD), chemical Other chemical deposition methods such as electrochemical
vapor deposition (CVD), and electrochemical deposition. deposition of the zinc oxide,65 gold clusters,109 or silver
Depending on the material and the deposition conditions, aggregates have been used to prepare superhydrophobic
different surface morphologies have been obtained from surfaces.60 In these examples, the deposited structures were
nanopins, nanotubes to nanorods. modified with SAMs to render hydrophobicity.
Hosono et al.106 have used CBD for the creation a of
nanopin film from a solution of CoCl2 and NH2CO in water. 3.2.2 Colloidal assemblies. Monodispersed particles can form
The film was deposited on commercial borosilicate glass slides close packed assemblies on surfaces because of van der Waals
in an autoclave. Because each metal complex in the solution interactions. The particle assemblies render roughness to the
is singly deposited on the surface based on thermodymanic underlying substrates. Further treatment such as plasma
equilibrium conditions, single crystalline-like structures are etching110 can also be applied to improve the roughness. The
formed. After deposition, the nanopin was modified with colloidal particles can vary from polymer beads to inorganic
lauric acid (with h = 75.1). A picture of the nanopin is shown spheres. Colloidal assembly is cost effective since no expensive
in Fig. 13. The top of the needle is very sharp with a diameter lithographic technique is required. This method is easy to
of 6.5 nm. The water CA of the resulted film is 178u, which is master and to apply under laboratory conditions.
the highest contact angle that has been reported so far. Monodipersed polystyrene (PS) beads can form closely
packed superhydrophobic surfaces by spin coating.110 Oxygen
plasma etching was used to control the solid–air fraction of
these nanostructures. The sizes of beads were reduced by
controlling the etching conditions. After plasma treatment, the
surfaces were coated with a layer of gold and eventually a layer
of octadecanethiol SAM to render hydrophobicity. SEM
images of the PS beads and the corresponding water CA are
shown in Fig. 14.
Zhang et al.59 have used binary colloidal assemblies for the
creation of superhydrophobic surfaces. CaCO3-loaded hydro-
gel spheres were dip-coated on silicon substrates (Fig. 15).
These assemblies were employed as templates for the self-
assembly of silica nanoparticles or polystyrene beads. Due to
the hydrophilicity difference between silicon wafers and
CaCO3-loaded hydrogel spheres, the regio- selective localiza-
tion of silica or polystyrene spheres leads to irregular binary
structures with a hierarchical roughness. The subsequent
modification with deposition of gold and SAM formation
yield superhydrophobic surfaces with water CA of 160u for
silica based assembly and 156u for PS based assembly.
Fig. 13 (a, b) Field emission SEM images of the cobalt hydroxide

3.2.3 Layer-by-layer deposition. Layer-by-layer (LBL)
films observed from the top and side, respectively. (c) TEM images of deposition takes advantages of the electrostatic charge
the cobalt hydroxide films. (d) A simple model of the film with the interactions between the different layers such as polyanion
fractal structure. (Reprinted with permission from Hosono et al.106 and polycation. The LBL technique is easy to perform and
Copyright 2005, American Chemical Society.) allows controlling the thickness of the resulting layer with
Fig. 14 SEM images (60u) of the size-reduced polystyrene beads and

the water contact angle measurement on the corresponding modified
surfaces (insets). The diameters of polystyrene beads and water contact
angles on these surfaces were measured to be (a) 400 nm, 135u, (b)
360 nm, 144u, (c) 330 nm, 152u and (d) 190 nm, 168u. Bar: 1 mm.
Fig. 16 SEM images of (PAH/PAA)100.5 films after a single acid
(Reprinted with permission from ref. 110. Copyright 2004, American
treatment (A) and after a combined acid treatment (B). (C) SEM image
Chemical Society.)
of the fully treated structure (B) with silica nanoparticles. (D) Water
droplet on this superhydrophobic surface. (Reprinted with permission
from Zhai et al.111 Copyright 2004, American Chemical Society.)
tested by extended immersion in water. It was found that both

