Renewable and Sustainable Energy Reviews 59 (2016) 620–635

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

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

Highly efficient antireflective and self-cleaning coatings

that incorporate carbon nanotubes (CNTs) into solar cells: A review
Hengameh Hanaei a,n, M. Khalaji Assadi a, R. Saidur b
a
Mechanical Engineering Department, UniversityTeknologi PETRONAS (UTP), Darul Ridzuan, Bandar seri iskandar, 32610 Perak, Malaysia
b
Centre of Research Excellence in Renewable Energy (CoRE-RE), King Fahd University of Petroleum and Minerals (KFUPM), Dhahran 31261, Saudi Arabia

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

Article history: Due to their useful atomic structure, carbon nanotubes (CNTs) have fascinating chemical and physical
Received 22 April 2015 properties, as exemplified by graphite and diamond. They have enabled major achievements in various
Received in revised form fields, such as materials, electronic devices, energy storage, separations, and sensors. Recently, antire-
27 December 2015
flective coatings (ARCs) with self-cleaning properties have been studied because of their interesting
Accepted 5 January 2016
characteristics and wide variety of practical applications. In this review, the basic principles of antire-
Available online 22 January 2016
flection and self-cleaning are discussed. Fabrication methods are also discussed, with specific attention
Keywords: given to silicon and silica substrates that incorporate CNTs. Additionally, ARCs and self-cleaning coatings
Solar cells on carbon nanotubes are briefly described. Finally, recent developments in antireflective and self-
Carbon nanotubes (CNTs)
cleaning coating using CNTs and some multifunctional ARCs are introduced.
Antireflection coating (ARC)
& 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 621
2. Recent progress in solar cell coatings using allotropes of carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 621
2.1. Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 621
2.2. Fullerene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 622
2.3. Carbon nano fibers (CNFs). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 622
2.4. Amorphous carbon (a-C) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 622
3. Photovoltaic properties of carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 622
3.1. Carbon nanotubes (CNTs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 622
3.2. CNTs in solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
4. Types of solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625
4.1. Silica-based solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625
4.2. Organic solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625
4.3. Dye synthesized solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625
5. Antireflection and self-cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625
5.1. Antireflection properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
5.1.1. Theoretical aspects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
5.1.2. Fabrication method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 627
5.2. Self-cleaning properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 628
5.2.1. Theoretical aspects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 628
5.2.2. Fabrication method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 628
6. Recent progress in CNT-solar cell coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
6.1. Single-wall carbon nanotubes (SWCNTs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
6.2. Multi-wall carbon nanotube (MWCNTs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 630
7. Nanotechnology vs. energy storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 632
8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633

n
Corresponding author.
E-mail address: Hengameh_Hanaei@yahoo.com (H. Hanaei).

http://dx.doi.org/10.1016/j.rser.2016.01.017
1364-0321/& 2016 Elsevier Ltd. All rights reserved.
 H. Hanaei et al. / Renewable and Sustainable Energy Reviews 59 (2016) 620–635 621

9. Future directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633

Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633

1. Introduction of reachable pores in the nanometer range helps to adsorb con-

Solar energy plays a vital type of renewable energy because of
its inexhaustible nature, environmental friendliness, and the
potential for high power conversion efficiency in solar energy
harvesting devices [1,2]. Enhancing the power conversion effi-
ciency is an essential research subject that informs the manu-
facturing of photovoltaic (PV) devices. Improving power efficiency
makes the devices more cost-competitive compared to traditional
sources of energy [1,3,4]. Solar cells with heterojunction arrange-
ments incorporating carbon materials have generated much
enthusiasm and could have applications in various innovative
optoelectronic devices, such as PV solar cells [5]. The use of carbon
nanotubes in PV solar cells, particularly in silicon-based solar cells,
organic solar cells and dye-sensitized solar cells, will be assessed.
There are many reports that have investigated different materials,
especially transparent conductive films of CNTs, graphene and
semiconducting polymers that can be conveniently deposited on
commercial Si wafers to improve the efficiency of solar cells [6].
Numerous experiments have predicted new advances related to PV
cells with the intention of increasing the yields of such envir-
onmentally friendly energy generation methods. However, to
produce economical optical coatings, it is still required to permit
the maximum solar emission to achieve semiconductor intersec-
tion. Applying an ARCs layer, with an advanced refractive index
(RI) and thickness to cover device can mostly eliminate this issue
[7,8]. Mostly, the coatings are a fundamentally porous silica-based
material offering tunable RI and thickness with a strong connec-
tion to the surface. Although SiO2 porous coatings can be beneficial
for solar cells, some researchers have reported that pure SiO2
porous coatings are not stable in water because they are suffi-
ciently soluble to be gradually worn down by friction from water.
This effect is increased by the porosity that accumulates on the
surface of the material. Additionally, the pores have hydrophilic
surfaces and are small enough to be filled with water at only
moderate humidity, which significantly increases the RI and
decreases the antireflective properties [9]. However, the existence
taminations from the environment. Importantly, this increases the
antireflection layer refractive index. Water uptake can be sig-
nificantly decreased by making the pores hydrophobic [9,10].
Therefore, chemicals should be used to build hydrophobicity into
the surface. When this is performed, contaminants cannot move
away except when non-open porosity is exposed to contaminants.
An alternative arrangement would be to coordinate the integration
of a photo catalyst species in the optical layer, whose role would be
to clean the porous surface [8–11].
2. Recent progress in solar cell coatings using allotropes of
carbon
Carbon is capable of forming many allotropes due to its valency.
When an element exists in more than one crystalline form, these
forms are called allotropes; the two most common allotropes of
carbon are diamond and graphite. Diamond is a well-known
allotrope of carbon that exhibits hardness and high dispersion of
light. It is the hardest known natural mineral and finds applica-
tions in cutting, drilling, and jewellery, and it is used as a potential
semiconductor material. Graphene is a single layer of carbon
atoms arranged in one plane; layers of graphene make up graphite
(See Fig. 1). Graphene is a material of interest due to its high
electron mobility and its possible applications in electronics.
Fullerenes are a class of carbon allotropes in which carbon takes
the form of a hollow sphere, ellipsoid, or tube.
2.1. Graphene
Graphene can be thought of as a structure that is shaped by
unrolling a CNT into a uniform sheet. Its two-dimensional struc-
ture, atomic thickness, and high bearer flexibility make graphene a
perfect electrode material to be used in thin film manufacturing.
Graphene layers synthesized by Chemical Vapor Deposition (CVD)
or other methods have been used as transparent conductive

Fig. 1. Allotropes of carbon.

