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Carbon Nanotube: Synthesis and Application in Solar Cell

Article  in  Journal of Inorganic and Organometallic Polymers and Materials · July 2016

DOI: 10.1007/s10904-016-0401-z

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J Inorg Organomet Polym
DOI 10.1007/s10904-016-0401-z

Carbon Nanotube: Synthesis and Application in Solar Cell

Utkarsh Kumar1 • Samiksha Sikarwar1 • Rakesh K. Sonker1 • B. C. Yadav1

Received: 29 March 2016 / Accepted: 19 June 2016

 Springer Science+Business Media New York 2016

Abstract Carbon nanotubes and fullerenes have a cylin- 1 Introduction

drical and hollow spherical molecular structure with out-
standing mechanical and electronic properties. Their Carbon nanotubes (CNTs) discovered by Sumio Iijima in
versatility is outstanding and envisioned by the wide 1991 [1], have promising applications in the field of
application range from field emission displays to impreg- nanoscience and nanotechnology. It has a large surface to
nated metal composites, battery storage media, and nano- volume ratio, and has a specific structured arrangement of
electronic devices. The combination of simple materials, carbon atoms. Multiple chiral carbon nanotubes are used
diverse behavior, and ease of fabrication make these for the solar cell application. Chirality will increase the
materials a cornerstone topic in current research. They absorbing power of CNTs so that the semiconducting
have very wide applications in electronic devices and nanotube yields the maximum photocurrent which increa-
identifying the potential applications which is due to low ses the border range of the solar spectrum. Carbon Nan-
bias transport at several nanometers. Since valance and otubes (CNTs) have received an extraordinary interest due
conduction bands are symmetric, so they have a direct band to their exceptional and highly desirable thermal, electrical,
gap and due to this it can be used in optical emission. CNTs and mechanical properties [2–5]. The combination of
can be synthesized via three techniques such as arc dis- CNTs with other nanomaterial or functionalized with dif-
charge, laser ablation and chemical vapor deposition, but ferent acidic groups is used as gas sensors or biosensors,
the CVD process is mainly used for the synthesis because sometimes it can also be functionalized for making dye
the CNT yield in such case will be more than 98 % pure. sensitized solar cell.
100 % pure MWCNTs having multiple chirality results the CNTs have been synthesized by many techniques, but
enhanced optical property and better employment as light CVD technique is the best method to synthesize the nan-
harvesting material. The dye sensitized solar cells are otube with the controlled conditions [32, 33]. As in the arc
fabricated using CNT composites and functionalized nan- discharge process if catalysts such as nickel, cobalt are
otubes. The synthesis of CNT and its application in solar used, then single walled carbon nanotubes (SWNT) are
cell are presented in this short review. formed and without using catalysts multi walled nanotubes
(MWNT) are formed. Some other parameters like length
Keywords Carbon nanotubes  CVD  MWCNT  Solar and the diameters are controlled by the flow of carrier
Cell gases, temperature and nature of evaporating materials in
case of CVD.

1.1 Carbon Nanotube

& B. C. Yadav
[email protected] Carbon nanotubes are the seamless cylinders formed by the
1 wrapping of graphene sheet along the axial direction.
Nanomaterials and Sensors Research Laboratory, Department
of Applied Physics, Babasaheb Bhimrao Ambedkar Depending on rolled graphene sheet, CNTs can be classi-
University, Lucknow, U P 226025, India fied as single walled nanotubes (SWNT) and multi walled

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nanotube (MWNT) [6]. The rolling vector (chiral vector)

decides the structure of nanotube which may be either in
zig-zag, armchair or chiral form. The physical, chemical Extrusion or root growth
and optical properties of carbon nanotubes are controlled
by the synthesis process. Metal
C C

