REVIEW
Perovskite Solar Cells
Causes and Solutions of Recombination in Perovskite
Solar Cells
Jiangzhao Chen and Nam-Gyu Park*
Organic–inorganic hybrid perovskite materials are receiving increasing
attention and becoming star materials on account of their unique and
intriguing optical and electrical properties, such as high molar extinc-
tion coefficient, wide absorption spectrum, low excitonic binding energy,
ambipolar carrier transport property, long carrier diffusion length, and high
defects tolerance. Although a high power conversion efficiency (PCE) of
up to 22.7% is certified for perovskite solar cells (PSCs), it is still far from
the theoretical Shockley–Queisser limit efficiency (30.5%). Obviously,
trap-assisted nonradiative (also called Shockley–Read–Hall, SRH) recom-
bination in perovskite films and interface recombination should be mainly
responsible for the above efficiency distance. Here, recent research advance-
ments in suppressing bulk SRH recombination and interface recombina-
tion are systematically investigated. For reducing SRH recombination in
the films, engineering perovskite composition, additives, dimensionality,
grain orientation, nonstoichiometric approach, precursor solution, and
post-treatment are explored. The focus herein is on the recombination at
perovskite/electron-transporting material and perovskite/hole-transporting
material interfaces in normal or inverted PSCs. Strategies for suppressing
bulk and interface recombination are described. Additionally, the effect of
trap-assisted nonradiative recombination on hysteresis and stability of PSCs
is discussed. Finally, possible solutions and reasonable prospects for
suppressing recombination losses are presented.
1. Introduction
Nowadays, in order to solve the energy issues that human faces,
various photovoltaic technologies have been developed, such as
silicon (Si) solar cells, gallium arsenide (GaAs) solar cells, thin-
film solar cells (copper indium gallium selenide (CIGS) and
cadmium telluride (CdTe)), and emerging solar cells (dye-sensi-
tized solar cells (DSSCs), organic solar cells, quantum dot solar
cells, and perovskite solar cells (PSCs)).[1] Although the solar
cells based on inorganic semiconductors (such as Si, GaAs,
Dr. J. Chen, Prof. N.-G. Park
School of Chemical Engineering
Sungkyunkwan Univeristy (SKKU)
Suwon 440-746, Korea
E-mail: npark@skku.edu
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201803019.
DOI: 10.1002/adma.201803019
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CIGS, and CdTe) demonstrated power
conversion efficiencies (PCEs) exceeding
20%,[1] their large-scale commercial appli-
cation is still impeded by high fabrica-
tion cost. Consequently, it is a feasible
and effective solution to replace the tra-
ditional inorganic semiconductor-based
solar cells through developing new solar
cells with high PCE and low cost simulta-
neously. Among all of the emerging new
solar cells, PSCs show tremendous poten-
tial in future photovoltaic field due to its
high PCE and amazing developing speed,
which captures widespread attentions in
industry and academia.[2–14]
The name “perovskite” was first put for-
ward by Russian mineralogist Lev A. Per-
ovski.[15] The family of perovskite materials
used in PSCs usually employs the chemical
formula of ABX3 with corner-sharing BX6
octahedra and AX12 cubooctahedra,[16]
where A is monovalent cation such as
MA+ (methylammonium), FA+ (forma-
midinium), Cs+ and Rb+ ions, B is diva-
lent metal cation such as Pb2+ and Sn2+,
and C is monovalent anion such as I−,
Br−, Cl−, SCN−, and BF4−.[10,17–23] In
2009, PSC with a PCE of 3.8% based
on liquid electrolyte was first reported
by Miyasaka and co-workers.[2] In 2011, Park and co-workers
achieved a nearly doubled PCE of 6.5% through adopting
high concentration perovskite precursor solution.[4] However,
extremely poor stability because of dissolution of MAPbI3 in
polar liquid electrolyte made this liquid junction PSC unsuc-
cessful to attract extensive attentions. Subsequently, Park
and co-workers first reported solid-state PSC by replacing
liquid electrolyte with solid-state hole-transporting material
(HTM) 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-
spirobifluorene to overcome the instability of liquid PSCs,
which realized a PCE of 9.7% and 500 h stability without
encapsulation.[3] Since then, gradually increased interest has
been devoted to PSCs based on organic–inorganic hybrid
perovskite absorbers, which have the appealing advantages
of excellent ambipolar charge mobility, high extinction coef-
ficient, long carriers diffusion length, tunable bandgap, small
exciton binding energy, solution-processable ability, low cost,
and high PCE.[5,10–12,17,23–26] Inspired by these unique and
intriguing advantages, huge attentions have been focused on
investigating this kind of organic–inorganic hybrid perovskite
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materials, which are also extensively applied into other fields,
such as photodetector,[27,28] light-emitting diode,[29,30] mem-
ristor,[31,32] etc. Benefiting from the excellent ambipolar charge
mobility,[5,25] inverted or normal planar PSCs[8,33–35] were devel-
oped, followed by normal mesoporous PSCs,[3] which paves a
way for the development of flexible PSCs.[36,37] In order to fur-
ther simplify the device structure and reduce device cost, hole
conductor–free PSCs were fabricated based on metal electrode
or carbon electrode.[23,25,38,39] For instance, Han and co-workers
reported hole-conductor-free fully printable PSCs based on
carbon electrode with an excellent photostability up to 1008 h
in ambient air.[38,39] Since first report on solid-state PSCs,[3]
perovskite compositions used for PSCs evolved from simple
MAPbI3 to presently complicated triple- or quadruple-cation
and mixed Br–I anions compositions, which greatly contributed
to improved PCE and long-term stability.[7,10,17,18] For realiza-
tion of high PCE, it is critical to further improve perovskite film
quality, which is beneficial for improving optical and electric
properties and thus minimizing various nonradiative recom-
bination losses. Encouraged by the above purpose, a variety
of methods were also developed to improve morphology and
crystallization of perovskite films, such as deposition method
(such as one-step deposition, sequential deposition,[6] vacuum
deposition,[40] vacuum-flash solution processing,[9] etc.), optimi-
zation of precursor solvents[41–46] and antisolvents,[44,47,48] addi-
tive engineering,[49] etc. In terms of optimization of precursor
solvents and antisolvents, the formation of intermediate phase
(CH3NH3I–PbI2–DMSO) was found to play an important role
in achieving highly efficient PSCs.[41] Subsequently, vast efforts
were made to optimize the precursor solvents and antisolvents
through investigating the intermediate phases.[42–44,46,48,50–52]
Except for device configuration, perovskite composition, fun-
damental procedure for preparing perovskite films and addi-
tive engineering, and interface engineering also play a crucial
role in enhancing the PCE and stability of PSCs.[8,15,53,54] As the
results of the above systematic approaches, a certified PCE as
high as 22.7% was obtained in single junction PSCs.[1]
Nevertheless, the presently achieved 22.7% is still far from
the theoretical PCE of 30.5% (open-circuit voltage (Voc): 1.33 V;
short-circuit current (Jsc): 25.4 mA cm−2; and fill factor (FF):
0.91) for bandgap of 1.6 eV according to the Shockley–Queisser
limit.[55] Presently, Jsc of most of the high-efficiency PSCs with
a PCE over 21% is in the range of 23–25 mA cm−2 that is very
close to the Shockley–Queisser limit value of 25.4 mA cm−2,
but Voc of 1.10–1.20 V and FF of 0.75–0.80 are much lower
than the calculated Shockley–Queisser limit values of 1.33 V
and 0.91, respectively.[10,12,17,26,56–58] It means that it is highly
desirable to improve Voc and FF if we want to further enhance
PCE being close to theoretically calculated Shockley–Queisser
limit efficiency (30.5%) in single-junction PSCs. It is well
known that Voc and FF of solar cells are closely related with
nonradiative and interface recombination. Therefore, it is an
important direction for further improvement of PCE to mini-
mize the above recombination loss through defect passivation
and interface engineering. Actually, defect-related perovskite
bulk recombination and interface recombination can affect
not only PCE but also hysteresis along with long-term sta-
bility.[59] Although many reports proposed that nonradiative
and interface recombination should be responsible for the
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Jiangzhao Chen received his
B.S. degree in applied chem-
istry from Northeast Forestry
University in 2011 and Ph.D.
degree in optical engineering
from Huazhong University
of Science and Technology
in 2016. Since then, he has
been working as a postdoc-
toral researcher in the School
of Chemical Engineering in
Sungkyunkwan University.
His current research interest focuses on perovskite
solar cells.
Nam-Gyu Park is pro-
fessor and SKKU-Fellow
at the School of Chemical
Engineering, Sungkyunkwan
University. He received
his B.S., M.S., and Ph.D.
degrees from Seoul National
University in 1988, 1992, and
1995, respectively. He worked
at ICMCB-CNRS, France,
from 1996 to 1997 and at the
National Renewable Energy
Laboratory, USA, from 1997 to 1999 as a postdoctoral
researcher. He worked as Director of Solar Cell Research
Center at Korea Institute of Science and Technology
(KIST) from 2005 to 2009 and as a principal scientist at
Electronics and Telecommunications Research Institute
(ETRI) from 2000 to 2005 before joining Sungkyunkwan
University as a full professor in 2009. He has been doing
research on high-efficiency mesoscopic nanostructured
solar cells since 1997. He is pioneer of the solid-state
perovskite solar cell, which was first developed in 2012.
losses of Voc and FF,[60–69] systematic and deep understanding
on the origins of recombination in PSCs is limited but impor-
tant. Additionally, great progresses have been made on tandem
solar cells.[70–74] Presently, the PCE exceeding 25% has been
achieved based on perovskite/silicon tandem solar cells.[71,72,74]
Consequently, it is a feasible and effective approach to further
increase PCE close to Shockley–Queisser limit PCE of single-
junction PSCs through multijunction tandem solar cells.
However, the main purpose of this review is to discuss how to
minimize the Shockley−Read−Hall (SRH) nonradiative recom-
bination in perovskite films and interface recombination in
single-junction PSCs from the perspective of perovskite bulk
and interface.
Here, we discuss the fundamentals and origins of recombi-
nation in PSCs and evaluation and characterization methods of
defect density and recombination. Furthermore, we investigate
the recent strategies for reducing and suppressing nonradiative
and interface recombination.
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2. Fundamentals and Origins of Recombination in
Perovskite Solar Cells
2.1. Shockley–Queisser Limit Efficiency
The Shockley–Queisser limit, which is also known as the
detailed balance limit, is described as the case that recom-
bination of electron–hole pairs is only radiative in a single
bandgap semiconductor.[66] The Shockley–Queisser limit is
usually used to calculate the limit PCE of single-junction solar
cells.[55,62,63,75] Upon calculation, radiative recombination is
only considered while ignoring nonradiative recombination.
According to the Shockley–Queisser limit, the calculated
limit PCE and the best PCEs of various solar cells are plotted
as a function of bandgap (Eg) of light-harvesting absorber,
as shown in Figure 1. Obviously, a certain distance exists
between Shockley–Queisser limit PCE and practical PCE for
all of the solar cells, which is ascribed to the following four
kinds of losses: I) collection losses, mainly coming from
photon reflection or absorption in poorly responding cell
regions; II) electrical losses, originating from series and shunt
resistances of a device; III) nonradiative recombination losses,
mainly resulting from defects or trap states induced by poor
film quality; IV) interface recombination losses, stemming
from all of the interfaces involved in cells. For crystalline
Si- and GaAs-based solar cells, the real PCEs are close to the
Shockley–Queisser limit PCE, while a larger gap is observed
for PSC. As mentioned in Section 1, low Voc and FF lead to
the PCE loss. Accordingly, overcoming the aforementioned
four kinds of losses is indispensable for decreasing the gap
between theoretical and practical PCEs. It should be stressed
that losses (I) and (II) are determined by cell design spe-
cifics. So, main losses in PSCs are from losses (III) and (IV),
that is recombination issues, which is directly associated with
Voc and FF.
Figure 1. Calculated Shockley–Queisser limit PCE (black line) and the
best PCEs (data points) of various solar cells as a function of bandgap
(Eg) of light-harvesting absorber.[63]
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2.2. Recombination Processes in Perovskite Solar Cells
It is well known that many recombination processes exist in
PSCs, including radiative recombination, nonradiative recom-
bination, and interface recombination. Furthermore, nonradia-
tive recombination includes Auger recombination, trap-assisted
recombination (SRH recombination), electron–phonon interac-
tion, and carrier–carrier scattering. Among them, the radiative
recombination and Auger recombination belong to the intrinsic
recombination processes.[62] It was reported that crystalline sil-
icon shows strong Auger recombination seriously deceasing its
efficiency limit (≈29%) much lower than ≈33% of the Shockley−
Queisser limit.[62] In contrast, much weaker Auger nonradiative
recombination was demonstrated in MAPbI3, which has a negli-
gible influence on photovoltaic performance of final device close
to the radiative limit in the absence of SRH decay channels.[62] In
addition, several other reports also proved that Auger nonradia-
tive recombination is not dominant nonradiative recombination
loss process and can be neglected in PSCs while trap-assisted
recombination (SRH recombination) is the main recombination
loss mechanism.[61,66–68,75] Different from Auger nonradiative
recombination, Shockley−Read−Hall nonradiative recombina-
tion is a nonfundamental decay channel mediated by defects.[62]
SRH nonradiative recombination can be minimized by adequate
trap passivation or by improvements in light outcoupling. Conse-
quently, it is highly expected to minimize the SRH nonradiative
recombination losses through improving perovskite film quality,
reducing grain boundaries, and passivating the defect traps at
the surface or bulk of perovskite film. Apart from Auger and
SRH nonradiative recombination losses, electron–phonon inter-
action and carrier–carrier scattering popularly appear in most of
the materials.[76,77] It has been reported by several groups that
electron–phonon interaction can be found in organic–inorganic
hybrid perovskite materials in PSCs.[78–84] Since electron–phonon
interaction has been demonstrated to be one of the nonradiative
recombination losses in PSCs which can be detrimental to car-
rier mobility,[82,84] it is urgently needed to further deeply inves-
tigate how charge carriers interact with phonons in perovskites,
how to evaluate electron–phonon interaction, and how the elec-
tron–phonon interaction affects the final device performance.
Finally, interface recombination must be considered and man-
aged when perovskites contact charge transport materials. Cer-
tainly, matching degree of energy level and interface defect trap
states should be mainly responsible for interface recombination
losses.[13,57,85] As we discussed above, although important effect
electron–phonon interaction on carrier mobility has been identi-
fied, in this review we mainly focus on discussing trap-assisted
SRH nonradiative recombination and interface recombination
considering the great advancements on suppressing the above
two recombination losses in recent several years.
As can be seen in Figure 2a,b, it is well known that PSCs
are usually fabricated by either normal structure (TCO/ETM/
perovskite/HTM/electrode) or inverted structure (TCO/HTM/
perovskite/ETM/electrode), where TCO, ETM, and HTM
represent transparent conductive oxide, electron-transport mate-
rial, and hole-transport material, respectively. In typical PSCs,
carriers simultaneously experience two opposite transport pro-
cesses: one is positive direction process, which is beneficial for
device operation; the other is negative direction process, which
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www.advancedsciencenews.com
Figure 2.  Schematically illustrated device structures depending on elec-
trode polarity and light absorption direction: a) normal structure with
n-type ETM facing incoming light and b) inverted structure with p-type
HTM facing incoming light. c) Energy level diagram showing carrier trans-
port and injection. Adapted with permission.[86] Copyright 2018, American
Chemical Society.
is detrimental to device operation. As shown in Figure 2c, posi-
tive direction includes first excitation process. When perovskite
is illuminated, electron is excited from valence band (VB) to
conduction band (CB) and hole is left in VB, which is followed
by transport process. Electron and hole are transported to ETM/
perovskite interface and HTM/perovskite interface, respectively,
which requires that perovskite materials have high carrier
mobility and lifetime so that excited carriers can be transported
to each interface. Third, charge injection process takes place in
order for electron and hole to be injected into ETM and HTM,
in which CB and VB of perovskite should be aligned well with
CB of ETM and VB of HTM, respectively. Fourthly, transport
process occurs in charge extraction layers, where high electron
mobility of ETM and high hole mobility of HTM can guarantee
efficient charge transport. Finally, charge collection is required
to generate photocurrent at short circuit. In contrast, negative
direction mainly includes the following two processes[55,62,63]:
I) SRH recombination: in intrinsic perovskite film, radiative
recombination is accompanied by nonradiative (SRH) recombi-
nation due to low external electroluminescence quantum yield
(EQYPL) resulting from poor film quality. II) Interface recom-
bination at charge transporting materials/perovskite interfaces:
electron (hole) injected into ETM (HTM) recombines with hole
(electron) in perovskite. Recombination will be affected by sev-
eral factors such as energy levels of charge extraction materials,
bulk and interface defects, charge mobility of perovskite and/or
selective contact materials, and charge diffusion length. Effec-
tive measurements are required to facilitate the positive carrier
transport process and suppress or block negative process.
2.3. How to Evaluate and Characterize Recombination and
Defect Density in Perovskite Solar Cells?
As we mentioned above, recombination closely related with
defect/trap density possesses a pronounced effect on the final
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device performance especially for Voc and FF. In the past sev-
eral years, many characterization methods used for calculating
defect density have been developed, including space charge
limited current (SCLC), thermally stimulated current (TSC),
thermal admittance spectroscopy (TAS), deep-level transient
spectroscopy (DLTS), and steady-state PL emission (SSPL).
Since a detailed review has been recently reported on these
measurement approaches,[59] here we just gave a brief over-
view and introduction about it. Additionally, we also introduced
recently developed ideality factor method, which is famous for
reliably evaluating for recombination.
2.3.1. Space Charge Limited Current
The defects in semiconductors can be filled by free charges and
thus leading to change in their electrical properties after all defects
are completely filled. Based on this fact, SCLC as one of the piv-
otal characterization methods for defect density has received
attention in PSCs, which plays a key role in gaining deep insight
into microscopic mechanism correlated with defects.[18,59,87–90]
Under sufficiently large electric field applied to perovskite mate-
rial via Ohmic contact, defects in perovskite will capture a part
of injected charges and accordingly decrease free charge density,
during which the current is limited by the space charge effect.
Based on the above theory, typical dark J–V curve can be obtained
through measuring the dark currents as a function of bias volt-
ages, as shown in Figure 3a.[87] Obviously, three regions occur in
dark J–V curves, including linear region, trap filling region, and
trap-free SCLC region. In the linear region exhibiting Ohmic
response, the current density has a linear relation with electric
field intensity (I ∝ V), which is followed by a trap filling region
showing a sharp increase in current as the electric field increases
(I ∝ Vn, n > 3). The trap density levels are continuously filled and
all the traps are filled until trap-filled limit voltage (VTFL) as bias
increases. Afterward, a trap-free SCLC region appears (I  ∝ V2).
The trap density (nt) is expressed by Equation (1)
2εε 0 VTFL
nt = (1)
eL2
where ε is the dielectric constants of perovskite, ε0 is the
vacuum permittivity, L is the thickness of perovskite film, and
e is the elementary charge.[18,88,90]VTFL is obtained by fitting the
dark J–V curves. The dielectric constant of the perovskite can
be obtained from Equation (2)
C gL
ε= (2)
ε0A
where Cg is the geometrical capacitance of the perovskite layer, the
permittivity of free space ε0 = 8.85 × 10−14 F cm−1, L is the thickness
of the perovskite films, and A is the active area of the device.[91] Cg
is obtained by fitting the impedance spectra of the corresponding
devices. It is well known that electron or hole traps can be charac-
terized through fabricating electron-only device (electrode/ETM/
perovskite/ETM/electrode) or hole-only device (electrode/HTM/
perovskite/HTM/electrode). Typical dark J–V curves of electron-
only and hole-only devices are exhibited in Figure 3b,c.[18]
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Figure 3.  a) Dark J–V curve of MAPbBr3. Dark J–V curves of b) electron-only devices and c) hole-only devices based on different perovskite films.
d) TSC curve for the devices based on CuSCN (green), PEDOT:PSS (red), and without transport layers (purple). e) Trap density of state curves of
devices without PCBM, with PCBM but without thermal annealing, with 15 min thermal annealing PCBM, and 45 min thermal annealing PCBM.
f) Deep-level transient spectroscopy of the control and target perovskite layers. a) Reproduced with permission.[87] Copyright 2015, American Association
for the Advancement of Science. b,c) Reproduced with permission.[18] Copyright 2017, Royal Society of Chemistry. d) Reproduced with permission.[92]
Copyright 2015, American Chemical Society. e) Reproduced with permission.[33] Copyright 2014, Nature Publication Group. f) Reproduced with permis-
sion.[12] Copyright 2017, American Association for the Advancement of Science.

