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Superamphiphobic surfaces
Cite this: DOI: 10.1039/c3cs60415b
Zonglin Chu and Stefan Seeger*

Superamphiphobicity is an effect where surface roughness and surface chemistry combine to generate
surfaces which are both superhydrophobic and superoleophobic, i.e., contact angles (yCA) greater than
1501 along with low contact angle hysteresis (CAH) not only towards probing water but also for low-
Received 15th November 2013 surface-tension ‘oils’. In this review, we summarize the research on superamphiphobic surfaces,
DOI: 10.1039/c3cs60415b including the characterization of superamphiphobicity, different techniques towards the fabrication of
surface roughness and surface modification with low-surface-energy materials as well as their functional
www.rsc.org/csr applications.

1. Introduction superhydrophobic surface, received continued but relatively

limited interest until 1997 when the explanation of the origin
Research on super-antiwetting and the observation of extremely and the universal principle of the ‘lotus effect’ in nature was
high yCA dates back to more than a century—a yCA of nearly provided by Barthlott and Neinhuis.2 They revealed that the
1801 was firstly achieved via coating a substrate with soot, epicuticular wax crystalloids on the surface (Fig. 1) are responsible
reported by Ollivier in 1907.1 Thereafter, a super-antiwetting for the superhydrophobicity and self-cleaning properties. Taking
surface with water yCA higher than ca. 1501 and the sliding the lotus leaf as an example, self-cleaning means that particles
angle (ySA) lower than ca. 101, which is now defined as a adhered to the surface can be removed easily while the droplet is
rolling off. Therefore, self-cleaning is a common characteristic of
Department of Chemistry, University of Zurich, Zurich CH-8057, Switzerland. superhydrophobic surfaces. Since then, research interest in
E-mail: [email protected]; Fax: +41 (0)44 6356 813; Tel: +41 (0)44 6354 451 superhydrophobicity has been motivated by mimicking nature,

Dr Zonglin Chu earned his BSc in Stefan Seeger studied chemistry

Applied Chemistry from Hunan at the Ruprecht Karl University
University, China, in 2006, of Heidelberg and at the
joined Prof. Yujun Feng’s group Technical University of Berlin. In
as a Master-to-PhD student at 1992 he attained a doctorate in
Chengdu Institute of Organic chemistry in Heidelberg. Sub-
Chemistry, Chinese Academy of sequently, Stefan Seeger led the
Sciences the same year, and Department of Biophysical
received his PhD in Chemical Chemistry at the Physico-
Engineering in 2011. His PhD chemical Institute at the
project in the field of University of Heidelberg, where
alkylamidosulfobetaine wormlike he was appointed a scientific
Zonglin Chu micelles and stimuli-responsive Stefan Seeger assistant later. Between 1988
worms resulted in more than 10 and 1992 he studied marketing
publications in high impact factor journals. After one year of and management at the University of Hagen. In 1995 he undertook
postdoctoral research in multi-step organic synthesis in the Lab a six month research stay at the Chemical Center of the University
of Organic Chemistry, ETH Zürich, he is currently working on of Lund, Sweden. One year later he attained his habilitation in
superamphiphobic surfaces in Prof. Dr Stefan Seeger’s group in the Heidelberg and in summer 1997 he was appointed as a professor of
Department of Chemistry, University of Zurich. His research biochemistry and biosensor technology at the University of
interests lie at the interface of organic synthesis, colloid and Regensburg. In November 1999 Stefan Seeger was appointed as a
interface science, hydrogels, smart materials, and functional professor of physical chemistry at the University of Zurich.
surfaces with special wettability.

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exhibits super-repellency towards probing liquids not only

water but also low-surface-tension ‘oils’.
The characterization of superamphiphobicity is one of the
key issues in the research of superamphiphobic surfaces. The
simplest method to characterize a super-repellant surface is eye
visualization, in which a gentle flow of a probing liquid is
applied to the surface, and the wetting and flowing behaviours
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are visualized. The surface can be roughly deemed as super-

Fig. 1 Lotus leaves in nature: self-cleaning behaviour (a) and the related antiwetting if both water and ‘oils’ can move freely on the
microstructures as observed by scanning electron microscopy, SEM (b).
Scale bar = 20 mm. (a) Reproduced with permission from ref. 3.
surface without any sticking. However, to characterize a super-
(b) Reproduced with permission from ref. 2, Copyright 1997 by Springer- antiwetting surface quantitatively, precise determination of static
Verlag Berlin/Heidelberg. yCA and CAH, which is normally performed using commercial
instruments, is needed.

and thereby great effort was devoted to the understanding of the 2.1. Static contact angle
surface structures of different plants and animals, and therefore More than 200 years ago, Thomas Young, the genius polymath
the fabrication of similar artificial materials.3,4 who made major contributions to vision, physiology, sound,
However, it remains a challenge to create superoleophobic light, language, solid mechanics, and Egyptology, described the
surfaces that resist wetting of organic liquids because of their forces acting on a liquid droplet spreading on a surface
low surface tension, for example, 23.8 mN m1 for decane, (Fig. 2a). The yCA of the drop is related to the interfacial
which is much lower than that of water (72.3 mN m1). To the energies acting between the solid–liquid (gSL), solid–vapour
best of our knowledge, the superoleophobic surface was first (gSV) and liquid–vapour (gLV) interfaces following:
developed through the design of re-entrant surface curvature,
gSL  gSV
in conjunction with chemical composition and the roughened cos yCA ¼ (1)
texture surface, by Tuteja et al. in 2007.5 Afterwards, it was gLV
well-recognized that the combination of appropriate surface The above equation known as Young’s equation is a clear
roughness and materials with a low surface energy (mainly oversimplification of the real situation as it is strictly valid only
fluoro-derived compounds) is a successful way to prepare for surfaces that are chemically homogeneous, atomically
superoleophobic surfaces. Therefore, a variety of superoleophobic smooth, and those that do not change their characteristics
surfaces were reported continuously,6–10 and the terminology due to interactions of the probing liquid with the substrate, and
‘superamphiphobic’6,10 or ‘superomniphobic’7 was used to describe any other outside force.11 Notably, there is absolutely no such
the nature of these surfaces—both superhydrophobic and ideal surface in the real world. Therefore, two different models,
superoleophobic. the so-called Wenzel regime12 (Fig. 2b) and Cassie–Baxter
This review summarizes the research in this field, describes regime13 (Fig. 2c), were developed to explain the wetting
the analytical methods for superamphiphobicity (Section 2), behaviour on a rough surface.
different techniques towards the fabrication of superamphiphobic In the Wenzel regime (Fig. 2b), the difference in the mea-
surfaces by combining design of surface roughness and surface sured yCA from the ‘true’ contact angle of a flat surface (yF) is
chemistry (Section 3), and a variety of existing functional applica- described as follows:
tions (Section 4). Finally, a brief overview of the current state and
gSL  gSV
future opportunities in this field is presented. cos yCA ¼ R (2)
gLV

where R is the ratio of the actual surface area of the rough

2. Characterization of surface to the apparent area. In this regime, surface roughness
superamphiphobicity can promote either wettability (yCA o 901) or non-wettability

A sessile drop will normally form in the shape of a sphere

sectioned by the surface when it is placed on a flat substrate.
There is a discrete and measurable yCA between the sphere and
the surface at the circular solid–liquid–vapour three-phase
contact line. Generally, the surface is regarded as hydrophilic
when yCA o 901; in other words, the surface is hydrophobic if
yCA > 901. Specifically, the surface with yCA > 1501, in addition to
a sliding angle ySA o 101, is usually named a super-antiwetting
Fig. 2 Schematic illustration of a droplet placed onto a flat substrate
(or super-repellant) surface: the surface is deemed as super- (a) and rough substrates (b) and (c). Depending on the roughness of the
hydrophobic if the surface displays only water super-repellency; surface, the droplet is either in the so-called Wenzel regime (b) or the
whereas the surface is acknowledged as superamphiphobic if it Cassie–Baxter (c) regime.

