Solar Energy Materials & Solar Cells 157 (2016) 604–623

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Solar Energy Materials & Solar Cells

journal homepage: www.elsevier.com/locate/solmat

Superhydrophobic surfaces with antireflection properties for solar

applications: A critical review
Umer Mehmood a, Fahad A. Al-Sulaiman a,b, B.S. Yilbas b,n, B. Salhi a, S.H.A. Ahmed a,
Mohammad K. Hossain a
a
Centre of Research Excellence in Renewable Energy (CoRERE), King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
b
Department of Mechanical Engineering, King Fahd University of Petroleum & Minerals, KFUPM, P.O. Box 1913, Dhahran 31261, Saudi Arabia

art ic l e i nf o a b s t r a c t

Article history: Antireflective surfaces with superhydrophobic characteristics are of considerable current interest owing
Received 8 February 2016 to their potential utility in solving key technological problems. Superhydrophobic surfaces possess self-
Received in revised form cleaning characteristics due to their unique surface texture and chemistry, which control wettability. The
2 July 2016
surface micro/nano texturing combined with low surface energy of materials lead to enhance anti-
Accepted 21 July 2016
wetting properties. Self-cleaning surfaces exhibit special anti-wetting properties owing to the water
contact angle greater than 150° leading to the ready rolling-off of water droplets. The surfaces can be
Keywords: made hydrophobic using two key pathways: i) making a rough surface from a low surface energy ma-
Superhydrophobic terial, and ii) making a rough surface and modifying it with material of low surface energy. Similarly,
Antireflection
transparent surface coatings with suitable optical path differences can suppress reflection from surfaces.
Self-cleaning
High transparency is crucial in improving the performance of optical equipment and devices, such as
Roughness
Substrate windows, lenses, solar panels, etc. A normal solar panel absorbs only about 25% of the incident solar
Solar cell radiation, the remainder being reflected. Design and implementation of transparent super hydrophobic
surfaces that repel atmospheric dust from solar panels, and thus reduce reflectivity of the surfaces are
thus highly desirable. In this review, recent developments in antireflective, transparent, and super-
hydrophobic surfaces, with particular emphasis on glass and polymer materials, are highlighted. The
review contains four sections as follows: (i) brief description of the basic concepts and principles of
antireflection and self-cleaning; (ii) detailed fabrication pathways and their mechanisms; (iii) challenges
faced in practical applications; and (iv) trends of future developments. Overall, a comprehensive over-
view of antireflective surfaces with superhydrophobic characteristics is provided in light of the current
challenges.
& 2016 Elsevier B.V. All rights reserved.

1. Introduction Leaves with superhydrophobic surfaces and corneal lenses with

Numerous examples of functional surfaces are present in nat-
ure. For instance, moths reduce reflection from their eyes by using
non-close-packed (ncp) nipples to act like an antireflection coating
(ARC) [1–3]. The outer surface of the corneal lenses of moths
consists of ncp arrays of conical bumps, termed corneal nipples,
typically of sub-300 nm [3] height and spacing. These arrays of
nipples of subwavelength size generate a graded transition of re-
fractive index, minimizing the reflection over a broad range of
wavelengths and angles of incidence [4]. In another example of a
functional surface, lotus leaves and rice leaves display self-clean-
ing behavior due to their surfaces being superhydrophobic [5,6].
n
Corresponding author.
E-mail address: bsyilbas@kfupm.edu.sa (B.S. Yilbas).
antireflection properties provide enormous inspiration for scientists to
mimic them for many important applications. For example, properties
of lotus leaves have been mimicked to conveniently fabricate super-
hydrophobic films with self-cleaning properties; learning from the
properties of the eyes of moths, antireflective surfaces have been fab-
ricated. ARC is a type of coating that is used to minimize the reflection
of light [6–11] on many optical instruments including high power lasers
[12], and outdoor applications and surfaces exposed to the elements,
such as glass windows [13], and modules of solar cells [14]. Basically,
these coatings are used to enhance the transmittance of incoming light.
Light is always reflected when it travels from one medium to another
medium due to the differences in refractive indices of the two media
[9]. Higher the difference the greater the reflectance and vice versa
[14]. Self-cleaning surfaces show superhydrophobic characteristics be-
cause of the very high contact angle with water (WAC4150°).

http://dx.doi.org/10.1016/j.solmat.2016.07.038
0927-0248/& 2016 Elsevier B.V. All rights reserved.
 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623
Superhydrophobic properties of naturally occurring surfaces are due to
a combination of micro/nanostructures and low surface energy. The
water droplets do not interact strongly with the slippery surface and do
not deeply penetrate into the surface [15].
Due to the high roughness of hydrophobic surfaces, combining
antireflective properties with superhydrophobic surfaces does not
seem to be feasible. As the roughness of a surface will increase
scattering, there is a need to have a tradeoff between scattering
and roughness [16]. Duparre et al. [17] investigated a rough surface
quantitatively and inferred that there can be a tradeoff between
both features (scatter loss and hydrophobicity) in the same
structure. For example, porous silica produced via the sol-gel
method by Xu et al. [18] and silicone nanofilaments fabricated via
chemical vapor deposition by Artus et al. [19] show a good tradeoff
between scatter loss and hydrophobicity. Silanization is a fre-
quently used method to introduce hydrophobicity to ARCs [20–
22]. Other approaches include the use of organically modified si-
lica [23,24] or postdeposition of polytetrafluoroethylene (PTFE)
[25]. The combination of antireflection properties with the su-
perhydrophobic effect allows solar panels to maintain a clean
surface, so that the performance of solar panel is sustained [26].
Owing to their industrial importance, antireflection and self-
cleaning surfaces have kindled the curiosity of scientists. Trans-
parent superhydrphobic surfaces are used to minimize the re-
flection of light and dust collection on many optical instruments
and outdoor applications including surfaces exposed to sunlight,
such as glass windows, high powered lasers, and solar modules. In
this review, the basic principles of antireflection and self-cleaning
surfaces, their fabrication strategies, and current challenges faced
in practical applications are discussed in detail. The novel ap-
proaches employed and challenges faced with regard to the ap-
plication of antireflection and self-cleaning surfaces published in
the open literature are presented. Commercialization challenges
are also described.
2. Fundamentals of superhydrophobic effect and
antireflection
The contact angle of a droplet of water resting on a surface can
be used to define the hydrophobicity/superhydrphobicity of the
surface. The WAC of a surface can be controlled by changing the
surface roughness and using chemical modifications. Similarly, the
refractive index of a medium is a major parameter which de-
termines the amount of light transmission through the medium. In
this section, the fundamentals of both superhydrophobicity and
antireflection properties are explained in detail.
2.1. Hydrophobic and superhydrophobic effects
The hydrophobicity of a surface depends on the contact angle
(CA) between a liquid drop and the surface. Generally, if water
CA o90° the surface is hydrophilic and when WCA approaches
zero the surface becomes superhydrophilic. On the contrary, if
WCA 490° the solid surface is hydrophobic and it becomes su-
perhydrophobic when WCA is greater than 150°.
2.1.1. Theoretical back ground
Wettability is an important property of a solid surface, and the
contact angle is commonly used to characterize the surface wett-
ability [27].
2.1.1.1. Young's equation. For a perfectly smooth and chemically
homogeneous solid surface, the contact angle of a liquid is given
by Young's equation [28]:
605
Fig. 1. (a) A liquid droplet on a smooth surface, (b) A liquid droplet in the Wenzel
state. (c) A liquid droplet in the Cassie state [27].
γSV − γSL
Cosθ =
γLV (1)
where, γSV , γSL and γLV are the values of interfacial tension of the
solid–vapor, solid–liquid, and liquid-vapor interfaces, respectively
(Fig. 1a).
However, the early theoretical work on the contact angle of real
world solid surfaces, which are rough and chemically hetero-
geneous, was undertaken by Wenzel and Cassie–Baxter.
2.1.1.2. Wenzel's equation. In the model developed by Wenzel, li-
quid completely penetrates into the grooves, as shown in Fig. 1b.
The Wenzel's equation is defined as follows [29]:
CosθW = r Cosθ (2)
where θW represents the CA on a rough surface, θ is the Young's
contact angle on an analogous smooth surface, and r is the surface
roughness factor. The above equation indicates that when θ is
o90° wetting is enhanced by increasing r, whereas when θ is
490° wetting decreases with increasing r.
2.1.1.3. Cassie–Baxter equation. The Cassie–Baxter model considers
the case where air bubbles are trapped due to the roughness of a
surface when θ 490°, as shown in Fig. 1c. Under such conditions,
the liquid forms two interfaces, namely, the L–S interface (Phase 1)
and the L–V interface (Phase 2). Therefore, the apparent CA is
defined by the following equation [30]:
Cosθc = f1Cosθ1 + f2 Cosθ2 (3)
where θc is the apparent contact angle; f1 and f2 are the surface
fractions of Phase 1 and Phase 2, respectively; and θ1 and θ2 are
the contact angles of Phase 1 and Phase 2, respectively. If f is the
fraction of the solid surface that is wetted by the liquid at the li-
quid-solid interface, the fraction of the liquid-air interface is (1
f).
With θ ¼180° for air, the apparent contact angle for this case can
be calculated as follows:
Cosθc = f Cosθ + ( 1−f )Cos180° = f Cosθ + ( 1−f ) (4)
In this model, the contact angle for a given type of interface is
assumed to be constant or is static. However, owing to chemical
heterogeneity, surface roughness, and surface reorganization,
contact angles can vary over the area of contact with the probe
liquid [31].
2.1.2. Natural superhydrophobicity
Lotus leaves and rice leaves exhibit excellent hydrophobicity
and/or superhydrophobicity [32,33], first observed by Ward and
his co-workers [34]. Although, lotus leaf grows in muddy water, its
leaves remain clean, with dirt and other contaminants not sticking
to the surface. The mystery behind this phenomenon was resolved
after the invention of the scanning electron microscope (SEM) in
1960 [35]. The studies by Mock U et al. [36] revealed that plant
leaves possessing super-hydrophobicity show two types of mi-
crostructures: a) hierarchical microstructures and b) unitary mi-
cro-line structures. This finding was the first step towards the use
606 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623