2.3.2. Thermally Stimulated Current
Except for SCLC technology, TSC is also one of the impor-
tant measurement methods to evaluate trap density although
it is relatively less used in PSCs in the past.[59,92] It is well
known that TSC is a powerful characterization method to
detect the trap states in semiconductors.[93–95] Here it should
be stressed that the fundamental principle of TSC is on the
basis of assumption that the optically excited electrons can
partially fill defect states at a very low temperature. The device
will generate charge carriers through illumination after it is
cooled to a very low temperature. Subsequently, a constant
temperature is imposed on the device to allow the charge car-
riers to relax in the density of states and occupy possible trap
states (this process is called as thermalization process). After
the thermalization process, the charge carriers are gradually
released from previously filled trap levels as the temperature
slowly increases at a constant rate, and thus the current is
allowed to flow within the device. It needs to be noted that the
release of charges captured by different defect traps requires
different thermal excitation energies, which are determined by
both energy depth and temperature. The activation energy (EA)
of the charge in defect traps can be calculated according to
Equation (3)[59]
 E 
I TSC = exp  − A  (3)
 K BT 
where ITSC is the current signal produced by thermally exciting
electrons to the CBM, KB is the Boltzmann constant, and
T stands for temperature. In addition, defect density nt can be
calculated through integrating the TSC spectrum over time
using Equation (4)[59,96]
∫peak
I TSC dt ≤ en tV

(4)
where V represents the volume of the sample. For example,
Baumann et al.[92] used the TSC method to investigate the defect
traps in MAPbI3-based inverted PSCs. TSC was plotted against
the temperature for different devices, as illustrated in Figure 3d.
For the reference device (ITO/CuSCN/MAPbI3/PCBM/C60/
BCP/Au), only one peak at T3 (163 K) was observed in the dark,
while a peak at T3 (163 K) appeared at the opposite direction
under illumination in the device without transport layers as
compared to reference device. It indicates that this peak comes
from the perovskite layer instead of charge transport layers and
this peak is not due to thermally excited current but phase tran-
sition between orthorhombic and tetragonal. When perovskite
is integrated with charge transport layers (CTL) using different
HTMs (PEDOT:PSS and CuSCN) in the illumination condition,
four peaks are clearly seen (T1 = 27 K, T2 = 60 K, T3 = 163 K,
and T4 = 194 K). In contrast, two peaks at T1 and T2 cannot be
found in the device without CTLs, which means that two peaks
at low temperatures T1 and T2 are attributed to shallow-level
defect traps from PCBM/C60 ETM rather than the perovskite
layer. Additionally, a very weak peak in the vicinity of T1 in the
device without CTLs under illumination is indicative of the
presence of very shallow trap states in the MAPbI3 layer. When
comparing the devices with/without CTLs, it can be concluded
that not only T3 (phase transition) but also T4 originate from
the perovskite layer and high-temperature peak at 194 K is

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contributed by defect traps. Furthermore, the activation energy
and defect density were calculated to be around 500 meV and
1 × 1021 m−3 according to Equations (3) and (4). The above suc-
cessful application of TSC measurement in PSC implies that
TSC characterization technology shows huge potentials in
investigating bulk and interface recombination in PSCs. Con-
sequently, extensive utilization of the TSC method in PSCs will
be highly expected in future for the purpose of further improve-
ment of PCE and stability.
2.3.3. Thermal Admittance Spectroscopy
Compared with the above-discussed TSC method, TAS has
been widely utilized to determine the defect density of states
(including shallow- and deep-level defects) in thin film solar
cells,[97] organic solar cells,[98] and PSCs.[33,59,99–101] The fun-
damental of TAS is mainly based on capacitance evolution
depending on charging–discharging of defects with changes
in the frequency of the alternating current (AC) voltage. The
defect occupancy of semiconductor is dependent on the posi-
tion of the Fermi level. Similar to the principle of TSC, filled
charge in defect states can be thermally activated and released,
during which the defect level is determined by both energy
depth of the defects and temperature. Finally, released charges
will contribute to the admittance signal. Consequently, junction
capacitance can reflect information on defects with different
EA at different modulated AC frequencies. The energy of the
defect energy level Eω at frequency (ω) can be estimated from
Equation (5)[33,59]
Eω = E d − E v (5)
where Ed and Ev stand for the energy depth of defects and the
VB maximum energy level, respectively. Subsequently, the
attempt-to-escape frequency (ω0) can be calculated based on
Equation (6)[33,59]
 E 
ω 0 = βT 2 exp  − ω  (6)
 K BT 
where β is a temperature-dependent parameter. The defect den-
sity (nt) can be derived from the angular frequency–dependent
capacitance according to Equation (7)[33,59]
Vbi dC ω
n t (Eω ) = − (7)
eW dω K BT
where C and ω represent capacitance and angular frequency,
respectively. The build-in potential (Vbi) is extracted from the
capacitance–voltage curve. The depletion width (W) is obtained
from Mott–Schottky analysis. Moreover, the depletion width
can be obtained based on Equation (8)[59,102]
ε 0ε r A
W = (8)
C defects based on a temperature scan rate of 0.81547 s−1, as
where εr and A stand for the relative dielectric constant and
the contact area, respectively. Figure 3e shows typical trap
density of states (tDOS) curve of MAPbI3-based PSCs.[33] It
is obviously observed from Figure 3e that three bands appear
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in the tDOS curve for the device without PCBM passivation.
After incorporation of the PCBM passivation layer, the tDOS
over 0.4 eV (Band 2 and Band 3) significantly decreases even
if no thermal annealing was applied, along with a slightly
reduced tDOS at relatively shallow trap states in the range of
0.35–0.40 eV (Band 1). Further decrease in tDOS at Band 1 was
observed after annealing the device with PCBM. It suggests
that PCBM can diffuse into the perovskite layer along grain
boundaries and thus passivate the shallow trap level. In other
words, significantly reduced tDOS is consistent with improved
PCE and reduced hysteresis upon incorporation of PCBM with
annealing.
2.3.4. Deep-Level Transient Spectroscopy
It is well known that DLTS is useful to detect deep-level
defects,[12,59,103,104] which is hardly detected by the above-dis-
cussed characterization techniques. When performing a DLTS
spectrum measurement, the emission rate window is set first
and then the instrument will exhibit a response peak at the
specific temperature through responding to different emission
rates induced by different temperatures in this window. The
fundamental idea of DLTS is to determine the energy difference
between different defect states, one of the band edges, and cap-
ture cross-section of defects through detecting the defect emis-
sion rates depending on temperatures.[103] During the DLTS
measurement, temperatures in the range from liquid nitrogen
temperature and room temperature or above are usually
employed. The bias-generated charges could fill the defect states
at the initial bias pulse at low temperature, during which the
emission rate of a defect trap is much smaller as compared to its
capture rate. At this time, the former can be neglected.[59] Upon
increase of temperature, DLTS peaks will occur gradually if the
emission rate is located in the rate window. The defect density at
a specific temperature can be expressed by Equation (9)[104]
n t = 2(∆C/C ) (N A − N D) (9)
where ΔC is capacitance change from t = 0, C is the capacitance
of the diode under reverse-biased condition. (NA  − ND) stands
for the net acceptor concentration on the p side of the junction.
Additionally, the EA of the defects below CB can be calculated
by Equation (10)[104]
 E 
en = (σ n υ n N D /g n ) exp  − A  (10)
 K BT 
where en is the thermal emission rate of the trapped charges,
σn is the charge capture cross-section, νn is the mean thermal
velocity of the charges, ND is the effective density of states in the
carrier band, and gn is degeneracy of the defects. For example,
DLTS spectra of perovskite films with or without I3− passiva-
tion were measured to determine the density of their deep-level
shown in Figure 3f.[12] The control perovskite film (before I3−
treatment) shows three evident DLTS peaks (denoted as A1, A2,
and A3). Through Arrhenius measurement, the energy levels
of defects were determined to be 0.78, 0.82, and 0.46 eV for A1,
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A2, and A3, respectively, which suggests that these defects stem
from interstitial Pb and antisite defects. After incorporation of
I3− into precursor, deep-level defects (A1 and A2) are markedly
reduced while semishallow level defects just slightly decreased.
2.3.5. Steady-State PL Emission
Actually, trapping process of the defects for charges can affect
not only electrical properties but also optical properties. SSPL
has been widely employed to determine the defect density of
perovskite films in PSCs.[59,105] When perovskite film was pho-
toexcited by increasing pump fluence, the excited charges are
either relaxed through band edge emission or captured by
defects. The turning point at low pump fluence indicates that
all the defect traps have been filled by the photogenerated
charges. The pump fluence corresponding to this turning
point is called threshold trap pump fluence (Pthtrap). Pthtrap can be
obtained by intersection of the linearly extrapolated PL inten-
sity and the pump fluence axis. The total defect density can be
obtained from Equation (11)[59,105]
α be found from Equation (12) that µ  =µoc,rad when EQYPL  = 1
n t = Pthtrap × (11)
E (without any nonradiative SRH recombination and interface
where α is the absorption coefficient and E is the energy of one
photon at the wavelength of the laser pulse.
2.3.6. Ideality Factor
The quantitative relationship between recombination and Voc
can be described in terms of external PL quantum yield (EQYPL)
using Equation (12)[55,62]
µ = µoc,rad + K B T ln (EQYPL) (12)
where µ is the free energy of photogenerated electron–hole
pairs, which is equal to the energy splitting of the quasi-Fermi
levels of electrons in the conduction (Fcb) and balance (Fvb)
bands, respectively. µoc,rad is the free energy when only radiative
recombination occurs (EQYPL = 1) under open-circuit condition.
EQYPL stands for the external electroluminescence quantum
yield. KBT is mainly responsible for the temperature depend-
ence of Voc.[60] The device Voc is obviously related to µ. EQYPL can
directly reflect the degree of nonradiative recombination. Con-
sequently, Voc is proportional to EQYPL while EQYPL is inversely
proportional to the nonradiative recombination. Therefore, the
only way to maximize Voc is to maximize the EQYPL by mini-
mizing nonradiative recombination losses and internal photon
losses, which translates into an improved Voc as expressed by
Equation .[12][62,69] In intrinsic perovskite semiconductor, it can
recombination). In this case, the Shockley–Queisser limit
Voc = µ = µoc,rad. As shown in Figure 4a and Equation (12), µ is
usually smaller than µoc,rad because of the presence of SRH

Figure 4.  a) Stand-alone intrinsic layer. The free energy µoc of photogenerated electron–hole pairs equals to the gap between the quasi-Fermi levels of
electrons in the conduction (Fcb) and valence (Fvb) bands. In the mid gap, an empty trap level Et is assumed. R stands for recombination rate per unit
of volume. b) Energy diagram for the heterojunction of intrinsic light absorber contacting with HTL and ETL. Similarly, the free energy is the difference
between Fcb and Fvb. At equilibrium in the dark, the concentration of trapped electrons varies across the intrinsic layer, showing SRH is crucial in the
bulk but negligible at interface. c) Effect of radiative, SRH, and/or interface recombination on photovoltaic parameters. For the ideal diode with only
radiative recombination, photocurrent, voltage, and fill factor approach Shockley–Queisser limit, while the presence of SRH recombination reduces
photocurrent, voltage and fill factor and the addition of interface recombination declines further voltage and fill factor. Reproduced with permission.[55]
Copyright 2017, Nature Publishing Group.

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www.advancedsciencenews.com
nonradiative recombination in real perovskite films. RSRH,e(h)
is the SRH recombination rate of electrons (holes) per unit of
volume, which affects Voc far from ideal Shockley–Queisser
limit Voc. Consequently, it is essential for increasing Voc through
reducing SRH recombination losses.
Except for Voc, nonradiative recombination also has a pro-
nounced effect on FF of devices. The maximum FFmax of PSCs
can be calculated as the following equation[106]
ν oc − ln(ν oc + 0.72)
FFmax = (13)
ν oc + 1
where νoc is proportional to the open-circuit voltage (Voc). As
revealed in Equation (13), the FFmax of PSCs is closely related to
Voc. Since Voc is highly dependent on nonradiative recombination
as discussed in Equation (12), FFmax is expected to be also affected
by nonradiative recombination. As illustrated in Figure 4b,
perovskite film contacts with ETM and HTM and forms hetero-
junction. In this case, recombination losses at perovskite/ETM
and perovskite/HTM interfaces must be taken into account to
evaluate Voc of real device (recombination (II) process as dis-
cussed above). In other words, in addition to SRH recombination
Voc is also determined by interface recombination. In order to
demonstrate how SRH and interface recombination have effect
on device performance, Sarritzu et al.[55] estimated photovoltaic
parameters: Voc  = 1.33 V, Jsc  = 25.4 mA cm−2, FF = 0.91, and
PCE = 30.5% (ideality factor m = 1) in the absence of SRH recom-
bination and interface recombination (Figure 4c). When SRH
recombination was considered, all of the photovoltaic parameters
were reduced to Voc = 1.16 V, Jsc = 23.6 mA cm−2, FF = 0.86, and
PCE = 23.4% (ideality factor m = 1.5). When interface recombina-
tion was further considered, except for the photocurrent density
(Jsc = 23.6 mA cm−2), all other photovoltaic parameters were fur-
ther reduced to Voc = 0.97 V, FF = 0.80, and PCE = 18.2% (ideality
factor m ≈ 2). It is obvious that reduction in PCE is mainly attrib-
uted to crucially decreased Voc and FF that are also related to the
ideality factor. We can see that Voc and FF gradually reduce as
the m increases from 1 to about 2. It implies that SHR recombi-
nation and interface recombination have a significant influence
on Voc and FF. Furthermore, the ideality factor can be used to
evaluate the recombination losses in a real device.[55,60,107]
Since recombination (including radiative, nonradiative, and
interface recombination) is directly related with Voc and FF, it is
crucial how to uncover and evaluate recombination. In the past,
impedance spectroscopy (IS) was usually used to investigate the
interfacial charge transfer.[22,108,109] However, it is difficult for
IS measurement to accurately correlate each of the recombina-
tion processes with Voc and FF. Recently, the ideality factor has
been proposed frequently to reliably evaluate the recombination
process in PSCs.[55,60,107] Tress et al.[60] reported that m can be
measured from one of the methods that is based on the light
intensity–dependent Voc, dark J–V and electroluminescence.
Among them light intensity-dependent Voc method can give a
reliable m because other two methods have parasitic resistance
component. m can be evaluated from the following light inten-
sity-dependent Voc in Equation (14)
I0
eVoc = E g − mK B T ln (14)
I than MA has been utilized. This strategy leads to higher
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where e is the elementary charge, I is the light intensity, I0 is
a constant with the same unit as I, and KB is the Boltzmann
constant.
3. Control of Recombination in the Bulk
Perovskite
3.1. Compositional Engineering
Since the first report on solid-state PSCs by Park et al.,[3] com-
position engineering strategy has been extensively employed
to tune the optical and electric properties of perovskite mate-
rials. Based on composition engineering method, the great
breakthrough was obtained by Seok and co-workers and a
certified PCE of 17.9% was achieved based on the optimized
perovskite composition (FAPbI3)0.85(MAPbBr3)0.15, which
was the highest value in PSCs at that time.[7] Subsequently,
more complicated triple- and quadruple-cation perovskite
compositions of (Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 and
Rb0.05[Cs0.05(MA0.17FA0.83)0.95]0.05Pb(I0.83Br0.17)3) were developed
by Saliba and co-workers and PCE over 21% was obtained with
excellent long-term operating stability.[10,17] Presently, most of
the highly efficient PSCs with the PCE exceeding 21% were
fabricated based on the classical triple- and quadruple-cation
perovskite compositions.[13,17,57,58,110] Rational composition
engineering can control the electric properties (carrier mobility,
carrier concentration, and defect density) because crystal struc-
ture, morphology, and crystallization can be modified. Form-
ability of perovskite after composition engineering in ABX3
perovskite is expected from estimation of tolerance factor t,
where t  = (RA + RX)/[21/2 (RB + RX)], based on ionic radii of A,
B, and X.[23] Perovskite can be stabilized when t is in the range
of 0.8–1.[23] In the organic lead halide perovskite, although
A-site organic cation might not directly affect the valence band
maxi­mum (VBM) and conduction band minimum (CBM), it can
indirectly affect them because PbI bond length and PbIPb
bond angle are likely influenced by A-site cation, which eventu-
ally contributes to the geometry stability and the electronic struc-
ture.[111,112] It is obvious that modification of B-site cation and
halide anion can directly affect VBM and CBM because BX
bond determines band structure.[111,113] Since all of the A, B,
and X sites can directly or indirectly affect the optical and elec-
tric properties of perovskite, they are also closely related with
recombination process in intrinsic perovskite. Subsequently, we
discuss how changes of ions in A, B, and X sites affect SRH non-
radiative recombination from the viewpoint of defect chemistry.
3.1.1. A-Site Engineering
In Table 1, photovoltaic parameters of PSCs are listed to show
how change or replacement of A-site cation affects the photo-
voltaic performance, where the data for replacement of iodide
with a small amount of bromide are also included.
It is well known that the commonly used perovskite com-
position is MAPbI3 at the early stage of PSCs development. In
order to extend light absorption, FA with larger ionic radius
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Table 1.  Photovoltaic parameters of PSCs depending on A-site cations.
Device structurea)
ITO/PEDOT:PSS/Cs0.1MA0.9PbI3/PCBM/Al
FTO/bl-TiO2/FA0.9Cs0.1PbI3/spiro-MeOTAD/Ag
ITO/Cu:NiOx/MA0.7FA0.3Pb(I0.9Br0.1)3/PCBM and C60/Bis-C60/Ag
FTO/bl-TiO2/mp-TiO2/ Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3/spiro-MeOTAD/Au
FTO/bl-TiO2/mp-TiO2/ Rb0.05[Cs0.05(MA0.17FA0.83)0.95]0.05Pb(I0.83Br0.17)3/spiro-MeOTAD/Au
a)
The perovskite composition is highlighted in bold; b)Average PCE.
Jsc.[20,116,117] As mentioned above, ion in A-site is proved to indi-
rectly affect bandgap and photovoltaic property. Yadav et al.[118]
reported that dynamics of charge transfer processes was found
to be strongly influenced by the nature of A cation, where the
interfacial charge transport was more rapid in FAPbBr3 than
CsPbBr3. According to the theoretical and experimental studies,
rotation of the MA cation is beneficial to heal deep trap states
created by lead and iodine vacancies.[119] The in situ photolumi-
nescence technique revealed that the perovskite crystallization
kinetics could be effectively controlled via incorporation of FA,
which reduced nonradiative recombination and thereby led to
a PCE of 12.81% with the (BA)2(MA,FA)3Pb4I13 (BA: butylam-
monium) quai-2D perovskite.[120] The examples described above
show that A-site cation plays an important role in affecting
interfacial charge transfer, defect, and device performance.
Alkali metals are usually considered as possible candidates
for A site. Choi et al.[114] reported that monovalent Cs cation
with an ionic radius of 1.81 Å was used to substitute par-
tially MA with an ionic radius of 2.70 Å in MAPbI3 to form
CsxMA1−xPbI3. It was found that incorporation of 10% Cs+
improved PCE from 5.51% to 7.68%, which was ascribed to
improved film morphology associated with reduced nonradia-
tive recombination. After many attempts, replacement of MA+
by FA+ was found to be one of the effective ways to improve
photovoltaic performance because of optically benign.[111] How-
ever, higher annealing temperature above 160 °C is required
for maintaining the thermodynamically stable black trigonal
α phase FAPbI3 and furthermore black perovskite phase tends
to be converted into yellow hexagonal nonperovskite δ phase
below the phase transition temperature.[100,117,121] In order
to stabilize the black perovskite phase of FAPbI3 and further
improve PCE, Lee et al.[100] inserted 10 mol% Cs in FAPbI3 for
the first time and then improved PCE to 19% from a normal
structure employing FA0.9Cs0.1PbI3 (Table 1). It is interesting
to see that the substitution of FA with an appropriate amount
of Cs cation is able to stabilize the black phase even at room
temperature. As shown in SEM images in Figure 5a–d,
FA0.9Cs0.1PbI3 perovskite exhibits larger grain and clearer grain
boundary as compared to the pristine FAPbI3. Such a large
grain grown by the insertion of Cs is found to lead to increase
in time constant for recombination (Figure 5e) and reduction
in trap density (Figure 5g) as measured by impedance spec-
troscopy (Figure 5f). Yang et al.[115] systematically investigated
the effect of substitution with FA+ and Br− on the structural,
optophysical, and photovoltaic properties of pure MAPbI3.
It was found that dual compositional tuning in MAPbI3
Adv. Mater. 2018, 1803019
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Jsc Voc FF PCE Year Ref.
[mA cm−2] [V] [%]
10.10 1.05 0.73 7.68 2014 [114]
23.4 1.07 0.76 19.0 2015 [100]
20.21 1.10 0.78 17.34b) 2016 [115]
23.5 1.147 0.79 21.17 2016 [17]
22.8 1.180 0.81 21.8 2016 [10]
improved crystallinity and morphology, which reduced defect
density as revealed by admittance spectroscopy. The optimized
MA0.7FA0.3Pb(I0.9Br0.1)3-based device showed an average PCE
of 17.34% that was much higher than 15.43% of the pris-
tine MAPbI3. In the early 2015, a solid solution of FAPbI3 and
MAPbBr3 was designed to obtain optimal composition (FAPbI
3)0.85(MAPbBr3)0.15 for PSCs, which delivered a certified PCE of
17.9%.[7] In order to further enhance PCE, Saliba et al.[17] devel-
oped triple cation perovskite Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3,
from which Jsc and FF were improved due to reduced nonradia-
tive recombination. Reduced phase impurity was explained as
one of the main reasons for suppressing nonradiative recombi-
nation as confirmed by XRD study in Figure 6a. Improved crys-
tallinity estimated from morphological evaluation (Figure 6b,c)
was considered as another reason for the reduced nonradia-
tive recombination. As illustrated in Figure 6b,c, as compared
to random growth of perovskite grains, columnar grains (per-
pendicular to the FTO substrate) are observed for Cs-included
(FA,MA) composition. It was interpreted that the vertical
growth of perovskite grains would be beneficial for inhibiting
nonradiative recombination via accelerating charge transport
toward vertical direction. This result offers important insight
into morphological control to improve photovoltaic perfor-
mance. From the lessen of the role of Cs+, Zhang et al.[122] also
introduced it into 2D perovskite (BA)2(MA)3Pb4I13 for further
enhancement of 2D PSCs. The (BA)2Cs0.15(MA)2.85Pb4I13-based
cell showed a higher PCE of 13.7% than that of 12.3% of con-
trol device, which was ascribed to controlled crystal orientation,
increased grain size, superior surface quality, reduced trap-state
density, enhanced carrier mobility, and charge transfer kinetics.
Therefore, reasonable composition engineering is an effective
approach because of controlling grain growth toward beneficial
direction for suppressing nonradiative recombination. On the
basis of triple cations perovskite, the same group[10] investigated
the other alkali metals (Li+, Na+, K+, and Rb+) except for Cs+
through calculating tolerance factor t to check whether they can
also be incorporated into crystal lattice. They found that t of RbPbI3
was very slightly deviated from the safety value of 0.8 < t  < 1,
while t of KPbI3 is far from this t range. This is indicative of pos-
sible incorporation of Rb+ in A site in the way of the so-called
“cation cascade.” As presented in Figure 6d, the peaks of yellow
phase of FAPbI3 and PbI2 nearly disappear after incorporation
of both Rb+ and Cs+, which eventually contributed to improved
PCE. The optimized Rb0.05[Cs0.05(MA0.17FA0.83)0.95]0.05Pb(I0.83
Br0.17)3-based PSC showed a PCE of 21.8% and the highest Voc
from the triple cation method was observed to be 1.24 V
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Figure 5.  Surface SEM images of a) FAPbI3 and b) FA0.9Cs0.1PbI3 films. Cross-sectional SEM images of PSCs employing c) FAPbI3 and d) FA0.9Cs0.1PbI3.
Scale bar is 100 nm. e) Time constant for charge recombination, f) capacitance–frequency, and g) calculated trap density (NT) of FAPbI3- and
FA0.9Cs0.1PbI3-based PSCs measured at room temperature. Reproduced with permission.[100] Copyright 2015, Wiley-VCH.

(Figure 6e,f). When considering the bandgap of 1.63 eV for
the composition with Voc = 1.24 V, potential loss is only 0.39 V,
which suggests that nonradiative recombination can be signifi-
cantly reduced by cation engineering.
Apart from Cs+ and Rb+, recently, incorporation of K+ was
also intensively investigated. Insertion of K+ into lattice of CsP-
bI2Br was confirmed by shift of the peak position to higher
angle in XRD associated with reduced lattice constants.[66]
Interestingly, several groups proposed that doping of K+ can
reduce or remove hysteresis.[18,90,123–125] Bu et al.[18] found that
the reduced hysteresis by incorporation of potassium ion was
attributed to the reduced defect density due to the increased
grain size and improved charge transportation because of the
increased carrier lifetime. Tang et al.[124] demonstrated that
the incorporation of potassium ion could reduce not only bar-
rier at the perovskite/TiO2 interface but also defect density in
perovskite films. Son et al.[90] compared the hysteresis of PSCs
depending on incorporation of different alkali metal iodides
and found that the hysteresis was highly dependent on alkali
metal ions, where complete removal of hysteresis was observed
for KI as shown in Figure 7a. For the smaller LiI or the larger
CsI, the hysteresis is hardly reduced. Impedance spectroscopic
studies in Figure 7b,c shows that low capacitance with saturated
plateau in the low-frequency region of 10−100 Hz is found for
the KI-doped perovskite, which is related to the removal of the
hysteresis. Reduced trap density is realized by doping with KI
(Figure 7d,e). Frenkel defect can explain the removal of the
hysteresis, where stable incorporation of proper ion such as
K+ in the interstitial octahedral site effectively inhibits Frenkel
defect and thereby hysteresis is removed. Abdi-Jalebi et al.[125]
also demonstrated that the introduction of KI could nearly
eliminate hysteresis of PSCs. KI-doped triple cation perovskite
showed increased external photoluminescence quantum effi-
ciency (PLQE) and PL lifetime, leading to substantial mitiga-
tion of nonradiative losses and photoinduced ion migration in
perovskite films (Figure 8a,b). As displayed in Figure 8c, they
proposed that halide vacancies were filled with iodide provided
by KI, which could passivate nonradiative recombination path-
ways and increase PLQE. The excess halides also could inhibit
underlying halide migration, which might suppress additional
nonradiative recombination. As mentioned in Figure 7, there
is optimal quantity for doping KI for achieving highest Voc
and PCE (Figure 8d–f), which indicates that there is a certain
density of defects affecting photovoltaic performance in PSCs.
Doping with KI can be universally adapted to reduce defects in
the perovskite layer.