1.2 Synthesis of Carbon Nanotubes Tip growth

C
Carbon nanotubes are produced by three main techniques; Metal

arc discharge, laser ablation and chemical vapor deposi-

tion. Growth of CNTs by arc discharge and laser involve Support

the addition of carbon dimers (C2) to the CNT edges. Fig. 1 Growth mechanism of carbon nanotubes
Sometime CNTs are also prepared by flame synthesis using
camphor or mesh like structure [7].
In the arc discharge process the atmosphere of inert gas electrons as carriers are generated at high temperature
or some carbon containing gas is created by an arc dis- which creates nucleation point for the growth of nanotube.
charge between two carbon electrodes [8] with or without Carbon atoms are decomposed from methane gas and
catalyst. In the laser ablation technique, a high power laser deposited on the surface of Ni particle dissolved into bulk
beam impinges on a volume of carbon containing feedstock and form sub-stoichiometric nickel carbide at the early
gas. Laser ablation produces a small amount of clean stage. This carbide phase then decomposes into metallic
nanotubes [10], whereas arc discharge method generally nickel particle and outside graphite layers which encapsu-
produces large quantities of impure CNTs. late the host nickel particles. The metal particle is then
CVD results in MWNTs or poor quality SWNTs. The squeezed out by a strong pressure buildup due to the for-
SWNTs produced with CVD have a large diameter range. mation of graphite layer at the internal surface of graphite
envelope. This is possible because of the liquid like
1.3 Different Mechanism of Synthesis behavior of the metal due to melting point depression from
the dissolution of carbon atoms that remained in the bulk;
1.3.1 Growth Mechanism the fresh surface of the squeezed out Ni particle will further
decompose the methane and continues the growth of car-
Nanotubes are formed by a gas phase process which starts bon nanotube.
with evaporated gas from the source of carbon; gases will
be evaporated from a surface due to heating by laser pulses
or through heating by arcs or solar radioactive fluxes. Each 2 Different Synthesis Techniques
technique has common aspect and they have various pro-
posed mechanism for the formation of SWNT. 2.1 Arc-Discharge
Such process consists of three steps; firstly the formation
of a precursor consisting of some metal nanoparticles that In this method, under the inert atmosphere, carbon vapor is
provides the nucleation point at high temperatures then created by an arc discharge between two carbon electrodes
dissociation of gas takes place. Later the carbon atoms are [8] with or without catalyst. The arc discharge method
deposited on the nucleation point and the growth will start initially used for producing C60 fullerenes [9], is the most
in two ways: in root growth the catalyst will be placed at common and easiest way to produce carbon nanotubes.
the bottom of the tubes and in tip growth the catalyst will at However, these techniques produce a mixture of compo-
the top of the tubes (Fig. 1). nents and require splitting of nanotubes from the soot and
the catalytic metals present in the basic product.
1.3.2 Reaction Mechanism This method produces nanotubes through arc-vaporiza-
tion by two carbon rods [11] placed end to end with distance
Carbon nanotubes are also formed by reactions, in which at approximately 1 mm and the chamber is usually filled with
the hydrocarbon molecules are decomposed on free Ni, Co inert gas (helium/argon) at low pressure (between 50 and
metal surface, producing carbon atom with the simultane- 700 mbar). In recent investigations, it is found that produc-
ous evolution of molecular hydrogen. tion of carbon nanotubes in liquid nitrogen, deionized water
Growth of carbon nanotubes and nano-fibers are based and NaCl solution are also possible. A direct current of
on decomposition on supported Ni crystal by magneto 50–100 A driven by *20 V creates a high temperature
metric using methane. This is due to the reason that high discharge of 2000–3000 C between the two electrodes. The

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Table 1 Synthesis of carbon nanotubes by an arc discharge method under various conditions
Arc discharge Circumstances Product Remark Ref.
method