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(yCA > 901), depending on the chemical properties of the

surface.
Interestingly, if the surface is composed of small protrusions
that cannot be filled by the liquid and are thus filled with air
(i.e., trapping of air underneath the liquid droplet), the wetting
phenomenon can be described by the so-called Cassie–Baxter
regime:
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g  gSV
cos yCA ¼ 1 þ FS 1 þ SL (3)
gLV

where FS is the fraction of the surface that is in contact with the

liquid. In such a case, the liquid touches only the top of the
surface with very limited contact area. The corresponding yCA is
always much higher than that of a flat surface composed of the Fig. 3 Static contact angles of water, diethylene glycol, and hexadecane
on flat silicon (Si), porous silicon (PS) with tilted pores, flat silicon coated
same material since the pores are filled with air, which is
with FTS (FTS-Si), and porous silicon with tilted pores coated with FTS
hydrophobic. Hence, surface topography plays a very profound (FTS-PS). Reprinted with permission from ref. 16, ACS Copyright 2008.
effect on the wettability.
2.1.1. Contact angle measurements with a sessile drop of
water. yCA measurement is one of the most important methods increase of the surface tension of the probing liquid (Fig. 3).16
for the characterization of a superamphiphobic surface. This can be That’s why ‘oils’ spread quickly on a solely superhydrophobic
performed on a commercial instrument [for example, Contact Angle surface15 and yCA analysis with ‘oils’ is needed for the characteriza-
System OCA (Stuttgart, Germany), Krüss DSA Series (Hamburg, tion of superamphiphobicity.9,15 As is clearly shown in Fig. 3, flat
Germany), Rame-Hart Goniometers (Succasunna, USA), and CAM silicon is both hydrophilic and oleophilic; porous silicon (PS) is
Goniometers (KSV Instruments Ltd, Helsinki, Finland)] using a superhydrophobic but superoleophilic; 1H,1H,2H,2H-perfluorooctyl
charge-coupled device camera that is used for recording the image trichlorosilane (PFOTS) coated silicon (FTS-Si) is hydrophobic but
of a water droplet on a surface, and analysis software that provides oleophilic; PFOTS coated porous silicon (FTS-PS) is both super-
different fitting models such as circle fitting, ellipse fitting, tangent hydrophobic and superoleophobic, i.e., superamphiphobic.
searching, and Laplace–Young fitting. The calculated yCA may vary a
lot for the same volume of water droplets (normally 5 to 10 ml) on
the same surface when using different fitting models. For example, 2.2. Contact angle hysteresis
the maximum yCA that can be obtained using circle fitting, ellipse Whether surfaces displaying yCA > 1501 for probing liquids both
fitting, and tangent searching models is around 1561; however, the water and ‘oils’ are truly superamphiphobic remains unknown
maximum value of around 1801 will be obtained when Laplace– if the corresponding CAH is not determined. For example,
Young fitting is adopted.3 This is because the deformation of a despite a high yCA (ca. 1601) for rapeseed oil on a superhydrophobic
water droplet caused by the gravity was calibrated in Laplace–Young surface composed of surface-fluorinated carbon nanotubes, the oil
fitting; whereas it was not excluded for the other fittings. Therefore, droplet remained pinned to the surface when the substrate was
the fitting model should be mentioned when reporting data for yCA. tilted.17
In our work,14 we realized that a good optical presentation of Any real surface exhibits two contact angles, the so-called
the water droplet is crucial to get reproducible yCA. Besides, the advancing contact angle (yAdv) and the receding contact angle
obtained value can also be affected by the focus of the camera, (yRec). The difference between them is a presentation of the
light intensity, contrast of the image, and the settlement of the surface ‘non-ideality’, and commonly referred to as the CAH,11
three phase contact baseline, especially when yCA > 1501. For which is intimately related to the adhesion of materials on the
example, the apparent value for the same droplet may vary from surface. Conventionally, superhydrophobicity means not only a
1651 to 1751 by only a small tuning of the above parameters. high yCA but also a low CAH because the low hysteresis
Therefore, yCA at various positions is normally recorded so as to is responsible for the self-cleaning behaviour.3 Therefore,
get a more trustable average value. CAH measurement is the other most important method for
2.1.2. Contact angle measurements with a sessile drop of a the characterization of a superamphiphobic surface. Many
low-surface-tension, organic liquid. Sessile drop measurement techniques have been developed to date to characterize the
with water is not sufficient for the characterization of a super- CAH, and amongst them yAdv/yRec and the tilt angle are the
amphiphobic surface; in such a case, yCA test with low-surface- most often used ones.
tension liquids should be performed in addition.9,15 Such probing 2.2.1. Advancing/receding contact angle. yAdv/yRec can be
liquids are mainly non-polar alkanes such as n-hexadecane, measured using a commercial instrument with an enhanced
n-dodecane, n-decane, and cyclohexane,9,15,16 but polar solvents video microscopy system incorporating digital image analysis,
such as toluene, diodomethane,9 and any other oils (e.g., mineral for example, Krüss DSA (Germany). A syringe pump is used to
oil and cooking oils) are also frequently used.9,16 Generally, yCA generate a water droplet on the substrate, and to control the
of different liquids on the same surface decreases with the rate of water pumping and suction through the needle to

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unable to roll due to their special surface structure and unique

surface chemical component.20–22
ySA becomes impractical when macroscopically rough sub-
strates such as cotton fabrics and wools are measured.19 In
order to characterize the superhydrophobicity of a macroscopic
textile, a new technique named shedding angle was developed
recently.14 In essence, a water droplet of defined volume is
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released onto the substrate from a defined height. The minimum

