nature reviews chemistry https://doi.org/10.

1038/s41570-023-00492-z

Review article Check for updates

Stabilization of photoactive phases

for perovskite photovoltaics
Xueping Liu    1, Deying Luo    2  , Zheng-Hong Lu    2, Jae Sung Yun    1, Michael Saliba    3,4  , Sang Il Seok    5 
& Wei Zhang    1 
Abstract Sections

Interest in photovoltaics (PVs) based on Earth-abundant halide perovs­­ Introduction

kites has increased markedly in recent years owing to the remarkable The demand for phase stability
properties of these materials and their suitability for energy-efficient and The promise of FAPbI3 light
scalable solution processing. Formamidinium lead triiodide (FAPbI3)-rich absorbers
perovskite absorbers have emerged as the frontrunners for commercializa­ The challenges of stabilization
tion, but commercial success is reliant on the stability meeting the high-
Fabrication and stabilization
est industrial standards and the photoactive FAPbI3 phase suffers from strategies
instabilities that lead to degradation — an effect that is accelerated under Upscaling towards
working conditions. Here, we critically assess the current understanding commercialization

of these phase instabilities and summarize the approaches for stabilizing Outlook
the desired phases, covering aspects from fundamental research to device
engineering. We subsequently analyse the remaining challenges for state-
of-the-art perovskite PVs and demonstrate the opportunities to enhance
phase stability with ongoing materials discovery and in operando analysis.
Finally, we propose future directions towards upscaling perovskite
modules, multijunction PVs and other potential applications.

Non-photoactive phase Photoactive phase

Decrease Gibbs free energy

Increase energy barrier

Advanced Technology Institute, University of Surrey, Guildford, UK. 2Department of Materials Science and
1

Engineering, University of Toronto, Toronto, Ontario, Canada. 3Institute for Photovoltaics (IPV), University
of Stuttgart, Stuttgart, Germany. 4Helmholtz Young Investigator Group FRONTRUNNER, IEK5-Photovoltaik,
Forschungszentrum Jülich, Jülich, Germany. 5Department of Energy Engineering, School of Energy and Chemical
Engineering, Ulsan National Institute of Science and Technology, Ulsan, South Korea.  e-mail: deying.luo@
utoronto.ca; michael.saliba@ipv.uni-stuttgart.de; seoksi@unist.ac.kr; wz0003@surrey.ac.uk

Nature Reviews Chemistry

Review article
Introduction
A milestone in the development history of perovskite photovoltaics
(PVs) was the discovery of formamidinium lead triiodide (FAPbI3) per-
ovskite absorbers, in which the archetypal methylammonium (MA)
cations are replaced by formamidinium (FA) cations on the A-site of
the ABX3 crystal structure1,2 (Box 1). Compared with the MA-based
perovskites, FAPbI3 absorbers show better thermal stability and nar-
rower bandgaps, which are beneficial for enhancing lifetime of the
device and maximizing the efficiency of solar energy harvesting3,4.
The past decade has seen reports of perovskite PVs using FAPbI3-rich
compositions (Box 1) with ever-increasing power conversion efficien-
cies (PCEs), culminating in a certified PCE of 25.7% in single-junction
devices, comparable to commercially available crystalline silicon
PVs5,6. These advancements have encouraged researchers to move
from l­ ab­oratory-scale single-junction and multijunction devices
towards modules7,8 (Box 1), and we predict that perovskite PVs will be a
game-changer in the future PV market.
Despite these fascinating features, pristine FAPbI3 absorbers
exhibit phase instability as a result of external stressors — including
light, heat, electrical bias, moisture and oxygen — during device manu-
facturing and operation against external stressors. In general, the
photoactive phase of pristine FAPbI3 (also known as the ‘black phase’) is
thermodynamically metastable and occurs only at temperatures above
390 K; below this temperature, a non-photoactive phase (also known
as the ‘yellow phase’) starts to dominate9–11. Non-photoactive phase
impurities existing within polycrystalline perovskite films on micro-
scales and nanoscales tend to seed device degradation under normal
working conditions12. Efforts to improve the phase stability of FAPbI3 at
room temperature have been initiated by precisely controlling chemi-
cal compositions through lattice site ion alloying, forming FAPbI3-rich
perovskites13,14. These alloyed perovskites have shown great potential
to maintain photoactive phases at room temperature with favourable
formation enthalpy (ΔHf; Box 2). However, lower photocurrent — owing
to a blue shift of the bandgap — and the occurrence of phase segrega-
tion of the alloyed perovskites under working conditions compromise
device performance15,16. Other methods, such as solvent-coordinated
intermediate phases17, additives18,19 and strain engineering20, can help
circumvent these issues; yet, the long-term stability remains subop-
timal. Indeed, the operational stability of perovskite PVs remains an
order of magnitude lower than the required product lifetime of at least
25 years, as dictated by the International Electrotechnical Commission
61215:2016 tests qualification21,22. Hence, the most pressing challenge
in enhancing the operational stability of perovskite PVs is stabilizing
the photoactive phases to pass the industrial lifetime assessment tests.
In this Review, we comprehensively investigate the causes for
the generation of non-photoactive phases of FAPbI3-rich perovskites,
encompassing the inherent material characteristics that facilitate the
phase instability when exposed to stressors under working conditions.
We then critically assess the effective means to stabilize the photoac-
tive phases while highlighting the opportunities they might offer in
the search for commercially viable perovskite PVs. Subsequently, the
effect of various scale-up processes on the perovskite film stability is
analysed. Finally, we extend the discussion towards impending future
challenges and propose potential directions to boost perovskite PVs
towards a wider set of applications.
The demand for phase stability
A light absorber can only absorb photons with energies greater than
or equal to its bandgap (Eg) to generate charge carriers. To maximize
Nature Reviews Chemistry
light harvesting and achievable PCEs of the perovskite PVs, the band-
gap of the absorber needs to be judiciously optimized (Fig. 1a). In a
single-junction PV, the ideal bandgap range to achieve the maximum
theoretical PCE should, in principle, be restricted to 1.1–1.4 eV, accord-
ing to the defined Shockley–Queisser (S–Q) limit23. The bandgap of the
polycrystalline FAPbI3 film (~1.5 eV) is narrower than that of the proto-
type MAPbI3 (~1.6 eV) and all-inorganic CsPbI3 (~1.7 eV) counterparts
and reasonably close to the optimal bandgap region2,24,25, as shown in
Fig. 1b. Sn–Pb-alloyed perovskites can achieve a bandgap as narrow as
1.1 eV, but the spontaneous oxidation of Sn in conjunction with high
trap densities imposes constraints on pursuing higher device perfor-
mances26. The distinctive material properties — such as optoelectronic
conversion and processability — render FAPbI3 extremely attractive for
the best-performing perovskite PVs5 (Fig. 1c), yet stabilizing the black
photoactive phase remains a tough challenge.
Indeed, the origin of the poor phase stability (Fig. 1d) of the FAPbI3
is associated with the large Goldschmidt tolerance factor (t) (Box 2).
A common assessment of the formation possibility and stability of a
perovskite crystal phase is to examine whether the empirical t value,
governed by the combined effect of ionic sizes in the ABX3 lattice, lies
in the range of the ideal cubic structure (between 0.9 and 1.0)27. On the
basis of perfect sphere approximations of all ions used in the FAPbI3,
the theoretically calculated t (~0.99) fits this geometric constraint
marginally11 (Fig. 1e). However, the non-centrosymmetric structure
of FA cation and the dynamic rotation within the [PbI6]4− octahedron
framework presumably lead to a t-value outside the ideal range9,28.
Consequently, the cubic atomic stacking of FAPbI3 naturally requires
a higher formation enthalpy and is prone to transformation from a
photoactive phase (cubic) to a non-photoactive phase (hexagonal) at
room temperature. Compared with the large ionic size of FA+ (2.53 Å)
in FAPbI3, the smaller MA+ (2.17 Å) results in the t value of MAPbI3 at the
lower edge of the ideal range, while even smaller Cs+ (1.67 Å) makes
CsPbI3 tend to form an asymmetric orthorhombic phase14. Alloying
multication or anion compositions in lattices to form a FAPbI3-rich
perovskite, as we defined in Box 1, has been broadly utilized as a strat-
egy to stabilize the photoactive phase at room temperature through
tuning the t-values11. Nevertheless, such alloying approaches bring
new challenges, including bandgap widening (beyond 1.5 eV), chemical
composition inhomogeneity and phase segregation under operational
stressors29,30 (Fig. 1f). Consequently, increasing attention has focused
on stabilizing photoactive phases without widening bandgaps and
inducing phase segregation31,32.
The promise of FAPbI3 light absorbers
Crystallographic modification by substituting MA+ with FA+ on the
A-site of the perovskite lattice bestows upon FAPbI3 perovskite a more
symmetrical crystal structure and exceptional optoelectronic prop-
erties5,33. Compared with MA-based and Cs-based perovskites, the
charge-carrier lifetime of FAPbI3 perovskite is significantly increased3,
which may arise from the large polarons formed by faster reorientation
motion of the FA+ in response to photogenerated carriers34,35. However,
it remains a matter of debate whether the polaron formation is more
closely related to dipolar [BX6]4− sublattice or A-site cations36. Further-
more, C=N double bond in FA+ (NH2CH = NH2+) is stronger than the C−N
single bond in MA+ (CH3−NH3+) owing to a sizeable contribution from
the conjugated π bond; meanwhile, the protonated FA+ in this case is
less acidic than MA+, enabling deprotonation to be more challeng-
ing37, resulting in improved thermal and light stability of the FAPbI3
perovskites3. Conversely, the relatively strong acidity causes MA+ to
Review article