Arc discharge KCl/FeS catalyst under the atmosphere of Ar DWNT (double walled Large and high quality, diameter [12–16]
nanotubes) 2–6 nm
Mixture of catalyst using Co/Ni/Fe with Large length and diameter of
small quantity of S in the atmosphere of Ar 4–7 nm
Catalyst used FeS, CoS in the atmosphere of Bundles of high quantity
hydrogen nanotubes
Using graphite electrode in the atmosphere Optimization process
of hydrogen
Plasma rotating Pure graphite electrodes using hydrogen CNT Large scale of production [17]
arc discharge atmosphere
Liquid arc Deionized water MWNT, carbon onions, CNTs Metal filled inside the tubes [18–30]
discharge NaCl solution with electrodes in liquid MWNT, carbon nano capsules, Irregular morphology with
environment SWNT disordered shape
Toluene with using different catalyst Tube like and spheroid Continuous production of tubes
nanocarbon,
Y/Ni and CaC2 catalyst under the SWNT, fullerenes, SWNT High purity and high yield with
atmosphere of helium fibers, metallo-fullerenes, the diameter of 0.9–14 nm
CNTs
Using polymer such as PVA and PVA/Fe and MWNTs, sheet like structures, The type of product totally
various Fe sources spherical particles, beaded depends on the catalytic
CNTs composition

discharge vaporizes from one carbon rod and deposited on for swnt
for mwnt
the other rod. The yield of nanotubes depends on the uni- Power supply
Power supply
formity of the plasma arc and the temperature of the deposit
form on the carbon electrode. Synthesis of CNTs by the Inert
discharge method using different conditions is presented in Inert atmosphere atmosphere
Table 1. Cathode
The above table describes how the nanotubes were graphite rod
Cathode Anode With catalyst like Anode
formed by changing the surroundings of arc discharge graphite rod Co, Ni,
chamber and material used in the electrode. For high yield
and purity of CNTs, fullerenes etc. Y/N2 and CaC2 were
used under helium atmosphere. Carbon onions, MWNT
and CNTs were prepared by using the deionized water in
liquid arc discharge method. Fig. 2 Arc discharge method for synthesis of SWNT and MWNT
The nanotubes obtained during this process are usually
short in range with the diameter ranging from 0.6 to 1.4 nm
for single walled and 10 –14 nm for diameter multi-walled 2.2 Laser Ablation Method
nanotubes. These tubes can be single walled tubes or
multiple walled nanotubes, depending whether the catalyst A standard laser ablation process occurs in a tubular
is placed in rod or not. This method is relatively easy to furnace in which a block of graphite mixed with the
implement, and has yield of *30 %. The nanotubes pro- catalytic metals such as Ni, Co, Pt etc. is heated from 700
duced in such process having high impurity and large to 1500 K. The graphite block is then targeted with a high
defects, in comparisons with other method; and lengths of energy laser and argon (Ar) gas is pumped in the direc-
the tubes are somewhat random. tion of laser. As laser ablates the target, carbon nanotubes
Both the single walled nanotubes and multi walled are formed and carried by the gas flow into a cooled
nanotubes created by this method are to be decided by the copper collector.
synthesis process followed by the doping of Ni/Co in anode The mechanism for the formation of nanotube is same as
which yields the SWNT and the use of pure graphite rod the arc discharge in which the laser will penetrate the target
without any doping yields the MWNT (Fig. 2). material and the vapor of carbon is created inside the

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Table 2 Synthesis of carbon nanotubes by laser ablation method at various conditions

Laser Materials Circumstances References

CO2 continuous SWNT bundles with bamboo like Laser power 400–900 W [31]
wave structure At room temperature
Ar atmosphere under 200–400 torr
SWNT bundles High temperature 1100 C with Ar and He atmosphere under 50–500 torr [32]
CO2 pulsed wave SWNTs Laser power 12-9-6 kW with Ar and N2 atmosphere 50–450 torr [33–35]
Pulsed Nd-YAG Thin SWNT Gas flow rate [36]
Laser SWNT bundles Laser intensity 532 nm, 1024 W [37]
Using catalyst C,Ni,Co under atmosphere of Ar
Furnace temp 800–1150 C
SWNT Laser intensity varies, furnace temperature 550 C and depends on gas [38]
flow rate and pressure
XeCl excimer SWNT bundles, fullerenes, Furnace temperature 1100–1350 C using catalyst C, Co, Ni under Ar [39]
atmosphere
KrF excimer MWNT, nano onions Target metals using composite of C/Co, C/Co/Ni in the atmosphere O2 [40]
and Ar at room temp
Carbon nano horns Using pure carbon in the atmosphere of Ar, Ne, He [41]