622 H. Hanaei et al. / Renewable and Sustainable Energy Reviews 59 (2016) 620–635
electrodes for polymer-based solar cells and other types of solar
cells [12,13]. Because of CNT–Si solar cells, one would expect that a
graphene–Si model would work admirably. Shi et al. demonstrated
a colloidal antireflection coating on a monolayer graphene–Si sun
oriented cell and improved the cell efficiency to 14.5% under
standard illumination (air mass 1.5, 100 mW/cm2) with stable
antireflection impact over a long time. Antireflective treatment
was performed by a simple spin coating procedure, which essen-
tially expanded the short out current thickness and the episode
photon-to-electron power conversion efficiency to approximately
90% over the visible range. Their outcomes show that it is possible
to develop graphene Si solar cells with high efficiency on CNT–Si
structures [14]. Miao reported single layer graphene/n-Si solar
cells with a Power Conversion Efficiency (PCE) of 8.6%. This
implementation, accomplished by doping the graphene with bis-
(trifluoromethanesulfonyl) amide, produced changes in current–
voltage, capacitance–voltage, and external quantum efficiency that
show improvement because of the doping-induced movement in
the graphene synthetic potential that expands the graphene
transporter thickness and builds the cell's inherent potential. Both
of these effects enhance the sun powered cell fill factor [15].
Despite the fact that the higher efficiency of graphene–Si cells is
between 7.7% and 14%, the effectiveness is still under 15%. This is
much lower than in the CNT–Si cells. Moreover, the degradation
(or stability) of graphene–Si cells has not been investigated pre-
viously. Whether the performance of graphene–Si cells could catch
up and compete with CNT–Si cells remains an open question and
will be investigated in future work.
2.2. Fullerene
Fullerenes have high electrochemical stability and large surface
area, and because of these features, they have attracted the
attention of solar cell researchers. They display rich photochemical
properties, and consequently they can act as an electron shuttle
[16,17]. It is possible to engineer a carbon nanostructured donor–
acceptor assembly to imitate photosynthesis. Chih-Yu Chang et al.
have successfully demonstrated high performance and stable
flexible polymer solar cells with a PCE up to 8.8%. A novel ther-
mally cross-linkable, n-doped conductive fullerene material was
developed by incorporating tetrabutylammonium iodide (TBAI) as
the dopant in an azido fullerene derivative called PCBN3 [18].
2.3. Carbon nano fibers (CNFs)
CNFs are mostly used as an alternative counter-electrode
because of their unique structure and differences from standard
platinum (Pt) counterelectrodes. Their electrocatalytic properties
are measured using Electrochemical Impedance Spectroscopy
(EIS), Cyclic Voltammetry (CV), and Tafel-polarization. Under 1 sun
illumination, solar cells made with a hollow SnO2 photo anode
sandwiched with a stable CNF counterelectrode showed a PCE of
2.5% in quantum dye solar cells and 3.0% for dye solar cells, which
is quite promising compared with a standard Pt counter-electrode
(QDSCs: 2.1%, and DSCs: 3.6%) [19].
2.4. Amorphous carbon (a-C)
Amorphous carbon is free, reactive carbon that does not have
any crystalline structure (also called diamond-like carbon).
Amorphous carbon materials may be stabilized by terminating
dangling-π bonds with hydrogen. These materials are then called
hydrogenated amorphous carbon. As with all amorfous solids,
some short-range order can be observed. Amorphous carbon is
often abbreviated to a-C for general amorphous carbon, a-C: H or
HAC for hydrogenated amorphous carbon, or tta-C for tetrahedral
amorphous carbon. Amorphous carbon films have many advan-
tages, including their low-cost, ease of mass-production, semi-
conducting characteristics, and tunable band gap. They can be
prepared with various characteristics by changing the sp2/sp3
ratio. Chen created Au/a-BC/SiO2/n-Si/Al solar cells using a reactive
sputtering system. The photovoltaic characteristics of Au/a-BC/
SiO2/n-Si/Al solar cells and the properties of the a-BC thin film
alloys that were used in them were evaluated. Field Emission
Transmission Electron Microscope (FETEM) results reveal that the
thicknesses of the SiO2 layer and the a-BC thin film alloys after
annealing were approximately 3 and 30 nm, respectively. The
results demonstrate that the a-BC thin film alloy exhibits amor-
phous carbon characteristics, and the Fourier Transform Infrared
Spectroscopy (FTIR) results show that a little hydrogen was
incorporated into the a-BC thin film alloy. X-ray photoelectron
spectroscopy (XPS) indicated that the B/C ratio of the a-BC thin
film alloy was 12.4%, and the amount of sp2 carbon bonds in the a-
BC thin film alloy was higher than that of the sp3 carbon bonds
[20]. Lana investigated a double-cermet structured thin film in
which an a-C: H thin film was used as an ARC layer and two
platinum-containing amorphous hydrogenated carbon (a-C: H/Pt)
thin films were used as the double cermet layers. A reactive co-
sputter deposition method was used to prepare both the anti-
reflective and cermet layers. The resulting films were character-
ized using X-ray diffraction, scanning electron microscopy (SEM),
and high-resolution TEM. The optical absorbance and emittance of
the deposited and annealed films were determined using UV–Vis-
NIR spectroscopy. They show that the optical absorbance of the
resulting double-cermet structured thin film is as high as 96% and
remains at 91% after heat treatment at 400 °C, indicating the
thermal stability of the film [21].
Recently, there has been growing interest in developing CNT
silicon heterojunction solar cells, and the PCE has been con-
tinuously improved to the range of 10–20% during the past several
years. Compared to traditional Si solar cells involving high-
temperature dopant diffusion and additional metal grids as the
top contact, the fabrication of CNT–Si heterojunctions is a low-
temperature process based on commercial wafers that still leads to
high efficiency. CNT–Si and graphene–Si solar cells have attracted
much interest recently owing to their potential to simplify the
manufacturing process and reduce costs compared to Si cells. Until
now, the power conversion efficiency of graphene–Si cells has
been less than 14% and well below that of the equivalent
nanotube-Si counterpart.
3. Photovoltaic properties of carbon nanotubes
Because of the incredible mechanical, electrical and thermal
properties and chemical stability of CNTs, they have been the
subject of extensive research in previous decades [22]. In the solar
energy field, it is conceivable to use CNT films as transparent
electronic materials and to use nanotube composites for solar cell
applications. In addition, carbon nanomaterials could be used to
deliver conductive ink for printed solar cells. One potential alter-
nate energy application is to use CNT films as coatings for wind
turbine blade edges [23]. CNTs are a promising building block for
innovative materials. Carbon is known as the most fascinating
element that exists in nature because it has a wide range of
properties due to how its particles are organized [24].
3.1. Carbon nanotubes (CNTs)
Carbon is the first element in group IV of the periodic table. It
has atomic number 6, and its electronic arrangement is 1s2 2s2 2p2
[26]. Carbon nanomaterials are molecules consisting entirely of
 H. Hanaei et al. / Renewable and Sustainable Energy Reviews 59 (2016) 620–635
carbon (Fig. 2). Depending on their arrangements, they are called
graphene, fullerenes or carbon nanotubes. Fig. 3 shows a macro-
graph of CNTs in the lab. Unlike graphite or diamond, CNTs have
metallic or semiconductor properties [27]. CNTs are an allotrope of
carbon in the form of hollow cylinders composed of rolled-up
sheets of graphene. The strong interatomic bonds increase the
mechanical properties of a solid made of CNTs. The covalent
Fig. 2. Various structures of carbon [5].
Fig. 3. Macrograph of CNTs [25].
Fig. 4. Structural models of a SWCNT (left) and an MWCNT (right).
623
bonding of carbon–carbon sp2 is an exceptionally strong interac-
tion. Because of the bond strength, carbon nanotubes show high
stiffness. Similarly, carbon nanotubes have a high Young's mod-
ulus, high tensile strength, and high axial strength [28–32].
Researchers have reported that the mechanical properties of car-
bon nanotubes and their diameter can be used to classify them
into two categories: single walled (SWCNTs) or multi-walled
(MWCNTs), as shown in Fig. 4. In SWCNTs, the Young's modulus
is expected to be free of tube chirality. A smaller diameter brings a
smaller Young's modulus. A few studies have reported that the
Young's modulus of MWCNTs is higher than SWCNTs [33,34]. The
electrical properties of carbon nanotubes have fascinated
researchers for many years. Theoretical and experimental results
show that carbon nanotubes can create a maximum electric cur-
rent that is 1000 times greater than the maximum current in
copper wires. Depending on the diameter and chirality of the
CNTs, they may have conducting or semiconducting behavior
[35,36]. The electronic properties of CNTs are valuable in numer-
ous applications. The high aspect ratio and small dimensions of
CNTs make them suitable for use in electronics. The armchair
structure of CNTs is metallic, but the other two configurations,
chiral and zigzag CNTs, can be either metallic or semiconducting
[37].
3.2. CNTs in solar cells
Nanotechnology has become very popular, and many
researchers are working on projects related to solar cells and solar
energy methods incorporating CNTs [38–43]. There have been
reports about applications of nanofluids in solar energy [44],
applications of nanotechnology in solar cells [45] a solar collector
using nanotechnology [46] and electrocatalysis using CNTs [47].
Carbon materials were introduced into flat cells in 1996 [48], and
CNTs were incorporated into energy conversion systems beginning
in 1999 [49]. In particular, there have been several reports on high
efficiency energy conversion [50–52]. The extraordinary properties
of CNTs, such as their light weight, excellent mechanical strength,
three-dimensional flexibility and outstanding electrocatalytic
properties can be used to improve the performance of solar cells
[53,54]. In addition to applications in solar energy conversion,
CNTs can be used in Dye-Synthesized Solar Cells (DSSCs) that have
been studied as part of damage sensing and structural health
monitoring (SHM) systems [52,55]. At a minimum, there must be a
technique for financially realistic energy conversion efficiency, and
CNTs are the most likely technology to significantly contribute to
renewable electricity generation by 2020 [56,57]. One of the most
recent PV solar cells to be introduced that uses CNTs for photo-
current generation is the nanotube-silicon heterojunction (NSH). It
is similar to a single intersection crystalline silicon solar cell, but
the emitter layer is replaced by a thin film of SWCNTs or MWCNTs.
624 H. Hanaei et al. / Renewable and Sustainable Energy Reviews 59 (2016) 620–635