the microstructure created by the combined acid treatments
and the nanostructure induced by the deposition of silica
nanoparticles are necessary to create stable superhydrophobic
surfaces.
Based on Zhai’s work, Jisr et al. have further developed a
simplified method for the preparation of superhydrophobic
surfaces using polyelectrolytes.112 The molecular structures of
the polyelectrolytes are shown in Scheme 1. The polyanions
and polycations are fluorinated polyelectrolytes, Nafion and
fluorinate poly(vinylpyridine) (PFPVP), and ‘‘normal’’
PDADMA and PSS. For the fluorinated polyelectrolytes, no
extra hydrophobic coating was necessary. The flat multilayer
showed a static contact angle of 114u with 10 double layers.
Incorporation of clay mineral attapulgite (naturally occurring
Fig. 15 Schematic illustration of the binary assembly procedure on
silicon wafers by consecutively dip-coating CaCO3-hydrogel particles
and silica or PS colloidal spheres. (Reprinted with permission from
Zhang et al.59 Copyright 2005, American Chemical Society.)
molecular precision. Polyelectrolytes are hydrophilic, there-

fore, a hydrophobizisation is always necessary. Nanoparticles
are often incorporated into the multilayer system in order to
enhance the roughness effects. However, the multilayer films
can also be roughened by some additional treatment. Zhai
et al.111 have prepared superhydrophobic silicon surfaces using
polyallylamine hydrochloride (PAH)/poly(acrylic acid) (PAA)
multilayers via LBL deposition. By using an appropriate
combination of acidic treatments, pores on the order of
10 microns and a honeycomb-like structure were formed on
the PAH/PAA films (Fig. 16(A) and (B)). The honeycomb-like
polyelectrolyte multilayer surface was further coated with
silica nanoparticles (Fig. 16(C)). Superhydrophobicity was
achieved by coating this highly textured multilayer surface
with a semifluorinated silane. The stability of the surface was Scheme 1
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nanorods) into the multilayers produced ultraphobic surfaces

(CA 168u) with a sliding angle less than 1u.
Han et al.52 have demonstrated another approach for the
incorporation of particles in the LBL assembly for the
preparation of superhydrophobic surfaces. PAA coated ZrO2
particles were deposited alternately with PAH (polyallyamine
hydrochloride) on clean silicon substrates. After 20 deposition
cycles, the surface showed water contact angle of 139u for
a PAH exposed outermost layer with a huge hysteresis (¡40u).