Box 1

Rapid progress in device performances for halide perovskite

photovoltaics
Perovskite semiconductors are an emerging family of photo­
voltaic materials with the general formula of ABX3. Monovalent
cations, such as formamidinium (FA+, NH2CH = NH2+), methyl­
ammonium (MA+, CH3−NH3+), Cs+, Rb+ or a combination thereof,
occupy the A-site at the corners of a cube; an octahedral inorganic
complex of the type [BX6]4−, in which X is a halide anion and B is a
divalent cation (such as Pb2+ or Sn2+), sits at the body centre of the
cube. Part a of the figure shows a schematic of the perovskite
crystal structure with a general formula ABX3. Formamidinium
lead triiodide (FAPbI3)-rich perovskites are typically formed upon
incorporating foreign halide perovskites (for example, MAPbBr3 or
CsPbI3) into the FAPbI3 host matrix at a molar ratio of less than 20%.
The world has witnessed the rapid advancement of state-of-the-art
single-junction and perovskite-based tandem photovoltaics (PVs)
on a laboratory scale (active area no more than 1.0 cm2). Part b
of the figure is a chart of reported power conversion efficiencies
(PCEs) against year for laboratory-scale perovskite PVs (including
single-junction and multijunction configurations) and illustrates
the rapid progress in device performance6,162. Promising laboratory-
scale PV technology has been transferred to upscaled devices
and minimodules with unprecedented PCEs. Part c of the figure
shows representative record efficiencies with respect to the area
(aperture or designated) for large-scale single-junction perovskite
modules, perovskite–perovskite and perovskite–Si tandem
PV modules. Most recently, single-junction minimodules (active
area of 23.9 cm2) with a PCE of 22.7% and monolithic perovskite–Si
tandem submodules (active area of 274.2 cm2) with a PCE of 26.8%
have been demonstrated7,162. The cost-effective features and
extended long-term operational stability of perovskite PVs (early
devices operated for just a few minutes, but devices have now
been operated for thousands of hours) show promise for the
next-generation PVs111,197. These accomplishments reported to
date are exclusively correlated with the development of FAPbI3-rich
perovskites.

a X: I–, Br–, Cl– b 35 Small-area perovskite solar cells (<0.1 cm2) 32.5% HZB
[BX6]4– Large-area perovskite solar cells (~1 cm2)
B: Pb , Sn
2+ 2+
Perovskite–perovskite tandem solar cells (<0.1 cm2)
30 28.0% NJU
Perovskite–Si tandem solar cells (~1 cm2)
A: FA+, MA+, Cs+ Perovskite–CIGS tandem solar cells (~1 cm2) 25.7% UNIST
25
Efficiency (%)

24.2% 23.7% U. Sci. Tech.

20
HZB

15
ABX3
10 12.3% 13.7% 10.4% KHU
ZJU MIT
3.8% Toin U 10.9% IBM
5

2008 2010 2012 2014 2016 2018 2020 2022 2024

Year

c
b
a c 28
Perovskite solar modules
Perovskite–perovskite tandem modules
26 Perovskite–Si tandem modules Oxford PV*

24
EPFL*
Efficiency (%)

22 UNIST
KIER/EPFL
NJU* KIER/EPFL
KAUST
20 WUT UNC
DICP WUT
18 UNC MS* Panasonic*
WUT
16
10 100 1,000
Area (cm2)

Nature Reviews Chemistry

Review article
(continued from previous page)
CIGS, copper–indium–gallium selenide; DICP, Dalian Institute
of Chemical Physics; EPFL, École Polytechnique Fédérale de
Lausanne; HZB, Helmholtz-Zentrum Berlin; IBM, International
Business Machines; KAUST, King Abdullah University of Science
and Technology; KHU, Kyung Hee University; KIER, Korea Institute
of Energy Research; MIT, Massachusetts Institute of Technology;
MS, Microquanta Semiconductor; NJU, Nanjing University; Toin U.,
dissociate readily and brings additional proton migration37, which may
be accelerated by light illumination38. Notably, the lower polarity and
orientational mobility of FA+ relative to MA+ potentially increase the
activation energy (Ea) of ion migration, thereby contributing to rela-
tively stable PV devices39,40. Additionally, the higher Young’s modulus
(Table 1) of FAPbI3, in contrast to MAPbI3, is thought to benefit from
strengthening the structural–functional integrity against mechanical
deformation and mitigating strain propagation under stress, which is
more pronounced in flexible PV devices41–43.
The challenges of stabilization
Phase polymorphism of the FAPbI3
Pristine FAPbI3 is a polymorphic crystalline material. There are four
crystal phases that exist over a broad range of phase transition tem-
peratures (Tc), including the cubic photoactive phase (α-FAPbI3, 390 K),
hexagonal non-photoactive phase (δ-FAPbI3, 293 K) and two low-
temperature photoactive phases, that is, tetragonal phase (β-FAPbI3,
140 K) and orthorhombic phase (γ-FAPbI3, 91 K)44 (Fig. 1d and Table 1).
Among these phases, only the cubic phase with high symmetry is
desirable for PV applications. Yet, the thermodynamically metasta-
ble cubic phase (α-FAPbI3) can only be transformed at temperatures
above Tc, that is, 390 K (standard atmospheric pressure)9. The change
in Gibbs free energy (ΔG) can describe the thermodynamic phase tran-
sition between two crystalline phases45, which is associated with the
changes of enthalpy (ΔH) and the Helmholtz free energy (ΔF), that is,
ΔG = ΔH + ΔF, where ΔF = −TΔS, ΔS is the entropy change and T is the
temperature (variations in volume and pressure are negligible)9.
As the formation enthalpy (ΔHf ) of the cubic phase is about 70 meV
(per formula unit cell) higher than that of the hexagonal phase, the
Gibbs free energy of the cubic phase at absolute zero (0 K) is higher
than that of the hexagonal phase9,11,39 (Fig. 1g). When the temperature
increases, the change in Gibbs free energy between a cubic phase and a
hexagonal phase originates from the contribution of entropy induced
by the rotational motion of the FA cations46. Specifically, when the FA
cations interact with the surrounding [PbI6]4− octahedra through the
formation of secondary hydrogen bonds47, the thermally activated
orientation of the FA cations results in high isotropy and thus high
entropy. Hence, when the temperature is higher than the Tc (390 K),
the increased entropy reduces the Gibbs free energy of the cubic phase
to a position well below that of the hexagonal phase, benefitting the
formation of the cubic phase9 (Fig. 1g). Nevertheless, when cooling
to room temperature, the FA cations are preferentially orientated
in the hexagonal FAPbI3 phase. At this point, the metastable cubic
perovskite with a higher Gibbs free energy can readily overcome the
phase-transition energy barrier and spontaneously transform back
to the energetically stable and asymmetric hexagonal phase9. Such
a phase transition of cubic to hexagonal must be avoided in efficient
Nature Reviews Chemistry
Toin University of Yokohama; UNC, University of North Carolina
at Chapel Hill; UNIST, Ulsan National Institute of Science and
Technology; U. Sci. Tech., University of Science and Technology
of China; WUT, Wuhan University of Technology; ZJU, Zhejiang
University. The symbol * represents certified efficiency. PV modules
can be classified into minimodules (<200 cm2), submodules
(200–800 cm2) and panel modules (>800 cm2)162.
and stable perovskite PV devices11. In this case, tuning the Gibbs free
energy and phase transition barrier are considered effective means to
stabilize the photoactive phase.
Phase segregation under working conditions
Beyond the aforementioned phase transition, phase segregation
of FAPbI3-rich perovskites also has a decisive role in dictating the
long-term stability of PV devices under working conditions. Phase seg-
regation at the nanoscale has been revealed as responsible for the large
open-circuit voltage (Voc) deficits observed for perovskite PVs in early
studies10. However, a recent study revealed that the Voc deficit in mixed-
halide perovskites is primarily due to a high density of traps before halide
segregation is initiated, which dictates non-radiative recombination48.
In the meantime, efficient charge funnelling formed by phase segre-
gation into low-bandgap iodine-rich domains was observed, which
selectively enhanced the quantum yield of photoluminescence at low
energies, and partially compensated for the Voc deficit associated with
the narrow-bandgap minority phases49. Additionally, halide segrega-
tion was demonstrated to be detrimental for photocarrier extraction
as a result of the funnelled photocarriers being constrained within the
narrow-bandgap iodine-rich phase, in which the current extraction effi-
ciency is reduced50. The phase segregation in FAPbI3-rich perovskites is
thought to occur spontaneously and slowly before exposure to external
stressors, including light, heat and bias. A qualitative phase diagram
of the thermodynamic equilibrium energies in mixed iodide–bromide
alloys at 300 K helps to rationalize these observations; a temperature-
dependent miscibility gap was revealed to act as a thermodynamic
driving force for spontaneous halide segregation51. Another potential
source for phase segregation is predicted to occur from local crystal
orientation mismatch, producing a local lattice structural strain dur-
ing the fabrication process52. As presented in Fig. 2a, the disordered
domains with nanoscale inhomogeneity landscapes or multiple phases
in perovskite alloys support this perspective, in which the spontaneous
phase segregation causes periodically ordered chemically segregated
domains, such as iodide-rich and bromide-rich regions53. The additional
energies supplied by the external stressors can further overcome the
phase segregation barriers by varying the activation energy of ion
migration, which has long been the origin of phase segregation under
working conditions. Hence, analysing the key challenges associated
with phase segregation under working conditions is paramount to
enhancing both device efficiency and long-term stability.
Typically, the FAPbI3-rich perovskites can be stabilized with a
negative Gibbs free energy difference of mixing (ΔGmix) at room tem-
perature51,54. However, ΔGmix can become positive and overcome the
kinetic barriers of phase segregation if perturbed by light illumina-
tion10,55. Density-functional theory calculations revealed that the mixed-
halide perovskites under light illumination have sufficient Helmholtz
Review article
free energies (ΔFmix) to overcome the entropically driven metastable
homogeneous states to phase-segregated states51, and the resulting
perovskite absorbers demonstrate dual-peak emission from band-
to-band recombination10,56 (Fig. 2b). Further studies indicated that
the phase segregation on a nanoscale might arise from the localized
lattice strain induced by the strengthened electron–phonon coupling
after light illumination57. This lattice strain was found in the high spatial
overlap between the lattice and single-charge density distribution, as
shown in Fig. 2c57–59. It has also been reported that the phase segregation
under light illumination depends on the type and stoichiometric ratio
of A-site compositions, which is related to the formation enthalpy of
mixing (ΔHmix) variation60. For example, the ΔHmix of the mixed A-site
FA1−xCsxPbI3 at 300 K is much larger than that of FA1−xMAxPbI3 or FA1−x−y
CsxMAyPbI3, which is likely to be segregated into FA-rich and Cs-rich
phases under continuous illumination, followed by the formation of
non-photoactive hexagonal FAPbI3 and orthorhombic CsPbI3 (ref. 54).
The overall gain in the ΔGmix of FA1−xMAxPbI3 and FA1−x−yCsxMAyPbI3
perovskites has been experimentally confirmed to stabilize the pho-
toactive phase during synthesis and operation under illumination13,54.
A growing consensus is that the broad tail states associated with the
electronic disorder would be enhanced for the perovskites under light
illumination, increasing defects such as halide vacancy (Vx+) and inter-
stitial (Xi−)61. The interstitial defects usually form metastable neutral
defects (Xi0) by trapping photogenerated electrons or holes and gen-
erating volatile X2 (I2 or Br2) through bimolecular processes62. Finally,
these increased defects, in turn, intensify phase segregation.
The heat effect associated with continuous light illumination is
another predominant factor that accelerates phase segregation. This
is related to overcoming the kinetic barriers to phase segregation by
localized heating or excess energy from hot-carrier thermalization near
the illuminated surface to activate halide migration63, thus facilitating
phase segregation64,65. Analogously, the light illumination-induced
heating (55–65 °C for PV panels under outdoor working conditions) has
been shown to activate the lattice expansion66,67 (Fig. 2d). The induced
lattice expansion was proposed to decrease the activation energy of
ion migration and be detrimental to phase segregation68. However,
a linear dependency of illumination intensity threshold (Iexc,threshold)
on temperature indicates that the Iexc,threshold for halide segregation
increases significantly with increasing temperature65 (Fig. 2e). Never-
theless, which factor dominates the process remains debatable: photo-
activated halide segregation or thermally activated halide remixing65.
Hence, decoupling the effects of thermal-driven and photo-driven
segregation under working conditions is urgently needed. Moreover,
heat-induced decomposition of volatile components of the perovskites
under continuous light illumination, such as MA, preferentially induces
vacancy defects on the film surface, which likewise promotes the phase
segregation process69. Some evidence suggests that the migration of VI+
is indeed assisted by coupling with thermally disordered MA+ (ref. 40).
The electrical bias, another key stressor, was also thought to
promote chemical inhomogeneities and phase segregation70. Light
illumination and electrical bias are always concurrently imposed on
the PV devices when assessing their operational stability. The effect
of the electrical bias on phase segregation can be analysed simply by
evaluating the ion migration as it is thought to coincide when phase
segregation occurs. For example, direct evidence for ion migration was
provided by monitoring I2− and Br2− elemental evolution in the biased
condition, enabling ions to move under the drive of an applied electric
field71 (Fig. 2f). A-site cations behave similar to halide ion migration,
albeit with higher migration barriers (0.4–0.6 eV) than halide ions
Nature Reviews Chemistry
(0.1–0.5 eV)72,73. Under the applied electrical bias, perovskite lattice
parameters are also observed to change, relating to the migrated ions
in the perovskite74. With considerations of ion migration and defects
predominantly present on grain boundaries and surfaces75, the local
surface potential analysis demonstrated a higher concentration of
the positively charged species at grain boundaries than that in grain
centres, which facilitates the formation of iodine-rich phases owing
to the preferential drift of iodine towards grain boundaries76. These
crystal terminations, therefore, served as channels for the occurrence
of phase segregation in perovskite films77. In addition, the different
Box 2
Key terms
Phase transition: in perovskites, phase transitions between different
crystal variants (including cubic, tetragonal, orthorhombic and
hexagonal, as shown in Table 1) are usually achieved through
crystallographic transitions, which involve sudden crystal lattice
rearrangement or a change in symmetry4.
Phase segregation: refers to the spatial compositional and
structural heterogeneity (such as iodine-rich and bromine-rich
regions, formamidinium-rich and Cs-rich regions) upon light
illumination in mixed-halide or mixed A-site cation perovskites4,10.
Formation enthalpy (ΔHf): the standard formation enthalpy is
defined as the change in enthalpy when one mole of a substance is
formed from its constituent elements in their standard states, under
standard conditions11,198.
Shockley–Queisser (S–Q) limit (also known as detailed balance
theory): describes the maximum theoretical efficiency of a single-
junction solar cell when only band-to-band radiative recombination
exists in a solar cell23.
Goldschmidt tolerance factor (t) and octahedral factor (μ): the
probable crystal structure and stability of ABX3 perovskite can be
evaluated by the Goldschmidt tolerance factor t and octahedral
factor μ199. t is defined as the ratio of the distance A−X to the
distance B−X in an idealized solid-sphere model:
t = (rA + rX )/[√ 2(rB + rX )],
where rA, rB and rX are the ionic radii values of the corresponding
components in the ABX3 structure. μ is defined as the ratio of rB/rX
for the [BX6]4−.
Bond energy (E): characterizes the strength of chemical bonds and
can be quantified by the magnitude of energy required to break the
bond. The higher the bond energy, the more stable the structure,
and vice versa.
Strain: describes the deformation strength of a material when
subjected to external or internal stress122.
Review article

