Review

Perovskite Solar Cells www.advenergymat.de

Capturing the Sun: A Review of the Challenges and

Perspectives of Perovskite Solar Cells
Michiel L. Petrus, Johannes Schlipf, Cheng Li, Tanaji P. Gujar, Nadja Giesbrecht,
Peter Müller-Buschbaum, Mukundan Thelakkat, Thomas Bein, Sven Hüttner,*
and Pablo Docampo*

following statement: These materials

Hybrid metal halide perovskites have become one of the hottest topics in can be processed from solution and yet
optoelectronic materials research in recent years. Not only have they sur- exhibit optoelectronic materials proper-
passed everyone’s expectations and achieved similar performance as tried ties described in classic solid-state physics
textbooks. This unprecedented combina-
and true polycrystalline silicon photovoltaic devices, but they are also finding tion has led to photovoltaic devices that
applications in a variety of different fields, including lighting. The main advan- can be processed at room temperature
tages of hybrid metal halide perovskites are simple processability, compatible and achieve performance levels similar to
with large-scale solution processing such as roll-to-roll printing, and abun- industry giant polycrystalline silicon, from
dance of ingredients, all coupled to materials properties reminiscent of GaAs. a starting point of 3.8% in 2009.[1–4] The
first light-emitting electrochemical cells[5]
On the road to this remarkable success, a series of challenges have been
and diodes[6–8] have also been introduced
overcome, while some still remain. In this review, some of these challenges recently, leading to tunable light emission
and possible solutions are described. In particular, understanding of the per- spectra and internal quantum efficiencies
ovskite crystallization process and how this knowledge can be harnessed to exceeding 15%.
enable better performing devices, how to overcome reproducibility issues and The road towards these achievements has
mitigate hysteresis, and the long-term prospects of the technology in terms of been marked by a constant improvement of
perovskite deposition techniques fueled by
stability and sustainability will all be discussed. our increasing understanding of the crys-
tallization processes. The choice of depo-
sition technique, either from solution or
1. Introduction vapor, and the composition and order in which precursor species
are applied has a great influence on the crystallization kinetics.
Recently, hybrid metal halide perovskite materials have become Here, one can distinguish one-step methods where the perovs-
one of the hottest topics in optoelectronic materials research. kite is formed from a precursor mixture dissolved in a common
The excitement of the community can be summarized in the solution, and two-step methods where the inorganic compound
is deposited first and transformed to the perovskite phase later
Dr. M. L. Petrus, N. Giesbrecht, Prof. T. Bein, Dr. P. Docampo by addition of the organic constituents.[9–11] Furthermore, many
Department of Chemistry and Center for NanoScience (CeNS) parameters during processing can have an effect on the crystal-
University of Munich (LMU) lization mechanism and consequently on film morphology, such
Butenandtstr. 11, 81377 Munich, Germany
as the choice of solvents, concentrations and processing additives
E-mail: pablo.docampo@newcastle.ac.uk
that are often not incorporated into the final product.[11–13] We dis-
J. Schlipf, Prof. P. Müller-Buschbaum
Lehrstuhl für Funktionelle Materialien cuss this aspect in Section 2, where we focus our attention on the
Physik-Department most commonly employed solution-based techniques. Addition-
TU München ally, as for any new technology trying to displace an incumbent
James-Franck-Str. 1, 85748 Garching, Germany technology, higher efficiencies, lower costs, reproducibility, sta-
Dr. C. Li, Dr. T. P. Gujar, Prof. S. Hüttner, Prof. M. Thelakkat bility, and sustainability are paramount. In particular, reproduc-
Macromolecular Chemistry I
University of Bayreuth ibility has been a major challenge in perovskite solar cells from
University Str-30, Germany the beginning: small variations in morphology, like crystal size,
E-mail: sven.huettner@uni-bayreuth.de film roughness, and pinholes can have detrimental effects on
Dr. P. Docampo photovoltaic performance.[14] On the other hand, current–voltage
School of Electrical and Electronic Engineering measurements often showed a hysteresis that is rarely seen in
Newcastle University
other photovoltaic technologies.[15] These topics are highlighted
Merz Court, NE1 7RU Newcastle upon Tyne, UK
in Sections 3 and 4. Finally, in Section 5 we discuss the frame-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.201700264. work for market introduction, such as cost reduction by choosing
low-cost charge transport layers, or how the lifetime of perovskite
DOI: 10.1002/aenm.201700264 absorbers can be extended by the choice of materials composition.

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2. Crystallization of Perovskites
Michiel Petrus is a
In order to tune the morphology of perovskite films and thus Postdoctoral Researcher in
the performance of the resulting solar cells, understanding the the Department of Chemistry
crystallization process is crucial. While developing a deposi- at the Ludwig Maximilians
tion technique that allows for full surface coverage of the sub- University (LMU), Munich.
strate initially led to large leaps in efficiency, this is only the He received his Ph.D. degree
first step towards pushing the performance to the limit. Various from Delft University of
studies additionally showed that it is important to maximize Technology in 2014, for his
the crystalline domains in the resulting perovskite solar cells work on donor materials
by introducing different crystallization strategies, which ena- for organic solar cells, and
bled longer crystal growth times.[16] Here we will elaborate the was a visiting scholar at the
different strategies employed so far, summarized in Figure 1. University of Cambridge.
In principle, there are many different pathways for crystalliza- His current research interests include the development
tion in solution, as discussed in great detail by Zhou et al.[17] of perovskite solar cells, with a focus on low-cost hole
While homogeneous nucleation is likely relevant for the forma- transporting materials, environmental impact, and stability
tion of large single crystals, e.g., by inverse temperature crys- of the perovskite.
tallization,[18] heterogeneous crystallization is considered the
dominant mechanism for thin film synthesis. It is induced by Sven Huettner currently
growth of particles or domains from the nucleation sites, e.g., works as an Assistant
the solution/substrate interface by precipitation or supersatura- Professor (Juniorprofessor)
tion, which might be induced by an antisolvent or by attach- at the University of Bayreuth.
ment to a colloid, like a solid–liquid complex.[17] He received his diploma in
physics from the University
of Bayreuth in 2005, and
2.1. One-Step (Solvent Engineering) worked on his Ph.D. degree
in a joint collaboration
Initial studies focused on achieving sufficient surface coverage with Prof. Ullrich Steiner
of the perovskite film by tuning the stoichiometry of the pre- (University of Cambridge) and
cursors. Thus, applying a 3:1 molar ratio of methylammonium Prof. Thelakkat (University of
iodide (MAI) and PbCl2 in dimethylformamide (DMF), Lee Bayreuth). From 2010–2013 he worked as a postdoc in the
et al. were able to fabricate the first perovskite solar cell (PSC) group of Prof. Sir Richard Friend (University of Cambridge)
with power conversion efficiency (PCE) exceeding 10%.[9] Sub- in the field of optoelectronics. His current research is con-
sequently, the influence of processing parameters was further cerned with investigating structure–function relations of
investigated with the focus shifting towards different solvent novel organic and hybrid semiconductors toward applica-
media, like dimethyl sulfoxide (DMSO) or N-methylpyrrolidone tions in photovoltaics, transistors, and sensors.
(NMP), which resulted in the first PSC without a mesoporous
scaffold and topping the 10% efficiency mark.[14] However, Pablo Docampo is currently
simple one-step fabrication methods seem to be more difficult a Senior Lecturer in Physics
to control than sequential deposition on both mesostructured at Newcastle University. He
and planar TiO2 substrates.[10,11] obtained his Ph.D. from the
Jeon et al. and Xiao et al. almost simultaneously reported University of Oxford in 2012,
that adding an antisolvent on top of the wet precursor film for his work on the electronic
during spin-coating induces fast crystallization.[12,21] In a basic properties of metal oxides
approach, Xiao et al. used an equimolar solution of MAI and in solid-state dye-sensitized
PbI2 in DMF, and tested the influence of a variety of antisol- solar cells. He was previ-
vents like chlorobenzene (CB), benzene, xylene, toluene, iso- ously a Marie Curie Fellow
propylalcohol (IPA), and chloroform. The use of the antisolvent and Assistant Professor at
promotes fast nucleation, which results in micron-sized crystals the LMU Munich, where he
and PCEs close to 14% using a planar device architecture.[21] started his group developing novel hybrid halide perovskite
Jeon et al., on the other hand, dissolved their precursors in a materials for optoelectronic applications.
mixture of γ-butyrolactone (GBL) and DMSO, and used toluene
as the antisolvent, and thereby achieved a certified efficiency
of 16.2% for an optimized mixed-MAPb(I1−xBrx)3 perovskite
on mesoporous TiO2, which was a record PCE at that time.[12] The influence of precursor stoichiometry was investigated by
Besides the influence of the solvent on the crystallization, the Nenon et al. using in situ XRD during thermal annealing.[30]
choice of the precursor species and their concentration has Depending on the composition, the film undergoes several
shown a strong impact. Several groups studied the role of lead phase regimes during annealing. Additionally, this has impli-
precursors, like PbI2, PbCl2 and PbAc2.[19,27–29] cations for the thermal stability of the film. Especially in the

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Figure 1.  Overview of the relations between perovskite thin film deposition methods from solution, starting from simple one-step, where often non-
stoichiometric precursor mixtures are used to achieve homogeneous films a).[14,19] Reproduced with permission.[19] Copyright 2015, Nature Publishing
Group, and two-step methods, where a predeposited metal halide film is converted to perovskite g).[11,20] Reproduced with permission.[20] Copyright
2016, American Chemical Society. The first was improved by either antisolvent drop to induce fast crystallization b,c). (b) Reproduced with permis-
sion.[21] Copright 2014, John Wiley and Sons. (c) Reproduced with permission.[22] Copyright 2016, Royal Society of Chemistry, or by application of
complex-forming solvents like DMSO in a mixed solvent approach e). Reproduced with permission.[12] Copyright 2014, Nature Publishing Group,
or by post-processing f). Reproduced with permission.[23] Copyright 2015, American Chemical Society. Two-step methods also use DMSO to form a
complex d). Reproduced with permission.[24] Copyright 2014, Royal Society of Chemistry, but also different conversion methods were explored either
by spin-coating and interdiffusion h). Reproduced with permission.[25] Copyright 2014, Royal Society of Chemistry, or organic vapor i). Reproduced with
permission.[26] Copyright 2013, American Chemical Society.

presence of chloride, either through methylammonium chlo-
ride (MACl) or PbCl2, the crystallization kinetics seem to
change dramatically. This is further discussed in Section 2.3.
2.1.1. Crystallization through Complex Formation
As mentioned before, crossing the 10% PCE mark for planar
perovskite solar cells was possible by choosing appropriate
solvents.[24] DMSO is frequently used as a solvent for fabrica-
tion of perovskite films and has been described as leading
to the formation of an amorphous PbI2 layer in the first step
of sequential film deposition.[24] As a further advantage, the
authors of this publication stated that PbI2 has a higher solu-
bility in DMSO (2 m) as compared to, e.g., DMF (1 m), due to
a strong coordination at a ratio of 1:2. This is apparent from
the PbO bond length of 2.38(6) Å in DMSO as opposed to
2.431(4) Å in DMF.[31,32] The strong complex bond between
the lead precursor and DMSO molecules leads to decelerated
reaction kinetics in the conversion to the perovskite phase
(cf. Figure 2a). As a result, crystallization becomes more con-
trollable, which leads to uniform crystals, often with increased
sizes.[23,24,33,34] Chemically, this complex can be described as the
solvent molecules donating a free electron pair to the Pb2+ ions.
These so-called Lewis adducts are comparable to the lead-halide
cage in the final perovskite structure.[35] Thus, complex-forming
solvents can be used to “pre-stretch” the PbI2 lattice for the
organic compounds that are incorporated into the structure via
a molecule exchange reaction.[36] An example of this is depicted
for DMSO and NMP in Figure 2b.
Subsequently, research into the ability of DMSO to form lead
complexes has been extended to other solvents as well.[36,38,39]
So-called polar aprotic solvents, implying solvents with func-
tional groups containing oxygen (O), sulphur (S), or nitrogen
(N), can act as Lewis bases in the vicinity of the Lewis acid PbI2.
They can be classified into O-donors, like DMSO, NMP, or

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Figure 2.  Various crystallization routes suggested in the literature for different deposition methods. a) Principle of crystallization through complex for-
mation. Reproduced with permission.[24] Copright 2014, Royal Society of Chemistry b) PbI2 structure intercalated with complex-forming solvents DMSO
and NMP. Reproduced with permission.[36] Copyright 2016, John Wiley and Sons, c) timescales of one-step methods employing different lead sources.
Reproduced with permission.[27] Copyright 2015, American Chemical Society, d) the influence of chlorine showing an intermediate phase. Reproduced
with permission.[30] Copyright 2016, Royal Society of Chemistry, e) mechanistic reorganization in a two-step method as a consequence of confined
growth close to the substrate and Ostwald ripening on the film surface. Reproduced with permission.[13] Copyright 2015, American Chemical Society,
f) in situ conversion of the precursor preserving crystal orientation and dissolution-recrystallization mechanism. Reproduced with permission.[37]
Copyright 2016, John Wiley and Sons.