These results are noteworthy since PAH is rather hydrophilic
(¡60u). Further deposition of silica nanoparticles and dipping
the film in the solution of perfluorinated dodecyltrichloro-
silane decreased the contact angle hysteresis and improved the
superhydrophobicity significantly. The substrates showed a
water contact angle of 170u with a hysteresis of 2u. Amidation
by thermal treatment of substrates at an elevated temperature
of 220 uC was utilized to render the film extra stability.
The LBL technique is easy to perform and allows
molecularly precise control of the film thickness. However,
polyelectrolytes are hydrophilic, therefore, a hydrophobizisa-
tion is often necessary. In addition, to generate rough surfaces,
some additional steps are needed such as the incorporation
of nanoparticles, thus making it less straight forward for the Fig. 17 AFM image of SH film in air measured over an area of
preparation of superhydrophobic surfaces. 13.5 mm 6 13.5 mm. The inset shows another image at a higher
magnification measured over an area of 1.5 mm 6 1.5 mm. (Reprinted
3.2.3 Sol–gel methods. A sol is usually prepared by with permission from Doshi et al.114 Copyright 2005, American
hydrolysis of the corresponding oxide in the presence of Chemical Society.)
solvent. During the network formation process, a large
amount of solvent are also impregnated in the network and superhydrophilic. A low-temperature, low-pressure technique
thus a gel is formed. Silica sols are normally prepared by was used to prepare a rough and highly porous organosilica
hydrolysis and condensation of orthosilicate. The sol can be aerogel-like film (Fig. 17). The superhydrophobic coatings
applied either directly or combined with fillers such as silica were made from a precursor solution containing mixed
nanoparticles. The resulting surface property depends on alkoxides 3,3,3-trifluoropropyltrimethoxysilane (TFPTMOS)
how the sol was prepared and surface functional groups of and tetramethylorthosilicate (TMOS). A film thickness of
the resulted gel.35,57,70,93–104 50 nm was obtained. CA consistently reached 155–160u, and
angles up to 170u have been observed. UV/ozone treatments
Shang et al.113 have prepared optically transparent super-
were used to control the surface coverage of hydrophobic
hydrophobic silica-based films by means of sol–gel processing
organic ligands on the silica framework, allowing the CA to be
and self-assembly. Desired surface roughness was obtained by
continuously varied over the range of 160u (superhydrophobic,
tuning the microstructures of the sol–gels through careful
with presence of organic ligands) to ,10u (hydrophilic, after
control of hydrolysis and condensation reactions of various
removal of the organic ligands).
silica precursors during sol–gel processing, whereas modifica-
The advantages of the bottom-up approach are the
tion of surface chemistry was done by introducing a monolayer
molecular control of the chemistry, composition, even the
through surface condensation reaction. Such coatings were
thickness of the products. Nevertheless, it is difficult to predict
obtained by dip-coating the silica sols directly onto substrates.
the hydrophobic properties until the last step.
The resulting silica-based coatings showed optical trans-
parency higher than 90% and a reflection lower than 10%.
3.3 Combination of bottom-up and top-down approaches
The best advancing and receding water contact angles were
approximately 165 and 115u, respectively, indicating a The combination of bottom-up and top-down approaches
relatively large contact angle hysteresis. The authors did not might have the apparent advantages of both techniques. It is
provide any solution to solve this problem. especially useful for the creation of architectures with a two-
Hikita et al.35 have used the sol–gel method for the scale roughness, resembling the structure of the lotus leaf. The
preparation of super liquid repellent surfaces. Both surface combination methods often consist of two stages. Typically,
energy and roughness were controlled using colloidal silica the first step is the top-down approach for the creation of a
particles and fluoroalkylsilane. For films with optimal ratio rough surface and the second step is bottom-up process for the
between colloidal silica and fluoroalkylsilane, the surfaces creation of the fine roughness. However, some combination
exhibited repellency to both water and oil. This method methods do not necessarily show a distinct two-stage process.
provides a simple one-pot coating for a large area. For example, phase separation involves casting of thin film
Doshi et al.114 used silica sol–gel for the creation of and subsequent phase separation by controlling the environ-
surfaces with tunable properties from superhydrophobic to mental conditions.
Fig. 18 SEM images of three-dimensional anisotropic ACNT micro-