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Figure 6. a) XRD patterns of Csx(MA0.17FA0.83)(1−x)Pb(I0.83Br0.17)3 perovskite films with different amount of Cs. Cs0M (without Cs) represents
MA0.17FA0.83Pb(I0.83Br0.17)3 and Cs5M (with 5 mol% Cs) stands for Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3. Cross-sectional SEM images of b) Cs0M and
c) Cs5M. d) XRD patterns of the annealed dual cation (MAFA) and quadruple cation (RbCsMAFA) perovskite films. Peaks with # and δ correspond
to PbI2 and yellow FAPbI3, respectively. e) J–V curve and steady-state PCE of the champion device. (f) J–V curve and steady-state PCE of the highest
open-circuit voltage device. a–c) Reproduced with permission.[17] Copyright 2016, Royal Society of Chemistry. d–f) Reproduced with permission.[10]
Copyright 2016, American Association for the Advancement of Science.

3.1.2. B-Site Engineering a result, the device based on optimized composition of

The substitution of lead in B-site by divalent (or trivalent) tran-
sition metal ions has been tried to control optical and electronic
properties of PSCs. Table 2 shows the effect of the modification
of B-site cation with indium, bismuth, cobalt, copper, and tin
on photovoltaic parameters.
As discussed above, B-site metal ions in ABX3 play an impor-
tant role in determining not only the CBM and VBM through
directly affecting the BX bond length and angle but also the
electric properties of perovskite. In the past, tremendous efforts
have contributed to investigate partial replacement of Pb2+
(ion radius: 1.49 Å) by Sn2+ (ion radius: 1.35 Å) for the pur-
pose of extending the absorption onset and reducing toxicity
of lead.[19,130–133] Although the absorption spectrum is much
extended, the device based on Sn suffers from poor chemical
stability due to oxidation of Sn2+ to Sn4+ in the presence of
oxygen and moreover poor PCE because of fast electron/hole
recombination.[127] Encouraged by both development of lead-
free or lead-less perovskite, other (transition) metal ions were
also employed to partially substitute Pb2+.[126–129] Although
In3+ is somewhat difficult to replace in part Pb2+ due to charge
imbalance, excess charge was tried to compensate by adding
additional anion such as Cl, leading to MAPb1−xInxI3Clx,[126]
which was applied in inverted planar PSCs (Table 2). As
MAPb0.85In0.15I3Cl0.15 exhibited improved Voc (1.03 V), Jsc
(21.90 mA cm−2), FF (0.78), and PCE (17.55%) as compared to
Voc (0.91 V), Jsc (19.07 mA cm−2), FF (0.72), and PCE (12.61%)
of a control device without In3+. It was noted that (110) and
(220) peaks dominate in MAPbIxCl3−x, while five main peaks
corresponding to (110), (220), (224), (312), and (310) planes
were observed for MAPb0.85In0.15I3Cl0.15, which implies that
multiple ordered crystal orientations were achieved via incorpo-
ration of In3+. They claimed beneficial effect of multiple ordered
crystal orientations for efficient charge transport along multiple
directions, which might reduce nonradiative recombination
as evidenced by the improved Voc, Jsc, and FF. This suggests
the importance of highly oriented structure. Apart from com-
positional engineering, of course, dimensionality engineering,
additive engineering, and interface (substrate) engineering also
enable highly oriented grain growth, which is discussed below.
Bi3+ ion in VA is isoelectronic structure of Pb2+ with 6s26p0
electronic configuration, which is thus expected as an environ-
mentally friendly alternative to Pb2+.[127,134,135] Chen et al.[127]
developed Bi-modified MA3Bi2Br9:FA0.83MA0.17Pb(I0.83Br0.17)3
perovskite for normal planar PSCs, which delivered a PCE of
19.4% that was higher than 18.3% of nonmodified pristine
perovskite as a consequence of improved Voc and FF as well as
slightly enhanced Jsc. XRD results confirmed the incorporation

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Figure 7. a) J−V curves of PSCs based on (FAPbI3)0.875(CsPbBr3)0.125 doped with 10 µmol of LiI, NaI, KI, RbI, and CsI, measured in reverse (from Voc to
0 V) and forward (from 0 V to Voc) scans under one sun illumination. Capacitance−frequency plots of KI-doped and undoped perovskite films with
b) selective contacts and c) no selective contacts. Dark J–V curves showing trap filled limit (TFL) voltages for d) undoped pristine perovskite and
e) KI-doped perovskite. Reproduced with permission.[90] Copyright 2018, American Chemical Society.

of Bi3+ into lattice of FA0.83MA0.17Pb(I0.83Br0.17)3. Incorporation
of Bi3+ reduced nonradiative recombination and trap density
as confirmed by PL data. From the light intensity-dependent
Voc measurement, defect density was confirmed to be reduced
after modification with Bi3+. Thus reduction in nonradiative
recombination would be responsible for the improved Voc and
FF. Recently, Co2+ was tried to partially replace Pb2+ in spite of
much smaller ionic radius (0.745 Å for high spin and 0.65 Å
for low spin) to produce MAPb1−xCoxI3, whose t is 1.01 close to
ideal 1 value when x = 0.4.[128] 3d orbital of Co2+ was expected to
affect the electrical properties of perovskite.[128,136] It was found
that substitution with Co2+ changed phase from tetragonal to
cubic and then mixed phase was obtained as the substitution
ratio increased. The grain size of perovskite was significantly
increased from 0.2 µm for pristine MAPbI3 to over 1 µm for
MAPb1−xCoxI3 (x  = 0.1, 0.2, and 0.4) as shown in Figure 9a,b.
MAPb0.9Co0.1I3 composition increased electrical conduc-
tivity and balanced charge mobility, as measured by Seebeck
coefficient, when comparing those of pristine MAPbI3 film
(Figure 9c). Such grain growth and improved electrical
properties contributed to the significant reduction in SRH non-
radiative recombination, which eventually led to remarkable
enhancement of PCE from 17.46% to 21.43% by substitution of
10% Pb2+ with Co2+ (Figure 9d).
Compared to researches on binary metal alloy (such as Pb–
Sn, Pb–Bi, and Pb–Co), relatively little attention has been paid
to ternary metal alloy. Li et al.[129] reported ternary metal alloy
MAPb0.9Sn0.05Cu0.05I2.9Br0.1 for PSCs. Ternary metal alloy of
Pb–Sn–Cu shows much better morphology with quite large
grain size than single or dual metal alloy systems as can be
seen in Figure 10a–d. In addition, Pb–Cu and Pb–Sn–Cu sys-
tems showed lower trap density than MAPbI3 (Figure 10e).
Pb–Sn composition exhibited unexpectedly higher trap density
than MAPbI3. MAPb0.9Sn0.05Cu0.05I2.9Br0.1-based device demon-
strated PCE as high as 21.08% (Figure 10f). It is important to
note that the introduction of Sn2+ contributes to the improve-
ment of Jsc and the introduction of Cu2+ can passivate trap
sites at the crystal boundaries of Pb–Sn perovskites. The above
results strongly suggest that B-site engineering is a promising
approach to control SRH recombination and electrical property.

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Figure 8. a) Internal and external photoluminescence quantum efficiency of perovskite films depending on the amount of KI, measured with a
532 nm laser under illumination. b) Time-resolved PL decays of the perovskite films before and after KI treatment and concentration of KI, using
a 400 nm laser and a pulse fluence of 0.5 µJ cm−2. c) Schematic diagram showing effect of doped KI on passivation of halide defect on surface. d) Forward
(open symbols) and reverse (closed symbols) scanned J–V curves of the champion devices with (Cs,MA,FA)Pb(I0.85Br0.15)3 perovskite passivated
without (x = 0) and with (x = 0.1) KI under one sun illumination. The inset shows stabilized PCE. e,f) Dependence of Voc (e) and Jsc (f) on concentra-
tion of KI. Reproduced with permission.[125] Copyright 2017, Nature Publication Group.

3.1.3. X-Site Engineering
Similar to B site, X site also has direct influence on the optical
and electrical properties of perovskite ABX3. Likewise, the
composition engineering of X site should abide by an appro-
priate tolerance factor t (0.8–1). First, it is easy to consider
that halogen ions (Br− and Cl−) can be used to replace the
commonly adopted I− while F− ion is hard to be considered
because t of MAPbI(3−x)Fx is not in the range of 0.8–1.[23] It
was reported in 2013 that the bandgap could be controllably
tuned by changing molar ratio of Br− and moisture stability
was significantly improved with x  > 0.6 in MAPbI3−xBrx.[21]
This work also provided insight into transparent or semitrans-
parent PSCs. Moreover, halide exchange route was developed
to produce MAPbI3−xBrx by spin-coating MABr solution in iso-
propanol (IPA) on the prefabricated pristine MAPbI3 film.[137]
This approach realized increment of grain size and prolonged
carrier lifetime, which resulted in higher PCE in MAPbI3−xBrx-
based device than counterpart device. Br doping in MAPbI3
was also found to increase the charge carrier lifetime as deter-
mined by transient photovoltage.[82] Since charge carrier life-
time, mobility, and diffusion length are directly related to SRH
nonradiative recombination and thereby to Voc and FF, Br
doping is one of the effective ways to step forward to realize

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Table 2.  Photovoltaic parameters for the perovskite materials with a particle substitution of Pb by transition metals ions.

Device structurea) Jsc Voc FF PCE Year Ref.

[mA cm−2] [V] [%]
ITO/PEDOT:PSS/MAPb0.85In0.15I3Cl0.15/PC61BM/Bphen/Ag 21.90 1.03 0.78 17.55 2016 [126]
FTO/bl-TiO2/ MA3Bi2Br9:FA0.83MA0.17Pb(I0.83Br0.17)3/spiro-MeOTAD/Au 22.5 1.12 0.77 19.4 2018 [127]
ITO/PTAA/MAPb0.9Co0.1I3/PC61BM/Al 24.42 1.07 0.82 21.43 2018 [128]
FTO/bl-TiO2/MAPb0.9Sn0.05Cu0.05I2.9Br0.1/spiro-MeOTAD/MoO3/Au 23.97 1.086 0.81 21.08 2018 [129]

a)The perovskite composition is highlighted in bold.

high-efficiency and stable PSCs. Actually, Br component has
been indispensable for perovskite composition (like classical
Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3) in most of the efficient
and stable PSCs up to now.[10,12,17,26] Except for Br−, Cl− anion
is used to replace I−.[138–143] However, it has been still argued
that whether or not Cl− ion can be incorporated into lattice
of MAPbI3 because of little change in lattice constant despite
its smaller ionic radius (1.81 Å) as compared to I− (2.2 Å).
Fortunately, Cl− in precursor solution can facilitate the crys-
tallization of perovskite and thus improve the electronic
properties (such as carrier lifetime, mobility, and diffusion
length), enabling the realization of suppression of nonradiative
recombination.[139,141,144–149] The role of Cl− in the crystallization
process of the perovskite film has been investigated widely and
deeply.[138,144,147] In general, Cl− could be incorporated through
adding Cl−containing materials (including PbCl2, MACl, FACl,
CsCl, etc.) to starting solution according to three ways: pre-
cursor solution in the one-step method,[149,150] PbI2 solution
in the two-step method,[148] and organic source solution in the
two-step method.[56,146]
Compared with halide ion substitution, little attention was
devoted to study the effect of pseudohalide substitution on
optical and electronic properties of perovskite materials. Thio-
cyanate anion (SCN−) is expected to be able to replace the
I− in MAPbI3 because of its similar ionic radius (2.17 Å) as I−
(2.2 Å).[151] PL measurement showed significant enhancement

Figure 9.  Top-view SEM images of a) pristine MAPbI3 and b) MAPb0.9Co0.1I3 films. c) The electrical conductivity and the Seebeck coefficient as a function
of Co/Pb ratio in the MAPb1−xCoxI3 (0%, 10%, 20%, and 40% for x = 0, 0.1, 0.2, and 0.4, respectively). d) J–V curves of the PSCs based on MAPb1−xCoxI3
for x = 0 and 0.1. Reproduced with permission.[128] Copyright 2018, Wiley-VCH.

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Figure 10.  Top-view SEM images of a) MAPbI3, b) MAPb0.95Sn0.05I3, c) MAPb0.95Cu0.05I2.9Br0.1, and d) MAPb0.9Sn0.05Cu0.05I2.9Br0.1 perovskite films.
e) Trap density of states (t-DOS) depending on B-site composition. f) J–V curves of PSCs depending on B-site composition measured under one sun
illumination. Reproduced with permission.[129] Copyright 2018, Wiley-VCH.

in the emission quantum yield of MAPbI3−x(SCN)x as com- 3.2. Dimensionality Engineering

pared to that of MAPbI3 due to the suppression of nonradia-
tive recombination channels. Chen et al. found that grain size
was increased and trap density was reduced by replacing a
small amount of iodide with SCN−, which yielded an efficient
and reproducible PSC.[152] Benign effect of substitution with
SCN− was also confirmed, where MAPbI3−x(SCN)x film showed
a less trap density and better intrinsic stability than the parent
MAPbI3 film.[22] Except for SCN−, BF4− (2.18 Å) molecular ion
was utilized to place partially I− to form mixed-anion perovskite
MAPbI(3−x)(BF4)x. It was found that the device based on opti-
mized MAPbI2.95(BF4)0.05 showed higher PCE of 13.24% than
10.54% of control device due to the improved Voc and FF, which
could be attributed to the increased interfacial and bulk recom-
bination resistances.[23] Since pseudohalide ions have some
unique effect on crystallization and optoelectronic properties
of perovskite compared with halide ions, extensive and deep
investigation on pseudohalide ion replacement are needed for
extending composition engineering.
As aforementioned, composition engineering of 3D perovskite
ABX3 must follow the Goldschmidt tolerance factor deter-
mined by ion radii of A, B, and X. In case that ion radius of
A-site ion is too large, the dimensionality of perovskite will be
reduced to quasi-3D, quasi-2D, and 2D.[153–155] Quasi-3D and
quasi-2D are often described as mixed 2D and 3D (2D/3D).[153]
One of the advantages of reduced dimensionality is better
moisture stability than 3D perovskite.[153,155–161] Nevertheless,
the optical loss due to increased bandgap, low absorption coef-
ficient, high exciton binding energy, and poor carrier transport
in low dimensional, such as 2D A2BX4, perovskite are draw-
backs.[160] Quasi-2D or mixed 2D/3D-based PSCs were pro-
posed to overcome such problems and great progress has been
made.[158,160] For instance, charge carrier mobility remains
unchanged (near 10 cm2 V−1 s−1) after 50% replacement of
MA+ by PEA+ (PEA+: phenylethylammonium) in MAPbI3.[162]
This implies that quasi-2D or mixed 2D/3D is an important

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research direction for simultaneous realization of stability and
high PCE.
Introduction of a small amount of 2D perovskite into 3D
perovskite was confirmed to not only improve the moisture
stability but also to suppress nonradiative recombination via
passivating the surface defect and/or bulk traps of 3D perov­
skite.[163–169] According to the report on FAxPEA1−xPbI3 used
for inverted PSC showing a PCE of 17.7%,[167] the PEA+ ions
at grain boundaries played an important role in not only sta-
bilizing the black phase of FAPbI3 but also passivating the
surface defects. Since bulky organic cations can terminate perov­
skite lattice and thereby lead to quantum well (QW) structure
(alternating perovskite/organic cation structure), the number
of inorganic perovskite layers (width of QW) can be controlled
by bulky organic cation. Proppe et al.[170] investigated the effect
of different bulky organic cations on the width of QWs in
L2(MA0.14FA0.81Cs0.05)9Pb10(I0.85Br0.15)29 (L = allylammonium
(ALA+), PEA+, and BA+), where the choice of organic cation
was found to control distribution of the QW width, where ALA+
resulted in narrower distribution and thus providing longer dif-
fusion length for holes as compared to PEA+ and BA+ cases.
As a result, ALA2(MA0.14FA0.81Cs0.05)9Pb10(I0.85Br0.15)29-based
device showed better photovoltaic performance than PEA and
BA analogs. The experimental results give important insight
into design of 2D/3D mixed perovskite to have high carrier
transport with less chance of recombination. Wang et al.[169]
incorporated BA+ into FA0.83Cs0.17Pb(IyBr1−y)3 3D perovskite to
produce 2D–3D heterostructured BA–Cs–FA lead halide perov­
skite for normal planar PSCs. As can be seen in SEM studies
(Figure 11a–d), 2D platelets were formed perpendicularly and
these could drive vertical growth of 3D perovskite. Therefore,
this 2D/3D alternating structure, as illustrated in Figure 11e,
resembles QW as discussed preciously. Grain growth perpendic-
ular to the substrate is expected to be favorable for charge trans-
port, accompanied by longer charge diffusion length and life-
time as proved by significantly increased PL studies (Figure 11f).
As a consequence, the composition of BA0.05(FA0.83Cs0.17)0.9
1Pb(I0.8Br0.2)3 yielded a stabilized PCE of 19.5% (Figure 11g).
Moreover, stability was also improved. 1D–3D hybrid perovskite
materials were proposed, where 2-(1H-pyrazol-1-yl)pyridine
(PZPY) was introduced into 3D Cs0.04MA0.16FA0.8PbI0.85Br0.15
perovskite.[166] PL lifetime was enhanced upon incorpora-
tion of PZPY due to the fact that nonradiative recombination
was reduced. In addition, thermodynamic self-healing ability
was discovered for the as-prepared PZPY-modified perovskite,
which was actually induced by blocking the A-site ion-migra-
tion channels because of the presence of flexible 1D perovskite
with less densely close-packed structure. Unique photovoltaic
property is likely to be related to the presence of organic cation
that however can cause thermal and/or moisture instability.
Complete replacement of organic cation in A-site with appro-
priate inorganic cation such as Cs+, leading to all-inorganic
halide perov­skites, may improve stability. However, α-CsPbI3
was reported to undergo phase instability under ambient condi-
tions.[171,172] α-phase of CsPbI3 could be stabilized by 2D perov­
skite of EDAPbI4 (EDA2+: ethylenediamine) and furthermore
surface of CsPbI3 was passivated by 2D perovskite.[109] As a
result, improved PCE from 7.66% to 11.86% was achieved
along with better phase stability using CsPbI3·0.025EDAPbI4.
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Pure Sn-based perovskite faces a serious challenge of
issues on the oxidation of Sn2+ and high nonradiative recom-
bination. Mixed 2D/3D (PEA2SnI4/FASnI3) perovskite was
proposed to solve such problems.[163] Even a small amount of
2D PEA2SnI4 could reduce grain boundary, suppress oxida-
tion of Sn2+ and increase carrier lifetime, which led to a PCE
of 9%. Examples discussed in dimensionality engineering
indicate that 2D materials play an important role in stabi-
lizing phase and enhancing optoelectronic properties of 3D
perovskite.
3.3. Perovskite Grain Engineering
Preferred orientation of perovskite grain becomes important
issue in terms of minimizing nonradiative recombination
losses and beneficial effects for carrier transport and extrac-
tion. Vertical recrystallization approach was tried to align
FA1−xMAxPbI3 normal to substrate (Figure 12a), which was
applied to inverted planar PSCs,[118] where MACl was found
to assist vertical growth of perovskite grains (Figure 12b). In
addition, grain size was also increased (Figure 12c,d), which
might be responsible for reducing nonradiative recombina-
tion as revealed by increased PL lifetime (Figure 12e). Conse-
quently, Jsc, Voc, FF, and PCE were significantly increased from
19.57 mA cm−2, 0.91 V, 0.74, and 13.24% to 23.09 mA cm−2,
1.10 V, 0.81, and 20.65%, respectively (Figure 12f).
For the case of 2D perovskite, out-of-plane charge transport
is relatively inhibited due to interlayer insulating organic cat-
ions. To address this issue, Tsai et al.[174] developed hot-cast pro-
cedure for fabrication of quasi-2D perovskite (BA)2(MA)3Pb4I13.
As presented in Figure 13a,b, grazing incidence wide-angle
X-ray scattering (GIWAXS) showed that strong intensities along
certain extended arc segments were detected for a room-tem-
perature-cast film, which is indicative of considerable random-
ness, while the hot-cast film exhibited sharp and discrete Bragg
spots along the same rings, suggesting a highly crystalline
nature with orientation of (101) planes parallel to the substrate
and with a 2D in-plane orientational randomness (Figure 13c).
The highly oriented and crystalline film can facilitate efficient
charge transport and accordingly reduce nonradiative recom-
bination. The device based on hot-cast film yielded a high
PCE of 12.52% with no hysteresis (Figure 13d). In addition,
moisture- and photostability were significantly improved in
the hot-cast quasi-2D perovskite as compared to its 3D coun-
terpart. Additionally, the hot-cast method was employed to
prepare the out-of-plane orientated (iso-BA)2(MA)3Pb4I13 film,
which increased cross-plane charge mobility and reduces SHR
recombination.[175] The hot-cast method was utilized to fabri-
cate highly crystalline (n-BA)2(MA)4Pb5I16 with the majority
of the inorganic slabs preferentially aligned out of plane to
the substrate.[121] In order to explore noble methods for ver-
tical orientation of perovskite films, ammonium thiocyanate
(NH4SCN) additive introduced into (BA)2(MA)n−1PbnI3n+1 (n = 3
and 4) led to vertically oriented perovskite,[7] which effectively
suppressed nonradiative recombination as a consequence of
reduced grain boundary and defect density. The composition
of (BA)2(MA)3Pb4I13 showed a PCE of 8.79%. NH4SCN was
utilized for the composition of (PEA)2(MA)n−1PbnI3n+1(n = 3, 4,
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Figure 11.  Top-view SEM images of BAx(FA0.83Cs0.17)1−xPb(I0.6Br0.4)3 perovskite films for a) x = 0 and b) x = 0.09. The insets show 2D XRD patterns. The
white arrows in (b) are indicative of new diffraction peaks due to the introduction of BA. Cross-sectional SEM images of complete devices employing
perovskite with c) x = 0 and d) x = 0.09. e) Schematic illustration of 2D–3D alternating structure. f) Comparison of TRPL between x = 0 and x = 0.09.
g) J–V curves of the best-performing PSC including BA cation. The inset shows steady-state PCE. Reproduced with permission.[169] Copyright 2017,
Nature Publication Group.