GBL, S-donors, like thiourea or thioacetamide, and N-donors,
like pyridine or aniline. However, it is crucial to take the stoi-
chiometry of the reaction into account and to select solvents
rationally. Foley et al. used computational screening to select
tetrahydrothiophene-1-oxide (THTO) as a solvent having a
stronger solvation efficacy than the commonly used solvents
as a result of its sulfoxide (SO) functional group that has a
coordination ratio of 3:1 with lead.[38] By suppressing the for-
mation of intermediate structures, crystallization is retarded
significantly as the density of nucleation sites is reduced. Thus,
this strategy runs counter to the antisolvent approach, where
orthogonal solvents are used to induce fast crystallization with
a high density of nucleation sites.[21] The result of the retarded
crystallization is a film of highly oriented perovskite crystals
that is formed directly from the stoichiometric precursor solu-
tion, as proven by in situ grazing incidence wide angle X-ray
scattering (GIWAXS). Although the photovoltaic performance
of these films was moderate, this approach nevertheless shows
the ability to tune the crystal orientation and film morphology
by rational selection of solvent media.[38] Examples from lit-
erature show that the highest efficiencies so far were achieved
with mixed solvent approaches, generally employing DMF and

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DMSO, where the stoichiometry of the precursor solution was
precisely controlled.[4,40] The latest records that have surpassed
the 20% PCE barrier followed an approach using a mixture of
solvents (4:1 DMF:DMSO, which would result in a molar ratio
between DMSO:PbI2 of ≈2:1) and the CB antisolvent method,
while mixing three to four different cations and two halides.[4,41]
The impact of solvents on the perovskite film morphology was
further investigated by post-deposition solvent annealing.[23]
2.1.2. Crystallization from Lead-Acetate Precursors
Besides the interactions of the solvents with lead, the lead(II)
salt composition also has a strong impact on the perovskite crys-
tallization. Computational studies by Buin et al. suggested that
iodine-rich conditions result in high trap densities. In contrast,
iodine-poor conditions obtained through the use of lead acetate
as the precursor result in fewer defects and a longer charge dif-
fusion length.[42] In a comparative study with other lead precur-
sors, Aldibaja et al. showed that films derived from lead acetate
resulted in the most homogeneous perovskite films, and a
photovoltaic performance comparable to the state-of-the-art.[43]
Zhang et al. further optimized the use of lead acetate as a pre-
cursor and showed that ultrasmooth and pinhole-free perovs-
kite films could be obtained with this method. With the aid of
in situ GIWAXS, it was later found that the activation energies
for crystallization are dependent on the lead salt, and that they
influence the optimum annealing time and temperature.[19,27]
In addition, the authors also determined that the primary
step in perovskite formation is the removal of excess organic
salt from the precursor,[27] while the fast reaction mechanism,
compared to precursors such as PbI2 and PbCl2, leads to homo-
geneous nucleation and thus results in the observed smooth
perovskite film morphology.[27] How the reaction times depend
on the employed lead sources is shown in Figure 2c. Here, the
most significant aspect is the low activation barrier for perovs-
kite crystallization with the lead acetate precursor, which results
in full crystallization while residues of the DMF solvent are still
in the film.[27]
Other factors that affect the growth include the presence of
water in the crystallization environment. Ling et al. suggested
that a controlled amount of water in the lead acetate precursor
helps the formation of an intermediate phase, which in turn
leads to more uniform perovskite films. The authors found
an optimum by using PbAc2 × 1.5H2O, which resulted in the
highest PCEs.[44] Several studies already showed that exposure
of the films to ambient conditions can have a positive effect
on perovskite film formation,[45] i.e., it was shown to trigger
the crystallization[46] or partly dissolve the reactant species and
accelerate mass transport within the film.[3]
In a recent study, Giesbrecht et al. used lead acetate as the
precursor for the crystallization of methylammonium lead
bromide (MAPbBr3) perovskite films.[47] The authors reported
a new synthesis approach based on the control of the deposi-
tion environment while the film is still wet. In contrast to lead
halide precursors, lead acetate allows for the crystallization
of the perovskite when the film still contains solvent.[27] This
is mainly due to the much faster growth kinetics and easily
removed organic byproducts, which drive the reaction. The
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authors maintained a solvent-rich environment during the
crystallization process that retarded solvent evaporation and
extended the crystallization time. This resulted in dense layers
with large grains of up to 10 µm in size, which are also per-
fectly oriented with the z-axis perpendicular to the substrate.
A high degree of crystal orientation can lead to enhanced
solar cell performance when directly compared to samples
exhibiting a lower degree of orientation.[47–49] For example,
Giesbrecht et al. correlated the photocurrent to the degree of
order in the system and showed internal quantum efficiencies
approaching unity for the perfectly oriented samples. These
findings are supported by the work of Cho et al. who showed
anisotropic charge transport in MAPbI3 films with a different
degree of oriented crystallites in the perovskite film.[50]
2.2. Two-Step (Sequential Deposition)
Burschka et al.[10] adapted a sequential deposition method intro-
duced by Liang et al.[51] for the preparation of perovskite solar
cells. The authors achieved PCEs of 15% by spin-coating a PbI2
solution onto mesoporous TiO2 and subsequent immersion
in a MAI-containing solution. This method was transferred
to the planar solar cell architecture by Liu et al.[52] Subse-
quently, Docampo et al. adopted the method and used a mixed
MAI:MACl solution for conversion.[11] This resulted in a PCE
of 15.7% and showed the great potential of the much simpler,
planar design. Soon thereafter, many possibilities were explored
in order to convert a predeposited PbI2 film into perovskite,
e.g., by spin-coating a more concentrated MAI solution on top
of a PbI2 film[25] or by exposing the PbI2 film to an MAI vapor
atmosphere (VASP).[26] Other groups modified the PbI2 film
itself, e.g., by solvent annealing[53] or by replacing DMF with
DMSO as the solvent.[24] In the latter case, a complex between
lead and DMSO molecules is formed, preventing the PbI2 from
crystallizing, and thereby slowing down the transformation to
the perovskite phase during the subsequent immersion. The
role of the complex was further discussed in section 2.1.1.
Yang et al. proposed two mechanisms for the transformation
of PbI2 to MAPbI3 for free-standing crystals that enabled them
to tune their shape: By so-called in situ conversion, the original
morphology of the PbI2 crystal is preserved while it is converted
to MAPbI3 via incorporation of MAI ions. In the dissolution–
recrystallization mechanism, on the other hand, the PbI2 crystal
dissolves and the perovskite recrystallizes in a thermodynami-
cally favored shape. These two processes compete during crys-
tallization, while in situ conversion is favored in environments
with a low MAI concentration.[54] Shortly after, this concept was
transferred to thin films as well.[13,37,55]
Schlipf et al. used GISAXS to gain quantitative information
on crystal-size distribution in perovskite thin films fabricated by
a sequential deposition method.[11,13] They found that starting
from a film of crystalline PbI2, where the crystals are arranged
in a pancake-like stack, the MAI diffuses from the top down
through the stack and begins the conversion into the perovskite
phase. As the structure expands upon the inclusion of MAI,
growth is constrained in the lateral direction, leading to pre-
dominant growth perpendicular to the substrate. Additionally,
lead iodide sheets below the top-most layer experience stronger
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confinement effects and begin to crack, leaving smaller grains
of perovskite. On the film surface, however, larger crystals are
formed by Ostwald ripening in a dissolution–recrystallization
process promoted by the higher MAI concentration.[13] This
process is depicted in Figure 2e. Further evidence that both pro-
cesses are contributing to the morphological features of these
films was later given by Oesinghaus et al., where GIWAXS
measurements suggested that every process results in a unique
crystal orientation. In particular, the in situ conversion process
is closely connected to the PbI2 morphology and results in crys-
tals being tilted at an angle of about 55°, which corresponds
to (202) planes being parallel to the substrate.[37] This phenom-
enon was reported in several other publications dealing with
different fabrication methods.[37,56–59] In their study, Oesing-
haus et al. further suggested that the presence of Cl– promotes
the dissolution of the PbI2 layer, leading to more crystals ori-
ented in (002) direction (cf. Figure 2f). This might be due to the
lower activation energy for the formation of methylammonium
lead chloride (MAPbCl3).[27]
2.3. Role of Chloride Ions
A particularly intriguing crystallization process is achieved
when incorporating chloride precursors into the precursor
mixture, which is beneficial for the optoelectronic properties of
the resulting perovskite film.[11,60–62] Yet the exact role chloride
actually plays has been rather puzzling: while earlier reports
suggested doping effects[63] that could explain the longer charge
carrier diffusion lengths, finding chloride in the final perovs-
kite films has been rather challenging.[11,62,64,65]
Chloride seems to have mainly an effect on the crystal growth,
as was suspected previously,[11,63] and it has since been shown that
it is released together with excess MA during film annealing, or,
in general, that it can facilitate the release of excess organic com-
pounds.[62,66] Binek et al.[67] showed that MAPbCl3 crystallizes
directly after the deposition of the starting solution, thus acting as
a template for the formation of the desired iodide-based perovskite
via a slow halide exchange from the iodide-rich environment. They
also showed that extending the time for the template formation
resulted in more beneficial crystal morphologies, resulting in per-
ovskite films with enhanced optoelectronic properties. Additional
in situ studies following alternative strategies suggest that the
presence of chloride in the precursor solution promotes the for-
mation of intermediate phases (cf. Figure 2d).[27,30,68] This, in turn,
changes the kinetics of the reactions leading to the formation of
more uniform films. In the case of two-step deposition methods,
chloride promotes the dissolution of the crystalline precursor pos-
sibly by forming thermodynamically favored intermediates, which
has an impact on the conversion mechanism and resulting film
morphologies.[37] When using a combination of Cl− additives with
complex-forming solvents such as DMSO, the timescales, as well
as the pathways of crystallization, are highly tunable.[37,38,69,70]
2.4. Alternatives to Solution-Processed Thin Films
While solution-based techniques have dominated the scene,
a plethora of alternative deposition techniques can also be
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employed to achieve high-quality perovskite films. One of the
most successful early reports by Liu et al.[71] includes the growth
of extremely uniform perovskite films by co-evaporation of the
lead precursor and the organic salt. This approach is particu-
larly interesting with a view on introducing perovskite devices
to the market: Today’s semiconductor industry employs many
vapor deposition techniques, which could take advantage of the
more energy-efficient processing of perovskites. For instance,
this could lead to the straightforward realization of tandem
devices with conventional semiconductors (like silicon), or for
energy level alignment by gradually controlling the doping level
in the perovskite. The process is also compatible with flexible
device applications, as demonstrated by Bolink and cow-orkers,
who showed the remarkable mechanical properties of sublimed
perovskite films in flexible devices.[72,73] An initial setback to the
process is that the perovskite crystallization during evaporation
seems to be affected by the choice of substrate. In particular,