Fig. 19 Typical SEM images of CNT arrays on silicon substrates: (a)
structures constructed by the CVD method on silicon substrates with a
cylindrical CNT arrays with 6 mm radius, 30 mm pitch, and 25 mm
well defined quadrate micropillar array. (A, B and C) Periodic ACNT
height; (b) cylinder CNT arrays with 10 mm radius, 60 mm pitch, and
arrays with pillar spacings of 20, 15 and 10 mm, respectively. (D)
11 mm height; (c) cylindrical CNTs arrays with 10 mm radius, 60 mm
Magnified image of mutually orthogonal ACNT arrays on a single
pitch, and 90 mm height; (d) as-grown CNT array surfaces. (Reprinted
silicon pillar of image (A); (a) vertical ACNT array on the top face of a
with permission from Zhu et al.116 Copyright 2005, American
pillar; (b) horizontal ACNT array grown from the side faces of the
Chemical Society.)
pillar; and (c) ACNTs grown from the bottom between the pillar
arrays. (Reprinted with permission from Sun et al.115 Copyright 2003,
American Chemical Society.) porous structures. Most polymer membranes are prepared by
casting a polymer solution via a suitable template, where
microscopic structures are formed through phase separation.
3.3.1 Combination methods based on chemical vapor deposi-
Phase separation occurs when a polymer solution close to the
tion (CVD). Sun et al.115 have demonstrated the preparation
cloud point is submerged in nonsolvents or subjected to heat
of superhydrophobic anisotropic aligned carbon nanotubes
treatments. Because of the interaction of solvent and
(ACNT) film by chemical vapor deposition (CVD) on silicon
nonsolvents with the macromolecules, the polymer nucleates
substrates with quadrate micropillar arrays prepared by photo-
resulting in polymer rich and polymer poor phases. At the
lithography. The carbon nanotubes packed densely and were polymer rich phase, the macromolecules nucleate and form the
quite uniform in length at about 10 microns as shown in Fig. 18. networks. In the polymer poor phase, after the solvent
Both hydrophobic and hydrophilic surfaces were observed removal, pores are formed.117
depending on the spacing between the pillar arrays, which was Erbil et al.118 have used isotactic polypropylene (i-PP) for
ascribed to the anisotropic nature of the carbon nanotube the preparation of superhydrophobic surfaces by controlling
arrays. However, when the film was coated with a fluorinated the selection of solvents and temperature. Xylene was used as
SAM of (2-(perfluorooctyl)ethyl)trimethoxysilane, all surfaces solvent of the polymer and different nonsolvents were tested.
are superhydrophobic and the spacing effects were not observed. A series of samples were tested at different solute concentra-
In a similar approach Zhu et al.116 also prepared surfaces tion, drying temperature, and different nanosolvents. It was
with two-scale roughness by controlled growth of carbon found that lowering the drying temperature facilitates a loose
nanotube (CNT) arrays by CVD (Fig. 19). To compare network formation (Fig. 20). Methyl ethyl ketone was found to
wetting on micropatterned silicon surfaces with wetting be the best nonsolvent and resulted in a surface with contact
on nanoscale roughness surfaces, two model systems were angle of 160u.
fabricated: carbon nanotube arrays on silicon wafers and Following Erbil’s work, Lu et al.119 used low density
carbon nanotube arrays on carbon nanotube films. In the polyethylene for the preparation of superhydrophobic surfaces
latter case, the CNT array size, pitch, and height have been by thermally induced phase separation. By changing the
varied to explore geometric effects on surface hydrophobicity. duration of heat treatment, they have been able to control
Compared to patterned Si surfaces with similar geometrical the structure of the eventual film and finally the wettability of
sizes, the nanoscale roughness does not significantly increase the surfaces.
the apparent water contact angle. Thus, the microscale Xie et al.120 have prepared super-amphiphobic polymeric
roughness determines the apparent water contact. However, coatings with a single casting process with two polymer
the introduction of nanoscale roughness can decrease the materials: poly(methyl methacrylate) (PMMA) and fluorine-
contact angle hysteresis to less than 1u and improve the end-capped polyurethane (FPU). For films containing only
stability of the superhydrophobic surfaces. PMMA, water CA of 145u was found. SEM studies showed
rough structures with micropapillae (Fig. 21(b)). For the
3.3.2 Combination methods based on membrane casting. mixture of PMMA and FPU, films posses both micro-
Membrane casting is normally used for the preparation of and nanopapillae with water CA of 166u. The lotus like
Fig. 20 SEM pictures of i-PP obtained from a solution (20 mg ml21)

in p-xylene on glass slides at drying temperatures of (A) 30 uC and (B)
60 uC. The i-PP was dissolved in p-xylene at 130 uC and the solvent was
evaporated in a vacuum oven at the specified temperatures. The
surfaces of the i-PP coatings were sputter-coated with 1-nm thick gold
before the measurements were taken. The measurements were taken at
1 keV. The magnification is 10006. (Images adapted from Erbil
et al.118 with permission.)
micro–nano binary structure and low surface energy of the

FPU was ascribed to the high CA and low sliding angle of the
surface.
Yabu and Shimonura121 have used block copolymers
containing equimolar fluorinated acrylate and methylmetha-
crylate monomers for the preparation of superhydrophobic
surfaces. The polymer solution was cast on a substrate by a
blade. Careful controlling the condensation of water droplets
and final evaporation of the solvent and water yielded a Fig. 22 Schematic illustration and scanning electron micrograph of
(a) the honeycomb-patterned film, (b) the peeling process, and (c) the
pincushion structure. (Reprinted with permission from Yabu and
Shimonura.121 Copyright 2005, American Chemical Society.)
honeycomb film (Fig. 22). The pore size over the major part of
the film was 300 nm. Pin cushion structures were obtained
after peeling off the upper layer of the honeycomb film. The
sizes of the honeycomb and pincushion structures were easily
controlled by varying the casting volume of polymer solution.
A superhydrophobic surface with the maximum contact angle
of 170u was observed for pincushion structures prepared from
honeycomb films with 1.6 mm pores.
Recently, Wessling’s group has reported superhydrophobic
surfaces with two-scale roughness prepared in a single step by
casting of membrane solution of Hyflon AD.122 This process is
denoted as phase separation micromolding (PSmM). The films
were prepared by casting Hyflon AD solution on a silicon
template patterned by photolithography. The patterns on the
templates were optimized separately. This method provides
a surface that contains roughness on two independently
controllable levels, i.e., the microstructure level (from the
template) and the level of porosity stemming from the phase
inversion (Fig. 23).
In conclusion, membrane casting is relatively easy to
perform because the roughness is generated during the film
formation process. However, in order to get optimized
results, many parameters have to be adjusted such as the
Fig. 21 SEM images of FPU/PMMA mixtures: (a) pure FPU film;
selection of solvents, nonsolvents, the solution concentra-
(b) film of pure PMMA; (c) enlarged image of (b); (d) mixture of tion, and the conditions for membrane casting. Nevertheless,
PMMA/FPU; (e) enlarged image of (d); (f) cross sectional view of the the phase separation micromolding122 appears to be a pro-
mixture surface. (Images reprinted with permission from Xie et al.120 mising technique in the preparation of superhydrophobic
Copyright 2004, Wiley–VCH.) surfaces.
Fig. 23 Surfaces prepared from Hyflon AD by PSmM.122 (A) a

