Perovskite solar cell

A perovskite solar cell is a type of solar cell which includes a perovskite absorber, most commonly a hybrid
organic-inorganic lead or tin halide-based material, as the
light-harvesting active layer, which produces electricity
from sunlight.

addressed by Noel et al. in 2014 with the introduction of a tin-based perovskite absorber, CH3 NH3 SnI3 , in
which the lead is fully replaced with tin, yielding a powerconversion eciency of more than 6%.[5][6][7]

Perovskite absorber materials such as methylammonium

or formamidinium lead halide are extremely cheap to produce and simple to manufacture. Solar cell eciencies of
devices using these materials have increased from 3.8%
in 2009 [1] to a certied 20.1% in 2014, making this the
fastest-advancing solar technology to date. Their high
eciencies and cheap production costs make perovskite
solar cells an extremely commercially attractive option,
with start-up companies already promising modules on
the market by 2017.[2][3]

2 Processing
Perovskite solar cells hold an advantage over traditional
silicon solar cells in the simplicity of their processing. Traditional silicon cells require expensive, multistep processes requiring high temperatures (upwards of
1000C) and vacuums in special clean room facilities to
produce high purity silicon wafers.[8] These techniques
are harder to scale up, while the organic-inorganic perovskite material can be manufactured with simpler wet
chemistry and processing techniques in a traditional lab
environment.[9] Most notably, methylammonium and formamidinium lead trihalides have been created using a
variety of solvent techniques and vapor deposition techniques, both of which have the potential to be scaled up
with relative feasibility.[10]

Materials

In solution processing, lead halide and methylammonium

iodide can be dissolved in solvent and spin coated onto
a substrate. Subsequent evaporation and convective selfassembly during spinning results in dense layers of well
crystallized perovskite material, due to the strong ionic
interactions within the material (The organic component
also contributes to a lower crystallization temperature).
However, simple spin-coating does not yield homogenous
layers, instead requiring the addition of other chemicals
such as GBL, DMSO, and toluene drips.[11] Simple solution processing results in the presence of voids, platelets,
and other defects in the layer, which would hinder the efciency of a solar cell.

Unit cell of the most commonly employed perovskite absorber

in solar cells: methylammonium lead trihalide (CH3 NH3 PbX3 ,
where X is on of the following halogen ions I , Br , Cl )

The name 'perovskite solar cell' is derived from the ABX3

crystal structure of the absorber materials, which is referred to as perovskite structure. The most commonly
studied perovskite absorber is methylammonium lead trihalide (CH3 NH3 PbX3 , where X is a halogen ion such as
I , Br , Cl ), with a bandgap between 2.3 eV and 1.57
eV depending on halide content. Formamidinum lead trihalide (H2 NCH3 NH3 PbX3 ) is a recently studied newer
material which shows promise, with a bandgap between
2.23 eV and 1.48 eV. This minimum bandgap is closer
to the optimal for a single-junction cell than methylammonium lead trihalide, so it should be capable of higher
eciencies.[4] A common concern is the inclusion of lead
as component of the perovskite materials; this has been

In vapor assisted techniques, spin coated or exfoliated

lead halide is annealed in the presence of methylammonium iodide vapor at a temperature of around 150C.[12]
This technique holds an advantage over solution processing, as it open up the possibility for multi-stacked thin
lms over larger areas.[13] This could be applicable for
the production of multi-junction cells. Additionally, vapor deposited techniques result in less thickness variation
than simple solution processed layers. However, both
techniques can result in planar thin lm layers or for use
in mesoscopic designs, such as coatings on a metal oxide
scaold. Such a design is common for current perovskite
or dye-sensitized solar cells.
1

5 HISTORY

Both processes hold promise in terms of scalability. Process cost and complexity is signicantly less than that of
silicon solar cells. Vapor deposition or vapor assisted
techniques reduce the need for use of further solvents,
which reduces the risk of solvent remnants. Solution processing is cheaper; however, there are still issues with
consistency and uniformity in thickness. Current issues
with perovskite solar cells revolve around stability, as
the material is observed to degrade in standard environmental conditions, suering drops in eciency (See also
Stability).

Physics

The physics of perovskites are still not fully understood. The most important physical characteristics of
the most commonly used perovskite, methylammonium
lead halide, are that it has a bandgap between 2.3 eV and
1.6 eV, controllable by changing the halide content,[4][14]
and that it has a diusion length for both holes and electrons of over one micron.[15][16] The long diusion length
means that it can function eectively in a thin-lm architecture, and that charges can be transported in the perovskite itself over long distances. It has recently been
reported that charges in the perovskite material are predominantly present as free electrons and holes, rather
than as bound excitons, since the exciton binding energy is low enough to enable charge separation at room
temperature.[17]

a) Schematic of a sensitized perovskite solar cell in which the active layer consist of a layer of mesoporous TiO2 which is coated
with the perovskite absorber. The active layer is contacted with
an n-type material for electron extraction and a p-type material
for hole extraction. b) Schematic of a thin-lm perovskite solar
cell. In this architecture in which just a at layer of perovskite
is sandwiched between to selective contacts. c) Charge generation and extraction in the sensitized architecture. After light absorption in the perovskite absorber the photogenerated electron is
injected into the mesoporous TiO2 through which it is extracted.
The concomitantly generated hole is transferred to the p-type material. d) Charge generation and extraction in the thin-lm architecture. After light absorption both charge generation as well as
charge extraction occurs in the perovskite layer.