and 5) and reported a PCE of 11.01% (n  = 5) as compared to
0.56% for the control device without NH4SCN.[176] Except for
low-dimensional lead halide perovskites, low-dimensional tin
halide perovskite also gradually attracts researchers’ interest.
Columnar structure of low-dimensional (PEA)2(FA)n−1SnnI3n+1
was prepared by controlling PEAI concentration and efficient
charge carrier transport was realized for n = 9.[177]
3.4. Nonstoichiometric Approach
Grain boundary (GB) is expected to have a negative effect on
photovoltaic performance in semiconductor Si- and CdTe-based
photovoltaics.[178,179] However GB in polycrystalline CuInSe2
film was found to be electrically benign without creating deep
levels.[180,181] A large number of GBs in polycrystalline perovskite

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Figure 12. a) XRD pattern of FAPbI3 recrystallized by aid of MACl.
b) Cross-sectional SEM image of FAPbI3/MACl vertical recrystallization
film. Top-view SEM images of FAPbI3 films prepared from precursor
solution c) without MACl and d) with 5 mg mL−1 MACl. e) TRPL of FAPbI3
with and without MACl treatment. f) J–V curves of PSCs employing pris-
tine FAPbI3 and MACl-treated FAPbI3. Reproduced with permission.[173]
Copyright 2017, Royal Society of Chemistry.
films are anticipated to be inevitably produced during wet chem-
ical process, which might act as carrier recombination centers in
spite of defect-tolerant nature of organic–inorganic lead halide
perovskite.[181] Several approaches have been attempted to passi-
vate GBs in the field of PSCs, such as in situ nonstoichiometric
precursor, additive engineering, interface engineering, post-
treatment, etc. In fact, composition engineering is one of the
effective methods for enlarging grain size and reducing number
of GBs, which has been discussed previously. In addition, addi-
tive and interface engineering methods will be summarized and
discussed in details in the following corresponding section. In
this part, in situ nonstoichiometric precursor approach will be
focused. As far as we are concerned, in situ nonstoichiometric
precursor method is classified into two categories: excess inor-
ganic iodide such as PbI2 or excess organic iodide such as MAI.
To date, in situ nonstoichiometric method with excess PbI2 has
been widely adopted in most of the high-efficiency PSCs with
PCEs exceeding 21%.[10,17,26,56,57] The unreacted excess PbI2 is
expected to be placed at GBs. Kapoor et al.[182] investigated the
effect of excess PbI2 on photovoltaic performance of HTM-
free fully printable PSCs, where Voc was only slightly improved
without substantial changes in Jsc and FF. This is strong indica-
tion of surface passivation by excess PbI2. Effects of excess PbI2
in both MAPbI3 and (FAPbI3)0.85(MAPbBr3)0.15 on photovoltaic
performance were investigated,[130] where a positive effect was
observed for both compositions. It was found from the KPFM
study that ionic defect migration was also suppressed by the
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excess PbI2 method. The question is how we determine the quan-
tity of excess PbI2 for achieving best performance. Bi et al.[183]
first optimized the quantity of excess PbI2 with respect to FAI
in (FAPbI3)0.85(MAPbBr3)0.15 (Figure 14a–d) and then explored
the origin of improved Voc. From current–voltage, photon flux–
voltage and external quantum efficiency of electroluminescence
(EQEEL) in Figure 14e, the ideality factor and recombination
type were evaluated. The diode ideality factor was determined
to be around 2 from current–voltage curve and almost 1 from
the emitted photon flux data. This indicates that most of recom-
bination occurs through SRH recombination, while emission
originates from band-to-band recombination. EQEEL was esti-
mated to be as high as 0.5% for the ratio of PbI2/FAI = 1.16,
which is responsible for highest Voc of 1.18 V. Much longer PL
lifetime (350 ns) further confirmed the basis for such a high Voc
for PbI2/FAI = 1.16 (Figure 14f,g). Light intensity dependent Voc
study in Figure 14h again confirms that Voc is mainly limited
by SRH recombination that is obviously reduced by excess PbI2.
Except for directly incorporating excess PbI2 in precursor solu-
tion, in situ passivation with excess PbI2 was also realized by
annealing perovskite film at high temperature.[56,184,185] A PCE
as high as 21.6% was achieved via in situ passivation method in
ITO/SnO2/(FAPbI3)1−x(MAPbBr3)x/spiro-MeOTAD/Au.[56] Par-
ticularly, femtosecond time-resolved transient absorption spectros-
copy was utilized to study the passivation effect of excess PbI2,[186]
where perovskite films with less PbI2 exhibited fast dynamics due
to charge carrier trapping at perovskite GBs, on the other hand,
the slower dynamics was detected for the case of excess PbI2
owing to suppressed SRH recombination. Although excess PbI2
could passivate GBs and led to better photovoltaic performance,
stability was getting worse.[187] Excess PbI2 was found to deterio-
rate stability of the perovskite film under illumination and even
under inert atmosphere. Consequently, it is required to investigate
why excess PbI2 can destroy the device stability in order to find
more effective passivation methods for the purpose of simulta-
neous achievement of both excellent stability and high efficiency.
Different from in situ passivation strategy, an effective and
reproducible way of treating GBs in MAPbI3 film.[14] Self-
formed grain boundary layer was produced by depositing non-
stoichiometric precursor solution with excess MAI based on
Lewis acid–base adduct approach (Figure 15a). As increasing
the quantity of excess MAI, Voc and FF were improved and
maximized at x  = 0.06 in (1 + x)MAI + PbI2 precursor solu-
tion (Figure 15b). Excess MAI with x  = 0.06 enhanced carrier
lifetime, while deficient MAI (x  =  −0.05) declined carrier life-
time as compared to the stoichiometric case (Figure 15c). It was
found that charge conductance was improved as measured by
c-AFM (Figure 15d), which indicates that GBs play an impor-
tant role in carrier transport. Nonstoichiometric approaches
are effective ways to passivate or heal GBs of perovskite and
thereby reduce recombination at GBs.
3.5. Perovskite Precursor Solutions Engineering
3.5.1. Colloidal Size
As we discussed above, excess PbI2 or MAI has a pronounced
effect on the electric properties of perovskite films and thus
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Figure 13.  GIWAXS maps of a) room-temperature-cast and b) hot-cast (BA)2(MA)3Pb4I13 perovskite films. c) Schematic illustration of the (101) orienta-
tion along with the (111) and (202) planes of a 2D perovskite crystal. d) J–V curves for planar devices based on (BA)2(MA)3Pb4I13 perovskites. Inverted
device layout is shown in the inset. Comparison of e,g) photostability and f,h) moisture stability of (BA)2(MA)3Pb4I13 with MAPbI3 perovskite devices
without (e,f) and with (g,h) encapsulation. Reproduced with permission.[174] Copyright 2017, Nature Publication Group.

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Figure 14.  Statistical photovoltaic parameters of a) Jsc, b) Voc, c) FF, and d) PCE with respect to the ratio of PbI2 to FAI. e) J–V curve in the dark, emitted
photon flux, and external quantum efficiency of electroluminescence (EQEEL) for PbI2/FAI = 1.16. f,g) PL decay of the perovskite films for f) PbI2/
FAI = 1.0 and g) PbI2/FAI = 1.16. h) Voc as a function of light intensity represented by Jsc. Reproduced with permission.[183] Copyright 2016, American
Association for the Advancement of Science.

the final device performance. However, it is highly desirable
to deeply understand the relation between precursor solution
chemistry and film morphology, as well as the final device
performance. Yan et al. first demonstrated that perovskite pre-
cursor solutions for PSCs colloidal dispersion solution rather
than real solutions through typical Tyndall effects.[188] They
investigated the effect of ratios of MAI:PbI2 or MACl:MAI:PbI2
on colloid size, film morphology and device performance.
It was found that the colloid is formed by soft coordination
complex between organic and inorganic components, where
soft coordination complex is in the form of lead poly-halide
framework. It is interesting that colloid size, film morphology
and device performance are highly dependent on stoichio-
metric ratio of organic:inorganic components. Through tuning
coordination degree and mode in original colloidal solution, the
excess organic halide can decrease the colloidal size and tune
morphology of coordination framework and thus final perov­
skite films. Based on optimized precursor component ratio

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Figure 15.  a) Schematic illustration of Lewis acid–base adduct approach to prepare MAPbI3 perovskite films, where excess MAI was formed at GBs.
b) Statistical photovoltaic parameters of Jsc, Voc, FF, and PCE as a function of x in (1 + x) MAI: PbI2. c) TRPL data for the MAPbI3 films prepared
from stoichiometric solution and nonstoichiometric solution with either excess MAI or deficient MAI. d) c-AFM images for the MAPbI3 perovskite
films for x = 0 and 0.06 measured at a bias voltage of 2 V in the dark. Insets show the corresponding topographies. Reproduced with permission.[14]
Copyright 2016, Nature Publication Group.

of 1:1.05:0.95 of MACl:MAI:PbI2, high quality perovskite film
was fabricated and the best-performing device delivered a PCE
of 17% without evident hysteresis. Although the above work
demonstrated that colloid size, film morphology and device
performance can be tuned through varying the ratio of organic
to inorganic compound in precursor solution, the method still
suffers from the following challenges. First, it is difficult to
remove the 1D PbI2 rod-like structure in the extensively utilized
stoichiometric 1:1 precursor solution through incorporation of
excess organic halide. Second, this method is not appropriate
for application in presently optimized high-performance triple-
cation perovskite composition because specific perovskite
composition ratio could change. In order to address the above
problems, Snaith group developed an effective approach, where
the acidic additives (HI or HBr) were added to FA0.83Cs0.17Pb
(Br0.2I0.8)3 perovskite precursor to trigger the dissolution of

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colloids in precursor solution.[189] When the concentration of
hydrohalic acids was fixed, the colloidal size in the precursor
solution can be controlled by varying solution aging time. Opti-
mization of aging time induced large grain size with improved
crystallinity, which was ascribed to the impact of colloids on
the crystal nucleation and growth kinetics. As a consequence,
significantly enhanced charge-carrier mobility and remarkably
reduced micro strain was demonstrated. Finally, the optimized
device exhibited a PCE of 18.8%. The above work strongly
indicates that deep understanding and rational control of pre-
cursor solution chemistry is crucial to improve morphology of
perovskite films and accordingly photovoltaic performance of
final devices.
3.5.2. Precursor Solvent Engineering
Except for stoichiometric ratio in the precursor solution, pre-
cursor solvents also play a key role in obtaining high quality
perovskite films with less defects and thus suppressed nonra-
diative recombination losses. At the early stage of PSCs devel-
opment, single polar solvents such as dimethylformamide
(DMF) or γ-butyrolactone (GBL) were usually used to prepare
perovskite precursor solution.[3,5,38] Because of relatively poor
solubility of PbI2 in DMF or GBL as compared to dimethyl sul-
foxide (DMSO), it is a huge challenge to prepare high quality
perovskite films with full coverage, less pin-hole and smooth
surface. In addition, weak coordination between DMF or GBL
and PbI2 makes PbI2 easily preferentially crystalize out from
precursor solution during spin-coating, resulting in poor
morphology.[41,42,44,46,190] In order to overcome the fast crystal-
lization problem of PbI2, DMSO as an alternative precursor
solvent attracts more and more attentions due to its much
stronger coordination ability with PbI2 compared with DMF
and GBL.[41,42,44,46,190] However, DMSO cannot be employed as
single precursor solvent in one-step deposition method consid-
ering its very high viscosity.[46] Wu et al.[190] used strongly coor-
dinated DMSO to take the place of weakly coordinated DMF to
prepare PbI2 solution in sequential deposition process. It was
found that it can effectively retard the crystallization of PbI2
and thus overcome the incomplete conversion problem of PbI2.
As a result, highly reproducible planar PSCs was fabricated
with a PCE of 13.5%. A series of PbI2(DMSO)x (0 ≤ x  ≤ 1.86)
complexes can be obtained through employment of mixed
DMF/DMSO solvents, which was formed by intermolecular
self-assembly.[42] Based on PbI2(DMSO)1.22 complex as the pre-
cursor of PbI2, the optimized device showed a PCE of 17.16%.
Besides, DMF/DMSO mixed solvents was utilized to prepare
bilayer mesostructured PbI2/TiO2 films, accomplishing rapid
and complete transformation of PbI2 into the perovskite for the
20.75% efficient PSCs.[191] Subsequently, DMF/DMSO mixed
solvents strategy was adopted in most of the highly efficient
PSCs based on two step sequential deposition approach.[12,56]
DMSO has been also widely employed in one-step method dep-
osition. As we mentioned in introduction, Seok and co-workers
demonstrated the formation of intermediate phase MAI–PbI2–
DMSO as confirmed by FTIR and XRD measurements.[41]
Combined with toluene as antisolvent, extremely uniform and
dense perovskite films were formed on mesoporous layers and
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the corresponding device showed a certified PCE of 16.2%
with no hysteresis. Motivated by this work, other groups also
demonstrated the formation of MAI–PbI2–DMSO interme-
diate phase and then investigated how intermediate phase
affects nucleation and crystallization of perovskite and mor-
phology as well as the final device performance.[44,46,50,51,192]
This implies that formation of MAI–PbI2–DMSO intermediate
phase in one-step method and PbI2–DMSO in two step method
plays a crucial role in fabricating high-quality perovskite films
required for highly efficient PSCs with minimizing nonradia-
tive recombination losses. In order to explore other Lewis bases
as a possible alternative to DMSO, thiourea with sulfur donor
was used to form Lewis acid–base adduct with Lewis acid PbI2,
where FAI·PbI2·((DMSO)1−xthioureax) was formed by par-
tial substitution of thiourea for MDSO.[43] Based on the opti-
mized composition of FAI·PbI2·((DMSO)0.8thiourea0.2), much
increased PCE and reduced hysteresis was proved. Because
of better charge transport and the reduced trap states, thio-
urea was considered to be better than DMSO for the FAPbI3
system. It means that the formation of specific intermediate
phase through specific Lewis acid–base interaction is critical for
preparing high quality perovskite films. Additionally, 1-methyl-
2-pyrrolidinone (NMP) was used as precursor solvent in hole
conductor–free fully printable PSCs based on carbon elec-
trode.[46] Chen et al. found that MAI–PbI2–NMP intermediate
phase can be formed but less stable than intermediate phases
MAI–PbI2–DMSO and MAI–PbI2–DMF due to stronger coor-
dination ability of DMSO and DMF than NMP as confirmed by
FTIR and XRD.[46] In addition, NMP-based precursor solution
shows poor wettability for mesoporous layer and carbon layer.
As the results of poor intermediate phase stability and poor
wettability, the worst photovoltaic performance was observed in
NMP-based device among all the investigated devices. However,
recently the higher interaction energy was found by Lee et al.[45]
between the FA and NMP (−1.407 eV) than between FA cation
and DMSO (−1.253 eV), which is in good accordance with
higher interaction energy of FAI·PbI2·NMP (−2.413 eV) than
FAI·PbI2·DMSO (−2.138 eV). As a result, the device based on
FAI·PbI2·NMP Lewis acid–base adduct using FA0.98Cs0.02PbI3
as absorber showed a high PCE up to 20.19%, which is attrib-
uted to much better film quality as compared to control films.
It was proposed that three fundamental aspects should be con-
sidered when engineering Lewis base solvents, including high
hydrogen bond accepting ability and low hydrogen bonding
donor ability, steric hindrance of electron donating atom, and
the hardness and softness matching of the Lewis acid and
base. This work highlighted that not only interaction between
solvents and PbI2 but also interaction between solvents and
organic components such as MAI or FAI should be taken into
account simultaneously.
3.6. Additive Engineering
Apart from perovskite composition engineering, additive engi-
neering also can suppress SRH nonradiative recombination by
increasing grain size, passivating defects and improving carrier
transport and separation. Effect of additives on photovoltaic
performance and stability was systematically reviewed from the
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perspective of additive category.[49] Here, we Table 3.  Photovoltaic performance of PSCs via additive engineering. C and T in parentheses
discuss the role of additives in suppressing stand for control device and target device, respectively.
SRH nonradiative recombination.
Additives Jsc [mA cm−2] (C/T) Voc [V] (C/T) FF (C/T) PCE[%] (C/T) Ref.
DIO 16.0/17.5 0.90/0.92 0.62/0.73 9.0/11.8 [193]
3.6.1. Grain Boundary Regulation IPA 22.41/23.54 1.070/1.103 0.67/0.76 16.02/19.70 [194]
HPA 17.2/20.4 1.07/1.07 0.72/0.74 13.20/16.20 [195]
As we mentioned above, it is a feasible and
effective approach to minimize the SRH HaHc 22.01/22.42 1.05/1.10 0.75/0.76 16.85/18.69 [196]

nonradiative recombination losses through 4-ABPACl 15.6/22.11 0.86/1.00 0.66/0.75 8.8/16.0 [197]
increasing grain size and decreasing the 2-NAM 22.08/22.79 1.06/1.09 0.77/0.79 18.00/19.33 [198]
number of GBs in perovskite films. In order MAAc+TSC-1 –/22.78 –/1.108 –/0.77 –/19.58 [199]
to realize the above purpose, additive engi-
BQ 18.23/21.03 1.01/1.02 0.58/0.72 10.73/15.66 [200]
neering strategy was usually adopted. Liang
MAF 21.7/22.7 1.16/1.14 0.72/0.71 19.1/19.5 [201]
et al.[193] proposed additive engineering
method, where 1,8-diiodooctane (DIO) was CC2 21.17/22.62 1.09/1.09 0.78/0.78 17.96/19.21 [202]
employed to improve the crystallization of 2-PTU 21.13/22.03 1.06/1.10 0.69/0.75 15.5/18.2 [203]
perovskite film. They proposed that DIO t-BP 18.94/21.39 1.03/1.06 0.74/0.77 14.49/17.41 [204]
could facilitate homogenous nucleation and
TDZDT 21.23/22.77 1.04/1.10 0.71/0.76 15.61/19.04 [205]
modulate the kinetics of crystal growth.
PEG –/22.5 –/0.98 –/0.72 8.0/16.0 [206]
Improved crystallinity and morphology would
be beneficial for charge transport. Except for PU 20.14/22.12 1.036/1.051 0.79/0.80 16.4/18.7 [207]
DIO solvent additive, isopropanol was used PVAm·HI 20.8/22.1 1.04/1.09 0.59/0.67 12.7/16.3 [208]
to increase grain size, as revealed by the SEM PMMA –/23.7 –/1.14 –/0.78 –/21.6 [26]
study, and enhance crystallization as con-
NaI 20.97/21.16 1.06/1.10 0.70/0.78 15.56/18.16 [209]
firmed by XRD data.[194] As listed in Table 3,
KCl 16.60/19.42 0.90/1.04 0.76/0.75 11.40/15.08 [210]
the PCE of control device was increased from
16.02% to 19.70%. Inorganic acids such as ZnCl2 21.09/22.04 1.05/1.09 0.74/0.76 16.4/18.2 [211]
HCl, HBr, and HI have received consider- N-RGO 20.77/21.80 1.12/1.15 0.73/0.74 17.31/18.73 [212]
able attention as potential additives. Gen- CNPs 22.2/22.1 1.12/1.16 0.71/0.71 17.7/18.3 [213]
erally, several unique roles were expected:
Pb(SCN)2 21.55/21.43 1.09/1.11 0.70/0.76 16.41/18.15 [214]
increase in precursor solubility; improve-
Pb(SCN)2 –/18.53 –/1.25 –/0.79 –/18.27 [215]
ment of stability through reducing oxidized
I2 to I−; suppression of poor crystallization Pb(SCN)2 22.46/22.05 0.944/0.995 0.66/0.74 13.97/16.20 [216]
via forming intermediate phase between Pb(SCN)2 21.26/22.08 0.970/1.009 0.67/0.76 13.9/17.0 [217]
PbI2 and inorganic acid. Encouraged by the MASCN –/22.33 –/1.085 –/0.77 –/18.76 [218]
above function of inorganic acid, Zhang
GUTS 21.46/21.6 1.041/1.077 0.65/0.70 14.59/16.37 [219]
et al.[195] added hypophosphorous acid (HPA)
in the precursor solution, which significantly KSCN 19.33/20.45 0.965/1.065 0.68/0.76 12.73/16.59 [220]

improved the film quality with enhanced

carrier lifetime. Furthermore, they claimed that HPA inhib-
ited formation of metallic lead by reducing iodide vacancies.
As a consequence, PCE was improved from 13.20% to 16.20%
after incorporation of HPA. Except for inorganic acids, exten-
sive attention was also focused on organic halide salt additives.
On one hand, heteroatoms like nitrogen could form hydrogen
bond with H atom in MA+ or FA+. On the other hand, halides
in additives can be incorporated into perovskite crystal or pro-
mote the crystallization of perovskite. Based on the above con-
sideration, bifunctional hydroxylamine hydrochloride (HaHc)
was used to improve perovskite film quality.[196] First, Cl− in
HaHc was thought to assist the formation of high-quality pero-
vskite film with increased grain size and reduced defect density.
In addition, OH in HaHc was considered to form hydrogen
bond with I− in perovskite film. As a result, better thermal
and air stability were demonstrated in HaHc-based device as
compared to control device. Li et al.[197] reported the incorpo-
ration of bifunctional butylphosphonic acid 4-ammonium chlo-
ride (4-ABPACl) additive in PSCs (Figure 16a,b), which could
crosslink the neighboring grains through hydrogen bonding
between I− in octahedral PbI64− and PO(OH)2 or NH3+ end
groups in 4-ABPACl (Figure 16c). Uniform and continuous
morphology was found in 4-ABPACl modified film (Figure
16d). Correspondingly, 4-ABPACl-based device exhibited sig-
nificantly enhanced PCE relative to counterpart (Figure 16e)
and the champion device with 4-ABPACl modification gave a
PCE of 16.55% (Figure 16f). From viewpoint of potential inter-
action between CO or NH3+ and PbI2, Wu et al.[198] designed
CO functionalized hydrophobic ammonium-based additive
2-(6-bromo-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)ethan-
1-ammonium iodide (2-NAM) for PSCs (Figure 17a). UV and
XRD results showed that 2-NAM would not be incorporated
into perovskite lattice but located at GBs (Figure 17a). Never-
theless, grain size was significantly enhanced upon addition of
2-NAM (Figure 17b,c), which was related to strong Lewis acid–
base interaction between CO and Pb2+. As mentioned previ-
ously, GBs will be reduced as grain size increases, which is in
accordance with enhanced PL lifetime as shown in Figure 17d.