Fig. 2. SEM images of hierarchical structures showing natural superhydrophobicity with (a) and (b) are the SEM images of lotus leaf with low and high magnifications;
(c) and (d) are the SEM images of rice leaf with low and high magnifications [38].

of synthetic superhydrophobic surfaces for commercial applica-
tions [37–39].
2.1.2.1. c. Plant leaves with a hierarchical structure. Fig. 2 shows the
SEM images of the hierarchical structures of lotus and rice leaves.
Fig. 2a shows the uniformly textured surface with 3–10 mm sized
ridges and valleys coated with a 70–100 nm thick layer of wax-like
material. A large number of nanorods, with an average diameter of
about 50 nm, are haphazardly distributed on the subsurface layer
(Fig. 2b). Surface of the lotus leaves, which possesses a WCA of
about 162° [36,40], shows super-hydrophobicity due to the tex-
tured nature of the surface. The morphology of a rice leaf, shown
in Fig. 2c and d, indicates that its upper layer possesses papillae
with an average diameter of about 5–8 mm (Fig. 2c). The surface of
the rice leaf has a contact angle of about 157° and the sub-layer of
the surface contains innumerable nanopins that are well dis-
tributed to improve the trapping of air (Fig. 2d).
Ji and his team [41] used a novel nanoscale casting technique to
fabricate superhydrophobic surfaces that mimic the structure of
lotus leaves. The SEM image (Fig. 3a) of the surface fabricated by
them shows surface morphology similar to that of a lotus leaf with
small papillae protrusions of an average diameter of 6 mm. Re-
searchers have used similar polymer casting and UV nanoimprint
lithography techniques to fabricate two other types of surfaces
that mimic the properties of a lotus leaf [42]. The morphology of
surfaces formed by these techniques is shown in Fig. 3b. Super-
hydrophobic surfaces can also be fabricated by replicating the
structures of other plant leaves. For example superhydrophobic
polystyrene film can be produced by replicating the structure of
the Taro leaf [43].
2.1.2.2. d. Plant leaves with a unitary structure. Fig. 4 shows the
SEM images of the ramee leaf which possess a unitary structure.
The ramee leaves show natural superhydrophobicity with a WAC
of 164°. Fig. 4b clearly demonstrates smooth fibers with a diameter
of 1–2 mm are uniformly distributed on the surface forming a
unitary structure. Chinese watermelon has a remarkably similar
structure (Fig. 4c and d) with a slightly different WAC of 159° [44].

Fig. 3. The SEM images of (a) super-hydrophobic surfaces prepared by mimicking lotus leaf template [40] and (b) A photopolymer mockup with UV-nanoimprint lithography
[41].
 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623 607

Fig. 4. SEM images (a and b) of unitary structure of ramee leaf and the enclosure of (b) is a WCA of about 164°; (c) and (d) are the SEM images of the Chinese watermelon
surface and the enclosure of (d) is a WCA of about 159° [44].

Thus, a hierarchical structure is not an essential condition for
naturally occurring surfaces to display superhydrophobic behavior.
Notably, surfaces with a unitary structure show better mechanical
properties than those with a hierarchical structure.
Developing artificial surfaces, which mimic the behavior of
natural surfaces, is not a simple process. Shiratori and co-workers
[45] fabricated the superhydrophobic membranes shown in Fig. 5
using a layer-by-layer coating on nanofibrous membranes. Fig. 5a
shows that cellulose acetate fibers are randomly oriented
throughout the surface forming a unitary structure similar to that
of the ramee leaf. Furthermore, water readily absorbs through the
smooth surface of fibers, indicating its superhydrophilicity, as
shown in Fig. 5a. After coating cellulose acetate fibers with fluor-
oalkylsilane (FAS), the fibers still maintained their shape and
smoothness (Fig. 5b) and the surface shows superhydrophobicity
with a WCA of about 140° due to the low surface energy of the C–F
groups of FAS.
2.2. Principle of antireflection
Reflection at surfaces is described by the Fresnel equation [46],
and the refractive index is the key parameter which determines
transmission of light in a medium. Fresnel equation, which is the
basic mathematical model describing reflection and refraction,
makes the following two assumptions for single-layer coatings:
1. All reflected waves have the same intensity and one wave is
reflected per interface.
2. Other optical interactions such as scattering, absorption, etc. are
negligible.
If there is destructive interference between the light reflected
from the coating-substrate interface and the air–coating interface
as illustrated in Fig. 6a, light will not be reflected from the surface.
Therefore, the refractive index of the coating, nc, for an ideal
homogeneous ARC has to meet the following conditions:
1. nc ¼(nans)1/2, na and ns are the refractive indices of air and the
substrate, respectively.
2. d ¼ λ/4 nc, d is the thickness of the coating; λ is the wavelength
of incident light.

Fig. 5. a) SEM images of unitary structure of cellulose acetate fibrous membranes having superhydrophilicity; b) Modification of acetate fibrous membranes with FAS
displaying superhydrophobicity [45].
608 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623

Fig. 6. Light Propagation through (a) a single-layer coating and (b) multi-layer coating on substrate (ns 4nn , ns and nn are the refractive indices of substrate and coatings,
respectively) [27].