chamber which will grow on the cooled copper collector by 2.4 Precursor
growth mechanism. This process may not be easily
implemented, but high heating furnace is required for yield Carbon containing compounds have been used as precur-
up to 70 %. sors and the most common ones are: carbon monoxide
Table 2 describes the production of nanotubes by using (CO) [46, 50, 51], methane (CH4) [52], ethylene (C2H4)
different types of lasers with varied target materials and [48], acetylene (C2H2) [53], benzene (C6H6) [45], toluene
atmosphere. Power and intensity of laser source cause the (C7H8), ethanol (C2H5OH) [45], and methanol (CH3OH).
phenomenon of ablation which gives CNTs of different Each gas decomposes at different temperatures, cause to
diameters and lengths. grow nanotube. Sometimes rate of dissociation will be
controlled by the pressure of the gases such as CO, which
will dissociate more at high pressure and causes to increase
2.3 Chemical Vapor Deposition (CVD) Method the yield of nanotubes. The flow rate causes growth of
nanotubes; sometime larger nanotube will be formed at
A typical CVD process involves a substrate, which is slow flow rate in comparison to higher flow rate. Some-
exposed to one or more volatile precursors, placed in times carbon precursor also produces unwanted nanotubes
quartz tube and heated to desired growth temperature. by premixed gas in the cylinder, therefore, for producing
Carbon carrying gas is flowing through the quartz tube with well aligned or well controlled nanotubes, a gas filter or
predetermined flow rate and temperature. After growth sometimes cleaning gas is used in the CVD chamber.
mechanism the furnace is slowly cooled down and the
wafer is inspected for the nanotube growth. 2.5 Electrical Properties of CNTs
Table 3 describes the synthesis of CNTs by using dif-
ferent substrates in CVD chamber by the variation of Electrical property of carbon nanotube can be easily
temperature and carbon containing gases in which the understood from the band structure of graphene [54]. By
lowest growth is found at 650 C using CO2, but in this analyzing the band structure by zone folding approxima-
case the gas released is very toxic. To avoid the formation tion we found that the allowed k-points in the Brillouin
of toxic gases, methane gas is used for this synthesis which zone are confined to parallel lines. The band structure of
easily gets hydrolyzed. the graphene gives an idea of finding the model of nan-
These techniques were firstly used for silicon substrate otubes and its electronic energies along the allowed lines as
to grow single walled nanotubes [49]. The CVD process shown in Fig. 4 in which the subfigures (a) (b) and
[42, 48, 50, 51] has also gained the popularity for pure (c) represent the band structure of graphene, p-type and
SWNT growth (Fig. 3). n-type nanotubes respectively.

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Table 3 Synthesis of Carbon Nanotube by Chemical Vapor with different gases on various types of substrate
Precursor Carrier gas Temp. Flow rate Advantage Disadvantage Reference.