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modulate the morphology and crystalliza-

Figure 16.  a) Schematic illustration of the complete PSC used in this work. b) Chemical struc- part in crystallization and nucleation.[209,211]
ture of alkylphosphonic acid ω-ammonium chlorides. c) Role of bifunctional alkylphosphonic Halide ions in metal halide salts could affect
acid ω-ammonium chlorides showing interaction between ω-ammonium chlorides and two crystallization kinetics via chelating with
neighboring perovskite grains. d) Top-view SEM images of perovskite films before and after
4 ABPACl treatment. e) Comparison of PCE before and after addition of 4 ABPACl additive.
f) J–V curves for the best-performing device based on 4-ABPA-anchored perovskite. Reproduced
with permission.[197] Copyright 2015, Nature Publication Group.
As a result, PCE was increased from 17.1% to 18.6% when
2-NAM was incorporated.
Ionic liquid mixed with molecule was used as a hybrid addi-
tive, where methylammonium acetate (MAAc) as an ionic
liquid additive and thiosemicarbazide (TSC-1) as a molecular
additive were used (see chemical structure in Figure 18a) to
tion of MAPbI3 via the one-step spin coating
process (Figure 18b).[149] As compared to a
single additive of MAAC, the hybrid addi-
tive of MAAc and TSC induced a substantial
enlargement of grain size, which is indica-
tive of importance of synergistic effect of
the hybrid additive system (Figure 18c,d).
As revealed in Figure 18e, many weak peaks
except for two main peaks at ≈14.0° (110)
and ≈28.4° (220) were detected in the film
prepared by aid of an single MAAC additive,
while strong two peaks were observed for
the film prepared based on the hybrid addi-
tive, indicating a preferential crystal growth
of (110) faces parallel to the substrate. Large
grain, and thereby reduced GBs, and pre-
ferred orientation are responsible for pro-
longed carrier lifetime as estimated from PL
data (Figure 18f). This method was proved
to be one of the effective methods because
high PCE of 19.58% was demonstrated
(Figure 18g). Other ionic liquids were also
tested. Seo et al.[201] incorporated an ionic
liquid methylammonium formate (MAF)
into perovskite precursor solution to prepare
high-quality perovskite film. Additionally,
Zhang et al.[202] used functionalized imidazo-
lium iodide modified with CH2CHCH2
(CC2), CH2CCH (CC3), or CH2CN
(CN) groups and found that the tested ionic
liquids increases MAPbI3 grain size but only
CC2-functionalized ionic liquid improved PL
decay lifetime and PCE. They also studied
physical properties of (CC2)PbI3, (CC3)PbI3
and (CN)PbI3.
Similarly to organic halide salts, metal
halide salts have been proved as an impor-
tant additive for improving crystallization
and morphology of perovskite films. NaI,[209]
KCl,[210] and ZnCl2[211] were used as additives
to increase grain size and improve photovol-
taic performance of PSCs. Regarding the roles
of metal halide salts, metal ion is considered
to partially replace the Pb ion,[211] and/or take
Pb2+.[210] It was also proposed that metal
or halide ions could recrystallize the small
grains and thereby passivate GBs and inter-
face defects.[210] Except for inorganic metal
halide salts, hydrophobic carbon materials
(including nitrogen-doped reduced graphene oxide (N-RGO)[212]
and carbon nanoparticles (CNPs)[213]) were employed to con-
trol the grain size. Similar to the halide ions (including metal
halide and organic halide salts) playing a key role in control-
ling and regulating the morphology and crystallization of pero-
vskite films, pseudohalogen ions (especially for SCN−) also can

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Figure 17.  a) The molecular structure of 2-(6-bromo-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)ethan-1-ammonium iodide and schematic illustration
of perovskite structure showing its role in perovskite structure. Top-view SEM images of perovskite films b) after and c) before addition of 2-NAM.
d) TRPL spectra of the reference and 2-NAM-treated perovskite films. Reproduced with permission.[198] Copyright 2017, Wiley-VCH.

control and modulate the crystallization of perovskite films
via its unique mechanism.[214,216–221] For example, the use of
a small amount of Pb(SCN)2 in precursor solution was found
to change perovskite morphology significantly.[214] Large grains
along with almost no GBs were obtained (Figure  19a–d) and
gradual increase in crystallinity was observed as the Pb(SCN)2
additive increased up to 5% (Figure 19e). Thanks to signifi-
cantly improved crystal quality, remarkably reduced nonradia-
tive recombination accounts for dramatically increased Voc and
FF along with reduced hysteresis (Figure 19f). Regarding the
role of SCN−, HSCN, and CH3NH2 gases were produced by the
reaction between CH3NH3+ cations and SCN− anions during
crystallization and the CH3NH2 gases enlarged the grain size
and crystallinity of perovskite films. Apart from Pb(SCN)2,
MASCN was also tried to fabricate the large-sized and high-
quality perovskite films at room temperature.[218] Grain size
increased (Figure 20a), crystallinity was simultaneously
improved (Figure 20b) and optical absorption was improved
with increasing MASCN concentration (Figure 20c). As a
result, PCE of 18.76% was achieved (Figure 20d). Regarding the
role of MASCN, authors explained from Tindall-effect tests and
dynamic light scattering (DLS) measurements that coordina-
tion between SCN− and Pb2+ can enlarge the precursor aggre-
gates up to the microscale before spin-coating. Moreover, SCN−
could compete with DMSO, in terms of Lewis basicity, for coor-
dinating with Pb2+ and then DMSO easily escaped from the
film even at room temperature with the assistance of vacuum.
SCN− also could react with MA+ to form volatile CH3NH2
and HSCN gases that led to enlarging grain size. As listed
in Table 3, except for Pb2+ and MA+ cations, SCN-containing
salts with other cations like K+[220] and guanidinium[219] enabled
grain size to grow, which supports that enlargement of grain
size is mainly due to SCN− instead of cations.
In PSCs, additive engineering can also be performed either
directly adding additional additive not belong to precursor
compound or adding excess precursor components into pre-
cursor solution. Generally, additionally added additives just
indirectly affect the nucleation and crystallization process of
perovskite. However, adding excess precursor components
(like 3:1 of MAI:PbCl2 or MAI:Pb(Ac)2) can directly affect the
nucleation and crystallization process of perovskite, which
is corresponding to addition of a large amount of additive
MACl or MAAc (Ac = acetate).[222–230] As we discussed above,
the introduction of Cl into perovskite precursor solution can
improve the crystallization and morphology of perovskite films
and thus increase carrier mobility, carrier diffusion length
and lifetimes, finally contributing to enhanced photovoltaic
performance of device with a inhibited nonradiative recombi-
nation losses.[138,139,141,222,224] Exploring other lead sources as
starting materials is extremely meaningful to enrich synthetic
methods of perovskites except for the commonly used PbI2 and
PbCl2. For the purpose, nonhalide lead source of lead acetate
(Pb(Ac)2) was employed to prepare perovskite film in planar
PSCs.[230] The perovskite precursor solution was prepared by
dissolving 3:1 of MAI:PbX2 (X = Cl, I, and Ac) into DMF, which
led to MAPbI3 final composition regardless of lead sources
as revealed by XRD measurement. It means that excess MAX
(X = Cl, I, and Ac) can escape from the perovskite films during
crystallization if annealing temperature is high enough. As we
mentioned above, it is still argued whether or not Cl is finally

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Figure 18.  a) Additive engineering using a hybrid additive of ionic liquid MAAc and molecular TSC. b) The additive-assisted one-step coating procedure,
where antisolvent dripping or vacuum treatment was not applied. Top-view SEM images of MAPbI3 films prepared based on c) a single additive of
MAAc and d) a hybrid additive with MAAc and TSC. e) XRD patterns of the MAPbI3 films based on a single additive and a hybrid additive. f) TRPL data
of the MAPbI3 films fabricated on the glass substrate. g) J–V curves of large area devices (1.025 cm2) employing MAPbI3 prepared based on a hybrid
additive. Reproduced with permission.[199] Copyright 2017, Wiley-VCH.

incorporated into perovskite crystal. Since ionic radius of Ac−
ion (0.162 nm) is much smaller than Cl− (0.184 nm), it is more
difficult for Ac− to be incorporated into the lattice of MAPbI3
in comparison with Cl−.[230] TGA results showed that MAAc
has a lowest decomposition temperature than MAI and MACl,
which means that it is easy to be driven out from the film.
Compared with PbI2 and PbCl2, Pb(Ac)2-based perovskite film
exhibited faster crystallization as a result of less stable MAAc
than MAI and MACl. SEM results showed much smoother
film with larger grain size obtained with full coverage through
Pb(Ac)2 route than PbI2 and PbCl2, which led to higher PCE of
14.0% ± 0.7% for Pb(Ac)2 than 12.00% ± 1.0% for PbCl2 and
9.3%  ± 0.8% for PbI2. Additionally, a PCE of 12.5% was real-
ized in inverted planar PSCs using Pb(Ac)2 as precursor lead
source with excellent reproducibility and less hysteresis.[229]
Effect of different lead sources of Pb(Ac)2, Pb(NO3)2, Pb(acac)2
(acac = (CH3COCHCOCH3)−), and PbCO3 on morphology and
device performance was systematically performed.[228] It was
found that device performance is highly dependent on sub-
strates and anions in different lead sources. In order to gain
deep insight into the origin of different crystallization kinetics,
morphology and device performance induced by different lead
sources, Moore et al.[227] calculated activation energy (Ea) from
precursor-to-perovskite transition in thin films and found that
change in Ea is strongly dependent on anions in different lead
sources. The Ea was determined to be 97.3 kJ mol−1 for I−,
86.6 kJ mol−1 for Cl−, 67.5 kJ mol−1 for Ac−, and 56.6 kJ mol−1
for NO3−. The theoretical calculation results show that MAAc
is easier to escape from the perovskite films as compared
to MAI and MACl, which is in excellent agreement with the
reported experimental results.[230] In light of the above suc-
cessful application of Pb(Ac)2, Zhao et al.[226] further optimized

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Figure 19.  Top-view SEM images of MAPbI3 films a) without and b) with 5% Pb(SCN)2 in the precursor. Cross-sectional SEM images of the full devices
employing MAPbI3 films c) without and d) with 5% Pb(SCN)2. e) XRD patterns depending on the Pb(SCN)2 concentration. f) J–V curves of the PSCs
based on MAPbI3 films with and without 5% Pb(SCN)2. Reproduced with permission.[214] Copyright 2016, Wiley-VCH.

the PCE of planar PSCs based on Pb(Ac)2 as starting material
through incorporating MABr as additive. Upon addition of
MABr additive, improved uniformity and surface smoothness
was achieved as confirmed by AFM and SEM results. Besides,
improved charge extraction was observed after the introduction
of MABr. As a consequence, significantly enhanced PCE was
demonstrated and the MABr-based device delivered a highest
PCE of 18.3%. Luo et al.[225] developed a dual-source precursor
approach for highly efficient planar PSCs, where dual-source
precursor was prepared by dissolving the two precursor solu-
tions together (PbAc2:MAI (1:3) and PbI2:FAI (1:1) in DMF,
respectively). Based on the dual-source precursor method, high-
quality and mirror-like perovskite films were obtained without
using additional antisolvent process. As a result, the best-
performing device produced a PCE of 20.15% with negligible
hysteresis.
Organic small molecules with specific functional groups
(such as CO, CS, NH2, etc.) also can act as excel-
lent additives for preparing high-quality perovskite film with
reduced recombination. Considering N-donor and S-donor
in 2-pyridylthiourea that can potentially coordinate with
Pb2+, 2-pyridylthiourea was added to perovskite precursor

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Figure 20.  a) Top-view SEM images, b) XRD patterns, c) UV–vis spectra, and d) J–V curves for the MAPbI3 perovskite films depending on the con­
centration of MASCN additive in the precursor. The scale bar in the SEM images is 1 µm. Reproduced with permission.[218] Copyright 2017, Royal
Society of Chemistry.

as additive,[203] which facilitated formation of uniform and
compact perovskite film with increased grain size through
suppressing perovskite crystallization. In addition, 1,3,4-thiadia-
zoleidine-2,5-dithione (TDZDT) containing two CS moieties
was employed to modulate MAPbI3 perovskite crystal growth.[205]
The presence of TDZDT additive increased grain size, reduced
defect density and eventually improved PCE from 15.61%
to 19.04%. Wu et al.[204] included 4-tert-butylpyridine (t-BP)
with Lewis base property in chlorobenzene antisolvent, which
improved the perovskite film quality and increased grain size
via suppressing perovskite nucleation. As a result, PCE was
improved due to improved Voc and Jsc. Besides organic small
molecules, polymer additives was found to improve not only
quality of perovskite film but also the stability especially toward
moisture.[26,206–208] Poly(methyl methacrylate) (PMMA) is good
example for this purpose. PMMA was dissolved in chloroben-
zene antisolvent, which induced high quality perovskite film for
high PCE of over 21% (Figure 21a,b).[31] Thanks to the increased
grain size and improved film quality (Figure 21c–e), nonradiative
recombination was significantly reduced (Figure 21f). It was pro-
posed that CO would interact with Pb2+ to retard the crystal
growth and improve the crystallinity of the perovskite film.
3.6.2. Defect Passivation via Additive Engineering
In polycrystalline perovskite film, all kinds of defects exist
(intrinsic and extrinsic), such as vacancies of I−, Pb2+, MA+,
or FA+, undercoordinated anion or cation, extrinsic impurity,
etc. These positively or negatively charged defects are presum-
ably related to SRH nonradiative recombination losses. Addi-
tive engineering as one of the important passivation strategies
emerges and attracts considerable attentions for the purpose
of maximizing efficiency. As listed in Table 4, various additives
have been developed to passivate the defects or trap state and
great progresses have been made. It can be concluded from
Table 4 that additives can be incorporated into perovskite film
according to the following several ways. i) The additive is added
to the one-step precursor solution. ii) The additive is incorpo-
rated in the solution of organic sources in two-step deposition.
iii) The additive is introduced into antisolvents. iv) The additive
is introduced by post-treatment. v) The additive is introduced
by thermal diffusion (like PCBM). The first three ways are able
to not only passivate the defects but also affect the crystalliza-
tion process, whereas the latter two methods potentially only
passivate defects.

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Figure 21.  a) Cross-sectional SEM image of a full device fabricated by the polymer-templated nucleation and growth (PTNG) method. b) J–V curves of
the champion PSC prepared based on the PTNG method. Top-view SEM images of perovskite films with different concentrations of c) 0 mg mL−1 and
d) 0.6 mg mL−1 PMMA. e) XRD patterns of perovskite films depending on concentrations of PMMA. f) TRPL spectra of perovskite films without and
with 0.6 mg mL−1 PMMA. Reproduced with permission.[26] Copyright 2016, Nature Publication Group.

In 2014, Abate et al. used iodopentafluorobenzene (IPFB)
with halogen bond donor to passivate undercoordinated halide
ions acting as halogen bond acceptor, which diminished SRH
nonradiative recombination losses,[231] leading to increments
of Voc and FF. Pyridine and thiophene with Lewis base prop-
erty enabled the electronic passivation of undercoordinated Pb
atoms, giving rise to significantly enhanced carrier lifetime.[232]
With this Lewis base passivation method, PCE was improved
from 13.0% (control) to 15.3% for thiophene and 16.5% for
pyridine. Recently, Guo et al.[240] introduced IT-4F nonfullerene
Lewis base into antisolvent to passivate the defects in perovskite
films and then achieved improved Voc. They proposed that IT-4F
could effectively passivate ionic defects induced by positively
charged undercoordinated Pb2+, which reduced trap density and
elongated carrier lifetime. Motivated by the above passivation
using Lewis bases, Niu et al.[242] systematically investigated the
effect of Lewis acid (PCBM) and Lewis base (ITIC, DTS, and
DR3T) on photovoltaic performance. It was found that all of the

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Table 4. Photovoltaic performance of PSCs achieved by perovskite were tested, where polymer poly(4-vinylpyridine) (PVP), poly-
defect passivation. C and T represent control device and target device, ethyleneimine (b-PEI), and polyacrylic acid (PAA) were intro-
respectively. Additive column—IPFB: iodopentafluorobenzene; Py:
pyridine; GA: guanidinium; F4TCNQ: 2,3,5,6-tetrafluoro-7,7,8,8-
duced in organic source solution (Figure 22a) and investigated
tetracyanoquinodimethane; Cu(Tu)I: Cu(thiourea)I; PVP: polymer to see the effect of different polymer additives on photovoltaic
poly(4-vinylpyridine); PBDB-T: poly[(2,6-(4,8-bis(5-(2-ethylhexyl) thio- performance in normal planar PSCs.[243] It was found that PVP-
phen-2-yl)-benzo[1,2-b:4,5-b′] dithiophene))-alt-(5,5-(1′,3′-di-2-thienyl- modified PSC showed the highest PCE of 20.2% among the
5′,7′-bis(2-ethylhexyl) benzo[1′,2′-c:4′,5′-c′] dithiophene-4,8-dione))]. studied polymers (Figure 22b). The enhanced PCE was mainly
as a result of markedly improved Voc and FF, which was related
Additives Jsc Voc FF (C/T) PCE Ref.
to remarkably increased carrier lifetime (Figure 22c). Except for
[mA cm−2] [V] (C/T) [%] (C/T)
(C/T) neutral molecules, guanidinium cation was found to passivate
the defects in perovskite films through suppressing formation
IPFBd) 23.80/23.38 1.02/1.06 0.57/0.67 13.0/15.7 [231]
of iodide vacancies and passivating undercoordinated sites at
Pyd) 20.7/24.1 0.95/1.05 0.68/0.72 13.1/16.5 [232] grain boundaries.[233] Liu et al.[235] used strong electron acceptor
GAa) 21.27/21.24 1.025/1.071 0.75/0.75 16.35/17.13 [233] F4TCNQ to passivate the perovskite defect. This passivation was
Cu(Tu)I a) 20.5/21.6 1.00/1.11 0.48/0.77 8.9/18.5 [234] realized by reducing metallic lead defects and iodide vacancies
CH3NH2a) 22.14/22.64 1.083/1.107 0.70/0.73 16.77/18.44f) [89] in the perovskite crystal lattice, leading to improved charge sep-
aration and transfer, enhanced and balanced charge mobility, as
F4TCNQa) 19.42/19.57 1.054/1.062 0.74/0.80 15.1/16.6 [235]
well as suppressed recombination. It is worth to note that Liu
C60a) 22.3/23.5 0.754/0.736 0.74/0.79 12.5/13.7 [236] et al.[89] reported chemical reduction strategy in which CH3NH2
PCBMa) 19.7/23.3 1.02/1.04 0.67/0.65 13.5/15.7 [237] additive was introduced into perovskite precursor solution and
PCBMe) – – – 7.3/14.9 [33] CH3NH2 reduced unionized I2 into I− and dissociated polyi-
PCBMa) 14.4/17.3 0.98/1.07 0.65/0.73 8.1/13.6 [238] odide colloids in the precursor solution via chemical reaction/
coordination, which greatly contributed to substantially reduced
PCBMa) 22.47/23.03 0.96/1.10 0.58/0.67 12.5/17.1 [239]
defect density and extended carrier lifetime. This led to a PCE
IT-4Fc) 20.79/21.35 1.06/1.12 0.71/0.77 15.59/18.35 [240] of 20.02%. Inorganic additive such as CaI2 was tried instead of
PBDB-Tc) 21.73/22.39 1.075/1.113 0.74/0.78 17.28/19.38 [241] excess PbI2, which was found to be more effective in terms of
DR3T c)
– – – 17.52/19.28 [242] passivation of defects.[244] In addition, quaternary ammonium
PVPb) 21.82/21.74 1.09/1.15 0.76/0.81 18.05/20.23 [243] or quaternary phosphonium anions and cations salts (tetrabutyl
ammonium iodide salt: TBAI; tetrabutyl phosphonium iodide
CaI2a) – – – 16.1/19.3 [244]
salts: TBPI; tetraphenyl phosphonium iodide salts: TPPI; tet-
−b) 23.5/24.1 1.07/1.1 0.81/0.82 20.3/21.6 [12]
I3 raphenyl phosphonium bromide salts: TPPBr; tetraphenyl
a)The additive was added to the one-step precursor solution; b)The additive was phosphonium chloride salts: TPPCl) were used as additives to
incorporated in the solution of organic sources in two-step deposition. c)The tune the perovskite crystallization and passivate the defects in
additive was introduced into antisolvents. d)The additive was introduced by post- it.[245] Significantly different morphology and crystallinity were
treatment. e)The additive was introduced by thermal diffusion. f)Average photo­ observed for perovskite films with TPPI, TPPBr, and TPPCl,
voltaic parameters.
which indicates that anions of additives have a pronounced
effect on the growth kinetics of perovskite films. Compared with
molecules used effectively passivated the defects in perovskite TPPI, TPPBr, and TPPCl, TBAI- and TBPI-based films show
films as reflected by improved Voc. Significant PL quenching unique morphology because the crystals were grown toward
and long carrier lifetime for the modified perovskite films are the lateral direction with much larger grain size over 10 µm.
indicative of effective passivation of defects and better charge The authors speculated that TBAI and TBPI could interact with
separation and transportation as well. The best performance perovskite and formed layered perovskites, which should be
was observed for DR3T-based device, which was attributed to responsible for their poor performance. As a result, the TPPI-
the following two reasons. First, DR3T effectively passivated the based device showed a highest PCE up to 11.7% among the
perovskite film. Second, CB and VB positions of DR3T matched investigated additives. This work suggests that anion or cation
well with those of MAPbI3 and spiro-MeOTAD. Besides small in quaternary ammonium or quaternary phosphonium salts
molecules like DR3T, PBDB-T polymer with Lewis base prop- play an important role in affecting morphology and crystalliza-
erty and proper energy level alignment was introduced in tion of perovskite films and the final device performance.
antisolvent, which could effectively passivate perovskite film It is widely recognized that PCBM has the following three
and facilitate hole transport and extraction.[241] As expected, functions. First, PCBM as efficient electron acceptor can pro-
the π-conjugated polymer PBDB-T was found to trigger a het- mote electron transport and extraction. Second, PCBM can
erogeneous nucleation over the perovskite precursor film and improve the device moisture stability because of its hydropho-
passivate the trap states of the mixed perovskite film through bicity. Third, PCBM can be located at GBs in perovskite film
the forming Lewis acid–base adducts between lead and oxygen and passivate the defects at GBs. In late 2014, Shao et al.[33] first
atom in PBDB-T. In addition, PBDB-T improved hole transport found that PCBM could diffuse into GBs of the perovskite layer
and extraction, along with improved moisture stability due to via thermal annealing and thus effectively passivate the defects
hydrophobic nature of PBDB-T. The above results strongly indi- in inverted planar PSCs (Figure 23a,b), leading to higher PCE
cate that incorporation of multifunctional additive is critical for along with reduced hysteresis (Figure 23c). Thermally annealed
achieving stable and efficient PSCs. Several polymeric additives PCBM was able to passivate not only deep trap state but also

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Figure 22.  a) Chemical structures of PAA, PVP, and b-PEI and their potential interactions with perovskite surface. b) J–V curves of PSCs based on
pristine and PVP, PAA, and PEI-modified perovskite films. c) Comparison of TRPL decay profile of the pristine perovskite with polymer-modified ones.
Reproduced with permission.[243] Copyright 2017, American Association for the Advancement of Science.

shallow traps (Figure 23d). A significant increase in carrier
lifetime for surface recombination but a slight improvement
in carrier lift time for bulk recombination, as measured by
impedance in Figure 23e,f, indicates that surface recombina-
tion relatively dominates in perovskite film rather than bulk
recombination. Xu et al.[238] proposed that PCBM could passi-
vate the antisite defects during the perovskite self-assembly as
confirmed by theory and experiment. Other groups also con-
firmed the effect of PCBM on passivating the defects in pero-
vskite films.[237,239] C60 was reported to have similar passivation
effect for defects in perovskite films.[236] When considering the
good hole conductivity of CuI[86] and the complexation of thio-
urea with Pb2+,[43] Ye et al.[234] first synthesized the novel p-type
conductor Cu(thiourea)I [Cu(Tu)I] and then incorporated it into
perovskite precursor solution for inverted PSCs, which deliv-
ered high PCE of 20.0%. Such an encouraging result was related
to shallower trap state energy level in Cu(Tu)I-incorporated
perovskite film (0.25−0.35 eV) than pristine film (0.35−0.45 eV).
In addition, the incorporated Cu(Tu)I accelerated hole transport
and reduced charge carrier recombination. Yang et al.[12] used
I3− ion to reduce the degree of iodide deficiency and prevent
generation of iodide vacancy defect. In Figure 24a,b, incorpora-
tion of I3− rendered a significantly enhanced PCE as compared
to without I3− treatment. Figure 24c shows that the triiodide
management reduced defect density significantly, which is con-
sistent with remarkably increased PL lifetime (Figure 24d). The
best-performing device exhibited a promising PCE of 22.6% in
reverse scan and 22.2% in forward scan (Figure 24e).