a 2.5
UV Visible Infrared b 40
Silicon S–Q limit (300 K)
35 32.9% 33.6% 31.6%
FAPbI3
2.0 MAPbI3 30.5%
28.6%
Irradiance (W m–2 nm–1)

30
CsPbI3
25 Indirect
1.5

PCE (%)
20
1.0 15

10 GaAs c-Si
0.5 CIGS FAPbI3
5 c-InP MAPbI3
CdTe CsPbI3
0.0 0
500 1,000 1,500 2,000 2,500 0.8 1.0 1.2 1.4 1.6 1.8 2.0
Wavelength (nm) Bandgap (eV)

c 28 FAPbI3 d e
Cs/MA/FA/I/Br 151 K
24 0.8~0.9 0.9~1 >1 FAPbI3
0.70 Orthorhombic Ideal cubic Hexagonal
FAPbBr3
20
285 K FAPbCl3
0.65
MAPbI3
Cubic phase (α) Tetragonal phase ( β)

Octahedral factor (µ)

16 MAPbBr3
PCE (%)

0.60
MAPbI3 MAPbCl3
Slowly

Ra coo

12
140 K
cool
390 K

CsPbI3
91 K
pi l

0.55
dl

42 CsPbBr3
y

8 3
K CsPbCl3
0.50
4 MDAPbI3
DMAPbI
Moisture 0.45
0 EAPbI3
2008 2010 2012 2014 2016 2018 2020 2022 GAPbI3
Year 0.40
0.80 0.85 0.90 0.95 1.00 1.05
FAPbI3 CsPbI3 X-site alloying Hexagonal phase (δ) Orthorhombic Tolerance factor (t)
MAPbI3 A-site alloying A-site and X-site alloying phase (γ)

f Phase homogeneous state Phase segregation state g With oriented FA+ With isotropic FA+

Driving
force Br–
Cubic
I–

Hexagonal
T=0 T = Tc T > Tc

Fig. 1 | The evolution of perovskite photovoltaics and characteristic prop-
erties of FAPbI3. a, Optical absorption ranges for silicon and several halide
perovskites in the solar irradiance spectrum. b, The maximum achievable power
conversion efficiency (PCE) as a function of the bandgap for single-junction
photovoltaics according to the Shockley–Queisser (S–Q) theory. c, The evolution
trend of perovskite compositions and the increasing prominence of FAPbI3-rich
perovskites. d, Temperature dependence of phase transition of the crystal struc-
ture of the FAPbI3 absorbers. e, Correlations between perovskite components
with tolerance factor (t) and octahedral factor (μ). f, Illustration of alloyed perovs-
kite lattices evolving from phase homogeneity to phase segregation under driving
forces, such as light and bias30. g, Diagram of the Gibbs free energy variation of the
cubic and hexagonal FAPbI3 phases at different temperatures9. The dashed yellow
line represents the Gibbs free energy landscape when temperature is 0 K, whereas
the solid blue line represents the Gibbs free energy landscape ascribed to the
entropy. FA cations have isotropic orientations in the cubic photoactive FAPbI3
phase above the phase transition temperature (Tc) but acquire a preferred orienta-
tion in the hexagonal non-photoactive FAPbI3 phase when the temperatures are
lower than Tc. DMA, dimethylammonium; EA, ethylammonium; GA, guanidinium;
MDA, methylenediammonium; UV, ultraviolet. Part f adapted from ref. 30,
Springer Nature Limited. Part g adapted with permission of AAAS from ref. 9
© The Authors, some rights reserved; exclusive licensee AAAS. Distributed
under a CC BY-NC 4.0 licence.

migration and hopping rates of iodine and bromide defects have pro-
ceeded to generate a vertical gradient distribution in terms of the
iodide and bromide ratio, which is another possible driving force for
halide segregation78.
Beyond the driving force for phase segregation we discussed earlier,
another intriguing and debatable topic around phase segregation is its
reversibility: whether phase-segregated inhomogeneous film can return
to its original homogeneous-phase state after eliminating or relaxing
external stressors10,79. For instance, when halide-segregated perovskite
film is placed in the dark, the driven enthalpy of phase segregation may
be counteracted by mixing entropy and lattice strain relaxation, bringing
it back to a well-mixed state10. Furthermore, locally isolated halides in the
mixed iodide–bromide perovskite could be redistributed to an entirely
homogeneous state at high carrier–polaron densities30. This observation