Si/SiO2 with CO with H2 900 C 1000 Sccm for both gases * Good growth is * Self deposition causes [42, 43]
some (30–70 %) achieved by adding amorphous carbon
catalyst like hydrogen deposited in quartz tube.
Fe * Efficient * Hazardous nature of CO
production of long so exhaust properly.
SWNT by fast * Metal impurity
heating technique destroying the flow rate
controller
Co either in C2H5OH 750 C without 450 Sccm for Ar 50 Sccm * Low temperature * Sometimes impurities [44, 45]
solution or with Ar H2 for H2 method for growing may be found as
in thin film and H2 gas 860 C with SWNT analyzed under Raman
form H2 * Ultra-long spectroscopy
nanotube and
* Multiple chiral
nanotubes are
found.
Silicon wafer CH4 with H2 940–980 C 2 sccm for CH4 and 4 * Low flow rate * High temperature [46, 47]
with Sccm for H2 required for the requires for growth
Mueller growth mechanism. mechanism
catalyst * Ultra long
Nanotube will be
obtained.
Si/SiO2 with Ethylene 750 C 150 Sccm for ethylene and * Ultra tall vertical * Defects may be created [48]
Fe catalyst with water 40 Sccm for Ar. forest of nanotube some time
vapor and Also cooled after growth is to found,
Ar gas with flow of Ar at 600 * Water will help the
Sccm and H2 at 400 self-cleaning and
Sccm increases the life
time

Fig. 3 Reaction mechanism in Main gas

CVD chamber flow

Gas phase reaction

Desorption and
Volatile reaction

Desorption of
precursor
Transport to
surface

Surface diffusion Step growth

Adsorption of
Film precursor Nucleation
Island growth

The length and orientation of these lines are determined the parameters can turn CNTs from metallic to semicon-
by the (n, m) pair of integers. Although this approximation ducting state.
also provides us many useful details about the electrical Each graphite structure has carbon, which contains two
properties of carbon nanotubes and a slight difference in 1s electron, one 2p electron and three sp2 electron [55]. The

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Fig. 4 Band structure of CNT

a band diagram of graphene,
b band diagram of metallic CNT
c band diagram of
semiconducting CNT

three sp2 electrons form three bonds in the band at the 3 Functionalization of CNTs
plane of graphene sheet, leaving an unsaturated p-orbital.
This p-orbital, perpendicular to the graphene thus the CNTs have inert surface property, but they are generally
nanotube surface, forms a delocalized p-network across the insoluble in solvent because of strong Vander Wall inter-
nanotube responsible for the electronic property. Armchair action that tightly holds them together forming bundles.
CNTs should show metallic behavior having band degen- For many other applications, the solubility will increase by
eracy between highest p valance band to lowest p con- some modification called functionalization. The function-
duction band. The point at which these bands meet, is alization method will be categorized into two following
known as Fermi level and a new type of CNT i.e. metallic major groups:
nanotube is formed. The conduction of metallic CNTs is
ballistic and least sensitive towards gate voltage. Semi-
conducting nanotube with small band gap is useful for 3.1 Inside Functionalization (Endohedral)
transistor and sensor applications (Fig. 4).
In this, nanoparticles of different materials are filled inside
2.6 Chemical Properties of CNTs the nanotubes for functionalization, which can be achieved
by spontaneous penetration of exploiting the situation
According to band structure nanotubes are bonded where nanotubes are filled with colloidal suspensions. This
according to sp2 hybridization so the pyram-idalization process followed by the capillary action of the tubes; or by
angle Hp is 0. Hamon et al. [56] and Niyogi et al. [57] wet chemistry, when the nanotubes are filled with some
observed that the angle of pyramidalization of a carbon compounds, they will react at a particular temperature and
atom is not 0 but it is 11.6 at the end caps, which is very pressure after several circumstances resulting nanoparticle
close to tetrahedral. But the angle of pyramidalization of which are trapped inside the nanotube [67, 68].
sidewalls of nanotube is 6 due to this finite value, the
tubular nanotube introduces strain. p-orbital mismatchs the
strain present in nanotube [58]. The end cap [59] has large 3.2 Chemical Functionalization From Outside
reactivity because it has a large pyramidalization angle and (Exohedral)
low reactivity for side walls [60] due to low pyramidal-
ization angle. This group can also be subdivided into three subgroups
Defect in nanotube may arise during the synthesis pro- based on the mechanism of attachment in which the dif-
cess due to the presence of stone walls like structural defect ferent groups or compounds are attached to the sidewall of
[61–63] builds sp3 character on the hexagonal network of the nanotube:
tubular nanostructures. Defects will increase the reactivity (i) Covalent functionalization in which the func-
of nanotubes thus the gases will adsorb on the surface so tionalization group is attached either on the
the rate of functionalization will be increased [64–66]. defect side or at the end of the tubes [69, 70].