MAI seems to have a varying affinity to physisorb on certain
substrates and might even decompose, which hinders the for-
mation of the perovskite phase in the first few nanometers.[74,75]
Nevertheless, this issue can be overcome by employing a
fullerene intermediate layer, allowing the fabrication of per-
ovskite solar cells with a high stabilized efficiency.[76] For more
details on vapor-based techniques, we refer the reader to the
recently published review by Ono et al.[77]
Another emerging research topic concerns lower-dimen-
sional perovskites that form by substitution of the organic
compound with bulkier molecules, generally employing
longer alkylammonium chains. This approach is particularly
interesting in terms of enhancing the stability of the struc-
ture against humidity, as these compounds generally exhibit
a higher resistance against the incorporation of water into the
crystal. Initial results showed rather poor device efficiencies,
mostly due to the preferential growth direction that results in
2D perovskite nanoplatelets aligned parallel to the substrate,
thus inhibiting charge transport.[78] A recent study, therefore,
combined these 2D perovskites with 3D perovskites in a sand-
wich approach, by converting the upmost layer of their more
efficient 3D counterparts into lower-dimensional species, to
form a multifunctional heterojunction, which exhibited a
higher open-circuit voltage and PCE, and longer stability in a
humid atmosphere.[79] The reverse approach, converting a 2D
perovskite into a three-dimensional form by interdiffusion of
simple MA+ cations, also showed very promising results.[80]
Currently, the highest efficiencies of lower dimensional per-
ovskites have been claimed by Tsai et al. using a hot-casting
method.[81]
Recent efforts have been focussed on single crystal studies.
Although photovoltaic devices based on single crystals cannot
compete with the standards set by thin films so far, the mate-
rials have proven themselves to be useful as photodetectors,
and are, furthermore, very interesting for fundamental mate-
rials studies. For instance, the dependence of the absorption
onset on the crystal size is apparent by the red-shift observed for
larger single crystals.[82] The best results are currently achieved
by taking advantage of the inverse solubility effect observed for
perovskites in certain solvents, like GBL for MAPbI3 and DMF
for MAPbBr3.[18,83] Recently, very thin perovskite wafers could
be realized by confined growth within a microreactor created
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from two glass slides with appropriate spacers, paving the way
for mass production of solution-processed wafers.[84] For fur-
ther information on the growth control of perovskite films and
single crystals by many different methods that could also be rel-
evant to industry, we refer the reader to the recently published
review by Chen et al.[85]
3. Reproducibility of Perovskite Materials
Although reproducibility is an important factor for the techno-
logical realization of PSCs, most authors mention reproduc-
ibility only in passing. In order to determine the reproducibility
and real device performance, device-to-device and batch-to-
batch statistics are absolutely necessary.[86] Histograms of a
large number of devices (ideally 30+) with batch-to-batch repro-
ducibility, should be a requirement to prove the desired device
reproducibility and narrow device fluctuation statistics.
The main challenge lies in processing high-quality perovs-
kite films along with crystallization at low temperatures, which
is different from most other inorganic and organic semiconduc-
tors. This can lead to substantial differences in the film quality
and device performance, depending on which method and
temperature were used to crystallize the perovskite.[87–89] While
solar cells with record PCEs can be achieved without good con-
trol of the perovskite crystallization, this generally leads to films
with large morphological deviations, leading to large PCE fluc-
tuations in the resulting devices.[90]
In this part of the review, we will discuss the reports on
reproducible PCE and solar cell parameters. It should be noted
that the reproducibility we are referring to is considered as a
narrow scatter of PCE and solar cell parameters of PSCs pro-
cessed under the same conditions. As outlined in the previous
section, thin film perovskites can be prepared by a variety of
methods. SEM images of films prepared by different typical
methods are shown in Figure 3, in detail: a) two-step sequen-
tial deposition with dipping, b) two-step sequential deposition
with a hot MAI solution containing 5% MACl, c) sequential
spin-coating of PbI2 and MAI, d) spin-coating a single mixture
precursor solution of both components, e) spin-coating a mixed
halide single mixture precursor, f) antisolvent engineering, g)
fast deposition–crystallization, h) solvent–solvent extraction, i)
full vacuum deposition method, and j) MAI-vapor-assisted solu-
tion process, respectively. In the following, we compare these
methods regarding their capability to enable reproducible thin
film morphologies and device parameters.
3.1. Two-Step Methods
Although more versatile, in principle, two-step methods gen-
erally suffer from less reproducible devices, as there are many
more parameters that have to be controlled. In terms of film
quality, the key parameters for two-step sequential deposition
and perovskite conversion by dipping are immersion time, tem-
perature of the conversion solution, and precursor concentra-
tion. In addition, the morphology not only depends upon the
immersion conditions of the PbI2 film, but it also depends on
small changes in the processing conditions of the PbI2 film
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itself. Initial results with this technique were reported by Bur-
schka et al.[94] for mesoscopic solar cells with an average PCE
of 12.0% and the highest PCE of 12.9%. A similar procedure,
with the addition of a pre-wetting step of the PbI2 layer in IPA
prior to its immersion in the MAI solution, led to a significant
increase in the PCE and its reproducibility.[10] A maximum PCE
of 15.0% and a certified PCE of 14.1% was achieved using the
two-step method, but data regarding average PCEs were not
published. As noted before, film crystallization can inherently
be different on planar substrates. Docampo et al.[11] studied the
influence of the addition of chloride additives in the immersion
solution as well as the temperature to optimize this process for
planar substrates.[48] These results pointed towards an increase
in device reproducibility at higher temperatures due to a
decrease in the orientational disorder of the perovskite crystals
due to a dissolution–recrystallization mechanism, described in
Section 2.2. and 2.3. An additional aspect of their method is
the spin-coating of PbI2 at an elevated temperature, which con-
trols the evaporation rate of the solvent (DMF) and leads to an
optimized film porosity to accommodate the volume expansion
during the transformation to the perovskite phase.[37]
Jiang et al.[95] and Ko et al.[96] studied the effect of PbI2 film
morphology on device performance and reproducibility and
found that it strongly affects these parameters. In order to
overcome large deviations in film morphology and composi-
tion, these authors proposed an alternative protocol where
the MAI solution with high ion concentration was spin-coated
onto the PbI2 film. This, in turn, creates a nanocubic perovs-
kite morphology with a high degree of control on the crystal
size, dependent on the concentration of the MAI solution and
waiting time.[91] In Figure 3a–c, we show that a small change in
fabrication parameters can change the complete morphology of
perovskite films.
Working with the complex-forming solvent DMSO, Wu
et al.[24] gained better control of the conversion step in the afore-
mentioned dipping method as the intercalation of MA ions was
slowed down (cf. Section 2.1.1.) As a result, the crystal size dis-
tribution is very narrow, centered around 200 ± 30 nm; whereas
when the deposition is done using DMF, the crystal size distri-
bution ranges from 50 to 400 nm. The narrow crystal size distri-
bution leads to very reproducible PCE values, with a maximum
efficiency of 14.2%, and a standard deviation of only 0.6%.
3.2. One-Step Deposition
One-step methods seem to be favorable in terms of mini-
mizing the uncertainties in each processing step. In most one-
step techniques, the precursors of MAI and PbI2 or PbCl2 are
simply dissolved in DMF or DMSO in a specific ratio, i.e., stoi-
chiometric or with an excess of one of the components,[97–101]
and are then spin-coated onto the substrate and annealed at
a particular temperature and time to obtain crystalline layers
of perovskite (Figure 3d,e). As mentioned before, simple one-
step methods often lead to inhomogeneous coverage of the
substrates.[14,102–104] In particular, Eperon et al. studied the
influence of the TiO2 underlayer and its impact on perovs-
kite-crystal formation when employing a non-stoichiometric
mixture of MAI and PbCl2. They concluded that there is an
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Figure 3.  Top-view SEM micrographs of perovskite thin films deposited by a) two-step sequential deposition. Reproduced with permission.[52] Copy-
right 2014, Nature Publishing Group, b) two-step sequential deposition with 60 °C hot solution of CH3NH3I with 5% CH3NH3Cl. Reproduced with
permission.[11] Copyright 204, John Wiley and Sons, c) sequential spin coating of PbI2 and MAI method. Reproduced with permission.[91] Copyright
2014, Nature Publishing Group d) coating a stoichiometric precursor solution. Reproduced with permission.[21] Copyright 2014, John Wiley and Sons,
e) mixed halide single precursor. Reproduced with permission.[3] Copyright 2014, Science Publishing Group f) antisolvent engineering of mixed halide.
Reproduced with permission.[12] Copyright 2014, Nature Publishing Group, g) antisolvent method with pure MAPbI3. Reproduced with permission.[21]
Copyright 2014, John Wiley and Sons, h) solvent–solvent extraction. Reproduced with permission.[92] Copyright 2015, Royal Society of Chemistry,
i) vacuum deposition method. Reproduced with permission.[71] Copyright 2013, Nature Publishing Group, and j) MAI-vapor assisted solution process.
Reproduced with permission.[93] Copyright 2016, John Wiley ans Sons.

unfavorable interaction between these layers, which leads to
the growth of perovskite “pores”, largely determined by the
thickness of the perovskite film.[14,105,106] Needless to say, the
reproducibility of the resulting devices suffers as a result. Sev-
eral improvements to the device performance can be achieved
by introducing a templating step, as described above,[67] or via
flash-annealing of the films;[49] however, the overall reproduc-
ibility of this deposition method still lags behind other one-
step approaches.
A more successful strategy involves the fast deposition–crys-
tallization of the perovskite film via the addition of an antisol-
vent during the spin-coating protocol. This leads to uniform
and smooth perovskite films (Figure 3f,g),[12,21] and thus more
reproducible devices. This approach really shines when com-
bined with the crystallization of an intermediate complex with a
solvent, typically DMSO.[2,22,98,107,108] In this case, device perfor-
mance with a standard deviation below 1% can be achieved,[21,40]
while the PCE reaches over 21% for mixed perovskites.[22] This
approach leads to both the highest efficiencies reported, as well
as the narrowest device parameter distributions, as shown in
Figure 4.
3.3. Solvent–Solvent Extraction Method
In the solvent–solvent extraction process, a mixture of a perovs-
kite precursor solution is spin-coated onto a substrate, and the
coated substrate is immediately immersed into a bath of another
(diethyl ether) solvent, in which the precursors and the final
product are insoluble. This results in efficient extraction of the
precursor solvent, and induces rapid crystallization of uniform,
ultra-smooth perovskite thin films over large areas (Figure 3h).
PSCs obtained by this method deliver PCEs up to 15.2%, and
an average PCE of above 13.0%.[92] When the solvent-extracted
films were annealed at 150 °C in air for 15 min, the average PCE
was improved to 17.0%, with the highest value of 17.8%.[110]

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Figure 4.  PCE histograms of perovskite solar cells prepared by different methods (TSSD: two-step sequential deposition method,[109] MH: mixed halide
method,[3] SSC: sequential spin coating of PbI2 and MAI method,[91] ASE: antisolvent engineering,[12] FDC: fast deposition crystallization,[21] VASP: MAI-
vapor assisted solution processing)[93] (No. of devices used for histogram is given in bracket).