Nature Reviews Chemistry

Review article

is considered that the sufficiently high carrier density eliminates the
strain gradient driving force that induces phase segregation by saturat-
ing large-area polarons and uniformly deforming the lattice30. However,
such an explanation remains speculative as it has not been fully verified in
other alloyed compositions, such as the mixed A-site cation perovskites.
On the contrary, an irreversible phase reconstruction process occurs as
a chain reaction after phase segregation under continuous light irradia-
tion; the charge flow from bromide-rich to iodine-rich domains induces
the expulsion of iodide from the lattice, followed by forming molecu-
lar iodine79. Overall, further efforts will be necessary to ascertain the
­underlying reasons for phase segregation and its reversibility.
Photoactive phase failure at ambient conditions
In addition to the stressors mentioned earlier, FAPbI3-rich perovskites
also tend to suffer from cubic-to-hexagonal phase transition and chemi-
cal degradation under moisture and oxygen stressors80,81. In a humid
environment, the FA+ rotational movement is inhibited, allowing the
preferential formation of the hexagonal FAPbI3 phase82. Furthermore,
the strong hydrogen bonding between FA+ and water disrupts the weak
interaction between FA+ and surrounding I− in the [PbI6]4− sublattice
and induces irreversible degradation from nanoscale hexagonal phase
impurities to PbI2 (ref. 83) (Fig. 2g). Moisture-triggered phase transition
kinetics in FAPbI3 strongly depends on perovskite grain sizes, relative
humidity and moisture exposure time80,84. A (pseudo) first-order reac-
tion kinetics model established for α-FAPbI3 and δ-FAPbI3 substantiates
that a rapid α-to-δ phase transition occurs mediated by a ‘liquid-like’
interface80 (Fig. 2h). The fast transformation kinetics is evident at the
localized grain boundaries of small-sized perovskite grains owing to
the increased contact area of moisture and perovskites. When MA+ and
Cs+ components are present in the FAPbI3-rich perovskites, their varied
polarization natures and charge carrier mobilities enable photoactive
phase failure in multistep pathways when exposed to a humid working
environment84. Typically, the failure products of the photoactive phase
may include: (i) wide-bandgap hydrated phase, that is, PbI2-CH3NH3I-
H2O; (ii) needle-like δ-CsPbI3 and δ-FAPbI3 and (iii) PbI2 (refs. 84,85).
Hexagonal polytypes are prevalent during the degradation process
in mixed-cation and mixed-halide alloys, such as 2H δ-phase (1D), 4H
and 6H phases (3D)86, which are most detrimental to the operational
stability. Moreover, moisture and an electrical bias render polarization
irreversibly on a timescale of minutes, leading to MA+ drift and perma-
nent degradation of perovskite films to PbI2 within hours87. Although
moisture has a decisive role in the photoactive phase failure process,
light and bias greatly accelerates this process.
In addition, the high affinity of halide vacancies for oxygen mol-
ecules enables their preferential adsorption and rapid diffusion into
perovskite films, where they then form highly reactive superoxide spe-
cies (O2−) under light, reaching complete saturation within 10 min81,88.
The formation of high-density superoxide in pristine MAPbI3 and FAPbI3
demonstrates this oxygen-induced degradation mechanism81 (Fig. 2i).
Superoxide ions contribute to the formation of extra mobile ions
and ion migration channels, which facilitate the degradation of per-
ovskite films under working conditions89. In this context, fabricating

Table 1 | Lattice parameters and material properties of different perovskites41,44,169–173

Material Crystal structure Tc (K) Space Lattice Octahedral Crystal Electronic Thermal expansion Young’s
group constants (Å) tilting volume (Å3) bandgap (eV) coefficient (α) (K−1) modulus (GPa)

FAPbI3 Cubic (α) 390 Pm3m a = b = c = 6.36 a0a0a0 257.5 1.43–1.50 20.3 × 10−5 16.5
α = β = γ = 90°
Tetragonal (β) 140 P4/mbm a = b = 8.92 a0a0c+ 298.4 ~1.62 20.2–20.6 × 10−5 –
c = 6.33 α = β = 90°
γ = 120°
Orthorhombic (γ) 91 P4/mbm a = 8.88 Disordered tilts – ~1.74  –  –
c = 6.28

Hexagonal (δ) 293 P63 /mmc a = b = 8.66 α = β = 90° 513.3 ~2.17 4.2 × 10−5  –
c = 7.90 γ = 120°
MAPbI3 Cubic (α) 330 Pm3m a = b = c = 6.39 a0a0a0 251.6 1.55–1.60 5.8 × 10−5 14.8
α = β = γ = 90°
Tetragonal (β) 293 I4/mcm a = c = 8.84 a0a0c− 990.0 ~1.62 6.1 × 10−5 14.3
b = 12.70 α = β = γ = 90°
Orthorhombic (γ) 165 Pnma a = 8.84 a+b−b− 959.6 ~1.69 – –
b = 12.58
c = 8.56
CsPbI3 Cubic (α) 593 Pm3m a = b = c = 6.15 α = β = γ = 90° 222.0 ~1.73 11.8 × 10−5 21.6

Tetragonal (β) 533 P4/mbm a = b = 5.97 β = 8°6 243.0 ~1.94 – 19.2

c = 6.27 δ = 0°
Orthorhombic (γ) 448 Pbnm a = 8.63 a0a0a0 947.3 ~1.67 11.8 × 10−5 18.3
b = 8.96 β = 14.75°
c = 12.64 δ = 9.68°
Orthorhombic (δO) 293 Pnma a = 10.40 b−b−a+ 887.8 ~2.82 11.8 × 10−5 –
b = 4.79 β = 11.5°
c = 17.80 δ = 9.9°

Nature Reviews Chemistry

Review article

a b t = –3 min c
t = 2 min
40
t = 3 min
t = 6 min

PL counts (arb. units)

30

20

10

0.95 1.00 1.05

Br:Pb (norm.) 0
600 700 800
Wavelength (nm)

d e f I2– Br2– SnO– reference

100 0.1
1.082
Peak position, Q (Å–1)

Segregation

Intensity/normalized
Iexc, threshold (µW cm–2)

80
Thermal
expansion
1.080
60 0.01

40 No segregation
1.078

20 0.001
20 25 30 35 40 45 50 55 290 300 310 320 330 340 350 360 370 0 2 4 6 8
Temperature, T (°C) Temperature (K) Fluence (1021 ions m–2)

g h α-Phase δ-Phase
i MAPbI3 FAPbI3
PbI2 Water soaking
1.0 1.8

δ phase ~50% RH, 3 days CsMAFA

0.8
Intensity (arb. units)

1.6
Normalized intensity

y = 1 – e–0.042t
Rb
I(t)/I(t0)

~30% RH, >90 days 0.6 R2 = 0.986

1.4
k = 0.042 h–1
0.4 y = e–0.042t
N2, 14 days R2 = 0.986 Cl
1.2
0.2

Fresh Cd
1.0
0.0
10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40 45 0 20 40 60
2 θ (°) Time (h) Time (min)

FAPbI3-rich polycrystalline films with large grains and low defect Optimizing the formation pathway
densities can mitigate ambient atmosphere erosion. Using effective During the perovskite fabrication process, the constituents of the pre-
encapsulation techniques is expected to overcome the challenge of cursor solution strongly influence the preferential transition pathways
atmospheric susceptibility damage90. by modulating the formation energies of photoactive phases. The
enthalpy of formation of the high-temperature cubic phase is greater
Fabrication and stabilization strategies than that of the hexagonal phase from the regular dimethylformamide
The aforementioned energetics control the stability of the photoactive (DMF)-based precursor solution. Thus the hexagonal phases begin to
phase of FAPbI3-rich perovskites and guide the various phase transition form in the solvent-coordinated intermediate phases and speed up
pathways. Thus, the key to achieving an ideal phase equilibrium is to as the solvent evaporates. The cubic phase can be formed upon high-
decrease the formation enthalpy of the photoactive phase during the temperature annealing91. When introducing intermediate phases with
fabrication process, while controlling the bulk and surface Gibbs free favourable energies, it enables the photoactive phases to form below
energy of the photoactive phase, and increasing the energy barriers the phase transition temperature and avoids phase inclusions92. To this
(ΔGc) for the transition from photoactive to non-photoactive phase end, solvent engineering by changing the composition of the interme-
and phase segregation. diate phase in the early crystallization stage has proven to be crucial in