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Figure 23.  a) Cross-sectional SEM image of PSC showing the perovskite layer with 45 min thermally annealed PCBM. b) Device structure with PCBM
layer showing penetration of PCBM in GBs. c) J–V curves for perovskite without and with PCBM layers thermally annealed for 0, 15, and 45 min.
d–f) Comparison of t-DOS (d), bulk recombination lifetime (e), and surface recombination (f) of perovskite films without and with PCBM layers ther-
mally annealed for 0, 15, and 45 min. Reproduced with permission.[33] Copyright 2014, Nature Publication Group.

3.6.3. Additive Engineering for ETM and HTM
Most of the reported additives are neither for ETM nor for HTM
at the early stage of PSCs, rather aiming at improving perovskite
crystallization. Afterward, researchers started to integrate mul-
tiple functions into one additive (defect passivation, improvement
of crystal quality and stability and enhancement of carrier trans-
port and extraction). Here we briefly discuss about improving
carrier transport and separation through incorporation of charge
transporting additives in order to avoid the overlap of contents in
defect passivation part. Aforementioned, PCBM can effectively
passivate the defects in perovskite films. Apart from passivation
effect, PCBM can also facilitate electron separation and transport
because of its electron accepting nature.[33,237–239,246] In order
to further explore possible candidates, hydrophilic fullerene
derivative[6,6]-phenyl-C61-butyric acid-(3,4,5-tris(2-(2-(2-methoxy­
ethoxy)ethoxy)ethoxy)phenyl)methanol ester (PCBB-OEG) was
considered as an additive for top-down gradient distribution.[190]
The gradient distribution of PCBB-OEG provided good electron
transport and extraction due to its well-matched energy levels
with PCBM, which led to the 20.2% and hysteresis-free PSC.
Except for fullerene series, several other organic small molecules

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Figure 24.  a) PCE as a function of the concentration of triiodide added to the dripping solution. b) J–V curve of the control and target devices.
c) Deep-level transient spectroscopy of the control and target perovskite layers. d) TRPL data for the control and target perovskite layers. e) J–V curves
of the best-performing PSC based on triiodide treatment. Reproduced with permission.[12] Copyright 2017, American Association for the Advancement
of Science.

or polymer charge transport materials were employed as addi-
tives in PSCs and improved carrier transport and extraction was
demonstrated.[241,242,247–249] Nitrogen-doped reduced graphene
oxide in mixed organic–inorganic halide perovskite was found
to passivate the perovskite defects, improve hole transport and
extraction, and reduce recombination losses.[162] Additionally,
graphene oxide (GO) in MAPbI3 increased charge mobility and
separation and reduced recombination.[250]
3.7. Post-Treatment and Other Strategies
Since many defects will inevitably exist on the top of perovskite
film or between grains, post-treatment could be expected to pas-
sivate defects and remove impurities. IPA solvent treatment was
used to remove the impurities like unreacted MAI and defects,
by which PCE was improved and hysteresis was reduced.[251]
In addition, alcohol-vapor solvent annealing treatment was

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developed to improve the crystal growth and increase the grain
size of the MAPbI3 crystal, which enhanced charge carrier dif-
fusion length, decreased charge carrier recombination and sup-
pressed dark currents.[252] Methylamine (CH3NH2)-induced
defect-healing approach was developed and applied to MAPbI3
perovskite films.[137] It is critical to form and spread an inter-
mediate MAPbI3·xCH3NH2 liquid phase during this unusual
perovskite–gas interaction. Dramatic enhancement in PCE was
found via this approach. NH4SCN was chosen as a post-treatment
material, which induced decomposition-to-recrystallization of the
perovskite films.[253] Remarkably enlarged grain size and signifi-
cantly reduced trap density were observed, leading to improved
PCE up to 19.44% using an inverted device configuration. Addi-
tion of ethylenediammonium (en) into MASnI3 and FASnI3
formed a new so-called “hollow” structure,[254,255] which was found
to improve carrier lifetime and reduce trap density. By utilizing
the extraordinary radiation hardness of perovskite, an interesting
method of proton irradiation was developed, in which proton irra-
diation created shallow traps but reduced deep trap states.[141]
4. Interface Recombination
As we all know, the PSC typically consists of TCO (ITO or
FTO), ETM, perovskite, HTM, and metal electrode (Au, Ag,
Cu, and Al). Consequently, several interfaces will be formed,
including TCO/ETM (metal/semiconductor contact), ETM/
perovskite (semiconductor/semiconductor contact), perovskite/
HTM (semiconductor/semiconductor contact), and HTM/
metal (semiconductor/metal contact) interfaces. Different
from organic semiconductors in organic photovoltaics, the
exciton recombination usually dominates in perovskite semi-
conductors. As described by Anderson model and thermal
equilibrium theory, free carriers will diffuse toward each other
spontaneously upon direct contact of two types of semiconduc-
tors, establishing a charge-depletion region owning a built-in
electric field.[53] When PSC is illuminated, free carriers will
be produced, transported and extracted across the interfaces
accompanied by interface recombination processes. First, inter-
face recombination could originate from unmatched or imper-
fect interfacial band alignment. Second, interface defects from
charge transporting materials and perovskite layers could be
one of the main recombination losses. This means that inter-
face engineering plays a vital role in reducing recombination
losses for the purpose of maximizing Voc and FF. In the past
several years, huge attentions have been devoted to achieving
efficient and stable PSCs through interface engineering. Sys-
tematic and detailed reviews on interface engineering have
been reported.[15,53,54,256] In this review, we focus on discussing
dependence of photovoltaic performance on perovskite/charge
transporting materials (selective contact materials) from the
viewpoint of interface recombination losses instead of carrier
injection and extraction process.
4.1. Recombination at Perovskite/ETM Interface
In PSC, the function of ETM is to extract photoexcited electrons
and transport them toward TCO or metallic electrode while
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block holes from perovskite to electrodes. Therefore, ETM
must have high electron mobility to ensure electron transport.
Moreover, well-matched energy level alignment is required to
guarantee efficient electron injection and extraction. Carrier
recombination at interface is known to be greatly determined
by the band offsets of HTM/perovskite and ETM/perovskite
junctions. It was reported that ≈0.2 eV band offset needs to
been provided for both interfaces to ensure efficient charge
extraction and minimizing interface recombination losses in
PSCs.[53] So it is necessary to modify the ETM/perovskite inter-
face via interface engineering strategy.
4.1.1. Suppression of Recombination at Perovskite/ETM Interface
in Normal Structure
In order to suppress the recombination between electron
injected into CB of TiO2 and hole in perovskite, Marin-Bel-
oqui et al.[257] used wide-bandgap Al2O3 to modify the TiO2/
MAPbI3−xClx interface. The electron transfer from perovskite to
Al2O3 is energetically forbidden because of higher CB (−0.9 eV)
of Al2O3 than that (−3.9 eV) of MAPbI3−xClx. By taking advan-
tage of this concept, Al2O3-coated device realized slower charge
recombination kinetics as compared to uncoated TiO2, which
led to improved Voc.[258] Insertion of inorganic salt CsBr between
compact TiO2 and perovskite layer improved the ultraviolet (UV)
stability and enhanced PCE from 13.1% to 16.3% mainly due to
the improved Jsc and FF.[259] In comparison with TiO2, SnO2 was
reported to have high electron mobility, better matched CB with
perovskite alignment and faster electron extraction.[260,261] Fur-
thermore, it was demonstrated widely that SnO2-based device
showed much smaller hysteresis as compared to TiO2-based
device.[56,89,262] SnO2 was first used to modify the TiO2 surface to
form bilayer ETM. This concept significantly improved electron
extraction and reduced trap states at perovskite/ETM interface,
resulting in an improvement in PCE from 19.76% to 21.92%.[261]
It was found that photovoltaic performance depended on crystal-
linity of SnO2. Photovoltaic performance of normal mesoporous
PSCs was investigated with respect to different SnO2 forms:
amorphous SnO2 (a-SnO2), crystalline (c-SnO2), and nanocrys-
talline SnO2 (SnO2-NC).[263] Interestingly, a-SnO2 based PSC
showed the highest PCE in case of using triple cation pero-
vskite. Higher CB of a-SnO2 than that of TiO2 but lower than
that of triple cations perovskite facilitated charge transfer and
effective inhibition of interface recombination, leading to
substantial enhancement of Voc (Table  5). Charge recombina-
tion lifetime between electron in TiO2 and hole in perovskite
was improved by treating NH4I on TiO2 ETM.[264] Mild halide
doping is another important and effective interface modifica-
tion approach. Chlorine-capped TiO2 colloidal nanocrystal was
synthesized and used as ETM in normal planar PSC.[13] It was
proposed by many studies that most of the detrimental defects
are antisites with relatively high formation energy.[265,266] In
the Cl-capped TiO2 work, density functional theory (DFT) was
utilized to investigate the defect of PbI2-terminated perovskite
surfaces (Figure 25a,b), where Pb–I antisite defect, which
is localized states near the VB edge, can capture holes and
becomes nonradiative recombination centers (Figure 25a).
However, Pb–Cl antisite defects at PbCl2-terminated interface
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Table 5.  Photovoltaic parameters of PSCs with modification of ETM/perovskite interface in normal PSCs. C and T stand for control device and target
device, respectively. EDT: 1,2-ethanedithiol; LA: l-alanine; 3-APA: 3-aminopropanoic acid; 3-APTMS: 3-aminopropyltrimethoxysilane; PA: 4-pyridinecar-
boxylic acid; PCBB-2CN-2C8: [6,6]-phenyl-C61-butyricacid-dioctyl-3,3-(5-hydroxy-1,3-phenylene)-bis(2-cyanoacrylate) ester; 3-APTES: (3-Aminopropyl)­
triethoxysilane; C-PCBOD: cross-linked [6,6]-phenyl-C61-butyric oxetane dendron ester; PMMA:PCBM: mixture of PMMA and PCBM; TOPD: titanium
oxide bis(2,4-pentanedionate).

Device structurea) Jsc Voc FF (C/T) PCE Ref.

[mA cm−2] (C/T) [V] (C/T) [%](C/T)
FTO/bl-TiO2/m-TiO2/Al2O3/MAPbI3−xClx/spiro-MeOTAD/Au 17.0/20.1 0.870/0.960 0.72/0.66 10.7/12.7 [257]
FTO/bl-TiO2/CsBr/MAPbI3−xClx/spiro-MeOTAD/Au 18.7/20.7 0.99/1.06 0.69/0.75 13.1/16.3 [259]
FTO/bl-TiO2/mp-TiO2/a-SnO2/ Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3/spiro-MeOTAD/Au 22.21/22.51 1.098/1.168 0.79/0.78 19.14/20.4 [263]
FTO/TiO2/SnO2 NPs/(FAPbI3)0.3(MAPbI3)0.7/spiro-MeOTAD/Au 22.50/24.79 1.113/1.114 0.79/0.79 19.76/21.92 [261]
FTO/bl-TiO2/m-TiO2/NH4I/(FAPbI3)0.85(MAPbBr3)0.15/spiro-MeOTAD/Au 20.69/22.49 1.06/1.07 0.71/0.76 15.6/18.31 [264]
ITO/bl-TiO2-Cl/Cs0.05FA0.81MA0.14PbI2.55Br0.45/spiro-MeOTAD/Au 21.6/23.0 1.129/1.151 0.76/0.79 18.5/20.9 [13]
ITO/CF4 plasma-TiO2/MAPbI3/spiro-MeOTAD/Au 19.7/20.3 0.824/1.033 0.55/0.76 8.8/15.8 [267]
ITO/ZnO/EDT/MAPbI3/spiro-MeOTAD/Au 21.18/23.15 1.07/1.10 0.72/0.79 16.51/19.65 [268]
FTO/ZnO-MgO-EA+/Cs0.05(FA0.83MA0.17)0.95Pb(Br0.17I0.83)3/spiro-MeOTAD/Au 23.08/23.86 1.12/1.12 0.78/0.79 20.05/21.08 [57]
FTO/bl-TiO2/m-TiO2/LA (SAM)/MAPbI3/spiro-MeOTAD/Au 17.08/22.40 0.95/0.99 0.66/0.64 10.76/14.22 [269]
ITO/ZnO/3-APA (SAM)/MAPbI3/spiro-MeOTAD/MoO3/Ag 19.12/22.51 0.99/1.07 0.63/0.65 11.96/15.67 [270]
FTO/bl-TiO2/(mp-TiO2/3-APTMS (SAM)/ZrO2/Carbon)MAPbI3 17.97/19.51 0.795/0.873 0.68/0.75 9.71/12.77 [271]
FTO/SnO2/3-APTES (SAM)/MAPbI3/spiro-MeOTAD/Au 20.84/21.23 1.065/1.16 0.66/0.69 14.69/17.03 [272]
ITO/SnO2/PA (SAM)/MAPbI3−xClx/spiro-MeOTAD/Au 21.65/22.03 1.06/1.10 0.75/0.77 17.19/18.77 [273]
ITO/bl-TiO2/PCBB-2CN-2C8/MAPbI3/spiro-MeOTAD/Au 20.18/20.68 0.99/1.06 0.72/0.79 14.38/17.35 [274]
ITO/bl-TiO2/C-PCBOD/MAPbI3/spiro-MeOTAD/Au 20.70/22.22 0.984/1.012 0.64/0.69 13.0/15.4b) [275]
ITO/TiO2:TOPD/PC60BM/MAPbI3/spiro-MeOTAD/Au 22.6/23.2 1.1/1.1 0.76/0.80 18.8/20.3 [88]
FTO/c-In-TiOx/m-TiO2/PMMA:PCBM/Cs0.07Rb0.03FA0.765MA0.135PbI2.55Br0.45/spiro-MeOTAD/Au 23.3/23.2 1.10/1.16 0.73/0.76 18.7/20.4 [276]
ITO/SnO2/NDI-Graphene/FA0.75MA0.15Cs0.1PbI2.65Br0.35/spiro-MeOTAD/Au 23.21/22.66 1.097/1.084 0.75/0.82 18.99/20.16 [277]
FTO/bl-TiO2/ITIC/MAPbI3/spiro-MeOTAD/Au 21.67/22.71 1.08/1.12 0.73/0.79 17.12/20.08 [278]

a)
The positions and functions of interfaced modifiers are highlighted in bold; b)Average photovoltaic parameters.

is less favorable to form due to higher formation energy
(Figure 25b). It means that Pb–Cl antisite defect is much shal-
lower and more delocalized compared with Pb–I antisite defect.
XPS results showed that Cl was incorporated into TiO2 and it
still remained in TiO2 even at high temperature up to 250 °C
(Figure 25c,d). As shown in Figure 25e, Jsc, Voc, FF, and PCE
were improved from 21.6 mA cm−2, 1.129 V, 0.76, and 18.5%
to 23.0 mA cm−2, 1.151 V, 0.79, and 20.9% by contacting
perovskite with Cl-capped TiO2. Although similar interfacial
charge transfer regardless of the presence of Cl at the interface,
much longer charge recombination lifetime was observed for
Cl-TiO2 case (145 µs) as compared to bare TiO2 (64 µs) as
revealed by transient photovoltage decay results (Figure 25f).
Similarly, CF4 plasma was employed to enable the fluorination
of TiO2 surface, achieving improvements in electron extrac-
tion and energy band alignment as well as adhesion between
TiO2 and MAPbI3.[267] Fluorination enhanced photovoltaic
parameters.
ZnO is one of the promising candidates for ETM because
of similar bandgap but much higher electron mobility than
TiO2. However, severe charge recombination and poor chemical
stability at the ZnO/perovskite interface impede its large-
scale extensive application in PSCs.[57,268] In order to conquer
the above issues, interlayer between perovskite and ZnO was
suggested using 1,2-ethanedithiol (EDT).[204] XPS confirmed
the formation of ZnS bonds after insertion of EDT. In addi-
tion, ZnO surface defects were passivated by replacing surface
oxygen-containing groups with ZnS bonds, which increased
lifetime for charge recombination as revealed by transient
photo­ voltage (TPV) spectroscopy and intensity-modulated
photo­current (IMPS) analysis. As a consequence of sulfur pas-
sivation, PCE of control device was dramatically increased from
16.51% to 19.65%. Similarly, bilayer was proposed to passivate
ZnO using a thin layer of MgO and a protonated ethanolamine
(EA), which enabled hysteresis-free, efficient, and stable PSCs
(Figure 26a).[33] The successful insertion of bilayer of MgO and
EA was confirmed by XRD and FTIR studies (Figure 26b,c).
Bilayer approach improved PCE from 20.05% to 21.08% due
to suppressed interfacial charge recombination (Figure 26d),
and removed hysteresis because of improved electron transport
owing to incorporation of protonated EA. The synergistic effect
of MgO and EA was found to effectively solve the poor interfa-
cial instability problem.
It was reported that work function, surface energy and
electron-transfer kinetics of metal oxides can be modulated
by dry treatments (such as plasma or UV–ozone), wet inor-
ganic treatments, buffer layers, redox active molecules and
organic monolayer (such as alkoxy/halosilane, carboxylic
acid, and phosphonic).[279,280] Among them, self-assembled
monolayer (SAM) shows great potentials in modifying work

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SAM-modified CBM of ZnO and thereby

more efficient electron extraction was
observed (Figure 27c). In addition, such a
surface modification accompanied by better
electronic band alignment was responsible
for the enhanced Voc and FF (Figure 27b).
As we mentioned above, tail groups in
SAM modifier play an important role in
crystallization of perovskite film in terms
of wettability and/or specific interaction
with composition of perovskite. Thus,
different functional groups such as ben-
zoic acid, 4-pyridine carboxylic acid (PA),
4-cyanobenzoic acid (CBA), 4-aminobenzoic
acid (ABA), and 3-aminopropanoic acid
(C3) were applied to modify the surface
of SnO2.[273] Photovoltaic performance
was found to depend on functional groups
of SAMs. Compared with control device,
PA-modified device showed higher PCE up
to 18.8%. This work highlights the impor-
tance of choice of terminal tail groups
which can significantly affect the chemical
interactions between perovskite and ETM.
Shih et al.[269] investigated the effect of alkyl
spacer length in amino acids on photo­
voltaic performance, where photovoltaic
performance was improved regardless of
chain length. It was found that perovskite
crystallites would tend to align in the direc-
tion perpendicular to TiO2 substrate with
the aid of amino acid based SAM, which
was beneficial to reduction in surface trap
state and improvement of electron transfer.
Except for modifiers containing carboxyl
anchoring group, alkoxy/halosilane was
found to be important anchoring group.
Figure 25.  DFT calculation results showing a) trap-like localized antisite defects form near the 3-Aminopropyltrimethoxysilane (3-APTMS)
valence band edge for the PbI2-terminated TiO2/perovskite interface and b) shallow and delo- was applied to TiO2 in hole conductor–free
calized Pb–Cl antisite defects at the PbCl2-terminated interface. XPS spectra of Cl 2p peaks of fully printable PSCs with carbon counter
c) TiO2 NC films. MeOH + CF stands for TiO2 redispersed in the cosolvent of methanol and electrode.[271] The schematic structure
chloroform. EtOH + TiAcAc stands for TiO2 redispersed in ethanol with titanium diisopropoxide was shown in Figure 27d,e. Substantial
bis(acetylacetonate) as stabilizer. d) TiO2-Cl NC films with various postannealing temperatures.
improvement of photovoltaic performance
e) J–V curves of PSCs with TiO2 and TiO2-Cl ETMs. f) Normalized transient photovoltage decay
of devices with TiO2 and TiO2-Cl as ETMs. Reproduced with permission. Copyright 2017, was observed by this method (Figure 27f).
[13]

American Association for the Advancement of Science.
function, surface energy and electron-transfer kinetics in
PSCs due to its advantages of simple procedure, precise con-
trol and possibility in choosing tail groups and spacer. The
organic mole­cules used for SAM modification generally are
composed of an anchoring (head) group, a spacer, and a tail
group. Encouraged by appealing advantages of the above
SAM method, SAM was prepared on ZnO by spin-coating
the solution of 3-aminopropanioc acid (C3-SAM) in meth-
anol,[270] which induced permeant dipole being beneficial
to electron extraction (Figure 27a). Since ZnO surface was
modified, crystal growth was affected toward better crystal-
lization, which was related to improved Jsc (Figure 27b).
Similarly, SAM with 3-APTMS improved
perovskite crystallization, band alignment
and higher resistance for recombination
(Figure 27g). 3-Aminopropyltriethoxy­ silane (3-APTES) was
also tested in SnO2, which also showed positive effect.[272]
PCBM is often employed to modify surface of metal oxides
such as ZnO, TiO2, and SnO2, in which appropriate energy
band alignment and better electron extraction are anticipated
because of its a little lower CBM than that of commonly used
perovskite compositions. Interface defects at perovskite/
metal oxides are also able to be passivated by PCBM treat-
ment. Fullerene derivatives PC60BM and C60-ETA were intro-
duced between perovskite and TiO2 and found to improve
PCE together with reduced hysteresis.[88] Although both
modifiers improved PCE, better band alignment was found