3.4. Vacuum Deposition Method and MAI-Vapor Assisted
Solution Process
A complete vacuum deposition process is favorable for smooth,
uniform, pin-hole free perovskite formation. Liu et al. reported
planar heterojunction PSCs obtained by a vacuum-deposition
process, with an average PCE of 12.3% and highest PCE of
15.4%, and noted that the vapor-deposition process was better
than the solution process in planar PSCs because of the smooth
film formation in the former (Figure 3i).[71] Bolink and co-
authors have been working on entirely vacuum-evaporation-
based methods for complete solar cells, and they could improve
the PCE from 12 to 19.1% with a narrow distribution of solar
cell parameters.[73,111,112] However, in this process it is difficult
to simultaneously control the deposition rate of PbI2 or PbCl2
and MAI, respectively. Chen et al. reported that most of the
devices fabricated with this method (perovskite layer deposited
by evaporation of PbI2, followed by MAI spin-coating with mod-
ification of TiO2/perovskite interface) exhibit PCE ≈16% with
fluctuations of PCE from 12 to 17.9%.[76] As a compromise, an
MAI- VASP was proposed to fabricate perovskite thin films,
where the solution-processed PbI2 film was treated with MAI
vapor.[26,93,113,114] VASP produces films with well-defined grain
structure, with grain sizes up to the microscale and small sur-
face roughness (Figure 3j). The as-deposited PbI2 films were
annealed in MAI vapor at 120, 150, or 165 °C in vacuum or
N2 atmosphere, to form the uniform and large-grain perovskite
films.
Recently, Gujar et al. have demonstrated relatively high-per-
formance PSCs with excellent reproducibility using VASP.[93]
Figure 5a shows the J–V characteristics of a set of 4 solar cells
fabricated on one FTO substrate, illustrating that a set of four
solar cells on one substrate exhibits high reproducibility with
all the cells having the same solar cell parameters, leading to

Figure 5.  MAI-Vapor assisted solution processed perovskite device performance, a) J–V curves of four different devices on the same substrate, b) his-
togram of highest PCEs from four different batches, c–f) histograms of the solar cell parameters JSC, VOC, FF, and PCE for the 35 devices from four
batches. Reproduced with permission.[93] Copyright 2016, John Wiley & Sons, Inc.

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www.advancedsciencenews.com
a constant PCE of 13.8%. To verify the batch-to-batch repro-
ducibility, keeping all the fabrication conditions constant,
four different batches of 36 devices were prepared, and solar
cell performance was measured. A histogram of 35 working
devices out of 36 devices (yield = 97%) shows a very small
fluctuation in the solar cell parameters. Figure 5b reveals that
the four different batches with the same device-preparation
conditions show a negligible variation for the highest PCE
value.
4. Hysteresis
Despite the tremendous progress in crystallization and pro-
cessing, the challenge of the anomalous hysteretic current–
voltage (J–V) characteristic in PSCs, as shown in Figure 6, still
needs to be resolved. Hysteretic J–V characteristics, noted as
hysteresis in this review, imply that the photocurrent response
exhibits a discrepancy between two sweeping directions
(from short-circuit towards open-circuit, and vice versa). In
this section, we focus on examining the microscopic models
behind hysteresis, and present some of the approaches devel-
oped to suppress hysteresis and the potential applications in
photovoltaics.
4.1. Origin of Hysteresis
Recently Snaith et al.[15] compiled several features related to
the hysteretic behavior: a) hysteresis is dominantly associated
with the perovskite material itself. b) Selective contact mate-
rials,[76,116] i.e., hole and electron transport layers (TLs), play
crucial roles in this behavior, including the material and the
morphology (mesoporous or planar) of the TLs. c) The time
Figure 6. A typical J–V curve hysteresis behavior in a perovskite solar
cell, with a scanning speed of ≈0.9 V s−1. The arrows exhibit the direc-
tions of voltage scanning. Inset indicates the kink in the J–V curve. The
dashed red line is the extension of the J–V curve below ≈0.75 V based on
a standard single-junction diode equation, and the blue ellipse indicates
the horizontal shift of the curves near the flat-band condition. This shift
will be discussed in the following part. Reproduced with permission.[115]
Copyright 2016, John Wiley & Sons, Inc.
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scale of hysteresis is in the range of ≈10 to 100 s,[117,118] which
is in great contrast to the typical charge generation/recombi-
nation processes (≈ns) in PSCs.[119] d) The hysteresis strongly
depends on the external scanning parameters,[120–122] such
as scan rate, amplitude of external electrical field, scanning
direction, pre-scanning conditions, etc. During the last years,
different mechanisms have been proposed to be responsible
including 1) ferroelectricity, 2) charge trapping/detrapping, and
3) ionic migration. Hereby, ionic migration seems to account
for the majority of the effects, as shown by the latest studies.
4.2. Ferroelectricity
Ferroelectricity relies on the hysteretic switching of ferroelec-
tric domains in an electric field. Even though the crystal struc-
ture of MAPbI3 belongs to the centrosymmetric tetragonal
space group I4/mcm, the reorientation of the organic groups
and the distortion of the PbI6 cages can result in a polariza-
tion, which is one of the prerequisites for any ferroelectric
behavior.[123,124] A second criterion is the ability to switch this
polarization by an external field. Several groups, such as Chen
et al.,[125] Coll et al.[126] and Kutes et al.,[127] have demonstrated
switching of spontaneous polarization, that is a piezoresponse
hysteresis loop in both amplitude and phase by using piezo-
electric force microscopy (PFM). Wei et al.[128] also presented
ferroelectric properties by employing traditional E–P measure-
ments on the basis of a classical Sawyer–Tower circuitry. Even
though ferroelectricity has been used to model and explain
hysteresis,[124,125,128,129] there are strong arguments that view
this interpretation to be quite controversial. These encompass
i) overall effects that are too small,[128] ii) the fast decay of the
polarized switching behavior,[127] and iii) disagreement between
the timescale of polarization switching and the one observed in
J–V curve hysteresis. Based on first principle simulations (e.g.,
DFT), the time interval for the polarization switching was in the
nanosecond region.[130] Leguy et al.[131] estimated the expected
time interval within a millisecond range, and noted that ferro-
electric materials require an electric field (larger than the coer-
cive field) to switch ferroelectric domains, which contradicts the
observations in step-wise J–V curve measurements, exhibiting
always a transition-like behavior.[132] Hence, although the con-
tribution of ferroelectricity to hysteresis is still under debate,[133]
the above discussion suggests that ferroelectric polarization
may not play a dominant role in the J–V hysteretic behavior. A
recent study employing PFM found periodic twin domains that
point towards the direction of ferroelasticity and would require
a noncentrosymmetric polar space group, I4 cm, that is also
often assigned to MAPbI3 in the literature.[134]
4.3. Charge Trapping/Detrapping
The possibility for low-temperature solution-processing of
perovskite films inevitably involves the trapping of a certain
amount of defects, which potentially impact the charge sepa-
ration/recombination and charge transport.[135] These defects
can be 1) defects located energetically at the CB/VB band
edge following an exponential decrease distribution, and
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www.advancedsciencenews.com
2) deep-level defects within the bandgap following a Gaussian
distribution.[136] For the first type, the evidence suggests that
the energetic width of the defect states near the band edge, i.e.,
Urbach energy, ranges between 20 and 40 meV, depending on
the fabrication methods.[137] This value is much smaller than
in many typical inorganic semiconductor materials, e.g., Si,
copper indium gallium (di)selenide (CIGS), CdS, etc.[138] For
the second type, these defects lay deep within the bandgap and
can serve as potential trap sites for the charge carriers, being
responsible for non-radiative (Shockley–Read–Hall) recombi-
nation.[139,140] Filling and releasing charges at these trap sites
could modulate the charge transport of photogenerated car-
riers, which ultimately leads to hysteretic behavior.
Figure 7 depicts the possible defect states that are prevalent
in these perovskite films, including vacancies, antisites, and
interstitials.[141] Atomistic simulations reveal their respective
energetic distribution. With the help of spectroscopic charac-
terization techniques, it could be shown that these traps are
dominantly accumulated at the interfaces or surface, where
the periodic crystalline structure is most susceptible to being
deformed.[142–144] Temperature-dependent admittance spectros-
copy enables one to further identify the energetic distribution
of these defects in the bandgap.[145,146] Furthermore, calcula-
tions showed that shallow level defects would only require low
formation energies, whereas deep-level defects require higher
formation energies. The latter would be responsible for nonra-
diative recombination acting as Shockley-Read-Hall nonradia-
tive recombination centers.[147] This explains the origin of the
excellent defect tolerance of these perovskite materials.
Furthermore, methods such as Kelvin probe force micro­
scopy (KPFM)[148,149] and electron-beam-induced current (EBIC)
measurements[150,151] allowed for the measurement of the
potential and current distribution within a device, providing
more direct evidence for a charge trapping and detrapping
process. In these experiments, the charge-carrier-density dis-
tribution across the cross-section of the device was measured,
allowing one to track the evolution of accumulated charges
after illumination. Illumination leads to an accumulation of
hole carriers at the interface between the perovskite and hole
transporting layer (HTL), which leads to a reduction of the
effective charge extraction through this interface and an unbal-
anced charge transport.
Of course, the question arises if those trap states could be
filled and passivated to avoid charge trapping. By employing
luminescence characterization, Motti et al.[152] demonstrated
that an exposure to small amounts of oxygen led to a significant
decrease of trap state density in the perovskite material. Noel
et al.[153] and Dane et al.[154] used Lewis bases such as pyridine
to treat the perovskite films in order to reduce recombination
centers, enhancing the photoluminescence intensity and life-
time. In addition, it has been widely observed that [6,6]-phenyl-
C61-butyric acid methyl ester (PCBM) molecules,[155,156] either
as an interlayer or mixed as bulk heterojunction structure,
are able to passivate defects and alleviate or even eliminate
hysteresis.[76]
Although the defect passivation process significantly
enhances the device performance and decreases the hysteresis,
it is found that the time interval for charge trapping and detrap-
ping ranges within milliseconds,[157] or even nanoseconds,[158]
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Figure 7.  Energy levels associated with the defect states in MAPbI3 per-
ovskites corresponding to neutral and charged vacancies (VPb, VI, VMA),
neutral and charged interstitials (Pbi, Ii, MAi), and neutral and charged
states associated with antisites (PbI and IPb). Reproduced with permis-
sion.[42] Copyright 2014, American Chemical Society.
which is much shorter than the typical time for the hysteretic
behavior.[159] The slow processes, such as the giant switchable
photovoltaic effect and the very slow (seconds range) increase
in photocurrent after poling, cannot be explained by a charge
trapping mechanism alone.[131] Van Reenen et al.[157] recently
proposed that rather than having a single origin, the hyster-
esis has to be interpreted in terms of a combination of factors,
including 1) charge trapping/detrapping and 2) the ionic migra-
tion, which will be discussed in the following section.
4.4. Ion Migration
Recently, a series of studies have presented direct and indirect
evidence that points to ionic migration as the dominant factor
in the origin of hysteresis. Examples are the estimation of
respective activation energies, the observation of band-bending
effects, and capacitance measurements, only to name a few.
Mobile ions not only influence the hysteresis in J–V curves[160]
but also the emission properties of the perovskite (e.g., pho-
toluminescence, electroluminescence, blinking), they induce
capacitive effects,[161–165] and affect transient measurements,
respectively.[166]
In general, an external electric field drives ions towards
the opposite interfaces (perovskite/ETL and perovskite/HTL,
respectively). These accumulated ions result in both a change
of the internal field and a concomitant modulation of interfacial
barriers, which ultimately results in the hysteretic behavior.[121]
This model can be simply depicted as an interfacial mecha-
nism, as shown in Figure 8.
4.4.1. Migrating Species
First, it is important to understand which species are actually
mobile and can drift within an electric field in MAPbI3 PSCs.
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www.advancedsciencenews.com
Figure 8.  Schematic diagram of the ionic migration under external elec-
trical fields in a PSC. Positive and negative ions drift towards opposite
electrodes and accumulate at these interfaces. Reproduced with permis-
sion.[167] Copyright 2015, The Royal Society of Chemistry.
There are several candidates for the migrating ions: a) proton,
or hydrogen ions, b) methylammonium, or MA+ ions, and
c) iodide ions.[168,169] In detail, these ions originate from defect
states during low-temperature fabrication and include vacan-
cies (e.g., VMA, VPb, and VI) (i.e., Schottky defects), interstitial
defects (e.g., MAi, Pbi, Ii), i.e., Frenkel defects, and anti-site
substitutions (e.g., MAI, PbI),[167,170] as previously mentioned in
Figure 7. Note that due to the high activation energy (explained
in the following part),[167,171] migration of Pb2+ ions can be
excluded in this discussion.
For a) hydrogen ions, on the basis of first principle calcula-
tions (DFT method), Egger et al.[172] proposed that hydrogen-
ion diffusion is enabled through the collective displacement of
iodide ions. However, it is rather difficult to maintain a high
concentration of H+ in PSCs due to the weak acidity of methyl-
ammonium.[169] Hence, even though H+ ions might exist, they
should rather play a minor role compared with other defects.
The migration of b) MA+ ions was proposed to be one of
the reasons for the observed giant field-switchable photovoltaic
effect in PSCs.[173] Employing the recently invented technique
of photothermal induced resonance microscopy (PTIR), Yuan
et al.[174] observed a MA+ ion concentration contrast between
before and after poling the device. This redistribution of MA+
ions induced by an external electric field clearly indicated the
migration of MA+ ions and Azpiroz et al.[167] proposed the same
on the basis of computational studies. However, the extent of
the contribution of MA+ ions to the hysteresis is still under
debate. Van Reenen et al.[157] estimated the diffusion coefficient
of mobile ions, without identifying the species with around
2 × 10−11 cm2 s−1. Eames et al.[171] estimated the diffusion of I−
ions with a coefficient of 10−12 cm2 s−1, whereas their estimated
value for MA+ ions was only 10−16 cm2 s−1,[171] which was four
to five orders of magnitude lower than the diffusion coefficient
of I− ions. These findings suggest that iodide ions play a more
important role in hysteresis effects compared to MA+ ions.[171]
Recent evidence consistently suggests that c) the migration
of iodide ions plays the major role in the hysteretic behavior of
PSCs.[121] Xiao et al.[173] proposed that positively charged iodide
vacancies, VI, were responsible for the n-type doping in PSC
under an external electrical field. Furthermore, long-term elec-
trical biasing in devices with lateral electrodes led to an obvious
degradation at the anode side. To elucidate the species of ions,
Yang et al.[175] conducted long-term high temperature biasing
experiments using a device structure of Pb/MAPbI3/AgI/
Ag. The formation of PbI2 at the Pb electrode could be char-
acterized by energy dispersive X-ray spectroscopy (EDX) and
X-ray diffraction (XRD), indicating that migrated iodide ions
caused this observed reaction. Similarly, by using X-ray diffrac-
tion (XRD) and energy-dispersive X-ray spectroscopy (EDX),
Yuan et al.[176] directly observed the migration of iodide ions at
higher temperatures (330 K) under an electric field. During the
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experiment, MAPbI3 first decomposed into PbI2, which could
be driven by the external field. In this context Li et al.[115] carried
out X-ray photoemission spectroscopy (XPS) measurements
of long-term biased perovskite films with laterally-configured
electrodes. After 30 min of applying a voltage, the perovskite
film was measured by XPS, which quantitatively characterized
the elemental distribution between the two lateral electrodes.
As shown in Figure 9f, it was demonstrated that at the positive
electrode the I/Pb ratio was 5.57, whereas the ratio was only
2.59 at the ground electrode. This result showed the significant
iodine redistribution, in which the ratio I/Pb was stoichiometric
(≈3) in the pristine device. In addition, as shown in Figure 9a,
analyzing the binding energy of Pb in the XPS signal revealed
the decomposition of MAPbI3 at the negative electrode, which
was consistent with the observed degradation characterized by
Xiao et al.[173]
4.4.2. Ion Migration Process
The detailed migration process of ions in PSCs can be theo-
retically treated using dynamics of defect states. Due to the
difficulty of directly characterizing the ionic movement,
most of the description is on the basis of theoretical DFT
calculations.[130,171,177]
Herein, the ionic transport is described as a hopping mecha-
nism, i.e., jumping between neighboring sites.[178] As shown in
Figure 10a,b, i) MA+ ions migrate into a nearby vacant cage,
ii) Pb2+ ions migrate via the diagonal direction, whilst iii) iodide
ions move along an octahedron in the Pb–I plane.[171] The
migration of these ions requires an energy to open the PbX3
framework, which acts as a barrier for the ionic migration. This
barrier results in an activation energy, Ea. Detailed DFT calcu-
lations have been provided by Mosconi et al.[177] and Meloni
et al.[130] The latter calculated the migrating pathways for each
defect, including iodide vacancies, MA vacancies, Pb vacancies,
and iodide interstitials, as shown in Figure 10c–e, respectively.
The migration pathways of individual ions/defects are con-
sistent with the ones proposed by Eames et al.[171]
Apart from hopping through point defects (Schottky and
Frenkel defects) within the crystal lattice,[178] as shown in
Figure 10f,g, a range of other possible ion migration chan-
nels can exist. Yuan et al. suggest local lattice distortion,
induced through charges or additional impurity atoms, light-
induced softening, and piezoelectric effects, as shown in
Figure 10h–l.[168] Furthermore, grain boundaries (GB) that pos-
sess a large density of defects may play an even more important
role, illustrated in Figure 10k. The influence of GBs has been
demonstrated by different groups. For example, Xiao et al.[173]
found that, compared with large crystal size devices, films com-
posed of smaller size grains can be more easily switched under
external electric fields. By carrying out conducting atomic force
microscopy (c-AFM), and scanning electron microscopy (SEM),
Shao et al.[179] concluded that GBs where these defects resided
were the fast moving channel for ion migration. Moreover, Yun
et al.[180] conducted Kelvin probe force microscopy (c-KFM) to
reveal that ion migration near GBs was much faster than inside
the grains. At the GB, ions exhibited higher diffusivity and
more effective charge separation. Xing et al.[181] also observed
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Figure 9.  XPS results of a CH3NH3PbI3−xClx device with lateral electrodes, a) and b) are XPS spectra of Pb and I elements near the ground electrode,
respectively, d) and e) are the XPS spectra of Pb and I elements near the positive electrode, respectively. c) Schematic illustration of the set-up for
the measurement of elemental distribution. The applied DC voltage is 1 V for 30 min. The lateral electrode distance is 200 µm. f) The ratio of I/Pb
distribution across the channel after applying a bias between two lateral electrodes. The dashed line shows the stoichiometry of perovskite, I/Pb ≈ 3.
Reproduced with permission.[115] Copyright 2016, John Wiley & Sons, Inc.