Nature Reviews Chemistry

Review article
Fig. 2 | External stimuli-induced photoactive phase failure mechanisms
of FAPbI3-rich perovskites under working conditions. a, Normalized Br:Pb
ratio map of the FA0.79MA0.16Cs0.05Pb(I0.83Br0.17)3 film extracted by tracking the
characteristic Pb Lα, I Lα and Br Kα lines in nano-X-ray fluorescence53 shows the
local nanoscale heterogeneity in alloyed perovskites. b, The heterogeneous
compositions segregate into two distinct phases demonstrated by dual-peak
emission in the in situ photoluminescence (PL) spectrum evolution for X-site
alloyed perovskite under 400 nm pulsed illumination56. c, Snapshot of the 99%
isosurface of excess charge density taken from the Gibbs free energy calculations
and molecular dynamics simulations58. The driving force for local phase
segregation was found to be the strain resulting from the high spatial overlap
between the lattice and single-charge density distributions. d, The position of
the (110) peak in the wide-angle X-ray scattering data of perovskite in the dark
as a function of temperature, showing thermally induced lattice expansion with
increasing temperature67. e, The linear temperature dependency of excitation
intensity threshold (Iexc,threshold) for halide segregation in MAPbBr1.5I1.5 films confirms
the interplay between thermally driven mixing and photo-driven segregation65.
acquiring the photoactive phase of FAPbI3-rich perovskites. Strongly
polar aprotic solvents, such as dimethyl sulfoxide (DMSO), benefitted
from their higher donor number (DN, which is a measure of the coor-
dination properties of solvents and solutes) and a shorter Pb–O bond
length (2.386 Å) compared with DMF (2.431 Å)93, exhibiting stronger
coordination ability with the species of perovskite precursors, in par-
ticular PbI2 (refs. 19,94). As a result, stable PbI2·DMSO is preferentially
formed rather than solvent-coordinated perovskite complexes when
DMSO is mixed with the DMF host solvent, dominating the nucleation
of hexagonal phases95. This preferred route allows DMSO intercalated
in PbI2 to be easily replaced by high-affinity FAI and forms hexagonal
FAPbI3 nuclei, which are then converted to cubic FAPbI3 after annealing
(Fig. 3a; ΔHf2), establishing DMSO as one of the most prominent pro-
cessing solvents96,97. Motivated by the pathway associated with forma-
tion enthalpy, other promising phase transition routes are explored.
More stable intermediate states induced by stronger polar solvents,
for instance, N-methylpyrrolidone91, tetramethylene sulfoxide98 and
methylamine formate17, have been reported to assist the direct trans-
formation into photoactive phases from PbI2·solvent intermediate
states (Fig. 3a; ΔHf1) while avoiding the energetic pathway involving the
non-photoactive phase which occurs in the DMSO or DMF coordinated
complexes98 (Fig. 3a; ΔHf2). These intermediate phases, through strong
Pb–O bond and additional N–H···I hydrogen interaction, suppress the
generation of hexagonal nuclei during early crystallization, resulting in
the formation of the photoactive phases in desirable perovskite films.
Another effective means to facilitate the formation of the photoac-
tive phase is associated with strain-controlled heteroepitaxial growth.
The strain originating from the hetero-interface with a higher energy
state owing to the additional contribution of surface or interfacial
energy drives local nucleation and epitaxial growth of the cubic FAPbI3
(ref. 20). A representative example was demonstrated in a layered
perovskite-templated epitaxial growth that facilitates the phase trans-
formation of hexagonal-to-cubic FAPbI3 (ref. 20). The induced hetero-
interface tensile strain and the increased entropy of FA+ in hexagonal
FAPbI3 delay the growth of the hexagonal phase, leading to tenfold
enlarged FAPbI3 perovskite crystals with a reduced defect density and
preferred orientation. Since the as-grown α-FAPbI3 is orientationally
aligned with the layered perovskite, the heterogeneous interface with
applied compressive strain acts as a nucleation site and triggers the
phase transition of hexagonal to cubic (Fig. 3b). Besides, applying an
Nature Reviews Chemistry
f, Time-of-flight secondary ion mass spectrometry depth profiles showing the
relative secondary ion intensity of iodine and bromine elements evolution across the
film depth in the biased condition71. g, Evolution of X-ray diffraction patterns of
the FAPbI3 films stored at different relative humidity (RH) levels and photographs
of the corresponding thin films83. h, Kinetics plots of 1H signal intensity build-
up of −CH sites (FA cations) in δ-FAPbI3 and the simultaneous 1H signal intensity
decay for the same sites in α-FAPbI3 as a function of exposure time to moisture in
the dark at 85% RH80. i, Normalized PL intensity of hydroethidine aliquots in which
perovskite films were aged under light and oxygen blow at 610 nm, representing
the yield of superoxide generation81. Part a reprinted from ref. 53, Springer Nature
Limited. Part b reprinted from ref. 56, CC BY 4.0. Part c reprinted with permission
from ref. 58, American Chemical Society. Part d reprinted with permission of
AAAS from ref. 67 © The Authors, some rights reserved; exclusive licensee AAAS.
Part e adapted with permission from ref. 65, American Chemical Society. Part f
adapted with permission from ref. 71, Royal Society of Chemistry. Part g adapted
with permission from ref. 83, Wiley. Part h reprinted with permission from ref. 80,
American Chemical Society. Part i reprinted from ref. 81, Springer Nature Limited.
appropriate compressive strain (2.4%) thermodynamically favours
the epitaxial growth of single-crystal α-FAPbI3 on a heterogeneous
MAPbCl1.5Br1.5 single-crystal substrate, resulting in increased lattice
tetragonality (Fig. 3c). Therefore, the applied compressive strain has
a notably positive impact on reducing the lattice mismatching with
the substrate99. Nevertheless, the epitaxial growth of phase-pure per-
ovskite polycrystalline films is still constrained by the limited choices
of underlying materials. Future work must expand the contact layer
library to avoid the concomitant growth of harmful phase impurities100.
Alternatively, developing ‘van der Waals epitaxy’, epitaxy proceeds
through Wan der Waals interactions with large degrees of freedom on
lattice mismatches, would be another choice for growing photoactive
perovskites101.
Enhance thermodynamic stability
Solid-state alloying, which brings the Goldschmidt tolerance factor to
near-optimal values (~0.95), has been thought to be a general design
protocol for forming thermodynamically stable FAPbI3-rich perovskites
with lower Gibbs free energy of mixing (ΔGmix)11 (Fig. 3d). Reducing
lattice constant and increasing bond energy of FAPbI3-rich perovs-
kites realized negative formation enthalpy of mixing (ΔHmix) at ~300 K
(refs. 13,54). Such reduction in the Gibbs free energy of mixing is also
thought to be inseparable from the contribution of mixing entropy
(ΔSmix); favourable gains in ΔHmix and ΔSmix reduce the phase transition
temperature of δ-to-α as low as 100 °C, such as Cs–FA, MA–FA–I–Br and
Rb–Cs–MA–FA–I–Br alloys15,102,103. As for the role of substitutable Rb+,
further research is required to elucidate whether it causes octahedral
shrinkage15, modifies the grain boundary104 or, conversely, forms extra
Rb-rich phase impurities105. Besides, these FAPbI3-rich perovskites
with alloyed small-sized ions suffer widened bandgaps, non-negligible
chemical inhomogeneity on multiscales and phase segregation29,53,
although the underlying mechanism is still under debate48. Recently,
trace alloy incorporation in FAPbI3 has been shown to have a beneficial
effect on the photoactive phase and thus improve the balance between
device performance and stability31,106. For example, a feasible solution
was demonstrated by incorporating a low concentration of MAPbBr3
(0.8 mol%) to successfully stabilize α-FAPbI3 (ref. 106). Furthermore, the
partial substitution of FA cations with methylenediammonium cations
(MDA2+), which has a slightly larger ionic radius and more H groups
than FA, was found to sustain the original narrow bandgap of FAPbI3
Review article

a b c (104) Cl0.60Br2.40 Cl1.50 Br1.50

0.70
Compositions 20 nm 5 nm
+
α (111)
solvents
+ 105
additives ΔGc2

Intensity (a.u.)
ΔGc1 LP (002)

QZ (Å–1)
0.65
PbI2• solvent ΔHf1 [110 ZA] α-FAPbI3
Intermediates 7.24 Å α-FAPbI3 α-FAPbI3
ΔHf2 LP(002)
101

3.11 Å 3.61 Å
α (002) 0% –1.2% –2.4%
α-FAPbI3 (111) 0.60
0.1 0.20 0.1 0.20 0.1 0.20
δ-FAPbI3 QX (Å–1)

d Metastable phase
e f EDTA-induced tilted octahedra
[001]c
ΔGc (α δ)
Free energy

ΔGc
(δ α)
α-FAPbI3
δ-FAPbI3

Stable phase
Free energy

0.7 Å–1

Increase ΔGc
Decrease ΔG Tetragonal phase

g h 1.2 At T = 0 K i
–3.920 Vacuum
0.9 Tensile
Activation energy (eV)

Compressive –3.940
0.6
E (eV)

–3.960

0.3 235 240 245 250

0.651
Hexagonal LP Cubic Nitrogen
0.0
0.648

–0.3 0.645
14.6 14.8 15.0 15.2 15.4
d (A) 247 248 249 250
Compressive strain / Lattice volume (Å3)
/ ΔGc (α δ) ΔGc (δ α) ΔH

Fig. 3 | Stabilized photoactive perovskites with optimal bandgaps. a, The
differences in Gibbs free energies for the transition from either intermediate
adduct or δ-FAPbI3 to α-FAPbI3 (ref. 91). b, The formed hetero-interface
between the layered perovskite and α-FAPbI3 in heteroepitaxial growth induces
compressive strain, such that the δ-FAPbI3 to α-FAPbI3 phase transition starts at
the hetero-interface, and the nucleus formed may grow towards the grain bulk20.
c, Reciprocal spatial mapping of the (104) asymmetric reflection as a function of the
magnitude of compressive strain for α-FAPbI3 films between 0% and −2.4% (ref. 99).
Qx and Qz denote the X-ray scattering vector components in the in-plane and out-
of-plane directions, respectively. d, A schematic (upper panel) shows the Gibbs
free energy relationship between α-FAPbI3 and δ-FAPbI3 at room temperature.
The metastable α-FAPbI3 with higher Gibbs free energy tends to transform into the
δ-FAPbI3 with lower Gibbs free energy spontaneously. A schematic (lower panel)
demonstrates energy-managed phase stabilization strategies by decreasing the
Gibbs free energy difference (ΔG) of the photoactive phase or increasing the
energy barrier (ΔGc) for the transition from the photoactive to non-photoactive
phase39. e, Density-functional theory calculations reveal the strong preferential
interaction between lead cations and sulfate anions in the FAPbI3 when the PbI2-
terminated surfaces are in contact with PbSO4 (ref. 113). f, Octahedral tilt-stabilized
FAPbI3 was formed through surface-bound ethylenediaminetetraacetic acid
(EDTA)-templated crystallization, identified by scanning electron diffraction
patterns near the [001]c zone axis. The superstructure reflections for P4/mbm
FA-rich perovskites are highlighted with white arrows in scanning electron diffraction
patterns121. g, Schematic of spatially compressive strain engineering. h, Formation
enthalpies of different phases and energy barriers from cubic to hexagonal
structure under strain-free and strained conditions, respectively20. ΔH, formation
enthalpy of the cubic phase relative to the hexagonal phase; d, interlayer spacing
of the crystal structure; E, energy of the phase. i, Activation energies for phase
segregation of alloyed perovskite (FAPbI3)0.8(MAPbBr3)0.2 as a function of lattice
volume under vacuum and nitrogen atmospheres, respectively52. Part a adapted
with permission of AAAS from ref. 91 © The Authors, some rights reserved;
exclusive licensee AAAS. Parts b and h adapted from ref. 20, CC BY 4.0. Part c
reprinted from ref. 99, Springer Nature Limited. Part d adapted with permission
of AAAS from ref. 39 © The Authors, some rights reserved; exclusive licensee
AAAS. Part e reprinted with permission of AAAS from ref. 113 © The Authors, some
rights reserved; exclusive licensee AAAS. Part f adapted with permission of AAAS
from ref. 121 © The Authors, some rights reserved; exclusive licensee AAAS. Part i
reprinted from ref. 52, Springer Nature Limited.