eld of dye-sensitized solar cells, so the sensitized architecture was that initially used, but over time it has become apparent that they function well, if not ultimately
4 Architectures
better, in a thin-lm architecture.[18] Certainly, the aspect
Perovskite solar cells function eciently in a number of of UV-induced degradation in the sensitized architecture
somewhat dierent architectures depending either on the may be detrimental for the important aspect of long-term
role of the perovskite material in the device, or the na- stability.
ture of the top and bottom electrode. Devices in which There is another dierent class of architectures, in which
positive charges are extracted by the transparent bot- the transparent electrode at the bottom acts as cathode by
tom electrode (anode), can predominantly be divided into collecting the photogenerated p-type charge carriers.[19]
'sensitized', where the perovskite functions mainly as a
light absorber, and charge transport occurs in other materials, or 'thin-lm', where most electron or hole trans- 5 History
port occurs in the bulk of the perovskite itself. Similar to the sensitization in dye-sensitized solar cells, the
perovskite material is coated onto a charge-conducting Perovskite materials have been well known for many
a solar cell was
mesoporous scaold - most commonly TiO2 as light- years, but the rst incorporation into [1]
This cell was
reported
by
Miyasaka
et
al.
in
2009.
absorber. The photogenerated electrons are transferred
based
on
a
dye-sensitized
solar
cell,
and
generated
only
from the perovskite layer to the mesoporous sensitized
3.8%
power
conversion
eciency
(PCE)
with
a
thin
layer
layer through which they are transported to the electrode
and extracted into the circuit. The thin lm solar cell ar- of perovskite on mesoporous TiO2 as electron-collector.
chitecture is based on the nding that perovskite mate- Moreover, because a liquid corrosive electrolyte was
rials can also act as highly ecient, ambipolar charge- used, the cell was only stable for a matter of minutes.
the same
conductor.[15] After light absorption and the subsequent Park et al. improved upon this in 2011, using
[20]
dye-sensitized
concept,
achieving
6.5%
PCE.
charge-generation, both negative and positive charge carrier are transported through the perovskite to charge se- However, the real breakthrough came in 2012, when
lective contacts. Perovskite solar cells emerged from the Henry Snaith and Mike Lee from the University of Ox-

3
ford realised that the perovskite was a) stable if contacted with a solid-state hole transporter such as spiroOMeTAD and b) did not require the mesoporous TiO2
layer in order to transport electrons.[21][22] They, almost
simultaneously with the Grtzel group of EPFL, showed
that eciencies of almost 10% were achievable using
the 'sensitized' TiO2 architecture with the solid-state hole
transporter, but higher eciencies, above 10%, were attained by replacing it with an inert scaold.[23]
Further experiments in replacing the mesoporous TiO2
with insulative mesoporous Al2O3 resulted in increased
Open Circuit Voltage and a relative improvement in eciency of 3-5% more than those with TiO2 scaolds.[13]
This led to the hypothesis that a scaold is not needed
for conductive purposes, which was later proved correct. This realisation was then closely followed by a
demonstration that the perovskite itself could also transport holes, as well as electrons.[24] This meant that planar thin-lm cells, with the perovskite transporting both
holes and electrons, became a possibility. However, efciencies remained low until it was realised the issue of
morphology was critical and a thin-lm perovskite solar
cell, with no mesoporous scaold, with >10% eciency
was achieved.[18][25][26]

with a power-conversion eciency of 24% was mentioned without more details being given.[35]

6 Stability
One big challenge for perovskite solar cells is the aspect of short-term and long-term stability. The watersolubility of the organic constituent of the absorber material make devices highly prone to rapid degradation
in moist environments.[36] Encapsulating the perovskite
absorber with a composite of carbon nanotubes and an
inert polymer matrix has been demonstrated to successfully prevent the immediate degradation of the material when exposed to moist ambient air at elevated
temperatures.[36][37] However, no long term studies and
comprehensive encapsulation techniques have yet been
demonstrated for perovskite solar cells. Beside moisture
instability, it has also been shown that the embodiment of
devices in which a mesoporous TiO2 layer is sensitized
with the perovskite absorber exhibits UV light induced
instability.[38] The cause for the observed decline in device performance of those solar cells is linked to the interaction between photogenerated holes inside the TiO2
and oxygen radicals on the surface of TiO2 .[38]