Fig. 5. Device schematics and energy diagrams for p–n (a,c) and MIS (b,d) solar cells [58].

The principal system is p–n heterojunction solar cell (Fig. 5a and

c), with nanotubes as the p-type emitter material. Photons are
absorbed fundamentally in the n-type silicon base area, with
approaching excitons diffusing to the space-charge district where
they are divided into free charge bearers under the activity of the
implicit potential structured by Fermi level equilibration at the
intersection. The second system is a Schottky intersection solar cell
or closely related metal separator semiconductor (MIS) solar cell
Fig. 5b and d. A Schottky intersection is formed between a metal
and a semiconductor and can be used as a solar cell device [58,59].
To address the production costs of silicon solar cells and the
toxicity and/or scarcity of other solid state semiconductors, there
is at present extraordinary enthusiasm for discovering alternative
semiconductor materials and/or elective methods for creating new
solar cells [58]. The inherent properties of SWCNTs have been the
subject of extensive research into different applications. In
numerous applications, the organization of SWCNTs at the micro-
scale is what determines their implementation in nanotube-based
devices, such as nano-sensors, nano-control systems, and micro- Fig. 6. Requirements for perfect antireflective coatings.
fluidic gadgets. Extensive efforts have been devoted to creating
synthesized routines for developing SWCNT specifically on sub- typically called ARCs. There are numerous antireflective surfaces in
strates with particular arrangements, such as vertically oriented nature. Antireflection innovation has been generally used as a part
forests [22,60,61]. This is especially demanding for SWCNTs as of high-accuracy optical segments, solar cells, flat panel displays
opposed to MWCNTs because the former are significantly more and light radiating diode lighting to expand the transmittance of
sensitive to catalyst structure and carbon feedstock than the latter. incident light [62–64]. For solar cells, because of reflection at the
Sometimes, compound adjustment of the nanotube surface has air/glass interface of the bundling glass and dissipation due to
been found to be essential to achieve a surface with stable accumulated dust on outdoor panels, some pieces of episode
superhydrophobicity. Thus, many researchers have emphasized vitality on solar powered modules are lost. On the one hand, ARC
that MWCNTs allow for maintenance of hydrophobicity despite on the glass can help reduce reflection in systems; on the other
variation in ionic strength, the nature of the electrolyte, or the pH hand, the self-cleaning properties can, to some extent, solve the
of the water droplet. Additionally, it was observed that the dro- dust accumulation problem [62]. Fig. 6 illustrates the requirements
plet's behavior can be changed from superhydrophobic to hydro- for perfect antireflective coatings such as those of CNTs. Roughness
philic by using an electric field. Using an electric field causes sig- is important to minimize reflection on surfaces. The reflection or
nificant changes in the hydrophobicity of the SWCNT micro- optical unsettling influence will be zero if the medium for light
structures of various structures [27]. proliferation does not change or the two media have the same
Transparent surface coatings with suitable optical properties refractive index [65]. Therefore, numerous materials with micro/
can smooth the impression of substrates. Such coatings are nano-structure can be used in the manufacturing of ARCs,
 H. Hanaei et al. / Renewable and Sustainable Energy Reviews 59 (2016) 620–635
including silicon, silica, titanium, zirconium, zinc oxide, cobalt
oxide, tin oxide, carbon, poly(ethylene terephthalate) (PET), poly-
styrene (PS), and gallium nitride [66–70]. ARCs with self-cleaning
properties have advanced rapidly in recent years from window
glass to various electronic devices. In this review, we describe
recent developments in antireflective and self-cleaning surfaces
[71–73]. A substantial number of exploratory articles have repor-
ted the creation of ARCs or superhydrophobic/superhydrophilic
surfaces in the past few years. This paper means to give a brief
survey of consolidating carbon nanotubes in solar cells and anti-
reflective and self-cleaning coating innovations, and it demon-
strates their extraordinary application prospects. There has also
been much work in recent years incorporating carbon nanotubes
into photo electrochemical cells (PECs) either on their own [74–77]
or as elements in donor–acceptor hybrids in conjunction with
fullerenes [78,79].
4. Types of solar cells
Solar energy is radiant energy that is produced by the sun. In
many parts of the world, direct solar radiation is considered to be
one of the best prospective sources of energy [80]. There are many
reports describing innovative solar cell structures with high power
conversion efficiency and low cost. One of most interesting
methods in the literature involves combining cheap materials with
well-established semiconductors to provide a new structure
manufacturing process. Fig. 7 illustrates various types of PV solar
cells, and different structures of carbon materials used in different
types of PV solar cells are reviewed. The roles played by carbon
materials in these photovoltaic cells are discussed.
4.1. Silica-based solar cells
The p–n junction is used to generate current in a specific way,
and it is critical for many optoelectronic devices. Different type of
silicon-based (P-type or n-type) solar cells can be made by using
processes such as doping. The fabrication of antireflective layers
on silicon surfaces has attracted much attention since the 1980s.
Antireflective layers can improve the efficiency of silicon solar
cells. Silicon has been explored in almost all types of ARCs, from
porous silicon on solar cells to Moth's eye inspired biomimetic
structures and silicon nanotips. Silicon oxide based materials, such
as glass, quartz, and fused silica are outstanding candidates for
ARCs. Many studies have been devoted to these materials and their
applications (Tables 1 and 2). Almost all of the methods discussed
in this review can be used for the preparation of silica ARCs [5].
The results show that silicon solar cells based on carbon are a great
combination for manufacturing PV solar cells, and they can be
used to produce solar cells with maximum power conversion
efficiency.
Fig. 7. Different types of solar cells (a) silicon-based solar cell, (b) organic solar cell and (c) dye-sensitized solar cell [5].
625
4.2. Organic solar cells
Polymers are large molecules with multiple structural forms.
Based on their micro-phase separation, self-assembly, or self-
organizing properties, the molecular level structure (chain con-
formation), secondary structure (aggregation structure), and ter-
tiary structure (self-assembly or self-organization) could be
modulated to achieve the desired polymer film nanostructure
(Tables 3 and 4). There are many excellent characteristics of
polymers, such as controllable morphology and porosity ratio,
adherence to the substrate, and flexibility and suitability for large-
scale preparation [5,94,95].
4.3. Dye synthesized solar cells
Over the past two decades, dye-sensitized solar cell (DSSC)
research has continued to gain momentum because of the low cost
and environmental sustainability of DSSCs, which provide a good
foundation for practical applications. Recently, CNTs have been
introduced into DSSCs to take advantage of their lower electrical
resistance, flexibility, excellent electrocatalytic activity and
mechanical integrity. This paper introduces the principle of
carbon-based solar energy conversion and reviews different types
of solar cells using incorporated CNTs as electrode materials. This
article also reports on the outstanding electrocatalytic functions of
CNTs in enhancing wire-shaped solar cell photo-energy conver-
sion. TiO2 is the most widely used white pigment because of its
brightness, high RI and excellent stability [94,107–110]. Tables 5–8
list studies reporting on the efficiencies of different types of DSSCs.
5. Antireflection and self-cleaning
Combining CNTs, graphene or conducting polymers with con-
ventional silicon wafers leads to promising solar cell architectures
with greatly improved power conversion efficiency [6]. Transpar-
ent surface coatings with suitable optical path differences can
suppress the reflection of substrates. Such coatings are usually
called ARCs. In addition to these excellent optical properties, ARCs
arrays also exhibit self-cleaning ability because of the high fraction
of air trapped between arrays [121,122].
Table 1
Performance of CNTs/Si in photovoltaic cells.
Year Reference Cell η (%) Note
structure
2011 [81] CNT–Si 8.9 Controlling the oxide thickness and
2011 [81] CNT-oxide– 10.1 tailoring the junction structure is
Si important for fabrication of high-effi-
2011 [81] PDMS–CNT- 10.9 ciency nanostructure Si-solar cells
oxide–Si
626 H. Hanaei et al. / Renewable and Sustainable Energy Reviews 59 (2016) 620–635