that devices with larger crystal size exhibited a higher activation
energy, that is, ions had to overcome higher barriers to migrate.
MacDonald et al.[182] revealed that GBs demonstrated a depth-
dependent resistivity, and that this inhomogeneity was one of
the limits for the improvement of PSC efficiency. In view of the
importance of GBs, further studies are expected to be dedicated
towards their detailed investigation.
Furthermore, ionic migration/transport can also take place
within the bulk of solids. This phenomenon has been inten-
sively investigated, especially in traditional perovskite materials

Figure 10.  Schematic diagram for ionic migration on microscopic and macroscopic scales, respectively. a) Iodide ions move along the octahedron edge,
Pb2+ ions move along the diagonal direction. b) MA+ ions move via neighboring vacancy sites. Reproduced with permission.[171] Copyright 2015, Nature
Publishing Group. c–e) Detailed view of migration events from blue (initial) to green (intermediate) to red (end) for c) I−, d) MA+, and e) Pb2+. Adapted
with permission.[130] Copyright 2016, Nature Publishing Group. Macroscopic schematic of ionic migration channels. f) Schottky defects or vacancies,
g) Frenkel or interstitial defects. Distortion of lattice due to h) accumulation of charges, i) impurities, j) light-illumination-induced lattice softening,
k) ion migration at the ground boundaries, and l) piezoelectric effect. Reproduced with permission.[168] Copyright 2016, American Chemical Society.

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(ABO3).[178] The movement of ions is facilitated by a hopping
mechanism in the atomic lattices via defect states (i.e., vacan-
cies, interstitials, etc.).[183] This hopping process to the neigh-
boring sites requires energy, i.e., an activation energy, Ea, to
overcome the barriers. This hopping process usually depends
strongly on temperature and is described as a thermally-acti-
vated point-defect movement. The migration can be empirically
derived by a thermally activated process in form of an Arrhe-
nius relation resulting in a hopping rate, rm.[115,130,167,184]
0.27 to 0.08 eV in polycrystalline MAPbI3, and from 1.05 to
0.47 eV in a single crystal, compared to dark conditions, specu-
lating that illumination may promote the decomposition of
MAPbI3 causing a larger number of vacancies and interstitials,
making it easier for ions to move. In addition, we note that
different contact materials, i.e., interfaces with the perovskite
layer, can also affect the ionic migration rates and effective acti-
vation energies, as reported by Levine et al.[116]

