Perovskite: A Breakthrough in Solar Cell Technology

Syuaibatul Islamiyah
Ecology : Energy Sustainability
Solar cells have been considered as a
notable source of renewable energy in the
future over the past 60 years [1]. Some
popular solar cells including a single-crystal
silicon and gallium arsenide (GaAs) singlecrystals based are up to 25% and 29% in
efficiency, respectively [2]. Meanwhile, a
thin-film polycrystalline based solar cell,
which is regarded as a feasible alternative of
silicon cells, has an overall efficiency over
than 20% [2]. A new comer of this family is
organic-inorganic halide perovskites [3,4].
The efficiency of these cells have increased
from 3.8% to 20% in just 5 years after it
was initially introduced in 2009 by
Miyasaka et al., an achievement that needs
decades effort for other
conventional
materials [5-9].

Figure 1. Power conversion efficiencies of

perovskite based solar cell in comparison to other
technologies

Perovskite or perovskite structure is

the material which has the same type of
crystal structure as calcium titanate
(CaTiO3). The general chemical formula for
perovskite compounds can be written as
ABX3, where site A and B coordinate

with 12 and 6 X anions to form

cuboctahedral and octahedral geometries
[10]. A and B sites are usually cations
with different size of diameter while X is
often oxygen or other large ions such as F
and Cl [11,12]. One of the perovskite
material which draws a great attention in the
solar cells research field is the organometal
halide CH3NH3MX3 (M= Pb or Sn, X=Cl,
Br,or I). The structure and physical
properties of this organic-inorganic hybrid
perovskite was first reported in 1978 by
Dieter Weber [13]. The general crystal
structure of this material is shown in Figure
2.

Figure 2. Crystal structure of cubic metal halide

perovskites with the general formula ABX3. A site
(green) are occupied by organic or inorganic cations
while B site (grey) and X (purple) are occupied by
metal cations and halides, respectively.

Its crystal structure, ABX3, is the key

to understand its potential as photovoltaic
material. The specification and practical
advantages of perovskite as photovoltaic
material are:

Band Gap.
The band gap is the minimum energy
required to transfer an electron from the
valence band to the conduction band. The
value of the band gap varies for each
material. In photovoltaic cells, the band gap
value shows the ability of the material to
absorb the photons from the sunlight.
According to Shockley-Quiesser limit, a
band gap value of 1.34 eV will yield the
maximum solar conversion efficiency of
33.7%. Comparing to the silicon which has a
band gap of 1.1 eV resulting 33.3% in
efficiency, perovskite has band gap of 1.55
eV which only reaches efficiency of 31%,
theoretically [14]. Yet the tunable band gap
characteristic of perovskite enables this
material to be optimized by varying the
chemical
elements
composition
to
synthesize this material. Recent research
shows that mixed Sn and Pb perovskite solid
solutions can reach a narrower band gap of
<1.3 eV, but its efficiency is still questioned
[15].
Low-cost Fabrication
Coming up with cheap and the most
efficient solar cell is the key to industrys
growth. One of the advantages of using
perovskite based solar cell is its simplicity
and cheap fabrication process. While silicon
or GaAs solar cell require multi-step
processes and relatively high temperature
and vacuum conditions, the making of
perovskite solar cell can be done in
laboratory environment with simple
chemical methods.
The formation of perovskite structure
usually follows this general formula AX +

BX2 ABX3. The following reaction is the

typical example for that formula:
CH3NH3I + PbI2 CH3NH3PbI3
The kinetic reaction of perovskite
formation is considered fast and controllable
by using mixed solvents in order to get the
most efficient film formation [16].
There are various techniques to
synthesize hybrid perovskite, mainly a onestep or two-step sequential deposition
methods are widely used now. Both of the
methods require the temperature below 1000
C and no special facilities needed.
Synthesizing CH3NH3PbI3 using a
one-step method is started by mixing two
precursors, CH3NH3I and PbI2, in organic
solvent such as N,N-dimethylformamide
(DMF) or dimethylsulfoxide (DMSO) at 60
C for 12 hours [17]. The ratio between two
precursors are varied according to the target
perovskite. The perovskite liquid then is
deposited directly to form a film and
followed by thermal annealing to produce
the final perovskite phase [18].
The two-step method or sequential
deposition is typically done by spin coating
the substrate with PbI2 dissolved in DMF at
70 C. After drying and cooling in the room
temperature, the substrates then are coated
with CH3NH3I for 20 seconds, followed by
rinsing with 2-propanol and drying at 70 C
for 30 minutes [18]. Figure 3 shows the
difference between one-step and two-step
method in fabricating the perovskite solar
cell.

Figure 3. Preparation of CH3NH3PbI3 solar cell

Regarding the cost of fabrication, a research

group in Northwestern University prepares a
laboratory scale of perovskite fabrication in
order to introduce perovskite solar cell to
undergraduate students. The overall cost to
produce one cell using the standard
laboratory equipment is estimated below 20
cents with 2-5 hours processing [19].
Flexibility
Unlike the other solar cell
technologies, due to its low temperature
processing, perovskite solar cells can be
made transparent or even in different colors.
This means they can be placed in spots that
wouldnt be appropriate for opaque silicon
panels, such as windows. They also require
less space and are not easy to break.
Basically, perovskite solar cells
function efficiently in two main device
architectures. The initial prototypes were
based on the classical architecture of dyesensitized solar cells known as mesoporous
structure. More recent works demonstrate a
simpler geometry which enables simplified
device configuration and fabrication
procedure, known as planar structure or thin
film perovskite solar cell. In the mesoporous
structure, perovskite mainly act as light
absorber while the charge transport occurs in