From here, both the planar and sensitized architectures

have seen a urry of development. Burschka et al. in
2013 demonstrated a new deposition technique for the
sensitized architecture exceeding 15% eciency by a 7 Hysteretic current-voltage betwo-step solution processing,[27] and at a similar time Liu
havior
et al. showed that it was possible to fabricate planar solar cells by thermal evaporation, also achieving more than
Another major challenge for perovskite solar cells is the
15% eciency.[28][29]
observation that current-voltage scans do not yield unamDocampo et al. also showed in 2013 that it was possible biguous eciency values.[39][40] The power-conversion
to fabricate perovskite solar cells in the typical 'organic eciency of a solar cell is usually determined by charsolar cell' architecture, an 'inverted' conguration with the acterizing its current-voltage (JV) behavior under simuhole transporter below and the electron collector above lated solar illumination. In contrast to other solar cells,
the perovskite planar lm.[30]
however, it has been observed that the JV-curves of perIn 2014, a host of new deposition techniques have led the ovskite solar cells show a hysteretic behavior: dependrace for the highest eciencies with no contender emerg- ing on scanning conditions - such as scan direction, scan
ing as a clear leader yet. Some potentially scalable depo- speed, light soaking, biasing - there is a discrepancy between the scan from forward-bias to short-circuit (FBsition techniques have also been reported.[31]
SC) and the scan from short-circuit to forward bias (SCA reverse-scan eciency of 19.3% has been claimed
FB).[39] Various causes have been proposed such as ion
by Yang Yang at UCLA using the planar thin-lm
movement, polarization, ferroelectric eects, lling of
architecture.[32] In November 2014, a device by retrap states,[40] however, the exact origin for the hysteretic
searchers from KRICT achieved a new record with the
behavior is yet to be determined. But it appears that decertication of a non-stabilized eciency of 20.1%.[33]
termining the solar cell eciency from JV-curves risks
In 2014, Luo et al. have demonstrated for the rst time to produce inated values if the scanning parameters exto drive photolysis of water using perovskite solar cells. ceed the time-scale which the perovskite system requires
By connecting two perovskite solar cells in tandem the in order to reach an electronic steady-state. Two possirequired voltage for water-splitting was attained and a ble solutions have been proposed: Unger et al. show that
solar-to-hydrogen conversion eciency of 12.3% was extremely slow voltage-scans allow the system to settle
achieved.[34]
into steady-state conditions at every measurement point
discrepancy between the FBIn November 2014, at the 6th World Conference on which thus eliminates any
[40]
Snaith et al. have proposed
SC
and
the
SC-FB
scan.
Photovoltaic Energy Conversion in Kyoto, Japan, the
'stabilized
power
output'
as
a
metric for the eciency of a
achievement of a single-junction perovskite solar cell
solar cell. This value is determined by holding the tested

device at a constant voltage around the maximum powerpoint (where the product of voltage and photocurrent
reaches its maximum value) and track the power-output
until it reaches a constant value. Both methods have been
demonstrated to yield lower eciency values when compared to eciencies determined by fast JV-scans.[39][40]
However, initial studies have been published that show
that surface passivation of the perovskite absorber is an
avenue with which eciency values can be stabilized very
close to fast-scan eciencies.[5][41] Initial reports suggest
that in the 'inverted architecture', which has a transparent cathode, little to no hysteresis is observed.[19] This
suggests that the interfaces might play a crucial role with
regards to the hysteretic JV behavior since the major difference of the inverted architecture to the regular architectures is that an organic n-type contact is used instead
of a metal oxide.
The observation of hysteretic current-voltage characteristics has thus far been largely underreported. Only a small
fraction of publications acknowledge the hysteretic behavior of the described devices, even fewer articles show
slow non-hysteretic JV curves or stabilized power outputs.
Reported eciencies, based on rapid JV-scans, have to
be considered fairly unreliable and make it currently difcult to genuinely assess the progress of the eld.
The ambiguity in determining the solar cell eciency
from current-voltage characteristics due to the observed
hysteresis has also aected the certication process done
by accredited laboratories such as NREL. The record efciency of 20.1% for perovskite solar cells accepted as
certied value by NREL in November 2014, has been
classied as 'not stabilized'.[33]

See also
Perovskite (structure)
Methylammonium halide
Solar cell
Thin lm solar cell
Third generation photovoltaic cell
Hybrid solar cell
Nanocrystal solar cell
Polymer solar cell
Dye-sensitized solar cell
Perovskite (mineral)
List of types of solar cells

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10

External links

Nie, W.; Tsai, H.; Asadpour, R.; Blancon, J.

-C.; Neukirch, A. J.; Gupta, G.; Crochet, J.
J.; Chhowalla, M.; Tretiak, S.; Alam, M. A.;
Wang, H. -L.; Mohite, A. D. (2015). Higheciency solution-processed perovskite solar cells
with millimeter-scale grains. Science 347 (6221):
522. doi:10.1126/science.aaa0472.
Shi, D.; Adinol, V.; Comin, R.; Yuan, M.;
Alarousu, E.; Buin, A.; Chen, Y.; Hoogland, S.;
Rothenberger, A.; Katsiev, K.; Losovyj, Y.; Zhang,
X.; Dowben, P. A.; Mohammed, O. F.; Sargent, E.
H.; Bakr, O. M. (2015). Low trap-state density and
long carrier diusion in organolead trihalide perovskite single crystals. Science 347 (6221): 519.
doi:10.1126/science.aaa2725.

EXTERNAL LINKS

11
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11.2

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