angle of inclination at which the substrate needs to be tilted for the
drop to completely roll or bounce off the substrate is determined
(Fig. 4c). Four parameters were controlled: the tilt of the substrate,
the needle-to-substrate distance, the relative distance of the impact
point to the lower end of the substrate, and the drop volume. More
details about the measuring procedure can be seen in ref. 14.
Fig. 4 Schematic illustration of the techniques for the determination of
contact angle hysteresis: advancing yAdv and receding contact angle yRec
(a); tilt angle, i.e., the so-called roll off angle or sliding angle ySA (b); and the
shedding angle ySHA (c). 3. Fabrication techniques towards
superamphiphobicity
perform the advancing and receding, respectively. After the In this section, the fabrication techniques towards the super-
drop-forming step, water is continuously and slowly pumped into amphiphobic surface will be described and discussed. As is
(or sucked from) the droplet at a rate smaller than 0.3 ml min1 well-known, the combination of appropriate surface roughness
and yAdv was recorded simultaneously by a frame grabber using a and surface chemistry is crucial to the preparation of super-
solid state charge coupled device camera (Fig. 4a, right). In the hydrophobic surfaces. Therefore, two steps, i.e., the generation
last step, the water droplet is receded and yRec is recorded of nanoscale roughness and the functionalization with low
(Fig. 4a, left).18 surface energy materials (mainly fluorinated small molecules
2.2.2. Tilt angle. The tilt angle refers to the critical angle or macromolecules), are involved. Depending on the sequence
between the substrate and the horizontal surface, below which of the above two steps in the preparation process of a super-
the droplet starts to move upon elevating one end of the amphiphobic surface, the fabrication strategies can be classified
substrate. It should be pointed out that the tilt angle reflects, into the following three strategies (Fig. 5): (1) the ‘pre-roughening +
but not equals to, the difference between yAdv and yRec.3 A low post-fluorinating’ technique (Section 3.1); (2) the ‘pre-fluorinating +
tilt angle is crucial to the so-called self-cleaning behaviour, and post-roughening’ technique (Section 3.2); and (3) the generation of
superamphiphobic surfaces should show a tilt angle lower than surface roughness and surface fluorination occurs in the same step,
101 for both water and ‘oils’. The tilt angle measurements are of i.e., one-pot or in situ fabrication techniques (Section 3.3). It should
two types—the sliding angle ySA (Fig. 4b) for macroscopically be pointed out that some of the so-called superamphiphobic
flat surfaces and the shedding angle ySHA (Fig. 4c) for macro- surfaces that are not truly superamphiphobic (because of their
scopically rough surfaces. relatively high CAH) are included in this section.
The sliding angle, also known as the roll-off angle, indicates
the angle of inclination of a surface when a droplet completely 3.1. ‘Pre-roughening + post-fluorinating’
rolls off the surface due solely to gravity. In experiments, the The pre-roughening and post-fluorinating methods available to
yCA measuring instrument is equipped with an additional date will be separately discussed in this section because each of
accessory—a tilt plate with a tunable angle between 01 and them contains a variety of different ways and there are a lot of
901. The tilt angle is increased continuously from 01 to 901, and combinations that may overlap with each other.
the angle is recorded as ySA while the droplet is sliding away or 3.1.1. Pre-roughening a substrate
rolling off the surface.9,15,19 Strictly speaking, there is a slight 3.1.1.1. Functionalization with nanoparticles (NPs). Functio-
difference between sliding and rolling since the way of droplet nalization with nanopartciles represents an important method
moving on the tilt surface is not the same (Fig. 4b). In the to generate nanoscale roughness on a substrate. The nano-
former case, the surface area of the droplet in contact with the particles can be nanosilicas, silicone nanofilaments, carbon
substrate is slightly higher and fixed because of the high nanotubes, carbon nanofibers, and so on.
adhesion force in between. In contrast, for the latter case, the Nanosilica is a common type of nanomaterial that is inexpensive
contacting area and the adhesion in between are slightly lower, and frequently used in the fabrication of surface roughness.23–25 For
and thereby the droplet rolls freely on the surface. Nevertheless, example, Leng et al.23 functionalized woven fibers with a layer of
in most cases they are treated equally since the only important microscale silica via in situ Stöber reaction, followed by further
thing is the tilt angle where the droplet moves away rather than modification with another layer of nanoscale silica via physical
the moving manner. The only exception is the case of slippery adsorption. Briefly, a piece of cotton textile was immersed in a room
liquid surfaces—liquids on such surfaces slide freely but temperature mixture of methanol, isopropanol, and ammonium

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Fig. 5 Three strategies towards the fabrication of superamphiphobic surfaces: pre-roughening + post-fluorination (Section 3.1); pre-fluorination +
post-roughening (Section 3.2); and one-pot in situ fabrication (Section 3.3).

solution in the presence of tetraethylorthosilicate for several coatings showed higher stability than those just fabricated by
hours, and then cleaned with methanol in an ultrasonic bath spin-coating nanosilica.
repeatedly so as to remove the physically adsorbed particles. For carbon nanotubes (CNTs), numerous applications have
Subsequently, the obtained textile was soaked in 3-amino- been found in many areas of science and engineering because of
propyltriethoxysiloxane solution to generate surface amine their excellent electronic, mechanical, and chemical properties.
groups which were then protonated with hydrochloric acid. The Recently, they were used to create surface roughness so as to
positively charged textile was then dipped into a suspension of impart super-repellant properties to the resultant surfaces.26,27
negatively charged nanosilicas, resulting in a layer of silica For example, Zhang and coworkers27 demonstrated that the
nanoparticles because of electrostatic attraction. In contrast, superamphiphobic surface could be obtained as perfluorosilane-
Hsieh and coworkers24 applied hierarchical silica sphere stacking rendered TiO2/single-walled carbon nanotube composite coatings.
layers to the glass surface via the self-assembly technique. It Interestingly, the wetting ability of such coatings could be tuned
involves a two-stage spin coating of two different silica spheres from superoleophobic to superoleophilic via ultraviolet irradia-
with a diameter of 20 nm and 300 nm, respectively. A gravita- tion. Moreover, by controlling the dose of UV illumination, super-
tional sedimentation for 2 days made the silica spheres fall onto phobicity and superphilicity can exist on the same surface for
the surface of the substrate, thus forming well-organized sphere probing liquids with different surface tensions. Except nanosilica
arrays—a closed hexagonal arrangement. A number of large and carbon nanotubes, carbon nanoparticles such as carbon
spheres were firstly stacked, followed by the secondary stacking nanofibers,28 fullerene, graphene as well as other inorganic
of small silica spheres. He et al.25 spun-coated a mixture of particles such as nano ZnO2, CuO, Ca(OH)2 and CaCO3 have also
polydimethylsiloxane (PDMS) and nanosilica onto glass sub- been reported to generate surface roughness (see the related
strates, followed by sintering at 500 1C for 2 h. And the obtained references in ref. 25).

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at room temperature.34 However, titanium cannot be etched by

either acid or base, but can be etched by electro-chemical
methods. For example, micro-textured Ti can be obtained by
electrochemically etching a titanium foil in a dilute NaCl
solution at a constant voltage of 15 V for 1 h, as reported by
Kim et al.36 Upon further immersing the micro-patterned Ti
into a concentrated NaOH solution at 120 1C for 3 h, and
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subsequently cleaning by dilute HNO3 and deionized water,