Hyflon AD H80 structure of square pillars prepared by evaporating a
Hyflon AD H80 solution on a mold; (B and C) Hyflon AD H80 Fig. 24 SEM images of the surfaces cast from a 5 mg mL21 micellar
microstructures of pillars; (D) a surface of Hyflon AD H60; (E) the solution of PS-b-PDMS in DMF in the (a) dry and (b) humid air and
protrusions of a microstructure of closely packed pillars with limited from 5 mg ml21 homopolymer solution of PS in DMF in the (c) dry
superimposed roughness. (Reprinted with permission from Vogelaar and (d) humid air at room temperature, respectively. The relative
et al.122 Copyright 2006, American Chemical Society.) humidity of the dry atmosphere is less than 10% while for the humid
air is 60.5%. (e) and (f) are the side view of (b) and (d), respectively.
3.3.3 Micelles. Surfactants in solution are often association Insets are the water CA of each surface. (Reprinted with permission
colloids, that is, they tend to form aggregates of colloidal from Zhao et al.123 Copyright 2005, American Chemical Society.)
dimensions, which exist in equilibrium with the molecules or
ions from which they are formed. Such aggregates are termed copolymers. The morphologies of the obtained films are
micelles. Similar to phase separation, micelles are formed due dependent on the casting methods, relative humidity of the
to the microscale phase separation. Block copolymers usually environment etc. Because of the availability of a diversity of
form micelles when dispersed in a selective solvent as a result polymer materials, superhydrophobic surfaces with diverse
of the different solubility of the blocks.123,124 The cast block structures have been reported.124,125
polymer micelles when exposed to humid environments will
form films of different morphology depending on the relative 3.3.3 Electrospinning. Electrospinning is normally used for
humidity. the preparation of polymer nanofibers. It is an extrusion
Micelle solutions of PS-b-PDMS block copolymer were process where an electrical bias is applied from the extrusion
used for the preparation of superhydrophobic surface by nozzle and a grounded collection plate.126 Electrospun films
vapor induced phase separation.123 Depending on the solvents consist of a continuous, nonwoven web of fibers. Along the
used, and humidity of the air, surfaces with different wetting trajectory of the extruded polymer fiber most of the solvents
behaviors were observed. For superhydrophobic surfaces, evaporate such that a thin film is formed. In addition to
enrichment of PDMS block in the outermost surface was surface roughness, the film properties can be optimized by
observed with CA of 163u (Fig. 24), which was attributed to chemical modification, such as the introduction of fluorine.74
the rearranging of PDMS block to the surface during the phase Electrospinning has been applied for the fabrication of
separation process. superhydrophobic films of polymers alone74,127 or in combina-
Han et al.125 used block copolymer of PtBA-b-PDMS-b- tion with other methods, such as chemical vapor deposition.63
ptBA micelle solution for the preparation of superhydrophobic The topography of the electrospun film can be tuned from
surfaces which gave surfaces with water contact angle up predominantly beads to only fibers by increasing the viscosity
to 163u. In a second approach, silica nanoparticles were of the polymer solution as shown by Acatay et al.74 The
incorporated into the micelle solution. The surface has a morphology was found to play an important role in the final
contact angle of 170u, the sliding angle is less than 2u. wetting behavior. Surfaces with beads are more hydrophobic
Similar to membrane casting, superhydrophobic films based than those containing only nanofibers. Based on these
on micelles depend on the selection of solvents and the block observations, lower molecular weight polymers were used
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giving even higher water contact angles because low molecular roughness factor). Further periodic spacing between the pillars
polymer yielded more bead formation than the high renders the substrate insensitive to whether a wetted contact or
weight molecular polymers. The highest static contact angle a composite contact is formed. The model was tested with the
of the films made of low molecular weight polymers was data of Bico et al.,128 which showed very good agreements.
around 167u. Lundgren et al.129 have reported molecular dynamics
Ma et al.63 showed the combination of electrospinning of modeling of the different wetting properties of the top and
poly(caprolectone) (PCL) with initiated chemical vapor deposi- the sides of the pillars, which play an important role in
tion (i-CVD) of polymerized perfluoroalkyl ethyl methacrylate determining the contact angle. For low pillar heights (h), the
(PPFEMA). The hierarchical surface roughness inherent to the system is in the Wenzel regime and a change to the Cassie–
PCL electrospun films and the extremely low surface free Baxter regime is seen when the pillar height was increased. The
energy of the coating layer obtained by i-CVD yields stable contact angles seem to be independent of the pillar height
superhydrophobicity with a contact angle of 175u and a when h exceeds 15 Å.
threshold sliding angle less than 2.5u for a 20 mg water droplet. Extrand130 has developed a linear model for predicting
Because of the low surface energy coating PPFEMA, the contact angle and hysteresis on rough and ultraphobic
resulting surfaces not only showed high hydrophobicity (water surfaces. In his model, a linear relationship between the
CA up to 175u) but also high oleophobocity (118u for decane). apparent contact angle and the Young’ contact angle was
used to predict the dynamic contact angles by taking into
4 Modeling the superhydrophobic surfaces consideration the contact line fraction of the asperities instead
of the solid fraction, which is a modified expression of Cassie–
As stated in section 2, both Wenzel and Cassie–Baxter theories
Baxter’s equation. Extrand compared his theoretical calcula-
give only a qualitative prediction of roughness effects. In
tion of Oner and McCarthy’s33 designs with the theoretical
practice, the conclusion comes always after the wettability
predictions of the Wenzel and Cassie–Baxter models. The
measurements. It is critical in designing superhydrophobic
comparison showed that the advancing contact angles and
substrates to predict accurately the wetting state. Moreover,
contact angle hysteresis fit Extrand’s prediction very well. For
often the question arises as whether there is an optimal surface
determining the state of wetting, a parameter was introduced
geometry for wetting. This problem has been addressed by
denoted as contact line density. This parameter is determined
many groups. The results have been controversial so far. In the
by the length of asperity perimeter per unit area that could
following paragraph, we will summarize the controversy and
potentially suspend a water droplet. The criteria for suspension
try to give an unbiased opinion on the results.
or penetration were established by a critical contact line
density, which was determined by examining the balance
4.1 The roughness factor
between the body weight of the drop and the surfaces forces.