Table 2
Performance of typical carbon based photovoltaic cells.

Year Reference Cell structure η (%) Note

1996 [82] P-C/n-si 6.45 The junction made by chemical vapor deposition
1998 [83] P-C/P-SiC/n-Si 8.8 –
2000 [84] n-C/P-C/P-Si 1.82 Amorphous carbon as a semiconductor in C/Si heterojunction photovoltaic solar cells
2001 [85] P-C/n-Si 7.9 Cell prepared by plasma chemical vapor deposition (PCVD) method
2004 [86] a-C:H/P-Si 2.1 Hydrogenated amorphous carbon films (a-C:H) were deposited on p-type silicon
2006 [87] n-C/P-Si 1.14 Successfully incorporated phosphorous (P) into a-C films
2007 [88] P-C/P-i-n-aSi 5.6 –
2008 [89] CNTs-/n-Si 7.4 –
2007 [90] P3HT/c60-CNTs 0.75 –
2008 [91] CNTs-P3OT/n-Si 0.175 Incorporation of MWCNTs in the polymer layer of a P3OT/n-Si heterojunction solar cell. Reference cells without
MWCNTs show much lower performance
2008 [92] MWCNTs/PEDOT-PSS 6.5 –
(DSSC)
2008 [93] Graphene/PEDOT-PSS 4.5 –
(DSSC)

Table 3
Performance of incorporating carbon in polymer-based solar cells.

Year Reference Cell structure η (%) Note

2007 [96] P3HT/PCBM 1.1 Effective anodes with MWNT back electrode
2006 [97] P3HT/PCBM 2.5 Fabricated flexible transparent electrodes with SWNT back electrode
2006 [98] MEH-PPV, HN-C60 1.6 MEH-PPV as the donor, HN-C60 as the acceptor
2008 [99] Cell based on C60 0.11 Decorated with MWNTs/P3OT
2014 [100] Cell based on nanowire 7.57 Nanowire/zinc oxide composite transparent electrodes