TiO2 nanotube arrays on top of the micro-textured Ti were
obtained.
P-type (100) silicon can be roughened via an electrochemical
etching process. As reported by Cao et al.,37 p-type Si(100) with
vertically aligned straight pores was fabricated by anodic etching
of Si(100) chips in a Teflon electrochemical cell in the presence of
a solution of HF–ethanol and a direct current at a density of
100 mA cm2. In contrast, p-type Si(111) film with tilted pores was
fabricated using a gold-assisted electroless etching process.37 In
such a case, the Si(111) film was first coated with Au nanoclusters
by dipping in a KAuCl4–HF solution; and then it was etched in a
Fe(NO3)3–HF solution at 50 1C, during which the Au nanoclusters
served as an electrochemical reaction center. Differently, n-type
Fig. 6 Surface morphology of the TCMS-coated glass slides at different
Si(100) film with surface pyramid structure can be prepared by
water concentrations in toluene during the TCMS coating procedure. etching the substrate in an aqueous solution of KOH and iso-
Scale bars: 1 mm, except for the image at the bottom right corner propanol at 85 1C for 20–30 min.38 Glass can be tailored by ion
(10 mm). Reprinted with permission from ref. 9, Copyright Wiley 2011. etching, and subsequently chemical etching in aqueous HF.39
Besides the etching techniques discussed above, other etching
methods such as plasma etching40 and water etching41 can also be
Coating a substrate with polyalkylsilsesquioxane filaments
applied, depending on the chemical properties of the substrate.
(named as silicone nanofilaments, SNF), first reported in 2004,
represents an economical and efficient way to prepare a super-
repellant surface.29 Using this technique,9,14,15,19,29,30 a dense 3.1.1.3. Lithography. Lithography is a useful method for
SNF layer can be grown on various substrates, including glass, fabricating rough surfaces with regular structures. For example,
silicon, ceramics, titanium, aluminium, cotton fabrics, silk, well-defined structures, including pillars with wavy side walls
wood, polyethylene, and so on, by either gas19,30 or liquid (Fig. 7a),42 straight smooth side walls (Fig. 7b),42 and overhang
(wet toluene)9 phase deposition of trichloromethylsilane (TCMS) re-entrant structures (Fig. 7c)42 as well as grooved textures
in the presence of a trace amount of water (ca. 50 ppm to 200 ppm)9 (Fig. 7d)43 were fabricated by Zhao and coworkers via roughening
at room temperature (Fig. 6). The as-prepared surface shows a silicon wafer with a conventional photolithographic technique
extremely water-repellant properties since SNF imparts the surface using a mask, transferring the pattern of the mask to the
with not only nanoscale roughness but also low-surface-energy. wafers.42,43 Similarly, on a large-size template of the transparent
Besides, such a coating exhibits excellent chemical31 and environ- PDMS elastomer surface, perfectly ordered microstructures with an
mental stability.32 inverse-trapezoidal cross section (Fig. 7e) were fabricated by Im
et al.44 via two consecutive PDMS replication processes and a three-
dimensional diffuser lithography technique.
3.1.1.2. Etching. Etching33–41 is a facile and inexpensive
In a recent work reported by Susarrey-Arce and coworkers,45
method that is frequently used in creating surface roughness.
arrays of microstructures were successfully fabricated by reactive
Depending on the nature of the substrate, etching techniques
ion etching of a silicon wafer, which was covered by a patterned
can be classified into the following types: acid etching,33 base
photoresist layer. By using the same pitch of a photolithographic
etching,34,35 electrochemical etching,36 Au-assisted electro-chemical
mask, the influence of SF6, O2 and CHF3 gases during the
etching,37 ion etching,39 plasma etching,40 and others.41
etching process was investigated. Further, it was demonstrated
Using engineering metal such as aluminium and its alloys as
that homogeneous pedestal-like structures can be fabricated
substrates, Yang et al.33 developed a simple method to achieve
by varying the loading conditions during the etching process.
hierarchical textured surface morphology by HCl etching and
The roughness of the microstructures could also be tuned by
boiling water treatment. Differently, copper substrate can be
changing the dry plasma etching conditions.
etched by a base-assist surface oxidation process,34,35 leaving
the surface with hierarchical structure composed of CuO micro-
flowers and Cu(OH)2 nanorod arrays.34 Briefly, copper sheets 3.1.1.4. Template-assisted synthesis. Template assisted synthesis
were immersed in a NaOH solution in the presence of NH4S2O8 is also frequently employed in fabricating surface roughness.3

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annealing, the coated silica membrane reinforced the SiO2

nanofibers and prevented the fibers from disintegrating into
nanoparticles, generating a hybrid silica network. The fiber
morphology plays an important role in assisting the hybrid
silica network to keep its roughness and surface texture.

3.1.1.5. Sputter deposition. Sputter deposition stands for

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another useful method that can be used for the fabrication of

surface roughness. For instance, Fujii et al.48 prepared hierarchical
submicrometer–nanometer dual pillar surfaces with optimized
pillar intervals via sputtering Al–Nb alloys onto aluminium sub-
strates, followed by further anodization. In a subsequent work,49
the authors replaced Al–Nb with Al, and as a result Al was sputter
deposited. Nanopores were developed through an anodization
process, forming a nanoporous anodic aluminium layer.

3.1.1.6. Galvanic replacement reaction. Galvanic replacement

reaction is a single step reaction that utilizes the differences in
the standard electrode potentials of various metal elements,
leading to the deposition of a more noble metal element and
the dissolution of a less noble metal element. For example,
Fig. 7 Well-defined structures prepared via Lithography. (a–c) Reprinted roughened hierarchical micro/nanostructured Ag deposited
with permission from ref. 42, ACS Copyright 2011; (d) reprinted with
permission from ref. 43, ACS Copyright 2012; (e) reprinted with permission
layers on Zn substrates were developed via galvanic replace-
from ref. 44. ment reactions by Zhang and coworkers.50 Briefly, Zn plates,
either those without any pre-treatment or those treated for 2 h
in a 20 1C refrigerator or in a 80 1C oven, could be used as the
Deng and coworkers46 reported a template-assisted synthesis substrates. The galvanic replacement reactions were carried out
of nanosilica by using candle soot as a template. The deposition of by simply immersing the substrates in aqueous AgNO3 for
a soot layer was completed by simply exposing a glass slide to the various time intervals, followed by cleaning with deionized
flame of a paraffin candle, which turned the glass black. SEM water and drying in air. The surface morphology and roughness
revealed that the soot consists of a fractal-like network composed can be altered through the tuning of the solution concen-
of carbon particles with diameters between 30 nm and 40 nm. tration, the immersing time, and the pre-treating temperatures.
However, the structure is fragile because the particle–particle
interactions are only physical and are weak. When water rolls 3.1.1.7. Sol–gel synthesis. Sol–gel transition represents another
off the surface, the drop carries soot particles with it, and finally useful technique that can be employed in fabricating surface
all of the soot deposit can be removed. Inspired by the promising roughness.51,52 For example, superoleophobic nanocellulose
morphology of soot, the authors developed a technique to aerogels have been prepared using unmodified cellulose nano-
coat the soot layer with a silica shell, making use of chemical gels, which normally have surface structure with a robust
vapor deposition (CVD) of tetraethoxysilane (TES) catalyzed by network at several length scales because of the presence of
ammonia. Similar to a Stöber reaction, silica is formed by the individual nanofibers as well as their self-assembly
hydrolysis and condensation of TES. The shell thickness can aggregates.51 These gels are usually prepared following a sol–
be tuned by the duration of the CVD process. For example, after gel transition process. A typical procedure is as follows: a pulp
24 h coating, the carbon particles were covered by a 20 nm-thick suspension was diluted to 3% consistency firstly, and then the
silica shell. Calcinating the hybrid carbon–silica network at cellulose nanofibers were disintegrated using an ultrafine friction
600 1C for 2 h in air resulted in the combustion of the carbon grinder, which consists of a lower and an upper stationary SiC
core and the decrease in the shell thickness, but the surface grinding stone with a gap of 100 mm. Water was added during
roughness and network texture could be retained. the grinding process, inducing the formation of a nanocellulose
In Ganesh et al.’s work,47 a one-dimensional morphology of hydrogel. Using silica aerogel as a model material, Jin and
nanofibers was used as a template to prepare a robust coworkers52 prepared superamphiphobic silica aerogel by
and transparent superamphiphobic coating. The template vapour phase deposition of a fluorinated monomer. Such a
was fabricated by the deposition of a thick layer of SiO2 surface displays excellent mechanical stability because of its
nanofibers on glass. The developed template was subsequently self-similar network structure, which allows fresh re-entrant
coated with a 25 nm porous silica membrane by vapour phase surface topography even after the removal of the uppermost
deposition of triethoxysilane. After 600 1C heat treatment, a layer upon mechanical abrasion.
transparent, superhydrophilic coating consisting of a hybrid 3.1.2. Post-fluorination of a pre-roughened surface. After
silica network (branched SiO2 nanofibers with a surrounding surface roughness is created, the substrates must be further
silica membrane) was obtained. It was observed that during chemically modified with low-surface-energy materials, normally