According to Wenzel’s theory, the roughness factor plays an When the textures have contact line density values higher than
important role in determining the wettability of the surface the critical value, drops will suspend, otherwise, the drop will
where the roughness effects enhance both the hydrophocity collapse. These criteria are quite useful in predicting how the
and the contact angle hysteresis. However, in the Cassie– designed surfaces will behave. It is also interesting, here, that
Baxter theory, no roughness effect is considered. again the superhydrophobic state is not related to the etch
Regularly textured surfaces are often used for modeling the depth of the posts as predicted in Cassie–Baxter’s theory.
surface wetting behavior because the shape, height, and surface Using Bico’s data, Extrand also showed the models’s ability to
coverage are easily monitored and many parameters can be correctly predict experimental observations. In conclusion, the
easily calculated. Bico et al.128 were among the pioneers in author suggested that for the superhydrophobic state, a sole
modeling regularly textured superhydrophobic surfaces with roughness or solid fraction is insufficient, other factors such as
spikes, holes, and stripes. Substrates with specified roughness asperity slopes, liquid density, and surface tension must be
were prepared via templation and sintering of silica gel. The considered.
surfaces were functionalized with silane SAMs to render them The Extrand models predict the contact angle variations.
hydrophobic. Regardless of the value of the roughness factor Since the model has been tested with many research data, it has
of the resulting surfaces, all surfaces showed contact angles proven to be very versatile in predicting contact angles and
that meet the CB prediction. Accordingly, it was concluded contact angle hysteresis. However, this model does not address
that for hydrophobic surfaces, the apparent contact angle is a the observed transitions from suspensions to collapsed drops.
sole function of solid fraction or air fraction. However, it must
be pointed out that for the surfaces with holes, the static
4.2 Transition state
contact angle is 131u with a huge hysteresis (63u). In this sense,
it is hard to conclude that the water droplet on the substrate is It has been observed that a water drop on a superhydrophobic
in a composite state as the authors have indicated and that the surface can transit from a composite to a fully wetted
large hysteresis was due to the water retained in the holes at the state.76,128 Water drops on these type of surfaces are in a
retraction. metastable state and upon external disturbance transitions
Patankar79 has modeled surfaces with square posts. The from one state to another are evident. He et al.76 have shown
modeling was based on minimized energy during the drop that depending on how the drop is placed, both suspension
forming process. Contrary to Bico’s conclusion, his results and wetting state were observed. Even a lotus leaf can be
recommend to use high pillars at given pillar size (high wetted depending on how the water drops were formed.131
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Nosonnovsky and Bhushan132 have used a stochastic model surfaces are prominent.4,25 These properties are desirable for
to simulate the metastable state. For a rough surface, increased many industrial and biological applications such as antibio-
solid–liquid interfacial area results in increased interface fouling paints for boats,14,15 antisticking of snow for antennas
energy and higher contact angle for non-wetting liquids. For and windows,16,17 self-cleaning windshields for automobiles,18
a very rough surface, a composite solid–liquid–air interface metal refining, stain resistant textiles, antisoiling architectural
may form air pockets trapped in the valleys between asperities, coatings,19 the separation of water and oil,137 and in the textile
as opposed to the homogeneous solid–liquid interface. Both industry such as in the manufacture of water-proof, fire-
the fully wetted and composite interface configurations retardant clothes.97,138–140
correspond to local energy minima of the system and therefore, Recently, antifouling behavior of superhydrophobic has
there are stable states associated with different energy levels. been tested on a silica nanoparticles embedded in polysiloxane
The system may transform from one stable state to the other materials.141 Comparison of the fouling behavior of a smooth
due to small perturbations, such as capillary waves. Based on polysiloxane polymer film and roughened superhydrophobic
this model, the authors propose that distances between the coatings revealed that the effect of nanoscale interfacial
asperities should be long. The energy theory also agrees with roughness is crucial as witnessed by the fact that micro-
others, however, the authors did not use any available data to organism did not attach to the superhydrophobic surfaces in
fit their model. the first weeks of the fouling tests.
Patankar78 explained the metastable state also in terms of The superhydrophobic phenomenon known for long time,
the energy argument. The two distinct contact angles are stable has been recognized and it has provoked a lot of research
equilibrium positions, i.e. they are all local minimum energy interests in the last decade mostly benefited from the fast
states, but one has a lower energy level than the other. The progress in nanotechnology. The advantages of superhydro-
lower contact angle has a global minimum energy. To move phobic surfaces are apparent, but before real applications
one equilibrium position to the other, an energy barrier has to come into our daily life some problems have to be solved or
be overcome, such as that squeezing the water droplet changes addressed.
the apparent contact angle reported by Bico et al.128
Zheng et al.133 have modelled thoroughly the underlying Contamination
mechanisms of stability, metastability, or instability of the
Cassie–Baxter and Wenzel wetting modes and their transitions The naturally occurring superhydrophobic surfaces such as
on superhydrophobic surfaces decorated with periodic micro- lotus leaves are living objects. The surfaces can be easily
pillars quantitatively. A pillar slenderness ratio g was repaired or regenerated, for example, epicuticular wax is
introduced and defined a function of the pillar height (H), secreted by the leaf continuously. For man-made super-
perimeter (L), and area (A). hydrophobic surfaces, the water repellent capability gradually
degrades during long-term outdoor exposure and accumula-
A H HL tion of contamination. This problem was addressed by
l~ g~ ~ (5)
L l A introduction of photocatalytic coatings, such as TiO212 and
apatite.142 Both catalysts can oxidize organic stains under UV
ge (i.e., the equienergy slenderness ratio) was derived by energy
illumination. However, a drawback of TiO2 is that the surface
analysis and is formulated as a function solid fraction (f) and
becomes superhydrophilic after the irradiation,143 which has
Young’s contact angle (h) as follows:
inherent higher affinity to stains. The apatite based catalyst
1{f 1z cos h does not transform the surface property under UV illumina-
ge ~{ (6)
f cos h tion, which seems promising.
For a structured surface, if g . ge, the composite state is Wear resistance