5.1. Antireflection properties

Table 4
Performance of organic-Si heterojunction solar cells.
It is common knowledge that smooth surfaces shine more than
Year Reference Cell structure η (%) Note rough ones. This recognizes the very basic idea of antireflection:
roughness is necessary to reduce the reflectivity of surfaces.
2008 [101] MWCNTP3OT/n-Si 0.175 Incorporating MWCNTs in
the silicon-based material Therefore, many materials with micro/nano-structures are used to
2006 [102] DWCNTP3OT/n-Si – Incorporating DWCNTs in fabricate ARCs, including silicon, silica, titania, zirconia, zinc oxide,
the silicon-based material cobalt oxide, tin oxide, carbon, and poly(ethylene terephthalate)
2007 [103] DWCNTP3OT/n-Si – –
(PET), polystyrene (PS), and gallium nitride [108].
2008 [104] DWCNTP3OT/n-Si – –
2008 [105] Metal nanoparticles 0.145 MWCNT decorated with
platinum metal 5.1.1. Theoretical aspects
nanoparticles As an optical phenomenon, reflection results from a transition
2007 [106] Single-crystal full- – –
in the medium in which light is traveling. The medium (glass,
erene nanorods
water, air, etc.) is characterized optically by a parameter called the
refractive index, which quantifies the speed of light in the current
medium with respect to a vacuum. As light travels, eyes can spot
Table 5 an optical disturbance if there is a change in RI. It is the Fresnel
Performance of Graphene electrodes Solar cells. equation that offers the basic preliminary mathematical model of
Year Reference Cell structure η (%) Note reflection and refraction. According to Augustin-Jean Fresnel, the
fraction of incident light reflected at the interface is measured by
2008 [111] Transparent gra- 1.53 Used as window electrodes in reflectance, and the fraction transmitted (refracted) is measured
phene thin films organic solar cells
by transmittance, as shown in Fig. 8.
2008 [112] Graphene based 1.1 Configuration of ITO/ PEDOT:
PSS/P3HT/graphene/LiF/Al The mathematical model or vector methods used to deduce the
2008 [112] Graphene based 1.4 Dispersed into organic solvent conditions for anti-reflection consider a thin film (RI¼n) on a glass
with P3OT and P3HT as a substrate (RI¼ns), as shown in Fig. 8a, and make the following
homogeneous solution
assumptions: The reflected waves have the same intensity, and
there is one reflected wave per interface. Other optical interac-
Table 6 tions, such as scattering and absorption, are negligible. Therefore,
Performance of window electrode solar cells. as shown in Fig. 8a, if the reflected waves R1 and R2 undergo
destructive interference, thereby canceling each other, there
Year Reference Cell η (%) Note
structure
would be no reflection. From this follow the two essential criteria
for Anti-Reflection. The reflected waves are p radians out of phase;
2008 [113] Solid-state 0.26 Ultra-thin graphene films were used thus, the phase difference, δ, is nπ/2. The thickness of the film (d) is
DSSCs as an alternative to metal oxides (ITO,
an odd multiple of λ/4, where λ is the wavelength of the incident
FTO, etc.) window electrodes
beam [4]. As illustrated in Fig. 8a, there is no reflection if
 H. Hanaei et al. / Renewable and Sustainable Energy Reviews 59 (2016) 620–635 627

Table 7
Performance of photo electrodes solar cells.

Year Reference Cell structure η (%) Note

2008 [114] SWCNTs/TiO2 0.13 Important for improving the efficiency of nanostructure-based solar energy conversion
2008 [115] DSSCs/TiO2 5.02 Incorporates MWCNTs
2008 [116] DSSCs/MWCNTs/TiO2 – Nanocomposite photo anodes obtained by the modified acid-catalyzed sol–gel procedure
2013 [117] MWCNTs/TiO2 – Composite structures have much higher photocatalytic activity compared to TiO2 nanoparticles

Table 8
Performance of counter electrodes (CE) solar cells.

Year Reference Cell structure η (%) Note

2008 [118] MWCNT/PEDOT:PSS 6.5 Pure CNTs and a composite film were used as the counter-electrode in a DSSC
2008 [119] graphene/PEDOT-PSS 4.5 Composite films deposited on ITO have also been applied as counter electrodes of DSSCs
2014 [120] Pt/MWCNTs/DSSCs Successful combination of DSSCs C processability, performance and stability enabled by using Pt/CNT hybrid CE

Fig. 8. Three basic types of propagation of light rays through (a) a single-layer coating and (b) a multi-layer coating on a substrate (ns 4nn, ns and nn are the refractive indices
of substrate and coatings, respectively) [108].

destructive interference occurs between the light reflected from b. Dip-coating

the coating-substrate and the air-coating interfaces [108].
5.1.2. Fabrication method
Most nanostructure-based ARCs can have their fabrication
techniques classified broadly as subtractive top–down or additive
bottom–up nanotechnology techniques (See Fig. 9). There are a
few other unconventional techniques, which will be examined in
detail.
5.1.2.1. Bottom–up approach. One of the most prevalent technolo-
gies for the production of porous ARCs is the sol–gel method. This
process involves the use of inorganic salts or metal alkoxides as
precursor materials that, when exposed to aqueous or organic
solvents, hydrolyze and condense to form an inorganic polymer
comprising metal-oxide–metal bonds. The different coating tech-
niques used to coat sol–gels will be discussed in brief here.
a. Layer-by-layer assembly (LbL)
The LbL assembly technique has several advantages for the
preparation of ARCs. First, as mentioned above, various
materials (building blocks) can be used to fabricate ARCs, and
LbL processing is substrate-independent. Second, it is possible
to deposit ARCs over large areas on non-flat surfaces by using
the LbL assembly technique. Third, it is easy to control film
thickness using the LbL assembly technique; thus, it is easy to
tailor the wavelength of maximum transmittance simply by
changing the number of film deposition cycles. The perfor-
mance of coatings could be further optimized by combining
the LbL assembly method with other techniques.
Dip-coating has advantages such as simplicity, controllability,
reliability and reproducibility. The steps in the process can be
summarized as immersion, start-up, deposition, evaporation
and drainage, as shown in Fig. 10b. Dip-coating is frequently
selected for the preparation of nano-structured coatings
because it is simple and fast, especially for double-functional
or multi-functional films.
c. Spin-coating
Spin-coating is widely used in the microelectronics industry,
where it is used to deposit uniform coatings of organic
materials or to uniformly distribute particulate matter on a
flat surface [104]. The group reported spin-coating fabrication
of highly antireflective coatings on Fresnel lenses by using
solid silica nanoparticles and mesoporous silica nanoparticles
as building block, as illustrated in Fig. 11a.
d. Spray-coating
Spray-coating is quite a facile method. It is not specific to a
particular substrate, and it can easily be applied to a large surface
area. The method for preparing a regenerative superhydrophobic
coating has the advantage of simplicity during fabrication, easy
availability of the materials, and applicability to a large surface
area. Additionally, multilayer coatings with multiple components
can be fabricated by the spray-coating method, as shown in
Fig. 11b.
5.1.2.2. Top–down approach
a. Etching
b. Lithography
628 H. Hanaei et al. / Renewable and Sustainable Energy Reviews 59 (2016) 620–635

Fig. 9. Fabrication methods for anti-reflection coatings.

Fig. 10. (a) Outline of LbL assembly through electrostatic interaction, (b) Steps involved in dip-coating [108].

Fig. 11. (a) Schematic illustration of spin-coating, (b) Schematic diagram of spray-coating. [108].

High-throughput and cost-effective processing methods have
been used to produce ARCs, microchips and micro-electromechanical
devices. These techniques always rely on expensive tools, such as
those used in deep-UV projection lithography and electron-beam
lithography. Currently, the top–down approach has been one of the
most widely used top–down techniques in the fabrication of anti-
reflective and self-cleaning coatings due to its several advantages,
such as full wafer processing and short exposure time. However,
drawbacks still exist, such as limited resolution and limited possibi-
lities for working with pre-existing topography or curved substrates.
Further research will be needed to overcome these limitations.
5.2. Self-cleaning properties
wettability. For a perfectly smooth and chemically homogeneous
solid surface, the contact angle of a liquid is given by Young's
equation. For a realistic solid surface that is rough and chemically
heterogeneous, the early theoretical work regarding contact angle
was performed by Wenzel and Cassie–Baxter. Wenzel's equation
[107] describes a situation in which liquid completely penetrates
into the roughness grooves, as shown in Fig. 12b. The next equa-
tion is the Cassie–Baxter equation [107,108]. In the Cassie–Baxter
state, under some roughness conditions, air bubbles may be
trapped when θ490 Fig. 12c. In this case, the liquid–surface
interface actually consists of two phases: the liquid–solid interface
and the liquid–vapor interface. Therefore, the apparent contact
angle is the sum of the contributions of the different phases.