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components that are frequently used for the surface modifica-

tion of a flat surface.
3.2.1. Spinning or spraying fluorinated silica nanoparticles.
Sheen et al.54 reported a method to prepare fluorinated silica
nanoparticles (FSN). Briefly, ammonium hydroxide was added to
a mixture of tetraethoxysilane (TEOS) and isopropanol, and the
reaction mixture was refluxed at 60 1C so as to induce the growth
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of silica nanoparticles via sol–gel transition. Finally, PFDTS was

introduced to terminate the reaction until the sol–gel process
was running for 100 min, leaving the silica nanoparticles with an
outer fluorinated layer. The substrates (glass slides) after being
spun-coated using these fluorinated silica nanoparticles become
superamphiphobic with yCA higher than ca. 1501 for both water
and a variety of ‘oils’.
Similarly, Campos and coworkers55 prepared FSN by fluoroalkyl-
functionalizing commercial nanosilicas also using PFDTS.
These functionalized nanosilicas were dispersed in a mixture
of 5 mg ml1 commercial fluoropolymer Viton ETP-600S
(DuPont) in 1,3-dichloro-1,2,2,3,3-pentafluoropropane, forming
a suspension with silica concentration ranging from 0% to 80%
(w/w). The fresh FSN suspension was spray-coated onto silicon
wafers through an airbrush with a 1.06 mm diameter tip using
compressed air, which was repeatedly passed over the substrates
laterally at a distance of ca. 15–20 cm. Finally, the samples were
air-dried for 1 h, followed by further drying at 60 1C for 12 hours.
The as-prepared surfaces showed superhydrophobicity when
FFNS concentration is higher than 20% (w/w). To achieve super-
oleophobicity for probing liquid of CH2I2 and rapeseed oil, FFNS
concentration of 40% and 70% is needed, respectively. While
Fig. 8 Chemical structures of functionalized-perfluoroalkanes used in
the surface modification of a roughened substrate. FFNS concentration equals 80%, the surface exhibited yCA about
1601 for hexadecane; however, the corresponding ySA is much
higher than 201 due to the extremely low surface tension of
fluorinated compounds, so as to achieve superamphiphobicity. hexadecane (gLV = 27.5 mN m1).
Generally, a fluorinated layer can normally be produced by 3.2.2. Spraying fluorinated carbon nanotubes. Wang and
depositing molecular perfluoroalkane with a functional group at coworkers56 synthesized fluorinated multi-wall carbon nano-
one terminal (F-monomer, Fig. 8), for instance, 1H,1H,2H,2H-per- tubes (MWCNTs–PFOL) by grafting 1H,1H,2H,2H-perfluoro-
fluorooctyl phosphate (PFOP),48,49 1H,1H,2H,2H-perfluorooctanoic decanol (PFOL) onto multi-wall carbon nanotubes (MWCNTs).
acid (PFOA),33,34 1H,1H,2H,2H-perfluorooctyl trichlorosilane Then a nanocomposite containing polyurethane pre-polymers,
(PFOTS),15,36–40,42–47,51 1H,1H,2H,2H-perfluorodecyl trichlorosilane PFOL, hexanediol, a mixture of acetone and toluene and
(PFDTS),9,27,41 1H,1H,2H,2H-perfluorodecane-1-thiol (PFDSH),35,50 MWCNTs–PFOL was spray-casted onto a glass slide. The
and 1H,1H,2H,2H-perfluorodecyl acrylate (PFDAE).53 However, obtained coating shows coralline-like structure (Fig. 9a) and
it can also be achieved by spin-coating a fluorinated-polymer displays yCA greater than 1501 for probing liquids not only water
(F-polymer) solution. While grafting a fluorinated layer by using but also ‘oils’ (Fig. 9b). The CAH is low for water (ySA = 51) but
F-monomers, the process can be carried out via either slightly higher for low-surface-tension oils such as surfactant
vapour39,42–47,51 or liquid33–38,40–41,48–50 phase deposition. solution (ySA = 151), glycerol (ySA = 101), CH2I2 (ySA = 301),
rapeseed oil (ySA = 351), and hexadecane (ySA = 401).
3.2. ‘Pre-fluorinating + post-roughening’ 3.2.3. Spraying a copper perfluorooctanoate suspension.
Different from the methods discussed in Section 3.1, ‘‘pre- Yang et al.57 reported a simple method to prepare copper
fluorinating + post-roughening’’ represents another strategy perfluorooctanoate by reacting copper acetate with perfluoro-
to fabricate a superamphiphobic surface. In such a case, octanoic acid in aqueous media. Uniform coatings with robust
fluorinated polymers or nanoparticles were synthesized firstly, superoleophobicity were produced by spraying the copper per-
and subsequently applied to flat surfaces via spin-coating, fluorooctanoate suspension onto various substrates. Such coatings
spray-coating, dip-coating, electrospinning, sol–gel transition, displayed apparent yCA greater than 1501 and low sliding angles,
or other physical techniques, generating roughened structures even with liquids possessing a significantly lower surface tension,
with a low-surface-energy layer on the surface. This section is such as hexadecane and dodecane. The robust superoleophobicity
organized according to the different techniques and chemical was ascribed to the re-entrant morphology and extremely low

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concentration and surface mobility of –CF2– and –CF3 groups,

along with the high ratio of –CF3/–CF2–, result in a strongly
hydrophobic material with low-surface-energy. A spin-coated
film on a flat Si wafer, which had a root mean square roughness
of 3.5 nm, exhibited yAdv and yRec about 124.5  1.21 for probing
liquid of water. Surprisingly, rough structure composed of beads-
on-strings fibers displaying superhydrophobicity and extremely
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oleophobicity (but not superoleophobicity) was prepared by