Nature Reviews Chemistry

Review article
and to avoid the phase segregation issue induced by mixed halide31,107.
In-depth studies show that the strong interaction of the MDA2+ with the
lattice can prevent the phase transition from the cubic to the hexagonal,
offering outstanding phase stability at room temperature. Besides, the
thermodynamically stable cubic phase can also be achieved by incor-
porating halogenated organics into the precursor solution, such as
methylammonium chloride (MACl)18,97. One major improvement stems
from the formation of ‘intermediate state’ cubic phase FAPbI3-MACl
before annealing, preventing undesirable hexagonal phase formation18.
Another benefit is that the degassing of the lightweight Cl− improves
the orientation of the cubic FAPbI3 after annealing, and the residual MA+
(~5 mol%) contributes to the tolerance factor, thus helping reduce the
formation enthalpy of the photoactive phase18,32.
The strategies discussed in this section work to optimize the per-
ovskite composition and are realized as a result of changes in the Gibbs
free energy of the perovskite bulk material. As the total Gibbs free
energy of the perovskite is composed of the bulk and surface energies,
researchers have paid more attention to the film surface energy39. Exotic
additives that are absent at lattice sites (such as K+, Na+, F−, SCN− or
HCOO−) have been actively investigated to strengthen film surfaces
and grain boundaries at the microscopic level, which offers a solution to
synthesizing thermodynamically stable photoactive perovskites with-
out bandgap widening18,32,92,108–110. For example, manipulating surface
Gibbs free energy by using pseudo-halide thiocyanate anions (SCN−)
has been attempted, which is beneficial in triggering the transition from
face-sharing hexagonal to edge-sharing intermediates (4H polytypes of
FAPbI3) and ultimately corner-sharing cubic FAPbI3 (ref. 92). The edge-
sharing intermediates with iodides replaced by SCN– on the surface of
hexagonal FAPbI3 drive ions rearrangement and stabilize corner-sharing
cubic FAPbI3 from surfaces to the bulk. Similar work has also revealed
that iodide vacancy defects at grain boundaries and perovskite surfaces
can be mitigated with the addition of 2% formate (HCOO−) — a pseudo-
halide anion — yielding perovskite films with favourable surface ener-
gies32. Although these approaches have considerably improved film
quality and device performance, the debate on the roles of these small
foreign ions and their spatial distributions has continued. Further break-
throughs have demonstrated that the surface energy of perovskite films
can be tuned by forming extra chemical bonds with perovskites77, such
as ionic bonds111, hydrogen bonds109 or coordination interactions112. For
instance, the Pb–S bond, which is much stronger than the Pb–I bond,
has been successfully used to suppress ion migration and stabilize the
perovskite interface, as identified by surface energetics from density-
functional theory calculations and experiment conclusions111,113 (Fig. 3e).
The formed compact crystalline PbSO4 phase is well matched to the
underlying perovskite lattice, avoiding the formation of strained per-
ovskites and improving phase stability. It is worth noting that decreasing
the dimension of 3D perovskite to 0D nanometre-sized quantum dots
(QDs) demonstrates better phase stabilization than perovskite bulk
materials owing to the significantly reduced surface energy114. FAPbI3
QD films with stable phases at room temperature have been achieved,
which benefit from the dominant contribution of the surface energy and
lattice contraction115. Nevertheless, so far, perovskite QDs-based solar
cells have yet to match polycrystalline thin-film counterparts in terms of
device efficiency and operational stability. Alternatively, incorporating
QDs such as Cs1−xFAxPbI3 and PbS onto the bulk perovskite surface offers
additional benefits in surface energy management116,117. These encour-
aging results suggest that regulating the Gibbs free energy of the bulk
and surfaces are promising directions to enhance the thermodynamic
stability of FAPbI3-rich perovskites.
Nature Reviews Chemistry
Increase the energy barrier for phase transition
Having obtained photoactive phases for FAPbI3-rich perovskites, main-
tenance of their long-term photoactivity under working conditions
becomes crucial to deploying perovskite PVs. The key to achieving this
goal is to increase the phase transition energy barrier, ΔGc, from the pho-
toactive to the non-photoactive phase (Fig. 3d, bottom). The alloying
strategies described earlier have led to the production of thermody-
namically stable photoactive phases and a substantial increase in the
energy barrier, preventing unexpected phase transitions11. The alloyed
FAPbI3-rich perovskites should, in principle, present cubic or pseudo-
cubic structures118–120. However, a recent study through nanostructure
atomic-level characterization techniques has disclosed that FAPbI3-rich
photoactive perovskites are non-cubic and exhibit ~2° octahedral tilt-
ing associated with the asymmetric tetragonal structure121. This result
was corroborated by the presence of the hexagonal phase impurities
in the infrequently localized regions without apparent octahedral tilt.
By comparison with the facile cubic-to-hexagonal transition with a low
energy barrier height (26 meV), the tetragonal-to-hexagonal transition
has a higher energy barrier (86 meV) and is less likely to occur under
similar conditions. The same minor octahedral tilt-stabilized phase has
been constructed by introducing the surface-bound ethylenediamine-
tetraacetic acid (EDTA) chelating agent (Fig. 3f). Although the impact
of EDTA on device performance has not yet been investigated, this
surface coordination approach presents an avenue for the stabilization
of desirable photoactive phases.
Spatial strain management (Fig. 3g), including microdomain and
macrodomain, is another effective approach to mitigate photoactive
FAPbI3 phase degradation99,122. It has been reported that compres-
sive strain applied to a perovskite film can compensate for the nega-
tive impact of tensile strain in the cubic phase lattice, thus raising the
transition barrier height of the cubic-to-hexagonal phase transition
by ~0.15 eV and favouring thermodynamic stability below the phase
transition temperature20 (Fig. 3h). From a microscopic perspective,
the mismatched sizes of the FA cation and the octahedral [PbI6]4− units,
along with its dynamic disordered nature, is susceptible to microstrain-
induced lattice distortions107, crystal lattice defects81 and lattice ori-
entation mismatch at grain boundaries123. These phenomena are the
thermodynamic driving forces that promote the phase transition to
relax the local microstrain. For example, an anisotropic strained lattice
in the (111) plane was believed to be the direct driving force, acting as
the nucleation site for the (001) plane of the δ-FAPbI3 (ref. 124). Partially
substituting lattice sites with small-sized ions induces lattice shrink-
age and has a crucial role in compensating the microstrain, stabilizing
the metastable pseudo-cubic or cubic phase107. From a macroscopic
perspective, the different thermal expansion coefficients of the per-
ovskite (~20 × 10−5 K−1) and the adjacent layers (~1 × 10−5 K−1) result in
tensile strain125. The cubic phase can be effectively maintained by com-
pensating the tensile strain with the in-plane compressive strain. This
can be achieved by reducing the interface energy of cubic FAPbI3 with
the substrate after optimization of the annealing process or contact
layers99,126. Nevertheless, future efforts to understand how mechanical
characteristics influence phases and optoelectronic properties are
still required.
Inhibit the phase segregation
The key to tackling the long-standing concern of phase segrega-
tion under continuous light illumination is to reduce the possibility
of ion and defect migration. To enhance the inherent phase stabil-
ity of FAPbI3-rich perovskites, the judicious selection of lattice-site
Review article
compositions with low migration capability is required54. For instance,
using the less polar Cs+ instead of MA+ in FAPbI3 can reduce electron–
phonon coupling strength and thus suppress phase segregation57,58. The
enhancement of phase stability was proposed to have another explana-
tion: the migration of iodine vacancies coupled to dynamically oriented
MA+ facilitates iodine migration, whereas less polar and orientationally
mobile Cs+ and FA+ slow down the halide migration40. This argument
is supported by the observed spatially homogeneous halides and Cs+
after incorporating small amounts of CsI (5 mol%)119. Note that higher Cs
fractions may be detrimental to compositional homogeneity. However,
a contrasting work demonstrated that the presence of the reorientation
of dipolar MA cation shifts the deep trap states to shallower levels owing
to its higher dipole moment capable of reorienting in response to local
electrical field changes caused by adjacent deep traps127. Therefore, a
small amount of MA cation alloying is considered to be beneficial for
healing deep-level defects without adversely affecting photostabil-
ity. In contrast to the common photo-induced phase segregation that
occurs in mixed iodide−bromide alloys, significant inhibition of phase
segregation in triple-halide alloys (iodine, bromine and chlorine) was
observed128. This may arise from the ability of Cl− to enter the perovs-
kite lattice (owing to its small size) and improving the thermodynamic
stability of the triple-halide alloys. However, more evidence is required.
Further enhancing the phase segregation barrier by increasing
the ion migration activation energy and reducing the number of ion
migration pathways can minimize the occurrence of localized phase
segregation. It was found that incorporating alkali cations, such as Rb+
and K+, increases the formation energy of mobile halide interstitial
defects129, binding and immobilizing undercoordinated halides to
suppress unwanted migration130. Forming larger grains with fewer
grain boundaries that eliminate ion migration pathways is also consid-
ered an effective strategy to alleviate phase segregation. By analogy,
single-crystal perovskites that possess reduced grain boundaries and
ion migration have better thermal and photostability than the polycrys-
talline perovskite counterpart76,131. Hence, developing single-crystal-
based perovskites may be another potential approach to acquiring a
phase-stable structure. Moreover, recent work has demonstrated that
the activation energy of the phase segregation for FAPbI3-rich perovs-
kites under operation in nitrogen atmospheres is positive, whereas it is
negative in vacuum52 (Fig. 3i), which inspires researchers to focus on the
effect of the working atmosphere on the lifetime of perovskite devices.
Upscaling towards commercialization
Upscaling efficient and stable PVs from large-area devices to solar
modules with suitable processing techniques has been the focus of
the current perovskite PV research activity. Although we have broadly
discussed a wide variety of approaches to resolving the phase stability
and phase segregation challenges in the previous sections, these issues
could still occur when processing techniques are transferred from
laboratory-scale cells into industrially viable upscaled modules. The
perovskite phase may differ markedly between small-area devices and
upscaled modules, an effect that is mainly attributed to differences in
the uniformity and crystallization kinetics, as well as the additional
degradation pathways introduced by module patterning design (known
as P1, P2 and P3 patterning lines)132. Herein, we examine the impact of
scalable processing techniques on storage and operational stability,
with changes to phase stability and film degradation.
To realize commercialization of perovskite PVs, the first challenge
that must be addressed is to uniformly coat a compact perovskite
absorber with photoactive phases and reduced spatial compositional
Nature Reviews Chemistry
heterogeneities. It is thus important to assess the impact of scalable
processes on phase stability and film quality. The current scalable tech-
niques reported for manufacturing perovskite modules can be gener-
ally classified into solution-phase deposition (including blade-coating,
slot-die coating, spray-coating and inkjet printing), vapour-phase depo-
sition methods (vacuum-evaporated deposition and chemical vapour
deposition)132 and hybrid deposition that combines solution-phase
and vapour-phase approaches. Among these scalable processes, the
differences in perovskite crystallization kinetics could affect the crystal
phases and thin-film quality, thereby influencing device performance.
In the light of solution-phase deposition methods, the key to
maintaining stable perovskite absorbers with photoactive phases is
to eliminate the degradation sites induced by microscale fluid flow to
the perovskite nuclei during the drying of large-area wet films with
increased surface tension133. This is achievable by controlling the fluid
dynamics by manipulating the viscosity, concentration, solid–liquid
contact angle and surface tension of the perovskite precursor solution.
Incorporating surfactants (for example, l-α-phosphatidylcholine)
is an effective route to lower surface tension and the contact angle
because of the Marangoni effect134, which is prominent in overcoming
uncontrollable increase in film thickness for blade-coating135. Fur-
thermore, pre-heating (70–145 °C) the substrate is another effective
means to improve the wettability by promoting uniform removal of
the solvent132. A combined strategy associated with the substrate pre-
heating and seed-assisted crystallization (KPb2Br5) has recently been
developed for slot-die coating FAPbI3-rich films with compact and
homogeneous surface coverage, producing stable minimodule (active
area of 57.5 cm2) that retains 82% of their initial PCEs (T82) after 4,800-h
storage136 (Fig. 4a). Such an impressive long-term shelf life is compa-
rable to spin-coating-based perovskite PV minimodules, offering the
promise of scaling-up modules. By contrast, the continuous-operation
stability of the minimodule manufactured by slot-die or blade-coating
is only half as stable as spin-coating137,138 (Fig. 4b). Therefore, there is
increasing demand for the understanding of fluid dynamics theory
and the design of suitable approaches for slot-die coating processes to
actively overcome solution-phase scalable process challenges, such as
non-ideal film thickness caused by a mismatch of solution flow rate and
coating speed during deposition, the formation of degradation sites
introduced by air entrainment defects or macroscopic voids caused
by discontinuous outflow during the coating process139.
In contrast to scalable solution-phase methods, solvent-free
vapour-phase deposition is a high-throughput fabrication technique
because it precisely controls the film thickness and shows compatibility
with large-scale production140. Nevertheless, to date, and despite the
availability of efficient upscaling minimodules (PCE of 19.87% with an
aperture area of 14.4 cm2), vapour-phase deposition has only been suc-
cessfully used to deposit stable perovskites on a small area141. Notably, a
remarkable lifetime of small-area FAPbI3-rich PVs that has been gained by
vacuum-evaporated deposition showed negligible efficiency loss (5%)
after 20,000 h of storage (Fig. 4a). We note that the crystallization pro-
cess of vacuum-evaporated FAPbI3-rich perovskites is a solid reaction at
high vapour pressures, especially the evaporation of FA-based halides,
which is markedly different from solution-phase processes. As such,
paths to control photoactive phases of perovskites in a vacuum cham-
ber during the dual-source or multiple-source vacuum co-evaporation
must be comprehensively considered. Motivated by this, appropriate
homemade vacuum systems are encouraged to develop by vaporizing
these perovskites in an ultra-high vacuum chamber. In addition, iodide-
based organic species present poor stability in an ultra-high vacuum
 Review article