Sunlight shows appreciable degree of polarization when light
reflects at shallow angles, owing to light reflecting at shallow
angles possessing a maximum intensity of p-polarized light. Re-
flected light from the interface ij between the adjacent layers i and
j of a multilayer coating (Fig. 6b) is defined as follows [27]:
⎡ ⎤
Rij = R mn exp⎣ −2( δi+ δj)⎦
in which Rmin = ⎡⎣ ni − nj / ni + nj ⎤⎦, δi ¼ 2πnidiCos θi/ λi, (θi is the
( )( ) wettability, which can also be controlled by changing the porosity
angle of refraction, di is the physical thickness of the layer).
Total light reflected, Rsum , from the coating is defined as follows:
Rsum = R 01 + R12 + R23+…+R ns
By adjusting the reflective index and the thickness of each
layer, Rsum can be minimized, and an ARC can be obtained.
3. Techniques for the fabrication of superhydrophobic
surfaces
(5)
The roughness of a surface plays a key role in controlling its
of the surface. A surfaces can be rendered hydrophobic by using
two main pathways: a) Making a rough surface from a low surface
energy material; and b) Making a rough surface and modifying the
(6) surface with a material of low surface energy [47]. A classification

Fig. 7. A flowchart explaining the summary of various materials and fabrication procedures.
 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623
Fig. 8. (a) SEM images of rough fluorinated materials to form superhydrophobic surfaces (a) The honeycomb-patterned film cast from a solution of the polymer shown in the
inset under humid conditions [50] (b) SEM images of the composite fluorocarbon coating surfaces: (b) PTFE/FEVE, (c) TiO2-PTFE/FEVE and (d) Modified TiO2-PTFE/FEVE [53].
of fabrication techniques of superhydrophobic surfaces using a
variety of materials is shown in Fig. 7.
3.1. Roughening a low surface energy material
3.1.1. Fluorinated polymers
As fluorocarbons possess extremely low surface energies they
are widely used to produce superhydrophobic surfaces [48–50].
Zhang et al. [48] fabricated a superhydrophobic polymer film by
stretching PTFE. This hydrophobic polymer is composed of fibrous
crystals with a large proportion of vacant spaces in the polymer
surface, which are responsible for cleaning of the surface. Shiu
et al. [49] obtained a rough surface with a WAC of 168° by treating
a Teflon film with plasma oxygen. Fluorinated polymers cannot be
used directly owing to their limited solubility and it is preferred to
use them as a blend [51] or linked [52] with other materials to
form superhydrophobic surfaces. Yabu and Shimomura [51] fab-
ricated a porous superhydrophobic membrane using a solution of
a fluorinated block polymer (Fig. 8a), which shows transparent
characteristics owing to the small pore diameter. Zhou et al. [53]
developed a hydrophobic composite by incorporating modified
TiO2 nanoparticles and micropowders of a hydrophobic material
(PTFE) dispersed in a fluorocarbon resin. The composite material is
sufficiently hydrophobic with a WAC of 133° and the surface free
energy of the composite coating is 4.11 mJ/m2. The SEM images in
Fig. 8 show the effects of the inclusion of TiO2 nanoparticles in the
coatings and the modification of TiO2 nanoparticles. The PTFE/
FEVE composite coatings form a relatively smooth surface, as
shown in Fig. 8b. Meanwhile, Fig. 8c shows an apparent biphase
interface and numerous microsized agglomerates because for un-
modified TiO2, due to the ready “agglomeration” of TiO2 nano-
particles owing to their high surface energy. The uniform mor-
phology of the coating surface shown in Fig. 8d is attributed to the
reduced surface energy of TiO2.
609
3.1.2. Silicones
Polydimethylsiloxane (PDMS) also possesses a low surface en-
ergy due to its intrinsic deformability and hydrophobic properties.
Several methods have been employed to form superhydrophobic
surfaces using PDMS [41,54,55]. Khorasani et al. [54] obtained a
surface with a WCA of 175° by treating PDMS with a CO2 -pulsed
laser as the excitation source. High porosity and chain ordering of
PDMS are considered as basic reasons for the high WCA of treated
PDMS. Jin et al. [55] fabricated a rough surface of PDMS with a
WCA of 160° and a sliding angle lower than 5° using the laser
etching technique. Zhang et al. [56] produced superhydrophobic
coatings by mixing of TiO2 nanowires with polydimethylsiloxane,
which showed almost complete wet self-cleaning of dirt particles
with water droplets. Ma et al. [57] used electrospinning of block-
blended PS-PDMS and polystyrene homopolymer to produce su-
perhydrophobic membranes with a WCA of about 163° (Fig. 9).
Enhancement of the hydrophobic properties due to the inherent
hyrdophobicity of PDMS surfaces combined with the small dia-
meter of the fibers (150–400 nm) increases the WAC and the
roughness of PDMS.
Fig. 9. A SEM image of a PS-PDMS/PS electrospun fiber mat and the droplets on it
[57].
610 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623

3.1.3. Organic materials

Non-wetting and superhydrophobicity can also be introduced
by using paraffinic hydrocarbons like fluorocarbons and silicones.
Many researchers have used organic materials to produce super-
hydrophobic surfaces. Lu et al. [58] produced a highly porous and
superhydrophobic polyethylene surface by controlling its crystal-
lization mechanism. They obtained a WCA of 173° with a floral
crystal structure (shown in Fig. 10a) by adding a nonsolvent (cy-
clohexanone) to the PE/xylene solution. Jiang et al. [59] fabricated
a superhydrophobic surface containing microparticles and nano-
fibers (shown in Fig. 10b) using electrostatic spinning and spraying
of PS in dimethylformamide (DMF). Other organic materials like
polyamide [60] polycarbonate [61] and alkylketene dimer [62]
have also been used to make self-cleaning surfaces. For example,
Yan et al. [63] fabricated a poly(alkylpyrrole) superhydrophobic
Fig. 11. A SEM image of aligned ZnO nanorods prepared by a two-step solution
film, which is stable when exposed to environmental conditions,
approach [64].
using electrochemical polymerization.
3.2.1. Lithography
3.1.4. Inorganic materials The structure and morphology of surfaces can be controlled
Some inorganic materials also reveal superhydrophobic prop-
using lithography. Researchers have fabricated surfaces with many
erties. For example, researchers have used a two-step solution
different patterns containing square pillars, indented square pots
method [64] to produce ZnO nanorods, which show super-
and stand arc-shaped pots with varying length and diameter using
hydrophobicity owing to the low surface energy of the (001) plane,
lithography [65–67]. The relationship between the structure and
as determined by XRD, and are shown in Fig. 11. When the ZnO
hydrophobicity/wetting state depends on the features of the self-
film is exposed to UV radiation, hydroxyl groups adsorb on the
clean surfaces [68,69]. Bhushan et al. [70] fabricated micro-, nano-,
ZnO film due to the generation of electron–hole pairs and the
and hierarchical structures by replicating a micro-patterned silicon
superhydrophobic film is transformed into a superhydrophilic
surface using epoxy resin. They then obtained a nanoscale struc-
film. It becomes superhydrophobic again when exposed UV irra-
ture with hierarchical architecture by the self-assembling of al-
diation (dark storage) for seven days.
kanes (e.g., n-hexatriacontane). Lithography has been coupled
with wet or chemical etching to fabricate dual-scale super-
3.2. Fabricating a rough substrate and modifying it with low surface hydrophobic surfaces. Shieh et al. [71] fabricated a super-
energy materials hydrophobic Si surface containing nanograss characteristics with
nanopillar arrays introduced using e-beam lithography with dry
Preparation of superhydrophobic surfaces by a totally different etching followed by hydrogen plasma etching. Finally, the surface
strategy, i.e., fabricating a rough substrate first and then modifying was hydrophobized with a CHF3 plasma. Sung et al. [72] fabricated
it with a low surface energy material, decouples the surface nanoscale pillar patterns on thermal shrinkage films (TSFs) using a
wettability from the bulk properties of the material and enhances similar strategy. They used nanoimprint lithography to fabricate
potential applications of superhydrophobic surfaces. The fabrica- the surface and then it was coated with a self-assembled mono-
tion technique in this category can be divided into two ap- layer to minimize the surface energy of the structured surface. The
proaches, i.e., top-down and bottom-up methods. Top-down surfaces fabricated using this technique show good hydrophobic
method includes lithography, template-based techniques, and characteristics with a WCA of about 105°.
plasma treatment. Bottom-up method includes chemical deposi-
tion, layer-by-layer (LBL) deposition, and colloidal assembly. In 3.2.2. Template method
some techniques, combined top-down and bottom-up methods, This method, which uses a template to produce a patterned
such as phase separation, electrospinning, and polymer solution surface, is an efficient technique to produce superhydrophobic
casting are used. surfaces [73–76]. When the template is removed material grows in