electrospinning a 5% (w/w) blend of FD-POSS–poly(methyl-
methacrylate) (PMMA) when FD-POSS mass fraction is higher
than ~0.1, though the corresponding spin-coated surfaces are
oleophilic. It was demonstrated that the local surface curvature
plays a key role in driving the oleophobicity, and the electro-
spinning coating technique can also be applied to fragile or
natural substrates so as to confer oleophobicity in addition to
superhydrophobicity. In a subsequent work,7 the authors
extended their work by developing four dimensionless design
parameters that describe the robustness of a composite interface
and the observed apparent yCA on a textured surface, given
the various thermophysical and geometric properties that para-
meterize the system. Guided by the design parameters, they
Fig. 9 SEM images of the surface morphology of perfluoroalkyl grafted
MWCNTs–PU nanocomposite coatings at different magnifications (a):
developed families of superamphiphobic surfaces by system-
multiscale structure with numerous micro-cavities, micro- and nano- atically varying the various chemical and topological surface
pores are formed; and profile images of liquids: water, glycerol, CH2I2, features. Beads-only, beads-on-strings, and fiber-only structures
and hexadecane from left to right (b). Reprinted with permission from are formed at a solute concentration of 2%, 5%, and 10% (w/w),
ref. 56.
respectively. Interestingly, yAdv, yRec, and ySA for hexadecane on
the beads-only surface are 1561, 1501 and 51, respectively. In
comparison, the beads-on-strings and fibers-only surfaces show
surface energy, which can effectively prevent the transition from the a slightly higher CAH with yAdv/yRec values of 1531/1411 and 1531/
Cassie–Baxter state to the Wenzel state. Such a facile technique 1341, respectively. Recently, the same research group demon-
shows great potential for a wide range of applications because it strated that similar textured surfaces can also be fabricated by
can be applied to a variety of substrates without limitations of spraying the FD-POSS–PMMA blend.59 Very recently, Pan et al.60
size and shape, do not typically require complicated application employed an electrospun coating of cross-linked poly(dimethyl-
methods and can be easily repaired after being mechanically siloxane) + 50% FD-POSS (w/w) on top of stainless steel wire
damaged. meshes to fabricate hierarchically structured surfaces. Such a
3.2.4. Electrospinning or spraying a blend of a fluoroalkyl surface possesses re-entrant curvature at both the coarser length
polyhedral oligomeric silsesquioxane and a common polymer. scale and the finer length scale. The hierarchical texture along
Electrospinning is a versatile technique for producing micro/ with the re-entrant curvature and the low surface energy of the
nanofibers from a variety of polymers.58 In a laboratory coating resulted in a superamphiphobic surface with extremely
environment, it requires a high-power supply, a syringe pump, high yCA and low CAH for a range of different polar and non-
a conducting substrate, and a polymer with high molecular polar low surface tension Newtonian liquids, including various
weight as a starting material. The electrospinning process is acids, bases, and solvents.
initiated by a high electric field between the syringe that Opposite to the procedures discussed above,5,7,59,60 by dis-
contains viscous polymer solution and the conducting substrate. solving FD-POSS in a low-molecular-weight fluorinated com-
A charged liquid jet is ejected from the tip of a distorted droplet pound, 1H,1H,2H,2H-perfluorobutyl triethoxysilane, Lin et al.61
because of the high electrical potential. The liquid jet experiences prepared a viscous solution, which was then dispersed in
whipping and bending instabilities within a sufficient distance to ethanol. Upon ultrasonication for 0.5 h, a stable, homogeneous
evaporate its solvent thoroughly and, consequently, becomes a suspension was obtained. Such a dispersion can be easily
solid micro/nanofiber membrane on the substrate. Recently, super- applied onto fabrics so as to impart superamphiphobicity to
amphiphobic surfaces have been fabricated by electrospinning a the surface through a wet-chemical coating technique such as
blend of a fluorinated polymer and a common polymer.5,7 spraying, dip-coating, or padding.
Tuteja and coworkers5 synthesized a class of hydrophobic 3.2.5. Coaxial electrospinning a fluorinated polymer and
polyhedral oligomeric silsesquioxane (POSS) molecules in which a common polymer. In contrast to electrospinning, coaxial
the rigid silsesquioxane cage is surrounded by 1H,1H,2H,2H- electrospinning expands the versatility of electrospinning by
perfluorodecyl or 1H,1H,2H,2H-perfluorooctyl groups (referred enabling the formation of core–sheath-structured micro/nanofibers.
to as FD-POSS and FO-POSS, respectively). The high surface A coaxial nozzle consists of a central tube surrounded by a

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concentric annular tube. As reported by Steckl et al.,58 a fabric was prepared by vapour-phase polymerisation of
fluoropolymer Teflon AF2400 solution and a common polymer 3,4-ethylenedioxythiophene on fabric in the presence of FD-POSS
poly(e-caprolactone) was used as sheath and core material, and 1H,1H,2H,2H-perfluorooctyl triethoxysilane (FAS). The
respectively. Both solutions were separately fed into the coaxial incorporation of FD-POSS and FAS into the polymeric layer
nozzle from which they were ejected simultaneously. A compound improved the washing and abrasion stability considerably but
pendant droplet was generated from the coaxial nozzle without had a very small influence on the conductivity. The coated
bias; upon application of a sufficient voltage, a Taylor cone was fabric can withstand no less than 500 cycles of standard laundry
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formed and a liquid jet was ejected that consists of the core and 10 000 cycles of the abrasion test without apparently changing
material enveloped by the sheath material. Then the polymer jet its superamphiphobicity, though the conductivity showed a small
underwent the same process as in conventional electrospinning: reduction. Besides, the coating exhibited self-healing properties,
being pulled by the electric field and whipped and stretched by the i.e., it auto-repairs its surface from chemical damage so as to
bending instability, followed by evaporation of the solvent causing restore its superamphiphobicity.
the formation of solid-state fibers. The coaxial electrospinning Saraf and coworkers67 developed three different techniques
technique allows the resultant fibers to combine different to achieve superamphiphobicity using hydroentangled nylon
characteristics of both the core and the sheath polymers. nonwoven fabrics as substrates: (1) pulsed plasma polymerization
3.2.6. Sol–gel transition of a fluoropolymer. In the work by of 1H,1H,2H,2H-perfluorodecyl acrylate; (2) microwave-assisted con-
Xiong et al.,62 a diblock copolymer, poly[3-(triisopropyloxysilyl)- densation of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (FS); and
propylmethacrylate]-block-poly[2-(perfluorooctyl)ethyl methacrylate], (3) FS condensation through wet processing. The coated nonwoven
which contains a fluorinated block and a sol–gel forming block, fabrics showed very high yCA for both water (yCA = 168–1741) and
was synthesized by sequential anionic polymerization firstly. dodecane (yCA = 153–1601).
And then the diblock copolymer was chemically grafted onto Darmanin and Guittard68 prepared superamphiphobic nano-
silica particles by inducing sol–gel transition of the poly- porous films by electrochemically polymerizing a fluorinated
[3-(triisopropyloxysilyl)propylmethacrylate] block using a,a,a- monomer 2-(2,3-dihydro-[1,4]dioxino[2,3-c]pyrrol-6-yl)ethyl 1H,1H,-
trifluorotoluene–tetrahydrofuran mixture as a solvent and HCl 2H,2H-perfluorodecanoate, which was synthesized from 3,4-
as a catalyst, generating a polymer monolayer on the surface of ethylenedioxypyrrole via a multi-step procedure (Fig. 10a). The
silica particles at sufficiently high P1-to-silica mass feed ratios. electrochemical polymerization of the monomer was carried out
Finally, the polymer–silica composite was cast-coated onto glass by cyclic voltammetry using a solution of a mixture of monomer–
slides and printing paper, leaving the substrate surface with tetrabutylammonium hexafluorophosphate in anhydrous aceto-
rugged polymer–silica films, which were superamphiphobic. nitrile. Polymerization was initiated on the surface of the platinum
disk electrode by repeated potential scans between 1.00 V and
3.3. One-pot methods 0.83 V, inducing a homogenous growth of an electroactive polymer
Compared with the two strategies discussed above, in situ film on the electrode. Then the polymers were very quickly
synthesis stands for a simpler way to fabricate superamphiphobic deposited on gold at a constant potential and deposition charge.
surfaces, and thus was also frequently reported. yCA measurements indicated that the polymeric surfaces are both
Jiang’s group63 developed a one-step electrodeposition process superhydrophobic (yCA = 1611 for water) and superoleophobic
for the fabrication of superhydrophobic surfaces on a series of (yCA = 1451 for hexadecane, Fig. 10d). SEM images revealed that
electrically conductive substrates such as copper, titanium, iron, the surface morphology consists of a very porous material at a
zinc, aluminium, and tin, using n-tetradecanoic acid as an nanometric scale and an assembly of spherical structures at a
electrolyte. Hierarchical micro/nanostructures with excellent micrometric scale (Fig. 10b and c). This two-scale construction
superhydrophobicity were obtained. Such coatings showed enables the surface with exceptional super-antiwetting properties
superhydrophobicity even for some corrosive liquids including because it allows the surface to trap air beneath the surface, which
salt solutions and acidic and basic solutions at all pH values. By supports the weight of a water–oil droplet more easily. In their
replacing n-tetradecanoic acid with nonadecafluorodecanoic subsequent studies,69,70 the authors found that the length of the
acid,63,64 the authors were able to prepare superamphiphobic alkylenedioxy bridge of the fluorinated 3,4-alkylenedioxypyrrole
coatings with a microcluster of flowerlike structures composed monomer plays a considerably important role in the surface
of nanosheets. The superamphiphobicity of the treated surface morphology of the electrodeposited conducting polymer film:
was attributed to the synergistic effect of their special surface the polymerization of the fluorinated 3,4-ethylenedioxypyrrole
compositions and textured structures. Compared with traditional monomer imparts the polymeric film with superamphiphobicity
approaches towards the preparation of superamphiphobic coatings, with extremely low CAH, whereas the polymerization of the
this one-pot method is much simpler and the procedure is more fluorinated 3,4-propylenedioxypyrrole monomer gives only
convenient to operate. superhydrophobic films with sticking property (ySA > 901). The
In Lin and coworkers’ work,65 electrically conductive super- different wettability was attributed to the presence of nano-
amphiphobic coatings were prepared in situ by one-step vapour- porosity in fluorinated poly(3,4-ethylenedioxypyrrole) films,
phase polymerisation of polypyrrole in the presence of a which increases both oil and water yCA and switches the system
fluorinated alkyl silane on fibrous substrates. In a subsequent from the Wenzel to the Cassie–Baxter state. Very recently, the
work,66 a robust, electrically conductive, superamphiphobic same group has found that the surface microstructuration

