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Atomic-scale understanding on the physics and control of intrinsic point

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Atomic-scale understanding on the physics
and control of intrinsic point defects in lead
halide perovskites
Cite as: Appl. Phys. Rev. 8, 031302 (2021); https://doi.org/10.1063/5.0052402
Submitted: 31 March 2021 . Accepted: 22 June 2021 . Published Online: 16 July 2021

Jun Kang, Jingbo Li, and Su-Huai Wei

COLLECTIONS

This paper was selected as an Editor’s Pick

Appl. Phys. Rev. 8, 031302 (2021); https://doi.org/10.1063/5.0052402 8, 031302

© 2021 Author(s).
 Applied Physics Reviews REVIEW scitation.org/journal/are

Atomic-scale understanding on the physics and

control of intrinsic point defects in lead halide
perovskites
Cite as: Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402
Submitted: 31 March 2021 . Accepted: 22 June 2021 .
Published Online: 16 July 2021

Jun Kang,1,a) Jingbo Li,2,3 and Su-Huai Wei1

AFFILIATIONS
1
Beijing Computational Science Research Center, Beijing 100193, China
2
Institute of Semiconductors, South China Normal University, Guangzhou 510631, China
3
Guangdong Key Lab of Chip and Integration Technology, Guangzhou 510631, China

a)
Author to whom correspondence should be addressed: jkang@csrc.ac.cn

ABSTRACT
Lead halide perovskites (LHPs) have attracted considerable attention as promising materials for photovoltaic and optoelectronic
applications. Intrinsic point defects play an important role in determining the performance of semiconductor devices. LHPs exhibit strong
ionic character and unique electronic structure; thus, their defect properties are quite different from conventional covalent bond
semiconductors. Understanding the defect science is crucial to the performance optimization of LHP-based devices. State-of-the-art first-
principles calculation methods enable one to explore atomistic mechanisms of various defect-related processes, and tremendous efforts from
theoretical simulations have provided invaluable insights to the defect physics and defect control of LHPs. In this review, we summarize
recent progress, made with the help of theoretical modeling, on atomic-scale understanding about intrinsic point defects and related pro-
cesses in LHPs. The fundamental properties of intrinsic point defects in LHPs are first introduced, including defect formation energy, charge
transition level, and defect tolerance and its origin. A particular emphasis is given to the effects of band edge position on calculated defect
properties. The impact of these defects on structural properties, carrier dynamics, and photoluminescence of LHPs is then presented.
Advanced strategies to engineer the defects in LHPs are also reviewed, such as growth condition, defect passivation, and doping. Finally, we
discuss open issues and outline directions toward a better understanding of defects of LHPs from a theoretical perspective. The goal of the
review is to provide a comprehensive summary of atomic-scale understanding of intrinsic point defects in LHPs and to help further related
research in the perovskite community.
Published under an exclusive license by AIP Publishing. https://doi.org/10.1063/5.0052402

TABLE OF CONTENTS E. Intrinsic point defects in lead-free halide

I. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 perovskites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
II. NATURE OF INTRINSIC POINT DEFECTS IN LEAD III. IMPACTS OF INTRINSIC POINT DEFECTS . . . . . . . . 9
HALIDE PEROVSKITES . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 A. Defect assisted degradation . . . . . . . . . . . . . . . . . . . . 9
A. Fundamental properties of lead halide perovskite. 2 B. Ion migration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
B. Formation energy of intrinsic point defects . . . . . . 3 1. Migrating species and activation energy. . . . . . 9
C. Defect tolerance and its origins . . . . . . . . . . . . . . . . 4 2. Ion migration–related phenomena . . . . . . . . . . 10
1. Defect tolerant band structure . . . . . . . . . . . . . . 5 C. Carrier trapping and dynamics. . . . . . . . . . . . . . . . . 12
2. Polaron effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 D. Defect-induced photoluminescence . . . . . . . . . . . . . 13
3. Self-inhibition of deep traps . . . . . . . . . . . . . . . . 5 IV. CONTROL OF INTRINSIC POINT DEFECTS . . . . . . . 14
4. Self-regulation of defects . . . . . . . . . . . . . . . . . . . 6 A. Growth condition . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
D. The effects of band edge position on calculated B. Passivation by functional groups . . . . . . . . . . . . . . . 14
defect properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 C. Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