Adv. Mater. 2018, 1803019 1803019  (36 of 56) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 26.  a) Schematic illustration of a bilayer approach using MgO and EA. b) XRD patterns
of MgO-treated ZnO depending on annealing temperature. c) FTIR spectra of the ZnO–MgO–
EA sample annealed at 450 °C for 30 min. d) J–V curves of the best-performing PSC employing
the bilayer-based Cs0.05(FA0.83MA0.17)0.95Pb(Br0.17I0.83)3. Reproduced with permission.[57] Figure 29a, which was expected to play tun-
Copyright 2018, Wiley-VCH.
in PC60BM than C60-ETA. By treating PC60BM, PCE was
enhanced from 17.6% to 20.3%. Another example is to use
PMMA:PCBM mixture that was inserted at perovskite/TiO2
interface (Figure  28a), which resulted in passivation of the
interface defects and accordingly suppression of the interfa-
cial recombination. Therefore, a high Voc up to ≈1.18 V was
achieved.[276] The ratio of PMMA to PCBM was found to be
critical for achieving high PCE and from the optimal ratio of
PMMA:PCBM = 1:3 the PCE was increased from 19.6% to
20.4% (Figure 28b) and the hysteresis was thoroughly sup-
pressed (Figure 28c,d). Except for PCBM, other fullerene
derivatives (such as C-PCBOD, C-PCBSD, and PCBB-2CN-
2C8) were also developed to modify the perovskite/TiO2 inter-
face.[274,275] Graphene is also candidate, where Zhao et al.[277]
reported the modification of SnO2 with graphene modified
chemically by N,N′-bis-[2-(ethanoic acidsodium)]-1,4,5,8-
naphthalene diimide (NDI) surfactant for normal planar
PSCs. Improved charge extraction and transport were asso-
ciated with improved PCE after NDI–graphene modification.
Ultrathin ITIC (electron acceptor based on a bulky seven-
ring fused core (indacenodithieno[3,2-b]thiophene, IT), end-
capped with 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile
(INCN) groups, and with four 4-hexylphenyl groups substi-
tuted on it) was deposited on the surface of TiO2 and found
that ITIC modification not only improved the perovskite crys-
tallization but also decreased defect density, [278]
which led to
20.08% efficient and hysteresis-less PSC.
Adv. Mater. 2018, 1803019 1803019  (37 of 56)
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4.1.2. Suppression of Recombination at
Perovskite/ETM Interface in Inverted Structure
Interface recombination at perovskite/
ETM interface in inverted structure may be
as important as in normal structure. It was
reported that insulating interlayer (or buffer
layer) inserted between ETM and metal elec-
trode effectively blocked back transfer of
holes from perovskite to metal electrode in
inverted PSCs.[282–285] Insulating interlayer at
perovskite/ETM interface can form tunneling
contact,[69,281,286] allowing photogenerated
electrons at CBM of perovskite to tunnel to
the excited electronic states in ETM, and then
the electrons are relaxed to the lowest unoc-
cupied molecular orbital (LUMO) of ETM
due to existence of energy-matching unoc-
cupied states in ETM. However, ETM has
no energy-matching states to allow holes to
tunnel into. In other words, insulating layer
can allow electron tunnel from perovskite to
ETM while block hole into ETM.[281] Based on
this concept, different insulating interlayers
(polystyrene (PS), Teflon, and polyvinylidene–
trifluoroethylene copolymer (PVDF–TrFE))
were inserted at perovskite/C60 interface
in inverted planar PSCs,[223] as shown in
neling role as schematically illustrated in
Figure 29b. Insertion of so-called tunneling
interlayer improved PCE (Figure 29c,d) due
to suppressed interface recombination (Figure 29e,f). Among
the tested tunneling materials, PS worked better than other
materials. Here it should be highlighted that whether tun-
neling layer is useful for PCE enhancement depends on the its
thickness to a great extent as presented in Figure 29d. Wolff
et al.[69] investigated the effect of different fullerene derivatives
(C60, PCBM and ICTA) on Voc in inverted PSCs. They proposed
that Voc is limited greatly by interface-mediated nonradiative
recombination. By inserting PS insulating tunneling layer at
perovskite/C60 interface, Voc was significantly increased from
1.03 to 1.16 V, which indicates that suppression of interfacial
nonradiative recombination is more important than energy
level alignment to maximize Voc. In another work, excep-
tional FF up to 0.84 was realized with efficiencies over 20% via
incorporation of PS insulating tunneling layer at perovskite/
C60 interface.[106] Poly(perfluorobutenylvinylether) (Cytop) was
used as one of the insulating tunneling interlayers, which was
employed to modify perovskite/PC60BM interface in inverted
PSCs.[286] Improvement of both Jsc and FF was related to facili-
tating charge transfer and restricting interface recombination.
PMMA was solely used to modify PCBM-based ETM, which
also showed positive effect on Voc and FF.[287] Alkyl bisphos­
phonic molecules and 2,6-dimethoxypyridine (2,6-Py) were
used to passivate the defects on the surface of perovskite films
at perovskite/ETM interface.[288,289] Homojunction may be
one of the solutions to control the interface recombination,
where 3D–2D (MAPbI3–PEA2PbI4) graded perovskite interface
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 27.  a) Schematic structure of PSC showing SAM layer on ZnO. b) J−V curves and c) TRPL before and after SAM. d) Schematic structure of fully
printable mesoscopic PSC based on carbon counter electrode. e) Energy band diagram change after the introduction of organic silane SAM between
TiO2 surface and perovskite. f) J–V curves and g) recombination resistance without (Device A) and with (Device B) silane SAM. a–c) Reproduced
with permission.[270] Copyright 2015, American Chemical Society. d–g) Reproduced with permission.[271] Copyright 2015, American Chemical Society.

was reported to significantly improve Voc in inverted NiOx- large amount of defects exist at the surface or grain bounda-
based PSCs.[290] The much shorter PL lifetimes in polycrys- ries of polycrystalline films which is no longer electronically
talline films than single crystal films strongly suggests that a benign.[33,59,87,291–293] These defects can not only dramatically

Adv. Mater. 2018, 1803019 1803019  (38 of 56) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 28.  a) Schematic illustration of PSC with an ultrathin interlayer comprising PMMA and PCBM. b) Statistical PCE data with respect to the ratio
of PMMA to PCBM. J–V curves of c) control device and d) the device with the interlayer of PMMA/PCBM (1:3). Reproduced with permission.[276]
Copyright 2017, Royal Society of Chemistry.
reduce device Voc but also degrade the device stability through
trap-assisted nonradiative recombination process. Considering
the ionic nature of perovskite materials, the defects in perovs-
kites are usually negatively charged or positively charged.[59]
Several kinds of quaternary ammonium halide anions and
cations salts (l-α-phosphatidylcholine, choline iodide and cho-
line chloride) together with nonsalts PCBM, Tween 20 and
PE-PEG (Figure 30c,d) were employed simultaneously to passi-
vate the negatively and positively charged defects in perovskite
films through spin-coating these passivating molecules on the
perovskite films, which was applied into inverted planar PSCs as
shown in Figure 30a,b.[291] It was found that PCBM-passivated
device showed much higher PCE mainly as a consequence
of much improved Jsc along with similar Voc than Tween- or
PE-PEG-treated devices. The authors concluded that Tween and
PE-PEG cannot effectively passivate the defects at the surface
of MAPbI3. However, we think that it is difficult to explain the
significant difference in current just from the perspective of
passivation. Tween and PE-PEG also could deteriorate electron
extraction and thus reduce Jsc. In sharp contrast, much higher
PCEs mainly as a result of much improved Voc were observed
in the devices with quaternary ammonium halide anions and
cations salts as compared to PCBM-based device. This indicates
that anions and cations in quaternary ammonium halide can
effectively passivate the charged defects as we expected. Signifi-
cantly increased PL lifetimes (Figure 30e) and device charge car-
rier lifetimes (Figure 30f) was demonstrated in the device treated
Adv. Mater. 2018, 1803019 1803019  (39 of 56)
www.advmat.de
by choline chloride compared with PCBM-treated device. Through
thermal admittance spectroscopy analysis as shown in Figure 30g,
we can see that deeper trap region (0.40–0.52 eV) which is due
to defects at the surface of films was remarkably reduced in
choline chloride-passivated device while slightly reduced for
shallower trap state region (0.35–0.40 eV) which is assigned
to the traps at grain boundary. As illustrated in Figure 30h–j,
a PCE of up to 21.0% was achieved based on choline chloride-
passivated FA0.85MA0.15Pb(I0.85Br0.15)3 device with negligible hys-
teresis. Additionally, moisture stability was significantly increased
after choline chloride passivation. This work shows that both
cationic and anionic defects in perovskites should be considered
simultaneously when developing passivation techniques.
4.2. Recombination at the Perovskite/HTM Interface
4.2.1. Suppression of Recombination at the Perovskite/HTM
Interface in Normal Structure
In normal PSCs, many efforts have been made to modify ETM/
perovskite interface as we discussed previously as compared to
perovskite/HTM. However, recently, it was widely recognized
that the perovskite/HTM interface is almost equally important
and thus attracts considerable attention. Since modifiers at the
perovskite/HTM interface should be deposited on perovskite
film, solvents used for dissolving modifiers should be inert
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 29.  a) Schematic device structure of PSC with insulating interlayer. b) Energy diagram showing the principle of suppressing surface charge
recombination by tunneling effect. c) J–V curves for PSCs with different insulating tunneling contacts. d) J–V curves of the devices with different con-
centration of PS. e) I–V curves of hole-only devices with and without PS interlayer. f) Carrier recombination lifetime of perovskite devices with and
without PS interlayer measured by transient photovoltage. Reproduced with permission.[281] Copyright 2016, Wiley-VCH.

for perovskite film to avoid unnecessarily film destruction.
Generally speaking, modifiers are expected to achieve the fol-
lowing several functions: passivation of defects on the surface
(or GBs) of perovskite films, better energy level alignment for
hole extraction, protection of perovskite film from moisture.
As we discussed on defect passivation in additive engineering
part, Lewis base can interact with undercoordinated Pb2+ and
effectively passivate the iodide vacancies. Lessened from this,
aniline, benzylamine, and phenethylamine (PEA) were used
to modify surface of perovskite film.[294] It was found that only
BA was working for enhancing photovoltaic property, while
negative effect from aniline and PEA was experienced. Ada-
mantane (AD) and 1-adamantylamine (ADA) were tested for
the purpose of defect passivation of perovskite films (see the
chemical structures of AD and ADA in Figure 31a).[235] TRPL
data revealed that ADA and AD showed longer lifetime than
untreated perovskite, indicative of reduction in nonradiative
recombination, and the lifetime was longer for ADA than for
AD (Figure 31b), which suggests that ADA passivate more
effectively the perovskite defects. As a result of post-treatment,
PCEs of 20.47% and 20.93% could be achieved for AD and
ADA, respectively, which was mainly attributed to the increased
Voc (Figure 31c and Table 6). Thiophene derivates of 3-alkyl­
thiophenes (thiophene (TP), 3-methylthiohene (MTP), 3-ethyl­
thiophene (ETP), 3-butylthiophene (BTP), 3-hexylthiophene
(HTP), and 3-dodecylthiophene (DTP)) were investigated to

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www.advancedsciencenews.com www.advmat.de

Figure 30.  a) The schematically illustrated device structure used in this work. b) Schematic illustration of perovskite with defect sites passivated by
quaternary ammonium halides (QAHs). c) Chemical structures of PCBM, Tween 20, and polyethylene-block-poly(ethylene glycol) (PE-PEG). d) Chemical
structures of L-α-phosphatidylcholine, choline iodide and choline chloride. e) TRPL spectra of perovskite films treated with/without choline chloride
layers treatment. f) Charge carrier lifetime of devices with/without a choline chloride treatment. g) Trap density of states obtained by thermal admit-
tance spectroscopy for devices with/without a choline chloride treatment. h) J–V curves of one-step-processed FA0.83MA0.17Pb(I0.83Br0.17)3 devices with
or without choline chloride layers. i) J–V curves of the champion device treated by choline chloride measured in reverse and forward scan directions.
Reproduced with permission.[291] Copyright 2017, Nature Publication Group.

passivate the perovskite/spiro-MeOTAD interface because delo-
calized π-electrons of thiophene rings was expected to be ben-
eficial for hole transfer and extraction at the perovskite/HTM
interface.[236] The conjugated π system can also be regarded
as a good electron donor. Among the tested molecules, HTP
yielded a highest PCE. Interestingly, Polymers such as P3HT,
PTAA, MEH-PPV, poly-TPD and PBDTTT-CT were also found
to show positive effect when they were inserted between perov­
skite and spiro-MeOTAD, where best performance with PCE of
19% was demonstrated using P3HT (Table 6).[237] Inspired by
the positive effect from PMMA upon applying at perovskite/
ETM interface as discussed previously, PMMA was tried to be
inserted between perovskite and spiro-MeOTAD, which also
reduced surface trap states and nonradiative recombination
centers.[295,296]
Inorganic metal oxides are good candidates for surface pas-
sivation. For instance, a thin layer of Al2O3 introduced at the
perovskite/spiro-MeOTAD interface by the atomic layer depo-
sition (ALD) method could provide a good tunneling layer for
hole transfer and a defect passivation layer for enhancing Voc
and FF.[297] Amphiphilic graphene oxide on perovskite film was
found to improve chemical interaction with both perovskite
and spito-MeOTAD via GOPb bonding and π–π interaction
between GO and spiro-MeOTAD.[298] Insertion of GO had effect
on blocking interfacial recombination leading to both increases
in Jsc and Voc. In order to enrich the application of GO as insu-
lating interlayer at the perovskite/HTM interface, chemically
modified GO by 4-fluorophenyl (rGO-4FPH) was synthesized
and incorporated at perovskite/spiro-MeOTAD interface.[299]
rGO-4FPH played an important role in narrowing t-DOS distri-
bution and reducing deep trap states.
The perovskite/HTM interface can be engineered by in situ
or ex situ perovskite composition engineering. The perovskite/
spiro-MeOTAD interface was modified by as-synthesized

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www.advancedsciencenews.com
Figure 31.  a) Chemical structure of adamantane and 1-adamantylamine used for passivation of perovskite film. b) TRPL spectra of perovskite films
before and after passivation by AD and ADA. c) J–V curves of PSCs before and after passivation by AD and ADA. Reproduced with permission.[300]
Copyright 2018, Wiley-VCH.
MAPbBr3−xIx quantum dots (QDs),[303] where hole extraction
was found to be energetically favorable for x  = 2.1 but unfa-
vorable for x = 1.8 and 0. Since composition of perovskite OQ
used for interlayer determines band position and gap, hole
extraction and inhibition of recombination depend on composi-
tion of QDs. Additionally, Zhang et al.[304] proposed dimension-
ally graded heterojunction strategy (bulk-nanosheet–quantum
dots or 3D–2D–0D dimension) to modify perovskite/PTAA inter-
face in all-inorganic PSCs, where 3D–2D–0D heterojunction
was formed by successively depositing 2D CsPbBrI2 nanosheet
and 0D CsPbBrI2 QD on the 3D CsPbBrI2 film. From 3D to 0D,
CBM and VBM gradually upshifted to form type II heterojunc-
tion, which made good circumstances for efficient hole transfer
while blocking electron back transfer. In addition to the above
ex situ interface composition engineering, in situ engineering
was extensively reported. Generally, in situ engineering is based
on the reaction between excess PbI2 or PbBr2 while preparing
perovskite films and post-treated organic halide salts. Cho
et al.[305] engineered a compositional gradient FAPbBr3−xIx layer
at the rear interface between perovskite and HTM in normal
PSCs, where FAPbBr3−xIx layer was formed by the reaction
between excess PbI2 in (FAPbI3)0.85(MAPbBr3)0.15 and spin-
coated FABr as shown in Figure 32a. This gradient composi-
tion engineering induced suppression of electron backflow and
improvement of hole collection as illustrated in Figure 32b,
which contributed to enhanced Voc (Figure 32e). Obvious
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morphology change was observed for FABr-treated film
(Figure 32c,d). Slightly blueshifted IPCE confirmed the formation
of FAPbBr3−xIx (Figure 32f).
For the purpose of improving stability of PSCs, inorganic
HTMs were suggested as alternative to organic HTMs.[85,86]
Among the commonly used inorganic HTMs, the device based
on room temperature solution-processed CuSCN HTM dem-
onstrated a promising PCE over 20%.[308] However, CuSCN-
based device has been issued on interface degradation.[308,309]
In order to solve the interface instability, 2D perovskite such as
(5-AVA)2PbI4 was used to modify the perovskite/CuSCN inter-
face, where (5-AVA)2PbI4 was in situ formed by the reaction of
excess PbI2 in (FAPbI3)0.88(CsPbBr3)0.12 film with 5-AVAI (aka
5-ammonium valeric acid iodide) (Figure 33a).[85] Type II het-
erojunction was formed through contacting 2D with CuSCN
(Figure 33b), which might be beneficial for hole extraction and
blocking electron back transfer. In order to investigate the effect
of 2D passivating layer, photovoltaic performance of devices A,
B, C, and D was compared (Figure 33e), where A is the perov­
skite prepared from stoichiometric precursor solution, B from
nonstoichiometric precursor solution with excess PbI2, C from
post-treatment of A with 5-AVAI, and D from the post-treatment
of B with 5-AVAI. Device D showed the highest PCE as a con-
sequence of improved Voc and FF and PCEs of devices B and
C were even lower than device A. This strongly indicates that
improved PCE is due to incorporation of 2D passivating layer
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Table 6.  Photovoltaic parameters of PSCs with a modification of the perovskite/HTM interface in normal PSCs. C and T stand for control device and
target device, respectively. BA: benzylamine; ADA: 1-adamantylamine; HTP: 3-hexylthiophene; 5-AVA: 5-ammoniumvaleric acid; BA in BA2PbI4: butyl-
amine; GO: Graphene oxide; rGO-4FPH: 4-Fluorophenyl-hydrazine hydrochloride (4FPH) functionalized reduced graphene oxide (rGO).

Device structurea) Jsc Voc FF (C/T) PCE Ref.

[mA cm−2] (C/T) [V] (C/T) [%](C/T)
FTO/bl-TiO2/FAPbI3/BA/spiro-MeOTAD/Au – – – 14.2/17.3b) [294]
FTO/bl-TiO2/m-TiO2/ Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3/ADA/spiro-MeOTAD/Au 22.47/22.57 1.083/1.155 0.79/0.80 19.32/20.93 [300]
FTO/bl-TiO2/Cs0.05FA0.81MA0.15PbI2.55Br0.45/HTP/spiro-MeOTAD/Au 22.90/23.24 1.12/1.15 0.70/0.75 18.08/19.89 [301]
FTO/bl-TiO2/MAPbI3/P3HT/spiro-MeOTAD/Au 22.1/23.4 0.949/1.043 0.72/0.78 15.0/19.0 [302]
FTO/bl-TiO2/m-TiO2/MAPbI3/PMMA/spiro-MeOTAD/Au 20.9/23.4 1.11/1.14 0.73/0.77 16.8/20.4 [296]
FTO/bl-TiO2/m-TiO2/MAPbI3/PMMA/spiro-MeOTAD/Au 21.5/22.0 1.01/1.03 0.67/0.72 14.6/16.4 [295]
ITO/bl-TiO2/MAPbI3−xClx/Al2O3/spiro-MeOTAD/Au 21.3/21.7 1.03/1.08 0.69/0.77 15.1/18.0 [297]
FTO/bl-TiO2/MAPbI3/MAPbBr0.9I2.1/spiro-MeOTAD/Au 18.09/19.51 0.937/0.948 0.61/0.72 10.34/13.32 [303]
FTO/bl-TiO2/CsPbBrI2/CsPbBrI2 NSs/CsPbBrI2 QDs/PTAA/Au 11.94/12.93 1.11/1.19 0.78/0.81 10.38/12.39 [304]
FTO/bl-TiO2/m-TiO2/(FAPbI3)0.85(MAPbBr3)0.15/FAPbBr3−xIx/spiro-MeOTAD/Au 22.4/22.5 1.1/1.16 0.77/0.78 18.9/20.5 [305]
FTO/bl-TiO2/m-TiO2/ (FAPbI3)0.88(CsPbBr3)0.12/(5-AVA)2PbI4/CuSCN/Au 21.13/21.93 0.986/1.068 0.66/0.72 13.72/16.75 [85]
FTO/bl-TiO2/m-TiO2/Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3/BA2PbI4/spiro-MeOTAD/Au 19.99/19.40 0.955/1.058 0.74/0.77 14.17/15.74 [168]
FTO/bl-TiO2/m-TiO2/Cs0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3/PEA2PbI4/spiro-MeOTAD/Au 22.83/22.89 1.05/1.11 0.71/0.73 17.02/18.51 [306]
FTO/bl-TiO2/m-TiO2/Cs0.1FA0.74MA0.13PbI2.48Br0.39/PEA2PbI4/spiro-MeOTAD/Au 21.81/22.73 1.098/1.14 0.78/0.76 18.65/20.08 [307]
FTO/bl-TiO2/m-TiO2/MAPbI3/GO/spiro-MeOTAD/Au 18.5/20.2 0.93/1.04 0.64/0.73 10.0/15.1 [298]
FTO/bl-TiO2/MAPbI3/rGO-4FPH/spiro-MeOTAD/Au 20.1/21.5 1.03/1.11 0.75/0.79 15.58/18.75 [299]

a)The interface modifiers are set in bold to highlight their positions and functions; b)Average PCE.

instead of excess PbI2 or 5-AVAI treatment. In situ formed 2D
perovskite layer effectively passivated the defects on the surface
of (FAPbI3)0.88(CsPbBr3)0.12 film as evidenced by significantly
increased PL lifetime (Figure 33c). Energetics in Figure 33b was
well aligned for hole extraction (Figure 33d). Introduction of 2D
layer at perovskite/CuSCN interface also reduced hysteresis.
Similar works were reported, where incorporation of the 2D
perovskite layer at the perovskite/HTM interface demonstrated
improved PCE and stability.[168,306,307] The above results show
that incorporation of insulating interlayer and compositionally
engineered perovskite layer at the perovskite/HTM interface are
promising in achieving highly efficient normal PSCs.
4.2.2. Suppression of Recombination at the Perovskite/HTM
Interface in Inverted Structure
Compared with normal PSCs, the perovskite/HTM interface
in inverted PSCs is scarcely investigated in the past. However,
similar to the role of ETM/perovskite interface in normal struc-
ture, the perovskite/HTM interface in inverted architecture
is expected to have influence on determining the final device
performance. Insulating mesoporous Al2O3 layer was inserted
between the NiOx layer and the perovskite layer in inverted
PSCs,[258] which blocked holes in NiOx layer backflow into
perovskite layer and thus retarded interfacial recombination.
PEDOT:PSS layer was modified by poly (2,2,6,6-tetramethyl-
piperidinyloxy-4-yl methacrylate)-co-(4-benzoylphenyl meth-
acrylate) (PTMA-BP),[310] which aligned HOMO of PEDOT:PSS
and VBM of perovskite to reduce interfacial charge carrier
recombination. In situ formed 2D (PEI)2PbI4 (PEI = polymeric
ammonium) at PEDOT:PSS/perovskite interface was found to
be able to improve hole extraction and reduce interfacial charge
recombination.[311]
4.3. Lessen from Conventional Thin Film Solar Cells:
Spike versus Cliff
Sometimes, old idea may give important insight into new
design. In the conventional inorganic thin film solar cells such
as CIGS, the band offset between buffer and light absorber layer
was found to form “spike” or “cliff” structure, which affected
carrier recombination at the interface and thereby Voc. Thus,
engineering band offset may be one of the methods to reduce
interface recombination in PSCs. According to the device simu-
lation on a planar normal PSC structure (TCO/buffer (ETM)/
interface defect layer 1 (IDL1)/perovskite/interface defect layer 2
(IDL2)/HTM) assuming perovskite is intrinsic and fully
depleted by contacting with ETM and HTM,[312] conduction
band offset (CBO) at ETM/perovskite and valence band offset
(VBO) at perovskite/HTM played an important role in deter-
mining Voc and PCE (Figure 34). The results suggest that CBO
of 0.0–0.3 eV and VBO of 0.0–0.2 eV are optimal values, which
indicates that appropriate “spike” structure is better than “cliff”
structure for minimal interface recombination.
5. The Effect of Trap-Induced Nonradiative
Recombination on Hysteresis
It is well known that notorious hysteresis extensively exists in
most of the PSCs, which seriously affects the accurate evalu-
ation of real device efficiency and stability as well. Since the