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such a basic function. Superamphiphobic surfaces display

characteristics of both superhydrophobic and superoleophobic,
and thereby they share most of the functions with superhydrophobic
surfaces with some exceptions. For instance, superhydrophobic
surfaces can normally be used for oil–water separation because
these super-water-repellant surfaces are wettable by low surface
tension oils;7 however, it is obvious that superamphiphobic surfaces
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cannot be used in such an application. However, compared

with superhydrophobic surfaces, the biggest advantage of
superamphiphobic surfaces is their super-antiwetting ability
not only for pure water but also for low surface tension aqueous
solution (for e.g., detergent solution, rain water, underground
water, waste water, and sea water) and organic ‘oils’ (for e.g.,
hexane, hexadecane, toluene, mineral oil, and cooking oil).9
In Seeger’s group, superamphiphobic coatings with super-
antiwetting ability for both water and various low-surface
tension organic liquids were prepared using silicone nano-
filaments through a grow-from approach.9 As mentioned above
(Section 3.1.1.1), with such a technique, a layer of SNF can be
grown on various substrates by chemical deposition of trichloro-
methylsilane (TCMS) in the presence of water. The coated glass
surfaces display super-antiwetting ability for probing liquid of
water (yCA = 1681, ySA = 51), but not for low-surface-tension ‘oils’.9
For example, yCA of diiodomethane which shows a surface
tension of 50.8 mN m1 is 911; other ‘oils’ such as mineral oil,
toluene, cyclohexane, hexadecane and decane which exhibit
surface tension between 32 mN m1 and 23 mN m1 can spread
on the surface quickly (yCA E 01), indicating that these samples
are superoleophilic. Such coatings (on textile substrates) can be
used for oil–water separation due to their superhydrophobicity
not superoleophilicity.72 Upon activating by O2 plasma and
surface modifying with PFDTS, the coatings show super-
Fig. 10 Synthesis (a) and SEM images (b and c) of the polymeric surface, amphiphobicity and cannot be wetted by both water and low
and a photo of a hexadecane droplet on the surface (d). The scale bar
surface tension ‘oils’ (Fig. 11a). For all of the liquids mentioned
represents 1 mm (b) and 100 nm (b), respectively. Reproduced with
permission from ref. 68, Copyright 2009 by Academic Press. above, a high yCA (>1551) and low ySA (o61) on the coated glass
surface were observed, indicating that all of the liquid droplets
on such a surface are in the Cassie–Baxter state. The liquid
increases with the fluorinated-alkyl chain length, whereas the droplets could easily roll off from the surface while it is slightly
surface nanoporosity goes the reverse way.71 tilted (o61). Even jets of toluene and decane could bounce off
the TCMS–PFDTS coated surface without leaving a trace
4. Functional applications (Fig. 11b). The TCMS–PFDTS-coated glass surface was reflective
in toluene and remained completely dry after taken out
With the increasing demand for functional materials with (Fig. 11c), implying the existence of an air cushion between the
excellent anti-wetting ability, a great deal of interest has been solid surface and the liquids. This means that most of the area
focused on the development of superamphiphobic surfaces beneath the liquid droplet is a liquid–vapour interface, and
displaying a wide range of applications.5,9 The discussion below thereby the interaction between the liquid and the coating is
will focus on how surface superamphiphobic modification brings extremely weak. Compared with superhydrophobic surfaces,
about new functions such as super-antiwetting, self-cleaning, superamphiphobic surfaces are more useful in antiwetting for
anti-freezing, anti-bacterial activity, corrosion resistance, and practical applications since the former surfaces can be easily
oil droplets manipulation, to name but a few, which are not contaminated by oily substances when the surfaces are exposed
available for the materials themselves. to an industrial or household environment and gradually lose
their superhydrophobicity, while the latter surfaces cannot be
4.1. Super-antiwetting contaminated (Fig. 11) and their superamphiphobicity can be
There is no doubt that most applications of superamphiphobic maintained for a long time.
surfaces are based on their versatile function in super- The super-antiwetting function can be applied to many
antiwetting, and all the other applications are derived from traditional materials such as glass,9,25,46,56 silicon,5,7,42,43,55

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to an increase in yCA of the liquid droplet, thereby facilitating

the de-wetting of the surface and enabling the droplet to roll-off
easily, taking away the dirt and other pollutants.46,47

4.3. Anti-freezing
Anti-freezing on the material surface has long been a technological
challenge because some outdoor infrastructures and high-
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technological devices such as aviation, space flight and radar can