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(ii) Covalent functionalization through ‘‘sidewall 5 Mechanism of Solar Cell

functionalization’’ [71, 72].
(iii) Non-covalent exohedral functionalization is the The working of solar cells is based on the transition of
process in which the nanotubes are wrapped free electrons by gaining the extra energy when photons
inside the polymer [73, 74]. are incident at the film surface. Now, after analyzing the
band structure of the solar cell, Bu Jong et al. found that
Table 4 describes the different methods for functional-
cell gains energy from the photons and generates free
izing nanotubes and their applications in different field
electrons, which recombines and generates some photo-
with various advantages and disadvantages. The sidewall
voltaic current so the binding energy of the film will
functionalization with cyclo and nucleophilic addition
decrease which indicates that the maximum number of
radical reactions is the best for solar cells.
electrons are generated. Therefore, for increasing the
efficiency of solar cell, thin film based method is used in
which large amount of light is absorbed for a broader
4 CNT as a Solar Cell range of the solar spectrum. Theory of solar cell is
defined in following steps:
In the present world most of the energy is produced by the (1) Photons in sunlight strike the solar panel and are
fossil fuel, but they also produce very dangerous and absorbed by semiconducting materials, such as
hazardous gases like carbon monoxide, which pollutes the silicon and germanium.
environment every second. Therefore for producing clean (2) Electrons (negative charged) are excited from their
energy we use solar energy which is eco-friendly and does current molecular/atomic orbitals. Once excited, the
not disturb the economical balance. For utilizing more and electron can either dissipate the energy and return to
more solar energy, solar cells may be fabricated which its orbital or travel through the cell until it reaches an
converts solar energy into the electrical energy and this electrode. Current starts flowing through the material
electrical energy may be stored in batteries through to cancel the potential and this electricity is captured.
charging. Operation of a solar cell depends on following Due to the special composition of solar cells, the
factors: electrons are only allowed to move in a single
• Absorption of light to create electron–hole pairs. direction.
• Diffusion of charge carriers. (3) An array of solar cells converts solar energy into a
• Separation of electron and hole. usable amount of direct current (DC) electricity.
• Collection of charge carriers. On analyzing those solar cells, it was found that the
efficiency had increased by a little amount. Therefore, for
further increasing the efficiency of solar cell, carbon nan-
4.1 Efficiency otubes were used in these cells which acts as a p-type
semiconductor and silica acts as n-type semiconductor and
The efficiency of solar cells is categorized in different thus hetro-junctions were formed between silica and
classes like thermodynamic efficiency, reflectance effi- SWNT as shown in Fig. 5.
ciency, charge carrier separation efficiency and reflectance From Fig. 5, we analyze that the CNTs act as p-type
efficiency. The overall efficiency of solar cells is the pro- semiconductor and silica based materials act as n-type
duct of all these individual efficiencies. semiconductor so the transition of electrons and holes
The solar cells usually have a high voltage dependent start when hetero-junction would be formed establishing
efficiency curves, temperature coefficients and shadow a certain band-gap between them. After emerging the
angles. Due to difficulty in measuring these parameters light on such cell the holes gain energy and transfer
directly, we use the ratio of powers to measure the effi- electrons from silica to CNT thus generating the photo-
ciency of solar cell. voltaic current which is stored in the battery. After
Solar cell efficiency (P) is defined as the ratio of output analyzing SWNT, it was found that the absorption power
power to the input power was increased on replacing the SWNT to poly chiral
MWNT. The MWNT absorbed a broad range of
Y output power frequency spectrum in comparison with all other solar
¼ : ð1Þ
input power cells.

