PUBLISHED: 6 DECEMBER 2016 | ARTICLE NUMBER: 16016 | DOI: 10.1038/NENERGY.2016.

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SOLAR CELLS

Stabilizing tin-based perovskites

Tin-based perovskite solar cells are less toxic than their lead-based counterparts, but suffer from severe stability
issues due to the susceptibility of tin to oxidation. Now, a CsSnI3 perovskite solar cell with a SnCl2 additive is shown
to exhibit remarkable stability.

Kai Shum and Anna Tsatskina

T
o combat toxicity concerns, efforts 50 correlates to stability in the PPVs in

CsSnI3
are being invested in developing high general, the team fabricate simpler devices

GaAs
efficiency, low cost photovoltaics with PC61BM as the hole-blocking layer

CuInSe2
40

CdTe
c-Si
based on tin halide perovskites1,2. This will (HBL) and CsSnI3 as the light harvesting

a-Si
enable them to properly compete against 30 layer, without using any physical electron-
Efficiency (%)

other perovskites, particularly the lead-
based perovskites3,4. One such candidate
is the black polymorph of caesium tin tri-
iodide perovskites, B-γ-CsSnI3, because not
only can it be synthesized by cost-effective
solution methods, but it also possesses some
of the most desirable physical properties.
As indicated in Fig. 1, the band-gap
energy of 1.3 eV (ref. 5) for CsSnI3 is in
the optimal range in which the power
conversion efficiency of a single-junction
solar cell can approach the high theoretical
limit 6. CsSnI3 also has high hole mobility 7
and small exciton binding energy 8 which
facilitates large photocurrent generation
in photovoltaic applications. However,
in an ambient atmosphere, B-γ-CsSnI3
readily degrades to the yellow polymorph
of CsSnI3 and subsequently to Cs2SnI6,
which features tetravalent tin. Cs2SnI6 has
much poorer light-harvesting properties
than B-γ-CsSnI3 (ref. 9). It is therefore
the undesired oxidation of Sn2+ to Sn4+
that causes poor device stability and low
power conversion efficiency of the CsSnI3-
based solar cells, greatly undermining
their viability in the photovoltaic market.
Writing in Nature Energy, Ross Hatton and
colleagues from the University of Warwick,
UK, now report 10 that incorporating a SnCl2
additive in the CsSnI3 based perovskite
photovoltaics (PPV) not only achieves the
highest efficiency to date, 3.56%, but also
yields much better device stability. Their
results may be a step forward for lead-free
perovskite PPVs.
Hatton and colleagues investigate a series
of tin halide additives for a CsSnI3 thin
film photovoltaic including SnF2, SnCl2,
SnBr2 and SnI2. SnCl2 provides the thin
film the greatest resistance to exposure to
ambient air. Monitoring the oxidation of
CsSnI3 by measuring the evolution of the
optical absorption spectrum with time, the
research team find that the film with the
20
10
0
0.5 1.0 1.5
Band gap (eV)
Figure 1 | Relationship between power conversion
efficiency and band gap. The curve shows the
theoretical limit of power conversion efficiency
under the conditions of AM1.5G illumination
from ref. 6. The vertical lines associated with the
semiconductors of CuInSe2, c-Si, CsSnI3, GaAs,
CdTe, and a-Si indicate the positions of their band-
gap energies.
SnCl2 additive is not only more resistant to
tin oxidation than the CsSnI3 films with an
excess of SnI2, but is more stable than the
films without any additives by a factor of
about seven.
Interestingly, the SnCl2 additive does
not seem to improve the morphology of
the thin film. In fact, scanning electron
microscope images have shown that the film
with the SnCl2 additive has a comparable
pin-hole density to that of its alternatives.
To find out what actually contributes to
the increase in the thin film’s resistance to
oxidation, the researchers devise various
experiments to test the distribution and
composition of the excess SnCl2. They find
that the SnCl2 additive does not assimilate
into the perovskite structure as one would
expect; instead, it forms a very thin layer on
top of the perovskite structure, effectively
behaving as a desiccant for the CsSnI3
structure. This particular functionality of
SnCl2 is reminiscent of the role of SiO2 in
Si-based devices.
To further investigate how the thin
film’s stability in an ambient atmosphere
blocking layer (EBL). They find that devices
with 10 mol% excess SnCl2 have a power
conversion efficiency of 3.56%, which is
the highest power conversion efficiency
for CsSnI3 based solar cells achieved so far.
The high device performance is partially
2.0
attributed to an exceptionally high fill factor
of 63%. These results are surprising, because
the device efficiency and the maximum
power output would normally plunge
without an EBL to ensure that the electrons
do not seep into the indium tin oxide (ITO)
hole-collection layer from the PC61BM at
the locations of the pin-holes. Hatton and
colleagues speculate that the thin layer of
SnCl2 is capable of transferring electrons to
the fullerene PC61BM layer. Essentially, this
would mean that an energy barrier forms at
the SnCl2/fullerene interface and prevents
electron transport from the fullerene layer
into the ITO electrode at the pin-hole areas,
effectively performing the same function as
an EBL would.
This work shows that the SnCl2 additive
may offer a solution to tackle the stability
issues that tin halide based PPVs have
been facing. The additive not only acts to
deter the degradation of the CsSnI3 when
exposed to an ambient atmosphere, but
also eliminates the need for an extra layer
in the device’s fabrication process while
increasing the device’s power conversion
efficiency. This is a promising step for
the tin halide PPVs. Nevertheless, there
are still a lot of issues to be resolved
before any commercialization. One of the
obvious and challenging issues is how
to enhance the low short-circuit current
density produced by the solar cells that
Hatton’s team have designed. In addition,
the physical mechanism of SnCl2 acting
as the protection layer needs to be fully
understood. This understanding may help
in finding a better material to enhance the
device stability so that tin halide based

NATURE ENERGY | VOL 1 | DECEMBER 2016 | www.nature.com/natureenergy 1

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news & views

perovskite solar cells can become useful in e-mail: kshum@brooklyn.cuny.edu 4. Best Research-Cell Efficiencies (NREL, 2016); http://go.nature.
practical applications.  ❐ com/2e3rq0e
References 5. Shum, K. et al. App. Phys. Lett. 96, 221903 (2010).
1. Kumar, M. H. et al. Adv. Mater. 26, 7122–7127 (2014). 6. Ruhle, S. Sol. Energy 130, 139–147 (2016).
Kai Shum and Anna Tsatskina are at the Photonics
2. Hao, F., Stoumpos, C. C., Cao, D. H., Chang, R. P. H. & 7. Chung, I. et al. J. Am. Chem. Soc. 134, 8579–8587 (2012).
Laboratory, Brooklyn College, City University of Kanatzidis, M. G. Nat. Photon. 8, 489–494 (2014). 8. Chen, Z. et al. J. Lumin. 132, 345–349 (2012).
New York, 2900 Bedford Avenue, Brooklyn, New 3. Kojima, A., Teshima, K., Shirai, Y. & Miyasaka, T. J. Am. Chem. 9. Zhang, J. et al. Sci. Rep. 4, 6954 (2014).
York 11210, USA. Soc. 131, 6050–6051 (2009). 10. Marshall. et al. Nat. Energy 1, 16178 (2016).

2 NATURE ENERGY | VOL 1 | DECEMBER 2016 | www.nature.com/natureenergy

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