Fig. 10. SEM images of (a) Floral like crystal structures of polyethylene [58];(b) PS surface prepared by electrostatic spinning and spraying [59].
 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623
the cavities left by the template. A platinum nanofiber array has
been used to form a superhydrophobic surface on a Ti/Al substrate.
Qu et al. [77] fabricated a platinum nanofiber array by electro-
deposition of platinum into the pores left by an AAO template on
the substrate following the removal of the template in alkaline
solution. They obtained a network of nanofibers with a highly
rough surface and treated it with fluoroalkylsilane to obtain a
surface with a WAC of 158°. Sheng et al. [78] fabricated super-
hydrophobic nano-structured high density polyethylene (HDPE)
by extrusion inside an AAO template. They were able to fabricate
numerous superhydrophobic HDPE nanofiber surfaces with a WAC
of about 150° (shown in Fig. 12) by tuning the AAO diameter and
pressure used for extrusion.
3.2.3. Electrospinning technique
Electrospinning allows the continuous formation of fibers with
diameters in the order of nanometers. Natural polymers, synthetic
polymers, and polymer composites can be made super-
hydrophobic by using this technique [79]. Acatay et al. [80]
showed that the electrospun film containing preponderantly
beads can be converted into one with fibers by raising the viscosity
of the polymer solution. Morphology of films plays a crucial role in
determining their wetting behavior. Studies also reveal [80] that
surfaces with a structure containing beads is more hydrophobic
than the surfaces containing fibers. Consequently, a hydrophobic
surface made from a low molecular weight polymer shows a
higher WCA than that of a surface fabricated from a high mole-
cular weight polymer. Low molecular weight polymers form bead-
like structures and the highest WCA achieved for a low molecular
weight polymer film is about 167°. Ma et al. [81] achieved a WCA
of 175° by combining electrospinning of poly(caprolectone) (PCL)
with initiated chemical vapor deposition (i-CVD) of polymerized
perfluoroalkyl ethyl methacrylate (PPFEMA). The hierarchical sur-
face thus obtained exhibits extremely low surface energy with a
stable superhydrophobicity. Gu et al. [82] prepared ultrathin su-
perhydrophobic–superoleophilic fibrous poly(vinylidene fluoride)
(PVDF) membranes for low-cost, high-efficiency water-oil se-
paration using electrospinning. The ultrathin electrospun fibrous
PVDF membranes exhibit a high WAC of up to 153° and a nearly
zero oil (diesel) contact angle.
3.2.4. Sol–gel method
A variety of materials can be made hydrophobic/super-
hydrophobic by using the sol-gel process [83,84]. Shirtcliffe and
his co-workers [85] fabricated porous foams using organo-trie-
thoxysilanes, which show a transition from superhydrophobic to
superhydrophilic when subjected to temperature treatment
Fig. 12. SEM images of (a) top and (b) cross-sectional HDPE nanofiber surface, (c) 3 mL drop on the superhydrophobic HDPE surface; (d) Scheme to fabricate HDPE nanofibers
[78].
611
(Fig. 13a). Hikita et al. [86] fabricated a sol-gel film (Fig. 13b) with
super liquid-repellency using colloidal silica particles and fluor-
oalkylsilane as the starting materials by hydrolysis and con-
densation of alkoxysilane compounds. Latthe et al. [87] fabricated
a transparent superhydrophobic surface using a modified silane
gel (modification accomplished with fluorinated silane) rather
than blending low surface energy materials in the sols.
3.2.5. Chemical vapor deposition (CVD)
In this method, chemical precursors in the vapor phase react
with substrates to form a thin film. CVD can be used to create
rough surfaces with a large WCA [88–90] and deposit a thin layer
of a hydrophobic compound on a rough surface [91,92]. Su et al.
deposited InGaN nanotip arrays using CVD (Fig. 14a and b) [93]
and modified them with octylphosphonic acid (OPA) to obtain a
superhydrophobic surface with a WCA of 154°. They also showed
that UV–vis light can be used to achieve a transition between su-
perhydrophobicity and hydrophilicity. Su et al. also fabricated ZnS
nanorods with a hierarchical structure by chemical vapor deposi-
tion on Au-coated silicon substrates [94]. The reticular structure of
ZnS is shown in Fig. 14c and d, in which the top layer is composed
of nano-sheets and slim nanowires. The WAC of this dual nano/
micro-hierarchical structure is more than 150°. Ishizaki et al.
modified magnesium alloys using microwave plasma-enhanced
chemical vapor deposition (MPECVD) using trimethyl methox-
ysilane as the starting material [95]. The roughness of the film
increases with deposition time and the surface morphology of Mg
alloys indicates granular particles and nanometer sized pores,
which imparts the anti-wetting properties to the surface. The WAC
increases as the time of deposition is increased to reach 150° over
20 min of deposition.
3.2.6. Layer-by-layer (LbL)
This technique allows the deposition of oppositely charged
layers composed of polyelectrolytes on glass substrates. Generally,
the substrate is alternatively dipped into the relevant solution, and
excess solution remaining after each treatment removed by
washing with a solvent, to form LBL structures consisting of po-
sitively or negatively charged layers. This method also allows the
fabrication of structures containing nanoparticles [21,96–101].
Amigoni et al. fabricated hierarchical composite surfaces of silica
nanoparticles using the LBL approach [96]. Sun et al. [102] as-
sembled silica nanoparticles on a PDMS substrate with a honey-
comb pattern. This method allows the assembly of different bi-
layers to fabricate superhydrophobic surfaces with both high and
low adhesion, indicating that different levels of nano-to-micro-
structural hierarchy can be obtained. Kim et al. [103] produced
612 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623

hierarchical structures using spontaneous wrinkling phenomenon nanoparticles using LBL assembly. The surface is spontaneously
of a polyelectrolyte multilayer. They produced a composite mate- wrinkled due to the compressive stress caused by the accumula-
rial composed of a polyelectrolyte multilayer (PEM) containing Ag tion of Ag nanoparticles in the PEM matrix. Cations exchange with

Fig. 13. SEM images of self-cleaning surfaces prepared by sol–gel process (a) Methyltriethoxysilane (MTEOS) sol–gel foam [85]. (b) AFM image of super hydrophobic surface
prepared by sol – gel method [86].

Fig. 14. SEM images of InGaN sample (a) Top-view and (b) side view (c) the cross-sectional and (d) top-view of the deposited ZnS product [94].

Fig. 15. SEM images of plasma-ashed surface [103].