more stable than the wetted state, and vice versa, which is
related to a global minimum free Gibbs energy. Furthermore a Wear resistance is an important issue in the application of
critical hydraulic pressure was introduced. This quantitative superhydrophobic surfaces. The lotus leaf itself is very fragile
study explains fairly well some experimental observations of in the micro- and nanostructures.7 To make robust micro- and
contact angles that can be modeled neither by Wenzel nor nanostructures is of key importance for the application of
Cassie–Baxter theory and eventually leads to proposals for a superhydrophobic surfaces. There are not many reports
mixed (or coexisting) wetting mode. addressing this problem. Wu et al.51 have used microwave
There are many more models describe the transition plasma enhanced CVD to prepare superhydrophobic thin
states.134–136 Most of models are based on analyzing the free films starting from trimethylmethoxysilane (TMMOS). The
energy or the pressure. Some models are very complex, thus mechanical properties of the resulting surfaces were tested.
are difficult to evaluate and to apply for surface analysis. The wear resistance of the film was studied by AFM and
Nevertheless, each model is based on certain assumptions, mechanical durability was tested by rubbing the surface with
which would in principle give the model some inherent limits. flannel cloth under 200 g of load. It was found that the water
repellent capability decreased and the contact angle dropped
approximately 20u. However, the CA after initial decrease
5 Applications
stayed stable even upon prolonged rubbing for 3000 times.
Applications of superhydrophobic surfaces are interesting These test conditions are relatively mild, depending on the
because self-cleaning and antisticking properties of the nature of the application and more realistic tests should be
View Article Online
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have been used from silica to polymers.12,49,61,83,94,113,121,144–149 18 D. Quere, Rep. Prog. Phys., 2005, 68, 2495.
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What Do We Need For A Superhydrophobic Surface? A Review On The Recent Progress in The Preparation of Superhydrophobic Surfaces