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Figure 32.  a) Schematic structure of PSC employing interface modification via in situ engineering. b) Energetics and role of FAPbBr3−xIx interlayer. Bend
bending was assumed (black dashed line). Top-view SEM images of perovskite film c) before and d) after post-treatment. e) J–V curves of PSCs before
(as-prepared) and after (passivated) post-treatment. f) EQE spectra and integrated Jsc of the devices before and after post-treatment. Reproduced with
permission.[305] Copyright 2017, Royal Society of Chemistry.

hysteresis phenomenon was first reported by Snaith et al.,[313]
huge efforts have been contributed to investigating the possible
origins, including ferroelectric effects,[314,315] charge accumula-
tion,[316] trap-state density,[18,33,90,123–125] ion migration,[158,317–322]
interfacial dipoles,[323] etc. Although many attempts made on
addressing this issue, it still lacks final conclusion on the real
reason of hysteresis. In the past several years, ion migration
was proposed to be the main reason of hysteresis.[317] Recently,
defect density which can induce nonradiative recombination
was demonstrated to be main origin of hysteresis (defect and
ion migration might correlate each other, actually).[18,90,123–125]
Consequently, it is an effective and feasible approach to
reduce or remove hysteresis through minimizing trap-assisted
nonradiative recombination losses from the viewpoint of bulk
and interface. Actually, during the discussion of controlling
methods of bulk and interface nonradiative recombination
(Sections 3 and 4), we have discussed the effect of trap-assisted
nonradiative recombination on hysteresis and stability. There-
fore, here we just give a brief comment on it. As we discussed
previously, perovskite composition engineering is directly
related with film quality and defect density. So composition
engineering is one of the feasible and effective methods for

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www.advancedsciencenews.com www.advmat.de

Figure 33.  a) Schematic device architecture with (5-AVA)2PbI4 interlayer between perovskite and CuSCN. b) The energy-level diagram of device compo-
nents. Film B and D represent (FAPbI3)0.88(CsPbBr3)0.12 prepared from nonstoichiometric precursor solution with excess 8 mol% PbI2 and passivated
(FAPbI3)0.88(CsPbBr3)0.12 with (5-AVA)2PbI4, respectively. c) Steady-state PL and d) TRPL of perovskite films A, B, C, and D with or without TiO2 and
CuSCN layer. e) J–V curves of the best-performing devices A, B, C, and D measured in reverse (RS) and forward (FS) scan directions. f) Recombination
resistance (Rrec) for devices B and D. Reproduced with permission.[85] Copyright 2018, Wiley-VCH.

reducing hysteresis through improving crystallization and
morphology and thus suppressing trap-assisted nonradiative
recombination. It was widely demonstrated that MAPbI3 always
shows serious hysteresis in traditional mesoporous normal
PSCs[158] while Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 composi-
tion exhibits much lower hysteresis in the same structure.[17]
Moreover, hysteresis was further reduced after incorporation of
RbI into triple cation perovskites (Figure 35a–d). As shown in
Figure 35c, hysteresis was nearly removed upon addition of RbI
into double-cation MAFA perovskite. It means that Rb+ plays
an important role in controlling hysteresis. In order to explore
the origin of reduced hysteresis by Rb+, carrier mobility of

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Figure 34.  Energy diagram of planar PSC with a) a negative (−0.2 eV) and b) a positive (+0.2 eV) CBO at buffer (ETM)/perovskite interface. c) A negative
(−0.2 eV) and d) a positive (+0.2 eV) VBO at the perovskite/HTM interface. Reproduced with permission.[312] Copyright 2015, Elsevier.

perovskite films with or without Rb was measured by transient
photoconductivity measurements. As displayed in Figure 35e,
carrier mobility was increased after incorporation of Rb. Fur-
thermore, significantly enhanced PL lifetimes were observed
when 1% RbI was added (Figure 35f). Increased carrier mobility
and PL lifetimes should be responsible for negligible hyster-
esis because of suppressed trap-induced nonradiative recom-
bination. As we discussed in the A-site engineering in Section
3.1.1, KI was also introduced into perovskite precursor solu-
tion and finally leaved in the perovskite composition to reduce
even eliminate the hysteresis.[18,90,123–125] Nearly all the reported
works proposed that reduced nonradiative recombination
resulting from reduced defect density should mainly contribute
to reduction in hysteresis. Except for A site engineering, B-site
engineering also can reduce hysteresis like the development
of MAPb0.9Sn0.05Cu0.05I2.9Br0.1 and MAPb1−xCoxI3 through
reducing defect density, as we discussed in Section 3.1.2.[128,129]
As for X-site, it has been widely recognized that Cl− in precursor
solution can facilitate the crystallization of perovskite and thus
improve the electronic properties (such as carrier lifetime,
mobility, and diffusion length), enabling the realization of sup-
pression of nonradiative recombination and accordingly reduc-
tion of hysteresis.[139,140,146] Introduction of a small amount of
2D perovskite into 3D perovskite was confirmed to not only
improve the moisture stability but also suppress nonradiative
recombination via passivating the surface defect and/or bulk
traps of 3D perovskite, leading to a reduced hysteresis.[158,163,167]
Additionally, negligible hysteresis can also be achieved by grain
preferential orientation growth engineering.[174] and in situ
nonstoichiometric precursor engineering.[14] Additive engi-
neering cannot be neglected as one of the effective methods
to reduce hysteresis through suppressing trap-assisted nonra-
diative recombination, such as SCN−containing molecules like
MASCN,[218] Pb(SCN)2),[214] PCBM,[33,238] etc. Except for bulk
engineering, interface engineering related with perovskite films
can also affect hysteresis through affecting surface or interface

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Figure 35. a–d) J–V curves for devices without Rb or Cs (a), with 5% Cs in MAFA (b), with 1% of Rb in MAFA (c), and with 5% Rb and 5% Cs in
MAFA (d). e) Effective THz carrier mobility for perovskite films on quartz slides. f) TRPL spectra for perovskite films on glass slides. Reproduced with
permission.[324] Copyright 2018, Royal Society of Chemistry.
trap-assisted nonradiative recombination. For example, PCBM,
other fullerene derivatives and quaternary ammonium halide
anions and cations were usually employed to passivate the inter-
face defects at perovskite/ETM in PSCs with much reduced
hysteresis.[33,88,276,291] Regarding the perovskite/HTM interface
in normal PSCs, many molecules with Lewis base have been
developed to passivate the surface defects of perovskite films
and reduce hysteresis.[294,300,301] In addition, the defects at the
surface of perovskite films can also be passivated by in situ or
ex situ perovskite composition engineering and thus reduce
hysteresis.[85,306] In other words, simultaneous passivating
engineering of bulk and surface defects of perovskite films
are highly required for minimizing trap-assisted nonradiative
recombination losses and thus reducing device hysteresis.
6. The Effect of Trap-Induced Nonradiative
Recombination on Stability
Although high PCE of 22.7% has been certified up to now,[12]
instability of PSCs is still one of the main barriers for its large-
scale commercialization. Generally, we usually think that insta-
bility of PSCs mainly comes from the structural instability of
perovskite materials induced by external conditions, including
the moisture, oxygen, illumination and thermal.[39,59,325]
Without the above external environmental factors, stability
of perovskites is mainly determined by the intrinsic phase
stability, which is usually estimated by tolerance factor. For
example, improved stability can be achieved by introducing FA
and Br into pure MAPbI3.[7,326] In addition, incorporation of
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Cs into FAPbI3 can stabilize its black phase and thus improve
photo, thermal and moisture stability.[100,121] This implies that
intrinsic phase stability could be effectively addressed by pero-
vskite composition engineering. However, instability problem
of perovskites is exacerbated significantly external environ-
mental factors and its degradation mechanism becomes more
and more complicated. Although the oxygen and moisture can
be effectively isolated from perovskite films by ideal encapsula-
tion technology, it could be inevitable to leave a tiny amount of
oxygen and moisture in perovskite films, which may come from
materials involved in the whole device. Furthermore, encap-
sulation cannot solve the intrinsic phase stability problem.
Consequently, it is urgently needed to deeply understand the
degradation mechanism of PSCs and thus explore the pos-
sible solutions for it before final commercialization. Except for
intrinsic phase stability, degradation of perovskites is affected
simultaneously by external environmental factors (including
oxygen, temperature, moisture, and illumination) and internal
intrinsic factors in perovskites (such as electron migration, ion
migration, and interfacial reactions).[59,327] Essentially, the above
all degradations induced by internal and external factors are
closely related to defects in perovskite films.[59]
6.1. Moisture Stability
In the PSCs, essential origin of moisture decomposition of
perovskite films is the attack of H2O for perovskite composi-
tion through specific chemical interactions. To date, moisture
degradation mechanisms have been proposed.[39] Although
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www.advancedsciencenews.com
slight difference can be found from the proposed mechanisms,
they face a common problem to answer. That is how waters
attack the perovskite films and where the water will first invade
in perovskite films. In order to answer this question, some
tentative works were carried out.[33,59,328] It was reported by
Ahn et al.[328] that moisture degradation of perovskites is ini-
tially triggered by trapped charges by the defects from grain
boundaries. They demonstrated that irreversible degradation
occurs along GBs upon simultaneous existence of moisture
and trapped charges. It means that trap-assisted nonradiative
recombination plays a decisive role in moisture degradation of
perovskite films. Besides, the synergistic effect of oxygen and
moisture on moisture-induced degradation was found. Since
GBs have a pronounced effect on moisture stability, all of the
methods that reduce GB density by increasing grain size as we
discussed in Section 3.6.1 (GB regulation) are beneficial for
improving moisture stability. In addition, as we discussed in
Sections 3.6.2 and 4.2.1, defect passivation via additive or
surface engineering could be another effective approach to
improve moisture stability.
6.2. Photostability
In addition to moisture stability, photostability is also critical
during the operation of PSCs. It was reported that light stability
of PSCs mainly depends on ultraviolet light stability especially
for conventional normal mesoporous PSCs using TiO2 as ETM.
The generation of defects at TiO2/perovskite interface because
of photocatalytic effect of TiO2 should be mainly responsible
for optical degradation of perovskites.[329–331] It is interesting
that replacement of TiO2 by photostable Al2O3 improves the
UV stability.[331] However, confirmation of photodegradation
of inverted PSC without TiO2 using UV filters indicates that
light-activated metastable defects is also one of the poor photo-
stability of PSCs.[332] Ultrafast vacancy-mediated ion migration
was observed under sunlight illumination in polycrystalline
perovskite films while not in single crystal.[321] This is because
single crystal with much lower defect density exhibits much
higher energy barrier for ion migration as compared to poly-
crystalline films. Furthermore, vacancy-mediated ion migration
will be accelerated under light illumination.[158,321] Vacancy-
mediated ion migration will result in phase segregation and
formation of I-rich and Br-rich domains.[333–335] Vacancy-influ-
enced halide ion migration and different affinity of Pb2+ for
Br− and I− were proposed to be responsible for phase segrega-
tion.[336] It was proposed that under long-term illumination ion
segregation could lead to serious degradation of PSC although
it is reversible under short-term irradiation.[337] In order to
enable long-term photostable PSCs, it is necessary to suppress
vacancy-assisted ion migration through reducing defect density.
6.3. Thermal Stability
Similar to moisture stability, thermal stability of perovskites
was thought to start from GBs or surface.[33,59,328] It is well
known that temperature has a great effect on crystal structure
and phase of perovskites. For instance, phase change from
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tetragonal to cubic occurs at around 54–56 °C as reported
previously.[39,338] Additionally, the ion migration and diffusion
in perovskites are also highly dependent on temperature. It
was reported that in MAPbI3 I− and MA+ ions migrate much
more easily than Pb2+ ions and ion migration is faster at GBs
than in the bulk.[158,317] In fact, it has been demonstrated that
single crystal shows much lower decomposition temperature
as compared to polycrystalline films. For example, MAPbI3
single crystal[339,340] with a defect density of 109–1011 cm−3 was
observed to start decomposition at 240 °C while polycrystal-
line[185,341] MAPbI3 with a defect density of 1015–1017 cm−3 nor-
mally decomposes at 150 °C. In another work, MAPbI3 single
crystal starts to decompose at >300  °C under N2 condition.[342]
This suggests that defect density plays a critical role in thermal
decomposition of perovskite films. Similar to moisture and
light stability, it is critical to enhance thermal stability through
suppressing trap-assisted nonradiative recombination and
reducing defect density.
7. Summary and Outlook
Although PSC achieved high PCE of 22.7%, there are still
rooms for further improvement of PCE toward theoretical value
of 30.5% for a bandgap of 1.6 eV. Since presently achieved Jscs
in most of the highly efficient PSCs were close to theoretical
value but their Voc and FF were lower than theoretical values,
strategy to push Voc and FF up should be developed for further
PCE enhancement. Voc and FF are commonly related to recom-
bination issue, including nonradiative (SRH) recombination
in perovskite and interface recombination. In case that both
nonradiative recombination and interface recombination are
presented in PSC, Voc will be lower than 1 V. If interface recom-
bination is removed, Voc will increase over 1 V but still lower
than 1.2 V due to nonradiative recombination. The real PSCs
reported so far showed Voc in the range between 1 and 1.2 V,
which indicates that nonradiative recombination is critical to
be controlled. For the case of nonradiative recombination, bulk
and surface nonradiative recombination are possible, where
surface recombination is probably related to GB and the sur-
face of perovskite contacting ETM or HTM. Therefore, inter-
face engineering and GB passivation become more and more
important to control recombination issue. In this review,
we have investigated possible and effective ways to deal with
recombination.
In order to inhibit bulk recombination in perovskite films,
various strategies have been developed, such as perovskite com-
position engineering (replacement of A, B, and X sites), dimen-
sionality engineering (like mixed 2D/3D), grain orientation
growth engineering, nonstoichiometric approach (excess PbI2
or excess MAI), precursor solution engineering, post-treatment
(CH3NH2 or NH4SCN treatment), etc. Regarding A-site replace-
ment in composition engineering, Cs+ and Rb+ were found to
not only stabilize the δ phase of FAPbI3 but also reduce nonra-
diative recombination. Voc of 1.24 V could be possible by partial
substitution of MA+ and FA+ with Cs+ and Rb+, forming quad-
ruple-cation RbCsFAMA perovskite, which is corresponding
to loss-in-potential of 0.39 V when considering a bandgap of
1.63 V. Reduction of nonradiative recombination is also possible
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www.advancedsciencenews.com
by B-site engineering. Both binary metal alloy MAPb0.9Co0.1I3
and ternary metal alloy MAPb0.9Sn0.05Cu0.05I2.9Br0.1 are good
examples to achieve a PCE exceeding 21%. Partial substitution
of Pb with Sn is a good strategy toward high Jsc via decreasing
bandgap. However, the Pb–Sn system was found to lead to very
low Voc due to severe recombination and poor morphology as
well. The Pb–Sn–Cu ternary system can overcome problems
in the Pb–Sn system. For X-site replacement, the presence of
Cl− showed great potential in extending carrier diffusion length
and lifetime because of better crystallization of the perovskite
film. Except for halogen elements, pseudohalide is a poten-
tial candidate for X-site substitution. So far, most works have
focused on the substitution of one or two sites in ABX3 and
great progresses have been made. For the purpose of further
enhancement of PCE approaching limit efficiency, simulta-
neous composition engineering for A, B, and X sites could be
desirable toward theoretical efficiency. In this case, pros and
cons in composition engineering should be well understood.
Moreover, the synergistic effect of A, B, and X site replacement
on crystal structure, crystallization kinetics, and optoelectronic
properties should be investigated in depth theoretically and
experimentally. Controlling or combination dimensionality is
also a promising approach in terms of reducing recombina-
tion and improving stability. Low bandgap and high absorption
coefficient are advantages of 3D perovskite, but poor moisture
stability is its disadvantage. On the other hand, low absorption
coefficient, high exciton binding energy, and poor carrier trans-
port are disadvantages of 2D perovskite, but moisture stability
is its advantage. Thus, the 2D/3D strategy is one of the prom-
ising approaches, where the introduction of a small amount of
2D perovskite into 3D perovskite demonstrated simultaneous
effects of improving moisture stability and suppressing SRH
nonradiative recombination via passivating the surface defect/
trap states of 3D perovskite. Grain orientation growth engi-
neering has been recognized as an important strategy to mini-
mize the nonradiative recombination losses. This method is
related to carrier transport recombination. Vertical growth of
perovskite grains is also related to composition engineering
(like mixed 2D/3D or incorporation of MACl into FAPbI3 film),
additive engineering (like incorporation of NH4SCN into 2D),
and procedure optimization (hot casting). In order to further
explore more effective methods for oriented perovskite grains,
understanding correlation between perovskite crystallization
kinetics and other factors (composition, dimensionality and
crystallization condition) is required. In addition, in situ non-
stoichiometric approach (excess PbI2 or MAI) is one of the
effective methods for suppressing nonradiative recombina-
tion because GBs can be passivated by this method. However,
since the introduction of excess PbI2 was reported to lead to an
intrinsic instability of the film under illumination and film deg-
radation even under inert atmosphere, it is important to inves-
tigate the basis for the instability in the presence of excess PbI2
so that alternative effective passivation methods are to be devel-
oped. Finally, post-treatment (CH3NH2 and NH4SCN treat-
ment) is a feasible method to reduce defects at GBs via decom-
position-to-recrystallization evolution of the perovskite films.
Additive engineering was found to suppress nonradia-
tive recombination through increasing grain size, passivating
defects and improving carrier transport and separation. Among
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the proposed additives, SCN-containing metal or organic
salts showed great potentials in preparing large-sized grain.
Of course, other more effective methods are required in near
future to maximize electrical properties (carrier mobility, diffu-
sion length, and lifetime) of perovskite films similar to those of
single crystal. From the perspective of defect passivation, small
molecules or polymers with Lewis acid or base properties can
be used to passivate the defects at GBs or surface of perovskite
films. Particularly, PCBM was identified to have extremely
good passivation function. Thus, it will be an important and
meaningful research direction to design and develop the best
material that can passivate completely defects in perovskite
films. For example, CH3NH2 was used to reduce I2 and I3− was
employed to fill the iodide vacancy. Development of multifunc-
tional additives being able to control grain growth, enlarge
grain size, passivate defects, and facilitate carrier transport is
vital to remove nonradiative recombination.
As compared to nonradiative recombination, interface
recombination is almost equally important. In this review,
we mainly discussed about methodologies to control recom-
bination at perovskite/ETM and perovskite/HTM interfaces.
Regarding ETM/perovskite interface in normal structure and
HTM/perovskite interface in inverted configuration, similar
functions are expected for modifiers, such as inducing energy
level alignment via tuning work function, facilitating perovskite
crystallization, reducing interface recombination through pas-
sivating interface defects, etc. Similar functions are required
for the perovskite/HTM interface in normal structure and pero-
vskite/ETM interface in inverted architecture. Various methods
have been developed to modify ETM/perovskite interface in
normal structure, mainly including inorganic salts, plasma
treatment, insulating metal oxides, self-assembled monolayer,
and electron acceptor materials (such as SnO2, fullerene, and
its derivative). Among the proposed methods, SAM is one of
the promising ways in tuning energy band alignment via regu-
lating work functions due to chemical bonding between metal
oxides and modifiers or between modifiers and perovskite.
Besides, as for interface defect passivation, fullerene and its
derivative have been testified to be promising. ZnO-based
normal PSCs have achieved PCE exceeding 21% together with
significantly improved stability through interface engineering,
which is indicative of importance of ETMs for the perovskite
layer. Although great advancements have been made through
interface engineering, it is required to further deeply under-
stand the effect of modifiers on microscopic electron coupling,
band bending, built-in electric field, chemical interaction, and
defects. Use of insulating interlayer (like PS) is one of the ways
to modify the perovskite/ETM interface in inverted PSCs, which
enables the realization of suppression of interfacial recom-
bination via tunneling electrons from perovskite to ETM but
blocking holes into ETM. Studies on interface engineering for
perovskite/HTM interface select Lewis base organic small mol-
ecules or polymers, insulating buffer layer (Al2O3), perovskite
QDs, and 2D perovskite layer. Particularly, perovskite QDs and
2D materials provide rich possibility for looking for the optimal
modifier at the perovskite/HTM interface. Among them, the
incorporation of the 2D perovskite layer at the perovskite/HTM
interface attracted considerable attentions. However, the devel-
opment of 2D perovskite materials is extremely limited, mainly
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
including PEA2PbI4, BA2PbI4, and (5-AVA)2PbI4. New 2D pero-
vskite materials are recommended to be designed and synthe-
sized for modifying the perovskite/HTM interface for the ulti-
mate goal of stable and efficient PSCs. Compared with normal
PSCs, the perovskite/HTM interface in inverted PSCs was
scarcely investigated. However, like ETM/perovskite interface
in normal structure, the perovskite/HTM interface in inverted
architecture will play an important role in determining the final
device performance. Further studies are required for inter-
face engineering of the perovskite/HTM interface in inverted
structure. We believe that further in-depth and systematic
investigation on perovskite-related interface will drive further
developments of efficient and stable inverted PSCs.
It is well known that trap-assisted nonradiative recombina-
tion can affect not only PCE but also hysteresis and stability of
PSCs. Considering deep-level defects mainly exist at GBs or the
surface of perovskite films, defects at GBs closely related with
trap-assisted nonradiative recombination should be reduced or
removed through increasing the grain size or defect passivation
engineering in order to improve device stability. Since defects
affect device stability through trap-assisted nonradiative recom-
bination, relation between defects and trap-assisted nonradia-
tive recombination as well as device stability should be deeply
investigated experimentally and theoretically.
In order to remove SRH recombination and interface recom-
bination, synergistic engineering for both bulk perovskite and
heterojunction interfaces should be simultaneously considered
toward theoretical Shockley–Queisser limit efficiency of over 30%.
Acknowledgements
This work was supported by the National Research Foundation of Korea
(NRF) grants funded by the Ministry of Science, ICT & Future Planning
(MSIP) of Korea under Contract Nos. NRF-2012M3A6A7054861 (Global
Frontier R&D Program on Center for Multiscale Energy System) and
NRF-2015M1A2A2053004 (Climate Change Management Program).
This work was also supported in part by NRF-2016M3D1A1027663 and
NRF-2016M3D1A1027664 (Future Materials Discovery Program).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
interfaces, nonradiative, perovskite solar cells, recombination,
Shockley–Read–Hall recombination
Received: May 10, 2018
Revised: July 10, 2018
Published online:
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