 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623 613

those in the PEM layer when it is dipped in a silver acetate solu- Table 1
tion. The Ag þ ions are incorporated into the PEM matrix and Summary of fabrication techniques of superhydrophobic surfaces.
subsequently reduced to obtain Ag nanoparticles. Finally, they
Method Materials WCA Ref.
removed the polymer phase using a plasma-ashing procedure. The
wrinkles on the surface are of micrometer size, while the Ag Oxygen plasma PTFE 170° [106]
structures formed nanometer sized flake-like topographies Oxygen plasma PTFE 152° [114]
(Fig. 15). The surface displayed superhydrophobicity with a WCA of Plasma fluorination PBD 175° [107]
Plasma deposition PET 172° [115]
170° when treated with a fluorinated compound. CF4 plasma PBD 175° [114]
CF4 plasma Si(100)/quartz 160° [116]
3.2.7. Plasma treatment Plasma deposition TFE 150
165° [117]
Plasma treatment process, which can be classified into plasma Plasma polymerization MDS 160° [118]
Phase separation (Mixed solvents) i-PP 160° [112]
etching and plasma polymerization [104], is a simple and effective
Phase separation (Crystallization) LDPE 173.08° [58]
technique to fabricate superhydrophobic surfaces. Washo, who Template PDMS 155° [119]
introduced the oxygen plasma treatment to produce self-cleaning AAO template paraffin 158° [120]
surfaces [105], fabricated superhydrophobic surfaces of poly(tetra Template-wetting PS/Al 162° [121]
fluoroethylene) (PTFE) with a WCA of 165
170°. Subsequently, Electrospinning PS/PVC/TiO2 178° [122]
Electrospinning PTFEMA 154° [123]
Morra et al. and Woodward et al. used plasma treatment to fab- Electrospinning Teflon AF 151° [124]
ricate superhydrophobic surfaces of fluoropolymers [106,107]. Electrospinning PVDF/FSM 170.2° [125]
Morra et al. [106] used the plasma etching process to produce Sol
gel Al2O3 165° [126]
porous PTFE surfaces with high roughness and good stability. Sol
gel PET/Al2O3 150° [127]
Sol
gel MTMS 173° [128]
Fresnais et al. [108] used argon plasma treatment to fabricate
Sol
gel Metal alkoxides 157° [129]
rough polypropylene (PP) surfaces in the presence of PTFE with a Sol
gel Silica 164° [130]
WCA of 172°. Layer-by-layer PVDMA/PEI 155° [131]
Plasma polymerization is another important technique used to Layer-by-layer Silica NPs 150° [96]
fabricate superhydrophobic surfaces. McCarthy and co-workers Layer-by-layer FAS/PS/silicon 160° [132]
Layer-by-layer SiO2 /silicon 157° [133]
[109] fabricated a superhydrophobic surface with a WCA of 174° by Plasma enhanced CVD CNTs 161.7° [134]
plasma polymerization of 2,2,3,3,4,4,4-hepta flouorobutyl acrylate One-step vacuum evaporation PFA 4150° [135]
(HFBA) on a smooth PET surface. Schreiber et al. [110] fabricated a Thermal evaporation Waxes 163° [136]
superhydrophobic surface of hexamethyldisiloxane by low tem- Vapor phase transport process Carbon 160.7° [137]
perature plasma polymerization, which has a WCA of 180°. Kang
and co-workers [111] fabricated a superhydrophobic film with a
WCA of 174° by the plasma polymerization of allypenta fluor-
obenzene (APFB) on plasma-pretreated polyimide (PI) films.

3.2.8. Phase separation methods

Phase separation approach is a simple method for constructing
superhydrophobic surfaces with rough structures by utilizing the
instability of a multicomponent mixture, especially polymers. As
the instability is introduced using two immiscible solvents, the
phase separation approach can also be identified as a solvent-non-
solvent method. Erbil et al. formed a gel-like porous super-
hydrophobic film on a variety of substrates (such as glass slides, Al
foil, stainless steel sheets, etc.) via vacuum heating, utilizing PP as
the raw material, and p-xylene as the solvent. They used MEK,
cyclohexanone, and isopropyl alcohol as non-solvents [112]. The
results demonstrate that the polymer concentration, temperature,
and the non-solvent have an effect on surface roughness. Subse- Fig. 16. Classification of fabrication techniques of transparent superhydrophopic
surfaces.
quently, Han and co-workers used the phase separation method to
prepare superhydrophobic polymer surfaces [58,113]. Han and co-
workers [58] fabricated LDPE superhydrophobic surfaces with detail here. Fig. 16 shows the classification of techniques used to
different structures by the adjustment of the crystallization be- fabricate antireflective surfaces.
havior of LDPE. Solvent evaporation at low temperature results in
the increase of the crystallization time and the nucleation rate, and 4.1. Conventional fabrication techniques: bottom-up method
thus increasing the CA.
Many methods including physical, chemical, and the combi- 4.1.1. Sol–gel process
nation of physical and chemical methods are currently being de- In the sol-gel process, inorganic salts or metal alkoxides are
veloped to obtain superhydrophobic surfaces in a simple and an exposed to organic solvents as the starting materials to form
environment-friendly manner. Table 1 summarizes these in- polymers consisting of the metal-oxide-metal bond. A variety of
novative techniques applied to different substrates. coating techniques, such as dip coating, spin coating, and meniscus
coating are employed to deposit sol-gels. These techniques will be
discussed in detail here.
4. Methods of fabrication of antireflective surfaces
4.1.1.1. Dip coating. The desired solution is prepared and substrates
A majority of the antireflective surfaces is fabricated using the are dipped and withdrawn at a controlled rate. Four steps, in-
top-down or bottom-up technique. Unconventional techniques are cluding immersion of the substrate, deposition of materials on a
also used to fabricate antireflective surfaces which are discussed in substrate, withdrawing of the coated sample, and drying, are
614 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623

Fig. 17. Demonstration of (a) dip coating and (b) spin coating, (c) technique of meniscus coating [46].

involved in the process. The steps of the dip coating process are
shown in Fig. 17a.
4.1.1.2. Spin coating. A thin film of the desired materials can be
deposited on flat or curved substrates using this technique. The
material is deposited while spinning the substrate at a high an-
gular speed, typically 3000 rpm. The thickness of the films de-
pends on the rotation speed of the substrate. The steps of the spin-
coating process are shown in Fig. 17b.
4.1.1.3. Meniscus coating. In this technique, the coating material is
deposited on the substrates through the pores of an applicator. The
key requirement of the technique, which can produce micron thick
films on a substrate, is to maintain the menisci of the coating
material between the applicator and the substrate. Typical me-
niscus coating steps are shown in Fig. 17c.
Sol–gel technique is widely used to fabricate porous ARCs. The
required pore diameter is attained by adjusting/varying the mixing
ratio of the precursor materials in the solvent [138]. For example,
the spin coating method allows the fabrication of a porous poly-
methyl-methacrylate (PMMA) by the use of polystyrene and
polymethyl-methacrylate in tetrahydrofuran (THF) and treating
the spin-coated film with cyclohexane to dissolve polystyrene.
Porous PMMA has a refractive index in the range of 1.225 and
1.285 with a transmittance of 99.7% [105]. Interference type ARCs
comprising of TiO2/SiO2-TiO2-SiO2 on glass [8,139–141] are used as
contrast enhancement filters for monitors. The SiO2 coatings de-
posited on low emissivity glazing (windows) by dip-coating result
in a 10% increases in transmittance in the visible region.
However, the un-reacted or un-removed solvent in films pro-
duced by the sol-gel method can affect the quality of the ARCs.
Furthermore, it is difficult to control the film thickness in the sol-
gel process.
4.1.2. Glancing angle deposition
This technique is similar to that of vapor deposition, in which
the vaporized material is condensed on substrates. An improved
version of this technique is the glancing angle deposition (GLAD),