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Table 4 Functionalization of carbon nanotubes by various methods
Functionalization type Mechanism Advantage Disadvantage Area of application Ref.

Exohedral functionalization
Covalent functionalization
Sidewall functionalization Cyclo and nucleophilic addition radical * Production of stable functionalized * Destruction and * Chemical sensors [69, 70]
reactions CNTs shortening of carbon * LED
* Easily dispersed in chemical solvent nanotube which
* Solar cell
with a high degree of disintegrate the chemical
and physical property * Transistor
functionalization
Defect or end functionalization Oxidation of carbon nanotubes e.g. * Easily produced and simply dispersed * Having small surface area * Chemical sensors [71, 72]
carboxyl functionalization in polar solvents with some destructed * LED
network
* Solar cell
* Transistor
Non covalent functionalization Vander wall interaction in which CNTs * Electronic, chemical property and * Unstable nanotubes will * CNT based polymer [73, 74]
are wrapped with polymers length of tubes will not be affected found and dispersibility in composite used in
covalent solution is low aerospace
* CNT based biomolecule
composite used in
biosensors
Endohedral functionalization Wet chemistry in which materials are * Structure is preserved and length is * Outer surface remains * Hydrogen storage [67, 68]
filled inside the tube by capillary also not affected unusual materials
action * Drug delivery system
J Inorg Organomet Polym
J Inorg Organomet Polym

CB Table 5 depicts the efficiency of synthesis techniques

p-type with advantages and disadvantages of different types of
solar cells. It can be seen that the efficiency of solar cell
VB
n-type increases on incorporating the carbon nanotubes inside the
cell. Bu-jong et al. had fabricated new solar cell by using
Carbon nanotubes (CNTs) which is twice efficient for
Light
converting sunlight into electrical power than the previous
CB one [75].
The other carbon nanomaterials like fullerene and gra-
phene can also be used for the fabrication of solar cell as
VB
they show the photovoltaic properties by enhancing the
absorption range. R.G. Shrestha et al. [82] synthesized one-
Fig. 5 Diagram showing the variation of band structure of CNT dimensional (1D) single-crystalline fullerene C60 nanorods
based solar cell
by using ultrarapid interfacial formation method at room
temperature. The nanorods were of *11 lm in length
and *215 nm in diameter with hexagonal close-packed
6 Thin Film Based Solar Cell
crystal structure. The optical transitions revealed the
dominance of charge transfer excitonic transitions with
Thin film technique reduces the amount of material
excellent charge transfer characteristic. In another work,
required for creating solar cells and most of the thin film
L.K. Shrestha et al. [83] reported the surfactant-triggered
based solar cells are manufactured by the sandwiching of
assembly of fullerene (C60) into 3D flower-like micro-
thin film between two panes of glass to make a module.
crystals at the liquid–liquid interface following the growth
Cost comparison for per unit power production between
of crystals using a liquid–liquid interfacial precipitation
fossil fuel combustion and silicon solar cells was found to
(LLIP) method by layering surfactant solution. These
yield a large difference. The main component of these cells
microcrystals have a better future scope in solar cell based
is a thin material coating. Fabrication of these solar cells
opto-electronic devices (Fig. 6). In another work [84], he
requires a very low quantity of material (compared to sil-
synthesized macroporous and mesoporous fullerene crys-
icon wafers, it is only 1 %). This is the main reason why
tals with bimodal pore architectures using the same (LLIP)
this technology is cheaper to some extent. The majority of
method which can be used for the fabrication of nanode-
this type of cells is made from amorphous silicon that is
vices including organic solar cells.
devoid of a crystalline structure. These are much cheaper
Graphene is different from most 3-d materials. Intrinsic
fabricators, but have a very low efficiency of about 8 %.
graphene is known to be a zero-gap semiconductor or a
Incorporation of nanomaterials into thin-film solar cells
semi-metal. It has very high electron mobility, almost two
enhances conversion efficiency at a lesser cost. Now-a-
times than that of Si thereby making it highly conducting.
days, many nanomaterials are investigated for photovoltaic
As well, since it causes a direct band gap, thus can absorb
applications. The following are the three benefits of using
more photons in a much thinner region as compared to
nano-structured layers in thin-film solar cells:
indirect band gap semiconductors like Si. Graphene, hav-
(a) The effective optical absorption path becomes larger ing special optical properties, can be applied as transparent
than actual film thickness because of multiple electrodes and interconnects the two sub cells in tandem
reflections. solar cells. It is a carbon sheet of one atom thickness,
(b) There is a reduction in recombination losses due to consisting of condensed six member rings. The carbon
the shorter path followed by light-generated electrons atoms are sp2 bonded and form a hexagonal 2D lattice.
and holes. The absorber layer thickness in traditional Ideal graphene has a very high carrier mobility of the order
thin-film solar cells is in lm, while in nano-structured of 105 cm2/(V–s) at room temperature. This exceeds the
solar cells it can be as thin as 150 nm. carrier mobility of Silicon by one or two orders suggesting
(c) Energy band gap of different layers, made for desired that graphene can be used as a replacement for Silicon in
design value, uses nanoparticles of various sizes. This nano-electronics. Besides its exceptional electrical prop-
allows more design flexibility in the absorber and erties, it has very high mechanical durability. Graphene
window layers of the solar cells. ‘Al’ and ‘W’ are used also has a tunable bandgap. 3D graphene is known as
as dopants for enhancing photovoltaic properties, Al- graphite. It is the thinnest material with highest strength; it
doped titanium dioxide and electrodes increase open is also highly transparent & highly conducting. This makes
circuit voltage (Voc), but reduce short-circuit current (Isc) graphene an attractive option to form transparent electrodes
[81]. in solar cells [89].