a Dark storage b MPP under AM 1.5 G

104
T95 = 20,000 h, ref. 140 T80 = 5,950 h, ref. 189
T72 = 10,224 h, ref. 136

104
T100 = 7,200 h, ref. 174
T100 = 7,000 h, ref. 175 T90 = 5,040 h, T87 = 2,400 h, ref. 188
T100 = 4,536 h, T82 = 4,800 h,
ref. 176 T90 = 1,600 h, T86 = 2,000 h, ref. 191
ref. 186 ref. 136
T100 = 3,720 h, ref. 187 T96 = 3,600 h, ref. 142 T98 = 1,500 h, ref. 193 ref. 190
T80 = 1,157 h,
T85 = 3,600 h, T95 = 1,187 h,

Working lifetime (h)

T99 = 2,880 h, ref. 179 ref. 192
T80 = 1,500 h, T90 = 1,300 h, ref. 184
Storage lifetime (h)

ref. 185 ref. 137

T93 = 1,500 h, ref. 184 103 T94 = 1,056 h, ref. 138
T92 = 1,000 h, T80 = 1,000 h, T99 = 1,000 h, ref. 195 T91 = 1,000 h, ref. 194
ref. 178
103 ref. 182 ref. 183
T90 = 960 h, T75 = 1,000 h,
T80 = 500 h, ref. 144
ref. 180 ref. 177 T80 = 535 h, ref. 142
T90 = 600 h,
ref. 181 T80 = 388 h, ref. 142

Spin-coating Spray-coating T83 = 200 h,

ref. 143 Spin-coating Spray-coating
Blade-coating Evaporation
102 102 Blade-coating Evaporation
Slot-die CVD
Slot-die CVD

0.1 1 10 100 0.1 1 10 100

Area (cm2) Area (cm2)

Fig. 4 | Long-term lifetime as a function of area (aperture or designated) for
laboratory-scale FAPbI3-rich perovskite photovoltaic devices and upscaling
modules produced by various manufacturing techniques. a, Storage lifetime
of the perovskite photovoltaic (PV) cells following the International Summit
on Organic Photovoltaic Stability-D-1 protocol (dark, room temperature). Data
from refs. 136,140,142,143,174–187. b, Working lifetime of perovskite PV cells
tracking at maximum power point (MPP) under continuous AM 1.5 G illumination
following the International Summit on Organic Photovoltaic Stability-L-2
protocol (light-soaking, 65–85 °C). CVD, chemical vapour deposition. Data from
refs. 137,138,142,144,184,188–195.  CVD, chemical vapour deposition; Tx, time
when the power conversion efficiency (PCE) of the PV device decays to x% of the
initial PCE.

atmosphere, thereby increasing the risk of non-stoichiometric ratios
for resultant FAPbI3-rich perovskites. We note that phase impurities and
defects caused by non-stoichiometry are typically the main channels for
ion and defect migration under operating conditions12. Thus, ongoing
deposition process improvements are required. Currently, the hybrid
processing technique that combines solution-phase (ultrasonic spray-
coating) and chemical vapour deposition allows modules to have a shelf
life (T96 = 3,600 h) close to that of solution-based methods142 (Fig. 4a).
Overall, the storage and working lifetimes of minimodules manufac-
tured by vapour-phase deposition still lag far behind the solution-phase
processed PVs143,144. There is thus plenty of room to improve both the
device efficiency and stability of perovskite PV devices.
Outlook
Preserving the optical activity of halide perovskites is a key factor in
achieving the long-term operational stability of perovskite PVs. In this
section, we first analyse the remaining challenges and opportunities for
FAPbI3-rich perovskites, including further reductions to the bandgap,
uncovering the origin of phase instability with cutting-edge machine
learning and in operando characterizations, followed by delineation
of the stability metrics that must be met for commercial PV. We then
highlight the potential future research directions that boost this emerg-
ing PV technology towards commercial deployments, such as upscaling
perovskite modules, exploring multijunction PVs and unlocking the
potential of multiple practical applications.
Challenges and opportunities
If the efficiency of single-junction FAPbI3-rich perovskite PVs is to sur-
pass that of crystalline silicon PVs, the first challenge is to continue
narrowing the bandgap value of the light absorber to approach the
optimal bandgap range defined by the S–Q limit. Compared with the
FAPbI3 polycrystalline film (with a bandgap of ~1.50 eV), a single-crystal
format shows more potential to expand to near-infrared response
owing to its narrower bandgap (~1.43 eV)145. Additionally, single-crystal
perovskite exhibits a lower defect density and fewer phase impurities,
which is beneficial for phase stabilization against external stimuli146.
However, the perovskite PVs based on these single crystal formats
are still inferior to those of polycrystalline perovskite PVs131. When
considering the upscaling techniques, single-crystal perovskite PVs
face a few challenges, such as the manipulation of film thickness and
the time-consuming process of large bulk single crystal growth. Simi-
larly, the bandgap of single-crystal-like FAPbI3 powders is estimated to
be ~1.48 eV when processing from solution-phase methods5,107. Hence,
one possible route to narrowing bandgaps is fabricating preferentially
oriented single-crystal-like thin film with fewer phase impurities131,145.
Moreover, strain engineering offers another possibility of bandgap
tuning. For instance, by applying a compressive strain, the bandgap of
FAPbI3 film has been reduced by ~35 meV99. Therefore, we expect that
there is still plenty of room to enhance the light harvesting of FAPbI3-
rich perovskite PVs by reducing the bandgaps that they can eventually
achieve device efficiencies approaching the S–Q limit.
Another pressing challenge beyond efficiency enhancement is to
meet the increasing demand for commercial PV stability standards55,84.
Although ex situ characterizations are broadly used, in operando
techniques can provide rich information on the operation of PVs.
Studying phase evolution against external stressors under operating
conditions can create a coherent and complete picture of the phase-
related degradation mechanism of the perovskite PVs147,148 (Fig. 5a,b).
An atomic-level understanding of the phase instability and degradation
mechanism still relies on destructive characterization techniques, for