Fig. 18. SEM images of (a) GLAD technique (b) modified GLAD technique [142] (c) slanted microstructure [144] (d) zigzag morphology [144] (e), helix morphology [144]
(f) double MgF2 layers with a capping MgF2 layer [144].
 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623
Fig. 19. Different alternative lithographic processes, (a) Injection molding, (b) solvent-assisted molding, (c) hot embossing, and (d) soft lithography [159,160].
in which the vapor flux is applied at an angle on a rotating sub-
strate. The advantage of this approach is that the thin film grows
with a gradually decreasing density, thereby increasing the por-
osity due to “atomic-shadowing” (Fig. 18a). This technique also
allows a high degree of control over the morphology of the re-
sulting nanostructure [142]. The porosity of the film depends on
the oblique angle of application of the deposited material, and
thus, is difficult to control. In order to overcome this shortcoming,
Robbie [142] proposed an improvement, in which the substrate is
subjected to types of motions; rotation about the axis perpendi-
cular to the substrate and rotation about an axis shown in Fig. 18b.
In the sculptured thin film (STF) deposition method [143], the
GLAD technique has been modified by various means to fabricate
films with slanted, chevron, helix, and vertical morphologies as
well as nanostructures with other morphologies (Fig. 18(c)–(f)).
4.1.3. Chemical vapor deposition
Chemical vapor deposition is one of the most extensively used
techniques to fabricate antireflective surfaces [145,146]. In this
technique, precursor materials undergo chemical reactions prior to
deposition on the hot substrate. Yang et al. [147] fabricated verti-
cally aligned carbon nanotubes (VA-CNTs) using water assisted
CVD to produce an efficient light absorbing material (greater than
00 nm) with a low density of 0.01–0.02 g cm
3.
Similarly, silicon nitride is the preferred anti-reflective material
to deposit on silicon solar cells using the plasma enhanced CVD
(PECVD) method, which is the most frequently used method in
industry . PECVD can also be used to apply multipurpose coatings
[148,149]. For example, antireflective, anti-scratch, and self-
cleaning properties (of SiOxCyHz and TiO2) can be combined on a
single substrate through this method [148]. In this method, the
precursor molecules are decomposed using a pulsed microwave-
induced plasma and for example, can have an adhesion layer fol-
lowed by an anti-reflective layer (TiO2/SiO2) and/or an anti-scratch
layer (SiO2).
4.2. Conventional fabrication: top-down method
4.2.1. Etching
Selective removal or dissolution of material from the substrate
is known as etching. The method can be divided into two main
categories, i.e., wet etching and dry etching. The dissolution of
615
material using a chemical solution is described as wet etching,
which is a fast and precise etching method. Typically, the solution
is water-based because water is corrosive to glass to some extent.
Though the dissolution mechanism remains unclear, there are
some reactions that are widely accepted to occur during dissolu-
tion: (1) hydration and hydrolysis; (2) ion-exchange; and (3) net-
work reconstruction. In most glass structures, the voids between
oxygen and the hydration sphere are not large enough to allow
water molecules to penetrate into the surface. Thus, the hydrolysis
reaction may be accompanied by a network dissolution by re-
leasing water-soluble species such as Si(OH)4 into solution and
leaving large voids for further reaction. By dehydration the silanol
groups (Si–OH) can condense into a Si–O–Si network, which leads
to a reconstruction of the glass surface, forming a porous material
[150,151]. Liu and He [152] reported a method that uses water to
create a hierarchical superhydrophobic surface, which involves a
relatively high process temperature (4 160 °C). Recently, Qi et al.
[153] demonstrated a simple method for creating hierarchical
pyramidal structures on an entire silicon wafer using alkali etching
at low temperature (65 °C).
Dry etching is currently used in the semiconductor industry
due to its unique ability, as compared to wet etching, to perform
anisotropic and directional etching or to create structures with a
high aspect ratio (e.g., deep via holes or capacitor trenches). Ty-
pically, the bombardment of ions (plasma of a reactive gas such as
fluorocarbons, oxygen, chlorine, and boron trichloride) is used to
dislodge portions of the material from the exposed surface when
masked patterns are used. And other benefits of dry etching are
reduced chemical hazards, treatment of wastes, and contamina-
tion, and ease of process automation and tool clustering [154].
4.3. Unconventional fabrication
4.3.1. Lithography
Recently, researchers have explored unconventional nanofab-
rication techniques, such as colloidal lithography [155,156], na-
noimprint lithography [157], and soft lithography [158], based on
molding, embossing and printing. Fig. 19 shows the fundamentals
of some of the techniques used in lithography [159,160], which
emerged due to their high throughput and cost-effective process
capabilities. They have been applied for the fabrication of ARCs,
microchips, and micro-electromechanical devices. However, these
616 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623

Fig. 20. Description of R2R MAP process concerning replication on PET [163].

techniques require expensive tools such as those used in deep-UV
projection lithography and electron-beam lithography.
Currently, photolithography is one of the most widely used top-
down techniques for the fabrication of antireflective and self-
cleaning coatings [161,162], owing to several advantages, such as
full wafer processing and short exposure time. However, draw-
backs such as the limited resolution and the limited applicability
for pre-existing topographies or curved substrates still exist, re-
quiring further study.
4.3.2. Micro replication technique
Fig. 20 shows the roll-to-roll micro-replication process (R2R
MRP), which involves replication of conical “moth's eye” nanos-
tructures on thermoplastic polymer film [163]. The main template
made of PC possesses an array of conical moth's eye structures,
which produces a tapered-hole array on polyvinylchloride (PVC)
when transferred to PVC film at 100 °C and 1 atm pressure. This
PVC template is then used to replicate the nanostructures on glass
substrates. A key finding of this study is that double-sided pat-
terned glass shows a transmittance of 96% as compared to 94% for
the single-sided glass. The ability to fabricate surfaces with ARCs
on a large scale is one of the main advantages of the micro re-
plication technique.
Table 2 summarizes the many innovative techniques that have
been developed to produce antireflective surfaces using different
substrates.
5. Techniques to make transparent (antireflective) super-
hydrophobic surfaces
High transparency is crucial to maintain the performance of
optical equipment and devices, such as windows, lenses, and solar
panels. As many of them are constantly exposed to various at-
mospheric conditions, it is necessary to apply self-cleaning coat-
ings that can prevent microbial growth, fouling, and corrosion.
To attain both high transparency together with super-
hydrophobicity the following are required:
(1) a rough surface with ridges and valleys of size o100 nm;
(2) a surface topography that could trap air within, which is often
achieved via hierarchical structures; and (3) a passivation layer
with low surface energy coated on the rough texture [178].
Transparent superhydrophobic surfaces can be fabricated by
using two main approaches: top-down fabrication and bottom-up
assembly or a combination thereof.
5.1. Top-down methods
Several top-down fabrication procedures have been used to
fabricate nanostructures less than 100 nm in size. The most com-
mon are plasma etching and soft lithography. These methods are
discussed in detail here.
5.1.1. Plasma etching
Ogawa et al. [179] used the plasma etching process to fabricate
transparent superhydrophic surfaces for the first time. They

Table 2
Fabrication techniques of antireflective surfaces with technical details.

Substrate Fabrication method AR material AR mechanism Reflectance Wavelength (nm) Ref.