 E  4.4.3. Modulation of the Energetic Environment at Interfaces

rm ∝ exp  − a 
 kBT 
where kB and T are Boltzmann constant and absolute
temperature, respectively. Since Ea strongly depends on
the type of ionic species, determining the value of Ea can
enable us to identify which ions are moving. Several
groups have determined the involved activation energies,
for example, Meloni et al.,[130] Eames et al.,[171] Li et al.,[115]
Yu et al.,[184] and Levine et al.[116] extracted Ea by fitting
temperature-dependent transient J–V curve measurements.
Yang et al.[175] obtained the Ea by carrying out temperature-
dependent conductivity and dielectric constant measure-
ments. Mosconi et al.[177] obtained the Ea using the fitted
slope of temperature-dependent PL dynamic measurements.
The values for Ea range between 0.2 and 0.5 eV for iodide,
and 0.5 and 0.8 eV for MA+ ions. The latest measurements
for iodide rather suggest values at the lower end of the
quoted range. Theoretical calculations correlate these values
with the respective ionic species.[167] The calculations also
show that much higher activation energies would have to be
expected for Pb ions (interstitials),[171] thus excluding these
species as migrating ions. The calculated value of H+ ion
activation energy, i.e., the barrier for the proton migration
of ≈0.29 eV[172] currently does not allow to rule out the con-
tribution of hydrogen ions to the ionic migration in PSCs,
however, it is likely to play only a minor role due to their low
concentration, as explained earlier.
Interestingly, illumination of the perovskite can significantly
decrease the barrier for hopping and facilitate ion migration.
In this regard, Xing et al.[181] observed that under 0.25 sun
illumination conditions, the activation energy decreased from
(1)
To fully understand the influence of ionic migration on the
device performance, an energy level diagram is a useful sche-
matic approach to illustrate the detailed process, not only the
field distribution inside, but also the interfacial barriers.[76,121]
Several groups have made efforts regarding the construction of
a band diagram, based on indirect evidence, such as transient
photocurrent[171] and surface potential characterization.[180]
On the other hand, electroabsorption spectroscopy[185,186] has
proven to be a powerful approach to study the internal elec-
tric field and to characterize the interfacial barrier modulation
under working conditions.[187] Li et al.[115] found that there is
a shift of the built-in potential during the device scanning. In
addition, the shift of the potential ξ is equivalent to the change
of the open circuit voltage, Voc. This indicates that the modula-
tion of Voc can be attributed to a change in the internal field,
caused by the ion migration.
Based on the above evidence, a band diagram modulated by
the ionic migration is presented in Figure 11. To simplify the
discussion, the work functions of both electrodes are the same.
Without an external electric field, a classical metal–insulator–
metal (MIM) junction can be assumed, and the voltage drops
across the whole film. When a field is applied to the device,
ions, i.e., positive and negative defects are driven towards
opposite selective electrodes, with concentrations of the order
of over 1017 cm−3 (Figure 11).[173,188] These ions accumulate at
the selective contacts, causing: a) changes in the internal field
of the device due to the screening of the external field, and b)
modulation of the perovskite/electrode interfacial barriers. In
the first case (Figure 11b), the electric field causes negative ions
to travel towards the HTL and positive species to accumulate at

Figure 11.  Schematic diagrams of band bending in perovskite solar cells under electrical fields. The red dashed arrows indicate the direction of the
effective work function movement. E presents the direction of the external electrical field. a) Before migration, the voltage drops uniformly across the
perovskite film. b,c) After the redistribution of ions, the internal field is shielded by the accumulated ions at the interfaces. In the meantime, interfacial
dipole layers emerge, influencing charge injection/extraction. Adapted with permission.[115] Copyright 2016, John Wiley & Sons, Inc.

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the TiO2 interface, which alters the built-in field. In the second
case (Figure 11c), the electric field drives the ions towards the
other electrode. These charges are compensated by opposite
charges within the electrodes, causing a change of the effective
band level. Therefore, the effective built-in field will be modu-
lated and either enhance (Figure 11b) or decrease (Figure 11c)
the original field. As a consequence, the separation of photo­
generated charges is either improved or deteriorated.[171] Apart
from the influence of an internal field, accumulated charges
also can modulate the interfacial barriers. The drifted ions
located at the interface between the perovskite and the selec-
tive electrode result in a modification of the charge injection/
extraction barriers. As a result, the effective charge-transfer pro-
cess through these interfaces can be changed by the distribu-
tion of ions, which are driven by the external electric field.[189]
Li et al.[115] also mentioned the often-observed kinks illus-
trated in Figure 6 in the J–V curve measurement. Several
groups have observed a similar behavior,[15,117,128,190,191] and this
phenomenon especially prevails when using fast scan rates. In
the context of the ion-migration model, the authors found an
explanation for this kink in the J–V curve. When scanning from
a negative bias (short-circuit to open-circuit), the flat band con-
dition is reached at some point. During the flat band condition,
where there is no electrical field inside, ion diffusion occurs,
driven through the concentration gradient (without ion drift)
and rearranges the internal field, which leads to the shift of Voc.
The prevalence of this kink is another evidence for the ionic
migration during electric field sweeping.
4.4.4. Suppression of Hysteresis
From a technological perspective, it is very desirable to avoid
hysteresis. In particular, the finding that mobile/drifting ions
play a major role makes it obvious that it would be very benefi-
cial to not only reduce the hysteresis, but also to increase the
long-term stability of photovoltaic devices. It seems promising
to suppress the hysteresis via three approaches: 1) reducing the
concentration of defects/ions, 2) hindering the motion of these
ions, and 3) avoiding interfacial barriers and enhancing the
interfacial charge-transfer process.
It has been demonstrated that processing perovskite films on
mesoporous TiO2 layers helps to create uniformly and densely-
packed large perovskite grains, leading to negligible hyster-
esis.[12] The careful exposure to additional humidity during the
growth of perovskite crystal films can enhance their quality
leading to a reduction in the hysteresis, too.[192] In this case, the
authors attributed this significantly decreased hysteresis to the
realization of large-sized crystal grains that possess 1) much
fewer defects that are the source of mobile ions, 2) fewer grain
boundaries serving as fast channels for ionic migration, and
3) better charge transfer at the interface.
It has been widely shown that the incorporation of PCBM
molecules, either used as a selective ETL[193] or intermixed
within the bulk of the active layer,[194] significantly reduces
the hysteresis and leads to a higher device stability. We note,
however, that even devices that appear to be hysteresis-free at
room temperature still show the effect at lower temperatures.
Moreover, just because there is no observable hysteresis does
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not mean that the device is free of ion migration.[195,196] As pre-
viously discussed, the accumulation of ions/defects leads 1) to
a high local p- and n-doping, effectively enhancing/decreasing
the built-in potential, and 2) to a change in the interfacial bar-
riers in the device. Hence, this significant reduction of hyster-
esis is interpreted in terms of these two origins.
It is important to note that in perovskite solar cells that incor-
porate a PCBM layer or a mixed perovskite/PCBM layer, PCBM
molecules will distribute within the bulk of the perovskite
film. Thermally activated PCBM molecules are easily driven
into the perovskite film by diffusion during thermal annealing
procedures. As shown in Figure 12a, PCBM absorbed at per-
ovskite defect sites, i.e., iodide interstitials or iodide vacancies,
passivate those and decrease or even completely impede ion
migration. Xu et al.[197] have demonstrated the formation of
PCBM–halide-radical species in perovskite–PCBM mixed sys-
tems using UV–Vis absorption spectroscopy. Specifically, iodide
ions form a strong bond with PCBM molecules by a direct elec-
tron transfer from the anions (iodide ions here) to PCBM or
C60, as shown in Figure 12c.[198] The reaction between PCBM
and I3 trimers associated with the PbI antisite defects leads to
the creation of anionic fullerene derivatives.[168] In this respect,
the iodide ions/defects are immobilized by combining with the
PCBM molecules in the bulk of the perovskite, thus impeding
their further motion towards the perovskite/TL interfaces.
Following this argument, PCBM is able to passivate surface
states and also to promote the charge transfer process through
the perovskite/ETL interface.[76] Wojciechowski et al.[200] pro-
vided spectroscopic evidence that C60 buckyballs formed a self-
assembled monolayer and passivated or inhibited the traps
states at the interface between TiO2 and the perovskite layer.
Xing et al.[199] observed an obvious reduction of the perovskite/
TiO2 interfacial barrier by inserting a PCBM layer on top of the
TiO2 electrode, as shown in Figure 12e–g. Shao et al.[146] attrib-
uted the elimination of hysteresis to the passivation of charge
trap states in the bulk of the perovskite film during the thermal
annealing process. The interdiffused PCBM molecules pas-
sivate traps at the surface and the GBs of the perovskite, and
therefore enhance the charge transport and charge extraction.
A further indication along this line of reasoning is given by a
study where TiO2 was treated with an ionic liquid that appar-
ently decreases trap state density and led to a certified PCE of
over 19%.[201] The suppressed hysteresis was associated with
both the reduction of ionic motion and the improvement of the
interfacial charge-transfer process.
5. Long-Term Viability: Stability and Sustainability
In order for perovskite materials to be viable in long-term solu-
tions, they must be stable under operational conditions, com-
pete with incumbent technologies on price, and address their
toxicity concerns. In this section, we review recent contribu-
tions towards fulfilling this rather tall order.
Photovoltaic technologies currently on the market, i.e., poly-Si
or CdTe, reach a remarkable raw device cost around $0.30 per peak
Watt.[202] Current record-breaking perovskite solar cells employ
expensive organic layers for optimal charge extraction, leading
to a projected cost just from the hole transporter, assuming
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(Spiro-OMeTAD) requires several steps with

a poor overall yield (15 to 30% depending on
the synthesis route)[203] and is therefore often
replaced by synthetically more accessible
cores. Simple moieties such as phenyl,[206]
biphenyl,[207] carbazole,[207,208] triphe-
nylamine, [209] or triptycene[210] can be used to
reduce the cost, and spiro-based alternatives
such as spiro[fluorene-9,9′-xanthene],[211,212]
spiro[cyclopenta[2,1-b:3,4-b′]dithiophene-4,9′-
fluorene] and spiro[cyclopenta[2,1-b:3,4-b′]
dithiophene-4,9′-fluorene] have been intro-
duced.[213] Li et al. introduced heteroatoms in
the core by using the simple 3,4-ethylenedi-
oxythiophene (EDOT) moiety. Additionally,
they were able to perform their reaction in
one pot to further reduce the cost.[214] Many
of these materials have shown a photovoltaic
performance in perovskite-based devices that
is comparable to, or even better than, state-of-
the-art Spiro-OMeTAD.
Another route to reduce the cost is
by employing low-cost chemistries and
reducing tedious product purification. Petrus
et al. introduced Schiff base condensation
chemistry to prepare low-cost azomethine-
based HTMs[203] that has several advantages:
it can be performed under ambient condi-
tions, does not require metal catalysts, and
water is the only side-product (Scheme 1).
Additionally, this chemistry greatly simpli-
fies the product purification up to the point
where it might not be necessary at all.[215] In
particular, the authors have designed a new
Figure 12.  Proposed mechanism for the reduction of hysteresis by using PCBM. a) Passivation small molecule, termed “EDOT-OMeTPA”
process via PCBM in perovskite through interdiffusion. PCBM absorbs on the antisite defects based on previous azomethine work.[215–218]
located at the GB. b) Thermal admittance investigation of trap density of states before and after
As a hole-transporting layer in perovskite
the annealing process. Adapted with permission.[146] Copyright 2014, Nature Publishing Group.
c) Electron transfer occurs between the perovskite anions and PCBM, forming PCBM–halide- solar cells, this material achieved device effi-
radical. d) Theoretical calculations (DFT) indicate that charge transfer leads to the transition ciencies comparable to Spiro-OMeTAD. The
of trap states, from deep traps towards shallow traps. Adapted with permission.[197] Copyright good photovoltaic performance has been
2015, Nature Publishing Group. Schematic energy diagram of e) pure perovskite material, attributed to the fast injection of holes in
f) perovskite/PCBM interface layer, and g) perovskite/TiO2 interface layer. Reproduced with the material, which outcompetes second-
permission.[199] Copyright 2015, John Wiley & Sons, Inc.
order recombination.[219] Cost analysis for
the developed EDOT-OMeTPA molecule
20% power conversion efficiencies, of ≈$0.30 per peak Watt.[203] shows a total estimated material cost of only $10 per gram,
Clearly, for perovskite photovoltaics to enter the market, new low- which results in a negligible material cost contribution of
cost charge-extraction layers are necessary. The commonly used ≈$0.004 Wp−1 in the final device. Condensation chemistry was
organic materials are expensive as a result of their multistep syn- recently also used by Daskeviciene et al. to synthesize the low-
thesis that requires stringent reaction conditions and transition cost enamine-based HTM “V950” (Scheme 1), which resulted
metal catalysts. The side products and catalyst residues need to be in power conversion efficiencies close to 18%.[220] The costs of
removed via purification methods like column chromatography these materials are comparable to those of the highly conduc-
or sublimation, which are time-consuming and expensive.[204,205] tive polymer PEDOT (not to be confused with PEDOT:PSS),
This generally leads to commercial prices exceeding $200 g−1, and which was used as the hole transport material on top of the
thus reaching lower module target costs is challenging. perovskite.[221]
In the past years, several research groups have put their The combination of clean and low-cost chemistry, in combi-
focus on synthesizing low-cost hole-transporting mate- nation with cheap starting materials, has been shown to result
rials (HTMs) by reducing the number of synthetic steps. in a dramatic reduction in the cost contribution of the HTM.[203]
Especially, the synthesis of the Spiro core in 2,2′,7,7′- With these materials in hand, commercial applications of per-
tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene ovskite photovoltaics can be targeted.