Nature Reviews Chemistry

 Review article
a In operando characterizations b Instability mechanism
Electron beam
Phase impurity–lattice mismatch
Ion beam Photon
Improve stability
X-ray Detector
Decoupling of
light–bias–heat stressors
Perovskite film
Stable
photoactive
Working phase
conditions Detector
d Laboratory fabrication e Commercial production
Lab-to-Fab
Direction
Precursors
P1 P2 P3
Precursors
Spin-coating Slot-die coating
Fig. 5 | Current challenges and future outlook for stabilized perovskites in
devices. a, Development of in operando characterization techniques could help
to reveal the origin of instability. b, An in-depth understanding of the mechanism
of photoactive phase instability is essential. c, Advanced machine learning
and high-throughput screening are likely to accelerate the discovery of stable
perovskites with ideal bandgaps with respect to the Shockley–Queisser limit.
d,e, The challenges from the lab-to-fab deposition techniques (insert figures
example, transmission electron microscopy, and we emphasize that
such approaches hinder the practical structural analysis of phase insta-
bility evolution100,149. As an alternative, cryoelectron microscopy may
mitigate electron beam-induced damage with a much higher critical
electron dose (46 e− Å−2 at 1.49 Å spatial resolution for MAPbBr3) when
compared with that at room temperature (~11 e− Å−2)150. Despite such
success, interpreting multidimensional signals is complicated, given
the strong correlations between characteristic signatures (such as
photon, electron and ion signals) under various working conditions.
Recently, a reported machine learning workflow promises to separate
the charging effect from beam destruction during mass spectrom-
etry151. It promises to provide an in-depth understanding of the phase
instability — such as predicting the formation of undesirable hexagonal
phase by-products under operating conditions12, thus helping to guide
the rational design of efficient and stable perovskite PVs (Fig. 5b).
The intrinsic instability of perovskite absorbers is a long-standing
challenge that must be circumvented. However, chemical degrada-
tion is also problematic but can be slowed down by industry-standard
encapsulation technology. Remarkably, avoiding FA+ deprotonation
and I− oxidation from photochemical and electrochemical reactions
should be considered to enhance the chemical stability of perovskite
materials. One approach involves incorporating additives with a higher
acidity than FA+ to adjust the chemical environment. Redox reactions
of the FAPbI3-rich perovskites under light and electrical bias could also
be mitigated by tailoring the precursor solution. Previous studies have
shown that a Eu3+-Eu2+ ion redox shuttle can recover lead and iodide,
Nature Reviews Chemistry
c Machine learning and high-throughput screening
Theoretical calculation: rA, rB, rX, ∆H, f(x)
Components Stable
Candidates
Feedback
Unstable
f Innovative applications
Precursors
ON
OFF
IoT
Roll-to-roll
Indoor PVs Smart window
91
are upscaling modules through slot-die coating and flexible module processed
by roll-to-roll coating196, respectively.) f, Schematic of innovative applications,
such as indoor photovoltaics (PVs), thermochromic perovskites-based smart
windows164. IoT, internet of things. Part e (left inset) adapted with permission of
AAAS from ref. 91 © The Authors, some rights reserved; exclusive licensee AAAS
and (right inset) adapted from ref. 196, Springer Nature Limited. Part f adapted
with permission from ref. 164, Elsevier.
thus preventing iodide oxidation152. Eliminating iodide-related deep-
level traps of FAPbI3-rich perovskites by iodide management in the
perovskite precursor solution has provided hints of record-breaking
PCEs in perovskite PVs153. The key to improving intrinsic phase stability
is to obtain the FAPbI3 photoactive phase at room temperature with
lower Gibbs free energy than the non-photoactive phase, a feat that has
been achieved for MAPbI3 (ref. 24). To obtain thermodynamically stable
perovskite crystal structures, integrating versatile machine learning
with graded screening criteria into established workflows based on the
phase energetics could accelerate the discovery of novel A-site cations
to replace FA cations or brand-new perovskite compounds154 (Fig. 5c).
Furthermore, exploring available ligands or bridging agents to stabilize
FAPbI3 photoactive phases will be an ongoing direction encouraged by
the recent success of the EDTA chelating agent121. In particular, the ani-
sotropy of Young’s modulus allows the strain to propagate in a preferen-
tial direction. The interplay of strain with defects, and the dislocations
as a result, may accelerate phase transition and chemical degradation155.
After rigorous and long-term operation, the strain propagation caused
by lattice mismatch might become more apparent. Importantly, relax-
ing deleterious strain can manage the propagation of strain in bulk
and at the interfaces of perovskite films. Better understanding of this
process may well spark future phase engineering approaches.
The keys to practical applications
The ultimate destination of FAPbI3 PV technologies is commercial
deployment, where upscaling will be a critical step in manufacturing
Review article
PV modules on the production line. It is well known that the nucleation
and crystal growth of the solution-processed FAPbI3 perovskite films
are more complicated during upscaling. The present difficulty lies in
achieving spatially uniform films with photoactive phases (without pho-
toactive inhomogeneities) from laboratory-scale devices conducted
by spin-coating to upscaled modules based on scalable deposition
technologies (Fig. 5d,e), which will dictate the commercial viability
of the modules. To reduce the lab-to-fab gap, understanding FAPbI3
crystallization kinetics on large-area substrates and optimization of
the upscaling deposition process may help to fabricate metre-scale
photoactive perovskite PV modules133. Lessons learnt from LaMer and
Ostwald’s ripening models may help determine the feasible ways to tune
the spatial uniformity of photoactive phases on upscaling substrates156.
Motivated by these, advances in upscaling perovskite submodules
with a 15.3% PCE (with an aperture area of 205 cm2) have been achieved
using slot-die upscaling coating technology, with suppression of the
hexagonal phase impurities157. Other upscaling techniques, such as
the vapour-phase deposition method, have also been used to fabricate
FAPbI3-rich perovskites. However, their performances lag behind those
prepared using solution-based methods and come with an increased
manufacturing cost133. In addition to the efficiency of upscaling PV
modules, the operational lifetime associated with phase stability with
FAPbI3-rich perovskites must also be evaluated by an industrial lifetime
assessment test, and the need to establish a link between operational
stability and phase stability through a scientific understanding of the
crystal structure evolution on atomic scales is an urgent one158. Despite
the great emphasis on FAPbI3-based device stability investigations,
previous research works have only barely passed the established indus-
try International Electrotechnical Commission 61215:2016 standards,
whereby over 95% of their initial performance can be sustained after
1,000 h under harsh conditions, such as damp heat test (85% relative
humidity at 85 °C)22. Another possible standard worth considering is
the International Summit on Organic Photovoltaic Stability protocols,
based on the consensus among researchers in the FAPbI3 perovskite
PVs on procedures for testing device reliability159.
Regarding practical applications, increasing device performance
effectively strengthens cost-effective features for PV panels. Tandem
and multijunction PV technologies tantalizingly offer prospects,
which can extend beyond the S–Q thermodynamic limit of single-
junction PVs128,160. The facile fabrication and tunable bandgap of
FAPbI3-rich perovskites render them comparable with the existing
PVs with textured surfaces161. Nowadays, all-perovskite and monolithic
perovskite-on-silicon tandem PVs delivered record efficiencies of
28.0% (~0.05 cm2) and 31.3% (~1.17 cm2), respectively6,162. Multijunction
PVs made from all-perovskite absorbers and perovskite-on-silicon
configurations lead to maximum theoretical efficiencies of 46.9% and
49.4% (ref. 163), respectively, which will be a considerable boost. Despite
the vast promises, several pressing challenges must be solved before
the full potential of perovskite tandem and multijunction PVs can be
exploited. For example, the higher bromide fraction (over 20 mol%)
is typically incorporated into the FAPbI3 matrix to widen the band-
gap approaching 1.75–2.0 eV for the top-cell absorbers in tandem
architecture, but severe phase segregation will be induced163. For the
all-perovskite tandem and multijunction PV, the FAPbI3-rich Sn–Pb
perovskite, which is necessary to achieve the optimum narrow band-
gap, presents further challenges with respect to obtaining a stable
photoactive phase in a real tandem PV. All of these effects together
have undoubtedly become the major roadblock for perovskite-based
PV applications. Hence, future efforts must move on to strengthening
Nature Reviews Chemistry
the device stability of tandem and multijunction PVs based on FAPbI3-
rich perovskites by improving phase stability and suppressing phase
segregation of each sub-cell perovskite absorber.
Innovative applications of perovskite PVs
Although phase instability is detrimental to long-term operation for
regular PV applications under sunlight illumination, stimulated phase
transition is potentially interesting for innovative applications, such
as smart windows and sensors164. A key metric for such applications
(and arguably more important than device performance) is cost–­
effectiveness, and the easy fabrication of perovskites is helpful here.
Although regular PV applications require a single stable phase under
sunlight illumination, these applications strongly rely on the reversible
chemical and structural transformations in response to stimuli such
as light, electric fields and the chemical atmosphere. Hence, a critical
concern is reliable switching over thousands of cycles. Perovskite PV
cells show great potential for applications in indoor (not in sunlit) con-
ditions. As a result, some prospective applications, including indoor
PVs and all-in-one smart windows (Fig. 5f), are already on the horizon
of commercialization164–167. Their uses have been extended into satel-
lites and spacecraft168. Thus, exploring applications associated with the
controlled phase transitions of FAPbI3 or FAPbI3-rich perovskites under
various working conditions is a future avenue for research.
In summary, we believe that exploring and screening perovskite
materials with robust photoactive phases will eventually overcome
their thermodynamic instability and withstand the harsh environment
for diverse applications. The near future will foresee the great prom-
ise of perovskite PVs with unique advantages for commercialization,
creating an exciting next-generation energy-harvesting technology
for a broad range of users.
Published online: xx xx xxxx
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Acknowledgements
W.Z. thanks EPSRC standard research (EP/V027131/1) and Newton Advanced Fellowship
(192097) for financial support. S.I.S. acknowledges financial support from the Basic Science
Research Program (NRF-2018R1A3B1052820) through the National Research Foundation of
Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (MSIP). The authors
acknowledge D. Liu for advice on figures and writing and T. Webb for revising the final
manuscript.
Author contributions
X.L. wrote the first manuscript, and D.L., M.S., S.I.S. and W.Z. revised the manuscript and
supervised the project. D.L., Z.-H.L., J.S.Y., M.S., S.I.S. and W.Z. contributed to manuscript
editing and comments.
Competing interests
The authors declare no competing interests.
Additional information
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