Glass Dip coating SiO2 Sol-gel Porous ARC 0.15% 480–500 [11]
Spin coating Aggregated SiO2 particles Porous ARC o1% 567–573 [164]
Electron-beam evaporation TiO2 Quarter-Wavelength ARC ∼2% 550 [165]
Magnetron sputtering ITO Quarter-Wavelength ARC ∼10% 540–560 [166]
Spin coating Liquid crystal polymer Porous ARC 0.1% 632.8 [167]
Layer-by-Layer deposition TiO2 /SiO2 Multilayer ARC o1% 400–700 [168]
Wet chemical processing SiO2 Quarter-Wavelength ARC ∼1% 520 [169]
Electrostatic attraction TiO2 /SiO2 Porous ARC o1% 530 [170]
Nanoimprint lithography AAO membranes Moth-eye ARC o1% 500–700 [171]
Nanoimprint lithography PVC template Moth-eye ARC ∼5% 550 [172]
Thermal nanoimprint lithography Perfluoropolyetherand Moth-eye ARC o3% 612 [173]
Dry etching Ag Nanomask Moth-eye o1% 200–500 [174]
Quartz Spinning or immersion and draining coating SiO2 Film deposited from Polymeric Porous ARC ∼1% 355 [12]
Reactive ion etching Micellar block copolymer Moth-eye ARC o1% – [175]
Polystyrene Layer-by-Layer PAH/PAA Multilayer ARC 0.01% 650 [9]
PET Roll-to-Roll UV replication Urethane acrylate and methacrylate Moth-eye ARC o2% – [176]
Polyurethane Soft imprint lithography Perfluoropolyether and polyurethane Moth-eye ARC ∼0.5% 500 [177]
PMMA Layer-by-Layer Hollow silica Nanoparticles Quarter-wavelength ARC 0.5% 300–650 [7]
 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623
observed that nanocraters are randomly distributed on the glass
substrate when subjected to plasma etching. They used mixed
CHF3 and O2 gases for plasm etching and the glass displayed hy-
drophilicity owing to the existence of many hydroxyl (–OH) groups
on the substrate surface after etching. The surface becomes su-
perhydrophobic with a transparency of 92% when made hydro-
phobic with heptadecafluorodecyltrichlorosilane (HFTS). Teshima
et al. [180] used a similar method to form a high density of na-
nohairs of sub-100 nm in diameter and  500 nm in height on a
poly(ethylene terephtalate) (PET) sheet using an oxygen plasma.
Vourdas et al. [181] formed PMMA nanohair clusters with100–
200 nm in height and 80–400 nm in width using a mixture of pure
O2 and C4F8 gases. In both structures, superhydrophobicity with a
high transparency of  90 were attained after hydrophobization of
the nanohairs by low-temperature plasma enhanced chemical
vapor deposition (PECVD) using fluorosilane.
5.1.2. Soft lithography
Soft lithography is a low cost and work-bench friendly process,
which involves molding, stamping, and transferring. This techni-
que has received a lot of attention in the past two decades to
pattern a variety of microstructures. Kim et al. [182] fabricated
propoxylate triacrylate (PPT) nanopillars ( 50 nm in diameter and
100 nm in height) on an anodic AAO membrane using soft li-
thography. Notably, they introduced a thin film of monoglycidyl
ether-terminated polydimethylsiloxane (PDMS) as both a super-
hydrophobic coating material and as anti-adhesion release layers
on the AAO membrane. The nanopillars showed super-
hydrophobicity with a transparency of more than 90%. Im et al.
[183] fabricated a transparent superhydrophobic surface from
PDMS using two consecutive replications in combination with 3-D
backside diffuser lithography [184]. They improved the super-
hydrophobicity and transparency of PDMS further by coating the
surface with low surface energy fluoropolymer Teflon.
5.2. Bottom-up texturing
Bottom-up self-assembly processes are used to produce trans-
parent superhydrophobic surfaces on a large scale. Some im-
portant self-assembly methods such as microphase separation,
templating, and nanoparticle assembly are described here.
5.2.1. Microphase separation
Yabu and Shimomura [51] fabricated a transparent super-
hydrophobic surface using microphase separation. They were able
to form a honeycomb template by depositing equimolar solutions
of fluorinated acrylate and methyl methacrylate on a glass sub-
strate and then exposing it to humid air at room temperature.
Water droplets which condense on the treated surface, subse-
quently pack into the honeycomb structure due to the capillary
forces. Evaporation of the organic solvent provides a porous film.
The pore size (200–300 nm to 5 mm) can be controlled by changing
the thickness of the liquid film (100 mm to 1 mm). The transmit-
tance of the porous film obtained by this method is 80% in the
visible region (300 nm-pore film). Levkin et al. [185] fabricated a
porous poly(butyl methacrylate-co-ethylene dimethacrylate) using
inert solvents (e.g., cyclohexanol and 1-decanol) as porogens,
which are miscible with the monomers but immiscible with the
crosslinked polymer network during the in situ copolymerization.
When the crosslinked polymer chains reach a critical size, the
porogens become phase separated from the matrix, resulting in a
highly porous structure consisting of interconnected globules. The
average globule size of the polymer network can be reduced from
486 nm to 45 nm by increasing the volume ratio of inert solvents
(total of 50%) in the polymerization mixture while keeping the
mass of the monomer and crosslinker unaltered. The porous film
617
can also be ground into powders to coat different substrates, in-
cluding rubber gloves and tissue paper. However, the super-
hydrophobicity is lost due to the decrease of the pore size and
roughness. By UV grafting 2,2,3,3,3-pentafluoropropyl methacry-
late with an average globule size of 48 and 45 nm onto the na-
noporous films, superhydrophobicity is regained with a slight
decrease of transmittance (by 5–10%) in the visible region. Kato
and Sato [186] fabricated a transparent superhydrophobic coating
with transparency greater than 95% for glass and fabric through
polymerization-induced phase separation (PIPS) between poro-
gens and the polymer network.
5.2.2. Nanoparticle assembly
Surface roughness is controlled by nanoparticles (NPs) to a
large extent [187–191]. Silica NPs are preferred over other NPs,
such as TiO2 and ZnO for the fabrication of superhydrophobic films
because they cost less and their size can be tuned. They are par-
ticularly attractive to generate transparent superhydrophobic
surfaces because most of the NPs with size  100 nm are readily
available commercially. NPs are appropriately coated on flat and
microstructured substrates over large areas by different coating
methods, such as spin coating, dip coating, and spray coating.
Morphology of the assembled nanoparticles is determined by the
attractive forces, such as van der Waals interactions and depletion
interactions, and repulsive forces, such as electrostatic repulsion
between charged particles and steric hindrance owing to a thin
coating of polymer on the surface of particles. In addition, dual-
scale micro-/nanoroughness can be attained by selecting different
coating methods, and controlling the coating order, solvent, con-
centration, and solvent evaporation rate, which is difficult in a top-
down process.
Cao and Gao [192] deposited multilayers of silica NPs (20 nm)
and polystyrene (PS) NPs (60 nm) using the layer-by-layer tech-
nique. The polystyrene nanoparticles act as a sacrificial material,
which can be removed by heating at 550 °C for 4 h, leaving cavities
in the film. A transparent (transmittance4 90%) super-
hydrophobic surface (WCA4 160°) is attained after treating the NP
film with TFCS. However, random distribution of silica NPs is cri-
tical to achieve superhydrophobicity [193].
6. Transparent superhydrophobic surfaces for solar collectors
and photovoltaic modules
Crystalline silicon is the most important material in terms of
the fabrication of solar cells. However, a common shortcoming of
doped silicon is its high RI, which causes more than 30% of the
incident light to be reflected back from the surface [194,195]. The
reflection loss at surfaces or interfaces, which negatively affects
the energy conversion efficiency of solar cells, is a significant
disadvantage. In order to overcome this problem, scientists have
devised a number of strategies to reduce the reflection of sunlight
from the surface of solar cells, such as appending coatings with
intermediate RI [196], embedding metallic nanoparticles to induce
surface plasmonic scattering [197], micro-texturing [198], and
forming absorption nanostructures with photonic crystals [199].
Bernhard et al. discovered that the moth cornea, with uniformly
arrayed conical protuberances, has the potential to prevent surface
reflection for the entire solar radiation spectrum in 1967 [200].
Since then, researchers have fabricated a variety of films of in-
organic, polymeric, and inorganic/polymer hybrid materials using
diverse techniques and assembled some of them on solar cells to
perform detailed performance tests. Simultaneously, researchers
have also used compounds, such as ITO, SnO2, SiO2, MgF2, ZnS and
ZnO, as ARCs on crystalline silicon solar cells [201]. The coatings
can raise the efficiency of silicon-based PV devices by reducing the
618 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623

Fig. 21. Measured specular transmittance spectra for the bare glass substrate and
the PDMS (P380)/glass as a function of incident light angle (θi) for un-polarized
light at λ¼ 350–800 nm. The SWT of calculated total transmittance spectra for the
corresponding samples is shown in the inset [202].

light energy lost due to reflection.