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Scheme 1.  Synthetic schemes for HTMs prepared using low-cost condensation chemistry.[203,220] For this synthesis, metal-free catalysts para-tolue-
nesolfonic acid (pTSA) and camphor sulfonic acid (CSA) were used, where water is the only side-product. The estimated material cost is displayed in
green.
5.1. Stability
5.1.1. Moisture
Water interacts strongly with commonly used perovskite mate-
rials for solar cells, such as MAPbI3.[90,222] As the structure is
soluble in water, the presence of humidity during film pro-
cessing can significantly influence the thin film morphology
and can lead to improved solar cell performance.[3,46,223] How-
ever, when fully-formed perovskite solar cells are exposed to air
with a water-vapor content above 50% at room temperature, a
loss in performance is incurred.[224] Understanding the effect of
moisture on perovskite materials is thus rather important with
a view towards achieving stable performance over a decade.
Leguy et al. have identified two distinct degradation path-
ways depending on whether water condensation occurs on the
surface of the film or not.[225] If the films are exposed to warm
humid air with a water vapor content above 50% at room tem-
perature, water condensation occurs, resulting in decomposi-
tion into HI (soluble in water), solid PbI2, and CH3NH2, either
released as gas or dissolved in water.[32,226,227] In this instance,
the process is irreversible and losses to device performance are
observed.
When the films are exposed to cool humid air, and no water
condensation occurs, then water is slowly incorporated into
the crystal to form a new crystal structure with isolated [PbI6]4−
octahedra.[228–232] The crystal structure formed depends on the
humidity content, temperature, and exposure time, with the
initial formation of a monohydrated phase, followed by the for-
mation of a dihydrated crystal phase. The water incorporation
process appears to be isotropic, meaning that it occurs more
or less homogeneously throughout the sample, rather than
crystallization beginning at the outside and moving inwards,
suggesting that water is highly mobile within the lattice and/
or along grain boundaries.[225] In this case, the process is
reversible in films and in solar cells, where the photovoltaic
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performance of “degraded” devices was recovered with a simple
drying step under a dry nitrogen stream for a few hours.
Moisture during processing can also affect the final perovs-
kite morphology and stability.[45,223] Petrus et al. have recently
investigated the influence of moisture on MAPbI3 films and
solar cells derived from nonstoichiometric precursor mix-
tures.[101] They followed both the structural changes under
controlled air humidity (Figure 13) through in situ X-ray dif-
fraction, and the electronic behavior of devices prepared from
these films. The results showed that a small excess of PbI2 in
the films improved the stability of the perovskite compared
to stoichiometric samples. This was attributed to excess PbI2
layers at the perovskite grain boundaries or to the termination
of the perovskite crystals with Pb and I, which is supported
by theoretical calculations from Mosconi et al.[233] In contrast,
the films with an excess of MAI composed of smaller perovs-
kite crystals showed increased electronic disorder and reduced
device performance, owing to poor charge collection. Upon
exposure to moisture (similar to solvent annealing) followed
by dehydration, these films recrystallized to form larger, highly
oriented crystals, with fewer electronic defects and a remark-
able improvement in photocurrent, photovoltaic efficiency, and
stabilized power output.
Thus, exposure to moisture can be beneficial to device perfor-
mance, but ultimately will degrade the device. For this reason,
strategies that protect the perovskite material from moisture
but still achieve high efficiencies have been a well-explored
research topic. An example was shown by Hu et al., who
employed moisture-resistant layered perovskite (LPK) struc-
tures (Figure 14a).[79] Here, they demonstrated a perovskite/
perovskite heterojunction solar cell obtained via a facile solu-
tion-based cation infiltration process, to deposit layered perovs-
kite structures onto methylammonium lead iodide (MAPbI3)
films. This led to an enhancement of the open-circuit voltage
and power conversion efficiency due to reduced recombination
losses, as well as improved moisture stability in the resulting
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Figure 13.  SEM cross-section of photovoltaic devices with a MAPbI3 perovskite layer prepared with different precursor ratios. Top figures show SEM
cross-sections of freshly prepared devices and the figures below show the samples after exposure to 90% RH for 45 min before applying spiro-OMeTAD.
While the sample with an MAI excess recrystallizes, resulting in large crystals, the other two samples appear to degrade. The bottom images depict a
schematic representation of the morphology of the perovskite film before hydration with an inset showing the hypothesized crystal surface termination
for the perovskite grains at an atomic level. Reproduced with permission.[101] Copyright 2016, John Wiley & Sons, Inc.

photovoltaic devices, due to the hydrophobic nature of the LPK
layer.[234] A similar strategy was employed by Yang et al.,[235]
who functionalized the surface of the perovskite with hydro-
phobic tertiary and quaternary alkyl ammonium (TAE) cations,
greatly enhancing the stability of perovskite films under high
relative humidity (R.H. 90 ± 5%) to over 30 days (Figure 14b).
Alternative approaches include employing other layers in the
solar cell to function as a barrier against moisture-induced deg-
radation. In particular, Spiro-OMeTAD, which is currently the
material used in state-of-the-art devices, forms layers that con-
tain many pinholes that poorly protect the perovskite against
the ingress of water,[236] while additionally also promoting the
formation of PbIOH as a degradation product.[237] As result,
several groups have focused on the synthesis of hydrophobic
HTMs that form pinhole-free films.[208,238,239] This generally
results in a reasonable improvement of the stability of the
device, with only minor losses of the performance. A particu-
larly interesting strategy has been developed by Habisreutinger
et al. who employed highly conductive carbon nanotubes encap-
sulated in a polymer matrix as the charge extraction layer.[240]
This approach leads to devices which can actually be placed
under a stream of water and suffer no degradation to the device
performance as a result.
Despite the development of these different strategies to pre-
vent moisture-induced degradation of PSCs, this is still one of
the major points of concern. In spite of the increased under-
standing and improvements made regarding the moisture
stability, encapsulation of the devices is still key for long-term
stability.[241]
5.1.2. Heat
Besides the impact of moisture, heating MAPbI3 also results
in structural changes. This material undergoes a reversible
crystal-phase transition between tetragonal and cubic sym-
metry in the temperature range of 54 to 57 °C,[228,242] which
is in the range of common solar cell operating temperatures
during summer.[243] Changes to the electronic band structure
can potentially reduce the photovoltaic performance to a large
extent, as high-efficiency solar cells employ fine-tuned charge-
extraction layers. Additionally, cycling between the two crystal
phases during the day and night cycles is likely to lead to mate-
rial fatigue and shorter device lifetimes.
Several related perovskite structures, such as MAPbBr3 or
caesium lead iodide (CsPbI3), are available in order to avoid
phase transitions at solar cell operating temperatures. How-
ever, exchanging the iodide for bromide leads to a sub-optimal
band gap of 2.3 eV,[47] and a correspondingly lower power con-
version efficiency. Similarly, the all-inorganic caesium-based

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Figure 14.  a) Schematic illustration of the crystal structures of methylammonium lead iodide (CH3NH3PbI3) and a layered perovskite (LPK), forming
a moisture barrier. The inset shows the solar cells after 19 days storage at 75% RH, with clear degradation of the perovskite without the LPK. Adapted
with permission.[79] Copyright 2016, American Chemical Society. b) The possible interaction pathway between the perovskite and water using MA- and
TAE-terminated surfaces. Reproduced with permission.[235] Copyright 2016, Nature Publishing Group.

perovskite CsPbI3 has a large bandgap of 2.8 eV at room tem-
perature, while the desired cubic phase, with a bandgap of
1.7 eV, is only stable at high temperatures.[244] Currently, the
best option is to exchange the organic cation from MA to for-
mamidinium (FA) in iodide-based perovskites.[245] This leads to
a slight narrowing of the bandgap to 1.53 eV for the trigonal
α-phase, which is near the optimum for single junction solar
cells, and a phase transition at 125 °C,[246] well beyond cell
operating temperature.
Unfortunately for formamidinium lead iodide (FAPbI3),
the thermodynamically most stable structure at room tem-
perature is not a “3D structure”. This material crystallizes
in a hexagonal structure, similar to the PbI2 lattice, with the
lead halide octahedra sharing edges, in the so-called δ-phase.
This disrupts charge transport and results in a wide bandgap
of approximately 2.2 eV, clearly unfavourable for solar cell
applications. However, depending on the synthesis tempera-
ture, FAPbI3 can also be crystallized in the ‘α-phase’, which
is a pseudocubic structure, i.e., the lead halide octahedra
share the corner atoms, with trigonal symmetry. Thus, the
challenge is to find a synthesis route that leads to FAPbI3
in the dark phase, which is stable at solar cell operating
conditions.
A popular strategy to overcome this issue is to mix the FA
cation with other cations.[247–252] For instance, the exchange of
approximately 15% of the formamidinium cation with meth-
ylammonium leads to the crystallization of a material with
the same crystal structure as FAPbI3.[247,249,252] Moreover, this
desired phase is stable between room temperature and 220 °C
(Figure 15).[247] The resulting material exhibits the same lattice
parameters, photoluminescence emission peak wavelength,
and bandgap as those found for neat FAPbI3, meaning that
no significant lattice contraction occurred after the inclusion
of the smaller MA cation.[247] Combining caesium, FA, and a
mixture of halides, additionally allowed for bandgap tuning,
which is necessary for inclusion in tandem architectures with a
low-bandgap bottom cell,[248] while also enhancing the stability
of the system. Finally, the best performing solar cells currently
incorporate a 3 or 4 cation mixture,[4] although their stability
still needs to be studied in detail.
Besides the perovskite, the thermal stability of the other
layers and interfaces in the device play an important role in
the thermal stability. While inorganic blocking layers such as
titanium dioxide (TiO2) and tin oxide (SnO2) are generally con-
sidered stable under operating conditions, organic blocking
layers and their interfaces are much more sensitive. The
hole-transporting material Spiro-OMeTAD has been shown to
crystallize over time, and this process is accelerated at higher
temperatures, even though the glass transition temperature
(125 °C) is well above the operating conditions.[236,253,254] Sev-
eral novel hole transporting materials have been introduced
in the last years, of which many show an improved stability
of the device under operating conditions, generally achieved
by either increasing the glass transition temperature or by
cross-linking the HTM.[255–258] We further note that the loss
in performance is often related to the use of additives like Li-
TFSI, tert-butylpyridine (tBP), and Co-complexes, necessary to
oxidize the HTM and achieve high enough conductivities to
ensure balanced charge extraction and maximum device per-
formance.[259–261] Therefore, several HTMs have been devel-
oped that do not require these additives in order to obtain
good performance. However, in general, devices without addi-
tives show lower PCEs than their counterparts containing the
additives.
Surprisingly, recent studies have highlighted the point
that the metal contact can also influence the device degrada-
tion.[262,263] In particular, MAPbI3 has been shown to form HI
and CH3NH2 in an equilibrium reaction, even in encapsulated
devices. The HI can then react with the silver top electrode,
which would further shift the degradation reaction of the per-
ovskite to the right.[262] This effect is enhanced in the absence
of the hole transporting layer, or upon illumination/heating. In
contrast, gold is inert and in principle does not react with the
perovskite. However, it has also been shown that gold can dif-
fuse through the hole-transporting layer under operating condi-
tions, and severely affect the device performance.[263]