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Table 5 Development of solar cells by various methods

Materials Deposition techniques Theoretical/experimental Junction Advantage Problem Reference.
efficiency

CdTe/CdS Evaporation sublimation, screen 30 %/16 % Controversial Good stability, Toxicity of [76]
printing technique high module Cd,
efficiency availability of
Te
CuIn (G)- Evaporation, sputter deposition, 28–30 %/20 % Homo- Good stability Multiple [77]
Se(S) electroplating, spray deposition junction binary
phase,
cell to cell
mismatch
CZTS(Se) PVD, sputtering, spray pyrolysis, 30 %/9.6 % Direct Band Abundant, Mixed [78]
screen printing gap 1.4- cheap, green phases,
1.6 eV material difficult to
synthesize
PEC using PVD, sputtering, 30 %/upto 12 % Direct band Lighter, flexible Difficult to [79]
dyed TiO2/ Electroplating gap manufacture
TCO
CNT based CVD, sputtering, electroplating More than 30 %/16 % Direct band Lighter, Costly [80]
gap flexible,
highly
efficient

Light
Ag
containing SWCNTs have so far suffered from limited
MoOx current and voltage, and therefore poor power-conversion
ZnO, NW
ITO efficiencies [75].
s-MWCNTs

Glass
7 Conclusion

A systematic development of carbon nanotubes as a func-

tion of synthesis, functionalization and application in solar
cells has been reviewed. Poly-chiral nanotubes absorb a
Fig. 6 Fabrication of solar cell using carbon nanotube broader range of the solar spectrum in comparison with the
mono-chiral nanotube and are employed as thin film based
Thin-film photovoltaic materials are better than con- solar cell. The efficiency is also very high in poly-chiral
ventional solar-cell materials (such as silicon) because they nanotube based solar cells.
are lighter, more flexible and cheaper to fabricate; working
Acknowledgments Mr. Utkarsh Kumar is grateful to Babasaheb
of these cells is based on the principle in which they absorb Bhimrao Ambedkar University, Lucknow for UGC fellowship.
photons from sunlight and convert them into electron–hole
pairs (or excitons). To generate electric current, an electron
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