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CRITICAL REVIEW www.rsc.org/csr | Chemical Society Reviews

What do we need for a superhydrophobic surface? A review on the recent

1 Introduction practical applications.5,6 A direct expression of the wettability

Dr. Xue-Mei Li was born in chemistry in 1969 with

self-cleaning properties. In nature, many natural species natural species

Many plant surfaces39 and animal furs22 exhibit water

cos hc = f(1 + cos h) 2 1 (4)

Thus, for the CB model, the apparent CA (hc) is a sole

3 Methods used for the preparation of

down approaches encompass lithographic and template-based

polymeric superhydrophobic coatings. Many materials can be

photolithography are easy to characterize and they are often

(h) was also varied from 1 to 4 microns. CA of the surfaces

3.1.2 Photolithography. In photolithographic approaches,

Table 2 Sample specifications and contact angle results of the

d/nm 105 138 157 156 124 117

3.1.3 Plasma treatment of surfaces. Plasma treatment of

Fig. 13 (a, b) Field emission SEM images of the cobalt hydroxide

Fig. 14 SEM images (60u) of the size-reduced polystyrene beads and

tested by extended immersion in water. It was found that both

molecular precision. Polyelectrolytes are hydrophilic, there-

nanorods) into the multilayers produced ultraphobic surfaces

a PAH exposed outermost layer with a huge hysteresis (¡40u).

Fig. 18 SEM images of three-dimensional anisotropic ACNT micro-

Fig. 20 SEM pictures of i-PP obtained from a solution (20 mg ml21)

micro–nano binary structure and low surface energy of the

Fig. 23 Surfaces prepared from Hyflon AD by PSmM.122 (A) a

For a structured surface, if g . ge, the composite state is Wear resistance

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