Adv. Energy Mater. 2017, 7, 1700264 1700264  (19 of 27) © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 15.  XRD pattern for a range of temperatures for neat FAPbI3 (left) and FAMAPbI3 (right), where 13% of the FA cations are exchanged with MA.
The two FAPbI3 crystal structures are depicted above the XRD patterns, and the characteristic reflection positions are marked with an arrow. Adapted
with permission.[247] Copyright 2015, American Chemical Society.
5.1.3. Mixed-Halide, Mixed-Cation Perovskites
The intrinsic stability of the MAPbX3 (X = Cl, Br, I) perovskites
has been studied with density functional theory (DFT) calcula-
tions,[264,265] and experimentally by measuring the formation
enthalpies.[266] Despite the differences between these studies,
all report that MAPbI3 was found to be the least stable, while
MAPbCl3 is the most stable. Partially substituting the iodide
with bromide or chloride would, therefore, be expected to
improve the thermodynamic stability of the perovskite com-
pared to the pure iodide material, while maintaining the good
photovoltaic performance. However, MAPb(BrxI1−x)3 mixed-
halide perovskites undergo a reversible phase separation into
iodide- and bromide-rich domains upon illumination.[267,268]
The de-mixing is expected to result in a large increase of recom-
bination centres, which limits the open-circuit voltage, leading
to a rather poor photovoltaic performance, combined with the
poor long-term stability of these materials.
Recent reports have shown that the unwanted halide segre-
gation can be suppressed by preparing a mixed-cation, mixed-
halide perovskite (CsyFA1−yPb(BrxIx−1)3).[248,269] These perovs-
kites with a caesium content between 0.10 < y < 0.30 show a
high crystallinity and good optoelectronic properties, and are
especially interesting for tandem applications. Upon the addi-
tion of a third cation to these mixtures (Cs/MA/FA), both
highly efficient solar cells and good long-term stability under
continuous illumination were demonstrated. Although theoret-
ical considerations would rule out its use, rubidium was added
as a fourth cation for the preparation of solar cells, further
increasing the photovoltaic performance.[4] Although very stable
devices were reported, introducing several cations and halide
anions could open the way for more degradation and demixing
pathways. Once one of the cations or halides segregates, it
could also influence the stability of the rest of the perovs-
kite,[269] making stability studies on these materials very com-
plex. Therefore, further studies regarding the thermodynamic
Adv. Energy Mater. 2017, 7, 1700264 1700264  (20 of 27)
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stability and possible degradation mechanisms of these multi-
cation, mixed-halide perovskites are essential for long-term
stability and potential commercialization of these complex
perovskites.
5.2. Sustainability
One final challenge that needs to be overcome is that of the
toxic nature of the current state-of-the-art perovskite structures.
Although a recent study has shown that the concentration of
lead in the soil would not dramatically increase, even in the
worst-case scenario of complete dissolution of a solar panel and
dispersion in the ground,[270] it is essential to take care of the
lead. The most elegant route would be to substitute the toxic
lead with another less toxic metal. Looking at the periodic table,
tin (Sn) based systems would, in principle, be the most viable
alternative. These materials have shown good charge mobili-
ties and efficiencies,[271] although these values still trail behind
the state-of-the-art lead system.[272,273] Unfortunately, by moving
up in the periodic table, the stability of the 2+ oxidation state is
decreased, which causes the perovskite to degrade very quickly
in the presence of oxygen and moisture. The high sensitivity of
the material not only decreases the lifetime, but also reduces
the reproducibility of the system. As an alternative, researchers
have looked into the possibility of incorporating bismuth
instead, which forms air-stable structures.[274–276] However, pre-
paring high-quality films has been challenging for these mate-
rials, and therefore the resulting device performance is still
lower than for their lead- and tin-based counterparts. Recently,
silver/bismuth-based elpasolites (more commonly known as
double perovskites) with the general formula A2AgBiX6, (A =
MA, FA or Cs; X = Cl, Br, I, Figure 16) have been suggested as a
promising lead-free and air-stable alternative.[277,278] Single crys-
tals of these double perovskites have shown good optoelectronic
properties and long charge carrier lifetimes. However, the
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 16.  Structure of the double perovskite Cs2AgBiBr6, time-resolved photoluminescence
and a fit for the PL decay. The inset shows a photo of a single crystal. Reproduced with permis-
sion.[279] Copyright 2016, American Chemical Society.
preparation of high-quality films has shown to be challenging,
and therefore photovoltaic devices have not been published so
far.[279] As lead-free alternatives are relatively early in develop-
ment, the general research focus of the community has been
on preventing exposure of the lead to the environment.
Encapsulation of the device prevents the contamination of
the environment with lead and, additionally, it is necessary to
reduce the degradation of the perovskite.[280] However, encapsu-
lation is not the holy grail, as devices may still degrade, as was
recently shown by Han et al.[262] Furthermore, the lead will still
be present at the end of the lifetime of the devices. In an effort
to ensure the viability of perovskite solar cell parks, Binek et al.
have recently followed an alternative route, whereby the solar
cells are recycled by collecting and reusing the toxic lead in the
structure.[281] This is not only necessary to avoid lead waste, but
is also required, according to international electronic-waste-dis-
posal laws. The reported procedure allows for the removal of
every layer of the solar cells separately (Figure 17), which gives
the possibility to selectively isolate the different materials and,
in particular, allows for reusing the expensive conductive glass
substrate without a loss of performance. Recycled perovskite
solar cells with a performance above 16% have been demon-
strated in this manner.[282]
Furthermore, the energy payback time (EBT) of perovskite
solar cells needs to be assessed. Recycling of individual parts of
PSC, as shown by Binek et al., can serve as an effective strategy
to reduce energy-intensive steps that are especially needed for
the electrodes.[283] As mentioned before, new HTMs can be
developed, not only to reduce costs, but also to limit environ-
mental impact.[203] Finally, low temperature processed ETLs,
such as PCBM or alternative TiO2 fabrication techniques, can
be employed to reduce energy consumption in this step.[283–285]
6. Conclusions
Hybrid halide perovskite materials are a very promising pho-
tovoltaic technology for low-cost solar energy generation, and
represent an extremely rich research platform to develop high-
quality, solution-processable optoelectronic materials. In this
review, we have identified several key research areas and chal-
lenges that need to be expanded upon and addressed, in order
Adv. Energy Mater. 2017, 7, 1700264 1700264  (21 of 27)
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to enhance the potential for the commerciali-
zation of the technology:
i. Perovskite crystal growth
ii. Device reproducibility
iii. Hysteresis
iv. Stability and sustainability
The first challenges are two sides of the
same coin; in order to avoid poor device repro-
ducibility and large scattering of the solar
cell parameters, we must learn about and
carefully control the crystallization process.
In particular, forming highly crystalline, pin-
hole free, surface-smooth perovskite films is
required for highly efficient and reproducible
PSCs. These parameters depend on the initial
nucleation and growth mechanism, so it is important to develop
new handles to control them. While several strategies have been
put forward, i.e., one-step, two-step, etc., the more successful pro-
cesses are based on slowing down the crystallization by inducing
the formation of an intermediate phase that is then converted
into the final perovskite film. This strategy offers the greatest con-
trol over the crystallization process and leads to a smoother and
more homogeneous film, and thus more reproducible solar cells.
Most notably, the technique leading to the highest-efficiency solar
cells employs the formation of an intermediate precursor–DMSO
complex, with a mixture of cations that is then converted into the
perovskite phase upon heating on a hotplate.
Secondly, we have covered the possible mechanisms for hyster-
etic behavior, including ferroelectricity, charge trapping/detrapping,
Figure 17.  Recycling procedure for perovskite solar cells. I) Removal of
Au electrode. II) Removal of the HTM. III) Transformation of the perov-
skite into MAI and PbI2 and extraction of MAI in water. IV,V) Removal of
PbI2 and TiO2. VI) Preparation of a new TiO2 film. VII) Formation of the
perovskite film on recycled FTO from recycled PbI2. VIII) Preparation of
the HTM layer. IX) Deposition of the Au top electrode. Reproduced with
permission.[281] Copyright 2016, American Chemical Society.
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
as well as ionic migration under an external electric field. Recent
experimental and theoretical results consistently suggest a com-
bined role of ion migration and charge trapping/detrapping,
whereby, considering the timescales for each of the processes,
the migration of ions appears to be a major factor causing the
hysteresis. We have presented, in detail, the different aspects of
ionic migration, i.e., the ionic species, migration channels, activa-
tion energies, and their influence on the band structure. We also
have presented the strategies developed to eliminate or alleviate
hysteresis, including increasing crystallite-domain size, improving
crystal quality, and employing PCBM molecules for passivation.
Finally, in order to achieve the ultimate goal of employing
hybrid halide perovskites in commercial applications, the systems
must fulfil the rather tall order of being stable, sustainable, and
able to compete with existing technologies on price. Cost-wise,
the devices currently employ rather expensive small molecules as
the HTM, which has driven research to push for materials with
a lower number of synthetic steps or alternative, simpler chemis-
tries. Chief among these, condensation chemistry promises a par-
ticularly attractive approach, as it both lowers the number of neces-
sary synthetic steps and greatly simplifies the purification of the
compounds. Stability-wise, the recently-developed mixed-cation
systems have greatly enhanced this parameter, leading to dem-
onstrated working lifetimes in the range of thousands of hours.
Approaches to encapsulate the perovskite material employing
hydrophobic molecules as HTM, or directly incorporating a hydro-
phobic element in the device stack, have provided real progress
towards protecting the materials from moisture, while main-
taining the high efficiency of the devices. Lastly, addressing toxicity
concerns is of chief importance in a technology that aims to be
widespread and possibly incorporated into buildings. While sev-
eral lead-free alternatives have been developed, they are neither
as efficient nor as stable as the lead systems. This has pushed
researchers to develop recycling schemes to extract the lead from
the system at the end of the life cycle of the device.
Acknowledgements
M.L.P. and J.S. contributed equally to the work. The authors
acknowledge funding from the Bavarian Collaborative Research
Project “Solar Technologies Go Hybrid” (SolTech), the Excellence
Cluster “Nanosystems Initiative Munich” (NIM), and the Center for
NanoScience (CeNS). The authors acknowledge funding from the
German Federal Ministry of Education and Research (BMBF) under the
agreement number 03SF0516B.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
crystallization, hybrid metal halide perovskites, hysteresis, solar cells,
stability
Received: January 27, 2017
Revised: March 28, 2017
Published online: June 28, 2017
Adv. Energy Mater. 2017, 7, 1700264 1700264  (22 of 27)
www.advenergymat.de
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