other materials. The typical configuration of

this structure is fluorine-doped tin oxide
(FTO)/dense, compact oxide such as TiO2,
mesoporous oxide/ perovskite/ charge
transporting layer/ electrode. The first
attempt to make perovskite as solar cell was
done by Miyasaka et al. at 2009 based on
this structure. The device only generated
3.8% of PCE with TiO2 used as mesoporous
oxide [5]. More recent work demonstrated
the replacement of mesoporous TiO2 with
Al2O3 resulted in increasing of open-circuit
voltage and improvement in efficiency of 35%. Later, it was realized that the scaffold is
not needed anymore since the perovskite
itself can act as the electrons and holes
transporter [20]. This finding then led to the
development of thin-film perovskite solar
cell. The difference between mesoporous
and planar architecture is shown in Figure 4.

Figure 4. Architectures of perovskite solar cells. (a)

Hybrid perovskite solar cell on mesoporous TiO2; (b)
Planar hybrid perovskite solar cell

Based on the planar structure,

perovskite shows ambipolar carrier transport
and long carrier life times. Due to this
nature, the electron and holes transport
occur in the bulk of perovskite itself. This
configuration exhibits the efficiency of 15%
better than those with the scaffold [20]. A
single step deposition was used in the initial
attempt to fabricate planar perovskite solar
cell. Removing the existing scaffold resulted
significant effect on the coating and growing

of the perovskite material that additional

optimization is often necessary when
convert a deposition method from
mesoporous to planar structure. In addition,
the perovskite film also can be prepared
through sequential deposition which resulted
in high performance (15.7%) [21]. Chen et
al. at also developed a method called vapor
assisted solution processing (VASP) that
used the reaction between CH3NH3I vapor
and pre-deposited PbI2 to form the final
perovskite film. The result was proved to be
excellent with full surface coverage, large
grain size on the micrometer level and
improved film conformity which provide a
great promise in future high performance
flexible and portable devices [22].
Moreover, by tuning the interface states and
matching band diagram, Zhou et al. obtained
an efficiency of 19.3% recently [8].
Challenges and Perspectives
Toxicity of Pb atoms
Since lead compounds are very toxic
and harmful to the environment, creating a
lead-free perovskite without sacrificing its
performance is a big concern in perovskite
solar cell research. Several attempts have
been done by scientist to synthesize leadfree perovskites. One of the most common
research is replacing lead metal with tin
metal. CH3NH3SnI3 and CsSnI3 show
promise, but their extreme sensitivity to
oxygen is another big issue to be concerned
before their practical application [23-25].
Subtituting lead with other nontoxic metal
element will also provide more tunable
bandgaps. A series of CH3NH3Sn1xPbxI3
showed various bandgaps ranging from 1.17
eV to 1.55 eV. The highest PCE were

yielded from CH3NH3Sn0.5Pb0.5I3 showing a

4.18% of efficiency. The other attempt is
CH3NH3SnI3-xBrx which exhibit a 5.73% of
efficiency [26]. Another alternatine is
CH3NH3SnI3 on TiO2 scaffold which
achieved a PCE of 6.4% [27]
Long-term stability
Although it has been proven that
perovskite holds a promising future for the
solar cell technologies, stability is still big
challenge for this material. CH3NH3PbI3, a
widely studied perovskite for solar cell, is
known to be sensitive to polar solvents like
water. It easily dissolves and decomposes
into PbI2. In addition, the material also
suffer from extreme instability with light
and heat. Both the perovskite material as
well as the transport material used in the
device contribute to the instability of
perovskite solar cell. As for the perovskite
itself, the organic species are easy to
evaporate when placing the film in the
environment containing moisture.
The
phase transformation of the perovskite
which occurred at 330 K resulted in
increased instability under solar cell
working conditions. Besides perovskite
itself, the transporting layer used in the
device such as TiO2, PCBM or PEDOT:PSS
can also cause the instability of the cell. For
example, TiO2 layer is sensitive to UV light,
PCBM is not stable in the air and
PEDOT:PSS becomes a concern when it
comes to the long-term stability of solar cell
due to its acidic nature [23].
Various attempts have been done to
reduce the instability and increase the
performance of the perovskite solar cell.
They include replacing TiO2 with Al2O3

which provide better stability with light

[20], applying encapsulation techniques to
get better stability with the air [28], and
using certain polymers to prevent thermal
instability [39]. Carbon material used as the
back layer contact is believed to act as
water-retaining layer as well. The efficiency
of the device did not show a decrease after
exposure for over 1000 hours.

[1] Reichelstein, S.; Yorston, M. The Prospects for

Future Outlook
Tandem Silicon Perovskite Solar Cell
Despite its lower cost of fabrication,
perovskite solar cell proven to be quite
competitive with traditional silicon cells in
term of efficiency. Although silicon cells
dominate current photovoltaic market, the
recent world researches only record the
highest efficiency of 25.6% which is still not
fully competitive with fossil and nuclear
energy resources taking into account their
return of investment [30]. In order to go
further beyond the practical limit of silicon
cells, which is 26% of PCE, scientists use
solar cells featuring multiple junctions,
combining absorber materials that harvest
different parts of the solar spectrum.
Perovskite solar cells seem to be attractive
candidate as top cells in tandem
configuration with c-Si or CIGS as bottom
cells. This technique offers a great promise
to the future of efficient and cheap solar cell
since both materials capture sunlight at
different wavelengths. Therefore a wide
range of solar spectrum will be captured so
if they are put together. For silicon-based
tandems, efficiencies of 28% to 30% seem
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