5.2.1. Theoretical aspects 5.2.2. Fabrication method

Wettability is an important property of a solid surface, and Techniques to produce self-cleaning surfaces can be generally
contact angle (θ) has been commonly used to characterize surface classified into two categories: (a) making a rough surface;
 H. Hanaei et al. / Renewable and Sustainable Energy Reviews 59 (2016) 620–635
(b) modifying a rough surface with a material of low surface
energy (for superhydrophobic surfaces) or high surface energy (for
superhydrophilic surfaces).
a. Fabrication of superhydrophilic surfaces
Superhydrophilic surfaces can induce “complete spreading” of
water, which would have a broad range of application,
including self-cleaning, antifogging, water harvesting and
biomedical applications. On the one hand, the roughness of a
surface plays a key role in controlling its wettability. On the
other hand, superhydrophilicity can be achieved through
photo-induced surface reactions by using certain semiconduc-
tors, such as TiO2, ZnO, WO3 and V2O5. Nano-scale porous
structures and some microstructures are known to exhibit
superhydrophilicity. However, film porosity also plays an
important role in creating superhydrophilicity. Wetting can
be controlled by changing the porosity and/or roughness.
There are three types of rough surfaces: regular (designed)
surfaces, irregular (random) surfaces, and hierarchically rough
surfaces. Films of nanoparticles are often deposited on sub-
strates by LbL, spin-coating, sputtering, or hydrothermal
synthesis. Microstructures can be grown by using polymeriza-
tion and lithographic and electrochemical techniques. Photo-
induced surface reactions are important for achieving super-
wetting properties, and a large number of methods has been
used to prepare superhydrophilic coatings with light-sensitive
materials, such as drop casting, peroxotitanate-complex
deposition, liquid-phase deposition, physical vapor deposition
[123], and atomic layer deposition. To avoid duplication, we
just describe a few novel preparation methods in this section.
Schematic illustrations of self-cleaning processes on (a) a
superhydrophilic surface and (b) a superhydrophobic surface
is shown in Fig. 13.
b. Fabrication of superhydrophobic surfaces
Superhydrophobic surfaces have a water contact angle greater
than 150° and low contact angle hysteresis (lower than 5). Because
of their unique water-repellent properties, these surfaces have
attracted significant attention over the last two decades. They can
potentially be used as surface structures for fluid applications and in
engineering and biotech research. Regardless of the material used
Fig. 12. (a) Schematic illustration of spin-coating, (b) schematic diagram of spray-
coating. [108].
Fig. 13. Schematic illustrations of self-cleaning processes on (a) a superhydrophilic surface and (b) a superhydrophobic surface.
629
and the structures formed on the surface (particles, rod arrays, or
pores), suitable roughness in combination with low surface energy
is required. Procedures for roughening the surface followed by
hydrophobization or transforming low-surface-energy materials
into rough surfaces have been commonly used to produce super-
hydrophobic surfaces. Since Tsujii et al. first theoretically and
experimentally demonstrated biomimetic superhydrophobic sur-
faces in 1996, various smart methods for attaining rough surfaces
that exhibit superhydrophobicity have been reported, such as LbL
deposition, dip-coating, lithography, chemical vapor deposition,
electro-spinning, sol–gel processing, plasma treatment, one-pot
reaction, and electrochemical deposition.
6. Recent progress in CNT-solar cell coatings
Superhydrophobic surfaces produce a large water contact angle
by improving the solar cells and using a carbon nanotube covering.
Silica covered carbon nanotubes have been successfully synthe-
sized by using liquid phase deposition, electro-deposition, and
sol–gel methods [125]. When contamination or fogging occur on
ARCs, their optical properties significantly break down. Con-
taminants gather and water molecules condense on the surface,
prompting diffusion and reflection of light. This issue may be
addressed by making a surface that has unique wettability
(superhydrophilicity or superhydrophobicity) and photocatalytic
properties. ARCs with self-cleaning properties have been devel-
oped rapidly in recent years, in applications ranging from window
glass to various devices [107]. In this review, we describe recent
advancements in antireflective and self-cleaning surfaces, with
specific attention given to silicon and fused silica materials
because they are both used in numerous practical gadgets. A
substantial number of exploratory articles have reported the
creation of ARCs or superhydrophobic/superhydrophilic surfaces in
the past few years. This paper represents antireflective and self-
cleaning coatings fabrication technologies and a basic realization
of their potential applications [108].
6.1. Single-wall carbon nanotubes (SWCNTs)
Yu investigated polymers as a leading interlayer inside silicon–
carbon nanotube heterojunction photovoltaics. Three types of
gadgets have been manufactured and described, including silicon–
carbon nanotube, silicon-directing polymer and silicon-conducting
polymer–carbon nanotubes. The expected conducting polymers
were polyaniline, poly (3-hexylthiophene-2, 5-diyl) and poly (3, 4-
ethylene dioxy thiophene), poly (styrene sulfonate). A leading
polymer interlayer essentially enhances photovoltaic execution by
making a superior exhaustion layer inside the fundamental silicon.
With the expansion of a top antireflection layer, a photovoltaic
gadget, silicon-poly (3,4-ethylenedioxythiophene):poly (styrene
630 H. Hanaei et al. / Renewable and Sustainable Energy Reviews 59 (2016) 620–635
sulfonate)–carbon nanotube – poly(styrene) has been manu-
factured with a photovoltaic conversion efficiency of 8.7% [94].
Gong reported that SWCNTs have highly desirable attributes for
solution-processable thin film photovoltaics (TFPVs), for example,
broadband absorption, high carrier mobility, and environmental
stability. However, past TFPVs built with photoactive SWCNTs have
been used in structural designs that have constrained current,
contrained voltage, and at last PCE. Here, we report a solar cell
geometry that maximizes photocurrent by using polychiral
SWCNTs while maintaining high photo voltage, prompting record-
high proficiency in SWCNT–fullerene solar cells. Additionally,
these cells show huge retention in the near-infrared part of the
solar spectrum that is currently inaccessible to many leading TFPV
technologies [126]. Combining CNTs, graphene or leading poly-
mers with traditional silicon wafers produces solar cells archi-
tectures with high power conversion efficiency.
Shi, et al. reported CNT–Si junction solar cells with efficiencies
of 15% obtained by coating with a TiO2 antireflective layer and
doping the CNTs with oxidative chemicals, under air mass (AM 1.5)
light at an aligned intensity of 100 mW/cm2. The TiO2 layer fun-
damentally hinders light reflectance from the Si surface, bringing
about highly improved short-circuit current (by 30%) and outer
quantum productivity. Their method is simple and decently con-
trolled, and it is extremely powerful in boosting the execution of
CNT–Si solar cells [6]. They have described the morphology of
CNT–Si cells and the TiO2 layer by using optical and scanning
electron microscopy. The typical device area (15 mm2) permits
spin-coating of a uniform TiO2 layer on top of the CNT film. Before
covering, the CNT–Si cell surface shows up brightly because the
CNT film is so thin and the planar Si substrate is reflective. Con-
versely, a cell covered with TiO2 shows dark blue-to-violet shad-
ing, indicating reduced light reflection. Fig. 14 illustrates the fab-
rication process of a TiO2–CNT–Si solar cell in their work. The TiO2
colloid covers the highest point of each nanotube package as well
as the porous region in the CNT system, thus forming good
adhesion to the Si substrate and guaranteeing uniform thickness
over the CNT film. Numerous CNT groups hang down on the bro-
ken cross-segment of the Si wafer, demonstrating great quality
and interconnection.
There are some small (nanoscale) bulges introduced into the
TiO2 layer, which could help with light catching as in nanocones
[6]. They also reported in their previous work that HNO3 doping
can improve solar cell efficiency by reducing the sheet resistance
of CNT films and possibly by forming oxide on the Si surface. In
Fig. 14. Illustration of the fabrication process of a TiO2–CNT–Si solar cell involving
the following steps: (1) creating a cell device window by transferring a CNT film
onto an Si wafer (with 400 nm oxide) and applying Ag paste around the film,
(2) etching away the oxide layer to form direct CNT–Si contact and junction,
(3) spin coating a thin TiO2 colloid on top of the CNT film as an antireflective layer,
and (4) chemical doping of the cell by vapor deposition of HNO3 and H2O2 [6]. (For
interpretation of the references to color in this figure, the reader is referred to the
web version of this article.)
summary, a CNT–Si solar cell with a proficiency of 15% was pro-
duced. This demonstrates that the TiO2 antireflective layer can be
used enhance the yield of CNT–Si solar cells and potentially other
comparable models, for example, graphene–Si structures. Liang
Zhang [11] reported that a progression of SWCNT clusters was built
by disproportionation of carbon monoxide on Co–Mo catalyst
films deposited on Si wafer substrates. The arrays incorporate a
two-dimensional SWCNT thin film arranged by spraying a SWCNT
suspension, and additionally irregular SWCNT systems, and verti-
cally adjusted SWCNT. Moreover, a novel SWCNT arrays was pro-
duced and termed SWCNT pillars, as shown in Fig. 15. These col-
umns are arranged by controlled union of SWCNT over a layout
substrate. At the point when water droplets are deposited on these
surfaces, it is clear that the static contact angle changes sig-
nificantly with the type of SWCNT arrays. The higher the level of
surface harshness that exists (at the nano- and micro-scales), the
higher the contact angle will be. The novel SWCNT columns show
superhydrophobicity. To evaluate the impact of surface roughness,
two basic models have been used. The Wenzel model can be used
to evaluate the conduct of the SWCNT thin films, and the Cassie–
Baxter model used for the SWCNTs exhibits three-dimensional
structure. They have built up a progression of SWNT micro-
structures, including 2-dimensional SWCNT film, irregular SWCNT
system (grass), vertically adjusted SWCNT (forest), and SWCNT
pillars, by controlled synthesis of SWCNT directly on level sub-
strates and/or treatment after combination.
Fig. 16 shows the hydrophobicity of the various arrays. The
static wetting angles of water droplets over the different arrays of
Fig. 15 were evaluated by imaging water droplets of similar size
(2 mm) sitting on the various surfaces. Hydrophobicity was pro-
duced on the surface of the SWCNT pillars, which displayed var-
ious leveled composite of roughness scales. Notwithstanding the
essential roughness at the nanoscale, the partition between pillars
produces an optional harshness at the microscale (Fig. 16e).
Extraordinarily, the deliberate contact angles (Fig. 16) on these
SWCNT arrays are more noteworthy than that on a Teflon surface
[11]. Wadhwa, et al. reported a new type of crystalline silicon solar
cell that is superficially similar to a photo electrochemical cell. A
liquid electrolyte creates a depletion (inversion) layer in an n-type
silicon wafer, but no regenerative redox couple is present to ferry
charge between the silicon and a counter-electrode. Instead, holes
trapped in the electrolyte-induced inversion layer diffuse along
the layer until they come to widely spaced grid lines, where they
are extracted. The grid lines consist of a single-walled carbon
nanotube film etched to cover only a fraction of the n-Si surface.
Modeling and simulation shows the inversion layer to be a natural
consequence of the device electrostatics. With electronic gating,
recently demonstrated to boost the efficiency in related devices,
the cell achieves a power conversion efficiency of 12%, exceeding
the efficiency of dye-sensitized solar cells [127].
6.2. Multi-wall carbon nanotube (MWCNTs)
Zhao et al. reported silica coated MWCNT composites (SiO2/
MWCNTs) that were prepared by means of a sol–gel method. By
improving SiO2/MWCNTs with vinyltriethoxy, the surface energy
of the materials was enormously decreased. Therefore, a solar cell
incorporating CNTs has a harsh structure. A superhydrophobic
surface with maximum contact angle (CA) of 156 was manu-
factured. The FTIR spectra of purified MWCNTs and SiO2/MWCNTs
indicated that new crests demonstrate successful silica coverage
over the purified MWCNTs, as shown in Fig. 17a. The unique
variety of the TEM picture demonstrates that the surface of
MWCNTs is totally covered with silica. After improving by VTEOS,
the TEM picture shows little change from the SiO2/MWCNTs
except in the size of the MWCNTs. The increased size can be
 H. Hanaei et al. / Renewable and Sustainable Energy Reviews 59 (2016) 620–635 631