be easily affected or even destroyed by the large amount of adherent
ice. For instance, supercooled water vapour and clouds in the
upper-air layers can easily condense and subsequently freeze on
aircraft surfaces during a flight, which results in the worst case in a
dramatic decrease of the ascending force and may lead to an
airplane’s crash, e.g., on October 31, 1994, when American Eagle
Flight 4184 crashed because of ice formation on the wings after
flying in icing conditions.
Surface superhydrophobic modification shows great
potential to address such a challenge. Quéré et al.73 demon-
strated that freezing could remarkably be delayed when water
droplets were deposited on cold superhydrophobic surfaces. It
was reported that the presence of microtextures dramatically
delay the freezing time of the water drops, by a factor between
3 and 5. Water droplets rolled off the cold superhydrophobic
surface quickly without freezing. In contrast, drops on an
untreated surface spread quickly and formed a thin film on
the surface, which was freezed immediately. The authors
Fig. 11 Images of the superamphiphobic glass slides with droplets of
pointed out that the air sublayer in a superhydrophobic surface
various non-polar liquids (a), immersed in toluene (b), and with a jet of could provide substantial thermal insulation and thus delayed
toluene bouncing off (c), and (d) untreated polyester fabric immersed in the freezing process. In the work by Song et al.,74 it was
hexadecane (left), a superamphiphobic fabric immersed in hexadecane observed that the presence of micro/nanostructural and
(middle) and heptane (right). (a–c) Reproduced from ref. 9, Copyright
chemical patterns is very important for the controlling of
Wiley 2011. (d) Reproduced from ref. Reprinted with permission from
ref. 53, Copyright Elsevier 2012.
coalescence of microdroplets as well as their quick self-
removal. Kulinich and Farzaneh75 discovered that CAH plays
an important role in anti-freezing and a lower CAH normally
zinc,6,50 aluminium,6,33 iron,6 steel,60 copper,34,63 nickel,6 contributes to a much longer delay of freezing time.73,75
engineering metal alloys,6 textile,23,53 polyester fabric,61 paper,62 Compared with superhydrophobic surfaces, superamphiphobic
gel,51,52 and so on, protecting their surfaces from being wetted, surfaces normally exhibit much lower water CAH (ySA close to 11
contaminated or fouled by water and oil pollutants. Besides, the or even lower), as documented extensively.9,25,46,47,60 Therefore,
superamphiphobic surface modification brings about not only the superamphiphobic surfaces are more promising in anti-freezing
super-antiwetting function but also other derived functions though the corresponding study in such an application for
such as self-cleaning, anti-fogging, anti-bacterial activity, corrosion superamphiphobic surfaces has not yet been reported.
resistance, and oil transportation, which will be discussed in the
following sections. 4.4. Anti-bacterial growth properties
In addition to extreme non-wettability, superamphiphobic sur-
faces also exhibit antibacterial activity.76–78 Vilčnik et al.76,77
4.2. Self-cleaning investigated the antibacterial properties of hydrophobic–
Self-cleaning coatings can be broadly classified into two major oleophobic sol–gel coatings for cotton fabrics by using Escherichia
types: photocatalysis-induced superhydrophilic coatings and coli bacteria as a model, and found that superamphiphobic
superhydrophobic or superamphiphobic coatings.47 In super- surfaces exhibited a long lasting antibacterial effect without the
hydrophilic coatings (yCA o 51), the surface is cleaned by the addition of any antibacterial agents. The antibacterial activity test
sheeting effect of water and also by breaking down the complex revealed that the reduction of the bacteria on superamphiphobic
organic substances into carbon dioxide and water—the photo- cotton fabrics was nearly 100%.77 In Huang’s group,78 superam-
catalytic effect. In contrast, in superhydrophobic or super- phiphobic cellulose (commercial filter paper) was fabricated by
amphiphobic surfaces, the air pockets that get trapped between chemical etching using alkaline solution to enhance the surface
the nanostructured substrate and the water droplet result in the roughness, followed by depositing ultrathin titania films via a facile
formation of a composite solid/air/liquid interface, which leads surface sol–gel process, and subsequently surface modifying using

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1H,1H,2H,2H-perfluorooctyl trimethoxysilane (PFOTMS). Due to the transferred from a low adhesive superamphiphobic surface to a
combined surface roughness and low surface energy of the metal cap, which was then reacted with another oil droplet
PFOTMS monolayers, the naturally hydrophilic filter paper was containing Br2 on a high adhesion superamphiphobic surface.
converted into superamphiphobic, which effectively inhibited the After the reaction of the two droplets, the final droplet was left
adhesion of bacteria such as lysogenic Escherichia coli. on the substrate due to its high adhesion to the surface. These
surfaces with controllable oil adhesion displayed promising
4.5. Corrosion resistance applications in microfluidic systems, no-loss oil droplet trans-
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The oxidation and corrosion of metals and their alloys in the portation, and other fields.
humid atmosphere limit their applications, causing serious
problems such as accelerated aging of the devices, huge waste, 4.7. Other applications
and environmental contamination.79 Surface superamphiphobic Except the functional applications discussed above, superam-
modification is a probable solution to these problems because the phiphobic surfaces also exhibit great potential in a variety of
super-repellant coating acts as durable barrier film that can other fields including breathable protective wear,23 enhanced
effectively prevent the metal surface from being corroded. Recently, solvent resistance,9 chemical shielding,60 drag reduction,81
a superamphiphobic CaLi-based bulk metallic glass,41 which was patterned superfunctional surfaces,15 smart devices,51 anti-
prepared by the construction of micro/nanoscale hierarchical reflection, and oil capture.
structures and subsequent fluorination, was reported to show
long-term stable anti-corrosion ability due to its durable super-
amphiphobicity that can be kept under ambient atmospheric 5. Conclusions and perspectives
conditions for more than three months. In Jiang’s group,8,63
engineering metals and their alloys such as zinc, aluminium, iron, This review summarizes the characterization, fabrication, and
nickel and Zn–Fe alloy are superamphiphobic-functionalized by functional applications of superamphiphobic surfaces. The
taking advantage of an electrochemical reaction in perfluoro- development of such surfaces is important for basic research,
carboxylic acid solution, which shows great promise in corrosion as well as, for numerous commercial applications. Through
resistance for real applications since these metals are the most years of endless efforts, great achievements have been made in
important and applicable materials in industry. In the work this field: a variety of different techniques towards the fabrication
performed by Zhang et al.,33 superamphiphobic aluminium was of superamphiphobic surfaces have been developed by combining
prepared in a facile way of HCl etching, followed by PFOA surface the design of surface roughness and surface chemistry. Never-
modification. In another study by the same research group,80 theless, there are still lots of challenges that need to be addressed.
superamphiphobic copper sheets were fabricated via a simple For example, a majority of the fabrication methods are limited to
and time-saving procedure: sandblasting and Ag deposition laboratory research and not suitable for industrial scale production.
processes were used to create surface roughness firstly, and then Even though the superamphiphobic coatings can be prepared on a
the resultant surfaces were fluorinated by simply immersing the large scale, they generally face the problem of poor mechanical
samples in PFDSH–ethanol solution (1 mM) for only 30 s. The stability. Mechanical durability is crucial to practical applications,
obtained superamphiphobic surfaces exhibited enhanced corro- i.e., they cannot find practical use without sufficient mechanical
sion resistance with a more positive corrosion potential and a stability. However, this aspect has been sparingly addressed in the
more negative corrosion current density. More interestingly, the literature and there is a need and an opportunity to develop
superamphiphobicity could be restored by a simple regeneration mechanically durable superamphiphobic surfaces. The relation-
process when loss of superoleophobicity occurred. The authors ship between mechanical stability and surface morphology as well
suggested that such a simple and time-saving fabrication as surface chemistry needs to be investigated. Quantitative ways
technique will make it possible for large-scale production of to characterize the mechanical stability of surperamphiphobic
superamphiphobic engineering materials. Very recently, Tuteja coatings should be established—probably there would be a critical
and coworkers60 developed superamphiphobic stainless steel force above which the superamphiphobicity of the surface
wire meshes by electrospinning a blend of cross-linked decreases substantially and methods for precise determination of
poly(dimethylsiloxane) and FD-POSS. It was observed that the such a critical force need to be figured out.
coated steel surface cannot be corroded by concentrated hydro- Future trends in this field may see an expansion towards
chloric acid and concentrated sodium hydroxide. self-healing superamphiphobicity because it shows great pro-
mise in practical applications—their oil-repellency can easily be
4.6. Oil droplets manipulation automatically restored after mechanical damage. Surfaces with
Recently, utilizing superamphiphobic surfaces with controllable controllable superamphiphobicity may also become one of the
oil adhesion, Jiang and coworkers constructed an oil droplet- focuses of future research, given the biological relevance of
based microreactor for oil droplets manipulation.35 The surface most of them.
adhesion to oil can be tuned through the adjustment of either Overall, we believe that an exciting future for superamphi-
surface nanostructures or external preload forces, making it phobic surfaces will be witnessed since many scientists and
possible for oil transportation in a drop-to-drop system. In their engineers contribute to the understanding and the design of
experiment, an oil droplet containing a styrene monomer was such surfaces.

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Acknowledgements 25 Z. He, M. Ma, X. Lan, F. Chen, K. Wang, H. Deng, Q. Zhang

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