Glass is one of the most important optical substrates. Although
the reflective loss is ca. 4% from each air/glass interface, which is
not as significant as that of silicon, it could still degrade the per-
formance of optical devices, especially when multiple components
are involved [9]. The use of glass with ARCs as covers for solar
thermal collectors increases the efficiency of the system. For ex-
ample, calculations have shown that the yearly energy output in a
solar heating plant, where the temperature of the solar collector
fluid is 100 oC, can be increased by about 20% by using ARCs on the
solar glass covers. Jung Woo et al. [202] employed Poly-di-
methylsiloxane (PDMS) as an antireflection layers on glass sub-
strate. They found that for a period of 380 nm, PDMS films lami-
nated on glass substrates exhibit a hydrophobic surface with a
water contact angle (θCA) of E 120° and solar weighted trans-
mittance (SWT) of E 94.2%, both significantly higher than those
(θCA E36° and SWTE 90.3%) of bare glass substrates (shown In
Fig. 21a). By employing PDMS films with a period of 380 nm on
glass substrates for organic solar cell, an enhanced power con-
version efficiency (PCE) of 6.19% is obtained mainly due to the
increased short-circuit current density (Jsc) of 19.74 mA cm
2
compared to the solar cell with the bare glass substrates
(PCE ¼5.16% and Jsc ¼17.25 mA cm
2), as shown In Fig. 22.
A water-repellent perovskite solar cell was developed based on
anti-reflective lotus leaf-inspired hierarchical pyramidal arrays
with enhanced self-cleaning characteristics was developed
by Kang et al. [203]. The PCE of CH3NH3PbI3 perovskite solar cell
was improved from 13.12% to 14.01% by employing PDMS film on
the perovskite solar cell due to an anti-reflection effect (shown, in
Fig. 23). Moreover, the PDMS film adhered to the perovskite solar
cell demonstrated excellent super-hydrophobicity, which makes
the perovskite solar cell water-repellent.
Generally, the material used as ARCs on glass is silicon dioxide
[204]. However, a drawback limiting the use of ARCs is the adhe-
sion of grime, which reduces transmittance constantly and sig-
nificantly. For staying clean, outdoor packaging glasses have a
nano-structured surface and are normally fabricated to mimic the
lotus leaf, on which dust and water do not stick. Thus, the ARCs are
often bestowed with superhydrophilic or superhydrophobic
properties also to prevent the accumulation of dust on modules,
which can reduce the net efficiency by 32–40% over the first eight
months and over 70% in a period of 15 years [205]. In addition,
TiO2 coatings are also used on solar cells for their photoinduced
superhydrophilicity and photocatalytic properties, which are very
suitable in the humid environments. The self-cleaning properties
Fig. 22.. a) J-V characteristics and (b) IPCE of organic solar cells [202].
originate from a combination of the photocatalytic oxidative de-
composition of organic contaminants and superhydrophilicity,
which causes water droplets to spread on the TiO2 surface, aiding
the cleaning process. However, it was also observed that most of
photocatalytic effect was lost within 5.5 years of outdoor exposure
[206]. For dry environments, the glass itself should have a nano-
structured surface so that dust does not settle on the surface, and
water is allowed to spread. Therefore, the combination of both
self-cleaning and antireflective properties is highly desirable for
applications in photovoltaic devices.
There are many other materials that can be used to prepare
ARCs. In the articles by Chen and co-workers, the structures of
solar selective surfaces are classified into seven categories as fol-
lows; (i) intrinsic selective materials, (ii) semiconductor-metal
tandems, (iii) multilayer absorbers, (iv) textured surface absorbers,
(v) transition metal oxides, (vi) carbon nanoparticles embedded in
ZnO and NiO, and (vii) metaldielectric composites [207]. ZnO
single crystal nanorods or nanowires, which are cheap, stable,
environmentally-friendly and nontoxic, have captured the atten-
tion of many researchers and show good prospects for optoelec-
tronic applications due to their large exciton energy of 60 meV
[208].
7. Concluding remarks and commercialization challenges
Nature can provide innovative solutions to technological pro-
blems in many fields. Many examples, such as the lotus leaf effect
clearly indicates that biomimicry cannot be achieved by simply
copying or duplicating biological structures. This review highlights
some of the recent advances, from examples available in nature to
 U. Mehmood et al. / Solar Energy Materials & Solar Cells 157 (2016) 604–623
Fig. 23. (a) J-V characteristics and (b) IPCE of water-repellent organic perovskite solar cells [203].
biomimetic surfaces and their functions. These surfaces with un-
ique wettability properties have potential promising applications
in industry.
Although various strategies have been developed to fabricate
these functional surfaces, most of them are limited to laboratory
research and not suitable for industrial scale production. Several
challenges still remain before these treated surfaces can be used in
practical applications. First, these surfaces are very susceptible to
mechanical contact during normal use, such as finger contact,
abrasive wear, washing cycles, and sand impact [209]. Mechanical
wear of the surfaces can destroy the microscopic roughness fea-
tures, or even remove the coatings from the substrates, leading to
a decline or complete loss of their unique optical properties and
wettability. Secondly, most of the reported fabrication techniques
involve multistep procedures or harsh conditions, or require spe-
cial reagents and equipment. Many of these techniques are ex-
pensive and only applicable to small flat surfaces or substrates of
specific materials [185]. The limited durability and the high cost of
the coated surfaces are the two main barriers to the commercia-
lization of these surfaces. Most of the current research is still fo-
cused on increasing the light transmission ability and controlling
the wettability of surfaces.
The immediate need is to pay more attention to the following
research areas:
 Conduct studies on the mechanism of formation of surfaces and
the relationship among their composition, structure, and
properties using a combination of theoretical simulations and
modern analytical technologies and tools.
 Explore avenues of fabricating antireflective surfaces with high
mechanical strength and abrasion resistance using cost-effec-
tive techniques, which can lead to large-scale industrial
production.
 Consider the entire range of pollutants present in the atmo-
sphere, which can contaminate surfaces, when fabricating sur-
faces coated with ARCs. Among the pollutants which can con-
taminate surfaces are fly ash, water slurries containing variety
of pollutants, oil, organic contaminants etc. Contamination of
surfaces with pollutants can change their optical and wetting
properties. Therefore, multifunctional surfaces with either en-
hanced durability or self-healing features are preferred for daily
use.
 Conduct further interdisciplinary research to identify and meet
challenges, to understand fabrication mechanisms, and to im-
prove durability and abrasion resistance of optically active sur-
faces. The development of novel materials and coating
619
techniques are also essential to expand the range of practical
applications.
Reaching a fundamental understanding of surface hydro-
phobicity at micro/nano scale and antireflective properties, re-
quired to perform accurate measurements and comprehensive
modelling, remains a challenge. Further investigations are re-
quired to include atmospheric effects such as temperature,
humidity, icing, etc., and dust accumulations and adhesion on
hydrophobic surfaces in calculations and modelling. Among the
required evaluations are the physical, chemical, thermal, and
mechanical properties of the surfaces in terms of cost-effective
processing, durability, and practical applications. However, re-
search to overcome these challenges and progress made are
promising.
Acknowledgment
The authors would like to acknowledge the support provided
by the Center of Research Excellence for Renewable Energy (CoRE-
RE) at King Fahd University of Petroleum & Minerals (KFUPM)
(IN14100), P.O. Box 5050, Dhahran 31261, Kingdom of Saudi Arabia.
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Bekir S. Yilbas re-
ceived his Ph.D. in
Mechanical En-
gineering from the
Birmingham Uni-
versity. He was
awarded the Doctor
of Engineering in
2005 by Birming-
ham University ow-
ing to his significant
contribution to his
field of study. He
has published over
600 journal papers
in reputable inter-
national journals
and presented over
100 papers at inter-