attributed to the changes. In their work, SiO2/MWCNTs composites
were produced by using the sol–gel system. By shifting SiO2/
MWCNTs with vinyltriethoxy, a superhydrophobic surface was
created, which showed good acid and alkali resistance and may be
reasonable to use in applications in the future [125]. Jia et al.
reported a metal-separator semiconductor heterojunction solar
cell created by depositing a carbon nanotube film onto a silicon
substrate. The nanotube–oxide–Si solar cells with polymer
embodiment showed stable efficiencies of over 10%, owing to
improved photon absorption, restrained charge recombination,
and diminished internal resistance. Parallel and arrangement
associations that maintained high cell efficiency were demon-
strated. Additionally, they reported CNT–silicon heterojunction
solar cells with power conversion efficiencies up to 7.4% in 2008
[81]. Kim reported that a superhydrophobic surface was created
through spraying with polystyrene (PS) and multi-walled
MWCNTs. Spraying is one of the least complex and least expen-
sive systems for manufacturing superhydrophobic surfaces.
In their method, MWCNTs were first sonicated for 1 h with
acetone and dried at room temperature. Acid-treated MWCNTs
and PS were blended with tetrahydrofuran for 5 h. Using the
blended MWCNT/PS arrangement, superhydrophobic cover glass

Fig. 15. SEM images of SWCNT arrays (a) random networks of SWCNT grass (array 1); (b) top of vertically aligned SWCNT forest (array 2); (c) two-dimensional SWCNT films
(array 3); (d) flip-over forest (array 4); (e) SWCNT pillars (array 5); (f) Si wafer surface [11].

Fig. 16. Frame images of falling-and-rebounding water droplet recorded in water repellence test [11].
632 H. Hanaei et al. / Renewable and Sustainable Energy Reviews 59 (2016) 620–635

patterns were created by using the spraying strategy. Spraying was
performed by a using a basic artificial tool with 400 mm distance
across nozzle and the following conditions: pressure of 2 bar,
separation from nozzle to specimen of 130 mm, and splashing
time of 10, 20, or 30 s.
After samples were manufactured, the superhydrophobicity of the
surface was represented through CA and sliding angle (SA) estima-
tions by using PS-sprayed specimens for reference. Additionally, to
observe the morphology of the manufactured specimens, field
emission scanning electron microscopy (FESEM) was used. This was
used to dissect the nanostructures observed in the SEM images [123].
According to their experiments, specimens built using their novel
technique could be a promising way to fabricate mechanically sus-
tainable super-hydrophobic surfaces, as shown in Fig. 18. Further-
more, their produced sample is not transparent enough to be con-
sidered a transparent superhydrophobic surface. However, if the
dispersion of MWCNTs could be controlled to provide sufficient
transparency after coating, a transparent superhydrophobic surface
suitable for applications could be produced.
7. Nanotechnology vs. energy storage
Although there are some nanotechnology-related products
already on the market, most areas of nanotechnology are still in
the basic research stage. Analyses of potential markets are often
vague and inconsistent. Nevertheless, market-relevant applica-
tions can be expected in fields such as optics, precision engineer-
ing, analytics, chemistry, automotive and mechanical engineering,
materials management, medical engineering, pharmaceutics and
biology. Nanotechnology is said to have the greatest influence on
the subfields of materials and production technology, with an
increase from 97 billion US$ in 2007 to 1700 billion US$ by 2015,
followed by the electronics sector (semiconductors, displays, bat-
teries among others) with a growth from 35 billion US$ in 2007 up
to 970 billion US$ by 2015, as well as on the health sector (phar-
maceuticals, medical engineering and diagnostics) with a growth
from 15 billion US$ in 2007 to 310 billion US$ by 2015. Considering
this level, even the services related to the nano-enabled products
seem to be integrated in the market data. the market forecasts for
the selected energy-technology-related market segments (Table 9)
have to be understood on the product level, i.e. where
nanotechnology-based materials or methods help to improve the
performance or quality of products [23].
The theoretical Carbon Nanotube Solar Cell is compared with a
commercial Space Solar cell in Table 10. A p–n junction diode
exhibits the best possible photovoltaic effect. Single walled Carbon
Nanotube are the only material that exhibit behavior of an ideal
diode. A 0.8 nm diameter SWCNT with a band gap of 1.4 eV would
show peak absorption in the solar band. Such a cell is calculated to

Fig. 17. (a) FTIR spectra of purified MWCNTs, SiO2/MWCNTs and v-SiO2/MWCNTs [125]. (b) Schematic diagram of CNT film coating.

Fig. 18. Fabrication of a superhydrophobic surface using the PS–MWCNT solution. (a) PS–MWCNT solution was fabricated with PS (1, 2, 3, and 4 wt% with respect to the total
weight) and MWCNTs (2, 4, 6, and 8 wt% with respect to mixed PS) in THF for 5 h. (b) The mixed PS–MWCNT solution was sprayed on the cover glass using an airbrush at a
distance of 130 mm from the cover glass for 10, 20, or 30 s (nozzle size¼ 0.4 mm, injection pressure¼ 2 bar) [123].
 H. Hanaei et al. / Renewable and Sustainable Energy Reviews 59 (2016) 620–635 633

Table 9 9. Future directions

Estimates of world nanotechnology-based product market volumes in selected
energy market segments [23].
There are several important issues that should be taken into
(CAGR ¼compound annual growth rate) account as future challenges in this field. Power conversion effi-
ciency should be compared between various allotropes of carbon
Market segment World market volume CAGR (%) with CNTs, for example. While initial results were based on Si, we
(year)
believe the concept will also be applicable to other cheaper or
Nano-optimized batteries US$169m US$1.1bn 46 more flexible thin-film substrates. The latest results indicate that
(2009) (2013) coating an antireflective layer on a CNT film could significantly
Nano-optimized fuel cells and US$2bn n/a n/a boost the short-circuit current and result in enhanced cell effi-
hydrogen storage (2008)
Supercapacitors US$275m US$713m 21
ciency of more than 15%. Currently, the maximum efficiency is still
(2009) (2014) under 15%, and future studies are essential for improving solar
Applications of superconductivity US$2bn US$3.4bn 11 cells with CNTs. Thus, although there are still quite a few barriers
(2010) (2015) preventing the realization of a commercial device, the future of the
Catalysts for energy technologies US$4bn US$6bn 8
(2010) (2015)
new generation of solar devices with polymer interlayers is pro-
Nano-optimized photovoltaics US$68m US$820m 43 mising. In terms of future work, using CNT–polymer composites as
(2010) (2017) the electrode to achieve better contact between CNT and silicon is
Microenergy harvesting for energy US$80m US$1.3bn 74
very attractive. Using different types of CNTs such as double-
autarkic sensors (2009) (2014)
Thermo-photovoltaic cells €1bn (2010) n/a n/a walled carbon nanotubes, which have been shown to have better
charge carrying capability than single-walled carbon nanotubes,
may make it possible to attain even better solar cell performance.
Table 10 Indeed, there is a need for more studies of the optical properties of
Comparison of existing Solar cells with the proposed SWCNT solar cells [128]. SWCNTs as superhydrophobic surfaces in solar cells, and other
Base material Commercial space solar cell SWCNT solar cell (metallic properties aside from thermal conductivity should be studied. In
(gaInP/GaAs/Ge on Ge SWCNT/semi conducting future studies, new approaches should be applied in several fields
substrate) SWCNT) to enhance the efficiency of superhydrophobic surfaces and make
the fabrication methods easier.
Efficiency 30% 35%
Surface o 86 mg/cm2 o25 mg/cm2
density
Peak energy/ 0.046 W/g 2 W/g Acknowledgments
Wt
Thickness 0.15 mm 0.25 mm
Cost/watt US$ 250 US$ 0.1 This work was supported by Yayasan University Technologi
PETRONAS (YUTP) grant, with grant number:0153-AA-A96.

have an efficiency exceeding 35%. This cell would produce 2 W/g

and a square meter of it would weigh just 230 g including
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8. Conclusion
The large carrier density and high mobility of CNTs increases
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The recent progress in ARCs and self-cleaning coatings, especially
coatings incorporating CNTs, has been described in this review.
There are still a few difficulties in the manufacturing of AR coat-
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for AR structures. Second, antireflective coatings must have special
properties, such as thermal and mechanical stability, for long-term
use in different situations. CNTs with different structures have
remarkable mechanical and electrical properties. Based on reports
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