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 Applied Physics Reviews
1. Defect suppression through doping induced
strain relaxation . . . . . . . . . . . . . . . . . . . . . . . . . .
2. Defect healing through doping of dipolar
cation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
V. CONCLUSIONS AND OUTLOOK . . . . . . . . . . . . . . . . . .
I. INTRODUCTION
In the past decade, lead halide perovskites (LHPs) have emerged
as promising materials for photovoltaic and optoelectronic applica-
tions.1–8 An area of impressive progress is the rapid growth in power
conversion efficiency of LHP-based solar cells, starting from 3.8%9 to
25%10 in a short period. Besides, LHPs have outstanding lumines-
cence properties. Near-unity photoluminescence quantum yield
(near-unity PLQY) can be achieved in LHP nanocrystals,11–13 and
LHP-based light-emitting diodes with over 20% external quantum effi-
ciency have been realized.14 Applications of LHPs in laser devices15–17
and photodetectors18–20 are also demonstrated. The remarkable device
performance stems from a series of excellent optoelectronic properties,
such as tunability of bandgap,5,21,22 high light absorption coefficient,23
and desirable emission bandwidth24,25 as well as long carrier diffusion
length and lifetime.26–28 Moreover, the simple and cost-efficient syn-
thesis of LHPs through solution-based processes29–31 greatly facilitates
their large-scale commercialization.
Defects in semiconductors, especially the intrinsic defects, play
important roles in determining the electronic and optical performance.
Compared with conventional covalent semiconductors, the defect
properties oingf LHPs are unique. The solution processes during the
fabrication of LHPs are likely to introduce considerable concentration
of intrinsic defects; thus, poor performance is generally expected.
However, LHPs exhibit good device performance despite the abun-
dance in defects, namely, the so-called defect tolerance.32–34 On the
other hand, further improvement on performance is still limited by
various defect-involved processes, such as degradation,35 ion migra-
tion,36 and non-radiative recombination.37,38 Many advanced strate-
gies have been shown to be capable of controlling the defects in LHPs
to minimize their negative effects.39–41 Fundamental understanding of
the nature of intrinsic defects and the underlying mechanisms of
defect-involved processes are thus crucial to further optimization of
LHP-based devices.
Atomic-scale defect modeling based on first-principles density
functional theory (DFT) calculations has been proven to be a powerful
approach that complements experiments and has shown the ability to
make reliable predictions. With over 30 years’ of development, the the-
ory of defect formation energy and transition levels has led to great
successes.42–45 In addition, several sophisticated methods have been
developed recently, allowing the simulation of defect-carrier interac-
tion from first-principles. For example, the rate of carrier capture by
defect can be evaluated from electron–phonon coupling constant cal-
culations and the multiphonon emission model.46–51 Defect effects on
carrier dynamics can be simulated by non-adiabatic molecule dynam-
ics simulations (NAMD).52–54 With the state-of-the-art theoretical
approaches, huge numbers of studies have provided invaluable insights
into the atomistic mechanisms of defect-involved processes in LHPs.
In this review, we discuss recent progress made with the help of
theoretical modeling on atomic-scale understanding about physics,
impacts, and engineering of intrinsic point defects in LHPs. In Sec. II,
Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402
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the nature of intrinsic point defects is introduced, including formation
16 energy, transition level, defect tolerance, and band edge effects. The
properties of lead-free halide perovskite are also briefly discussed.
17 Section III is devoted to the impact of defects such as degradation, ion
17 migration, defect-carrier interaction, and photoluminescence. Defect
engineering through growth condition control, functional group pas-
sivation, and doping is discussed in Sec. IV. Conclusions and outlook
are presented in Sec. V.
II. NATURE OF INTRINSIC POINT DEFECTS IN LEAD
HALIDE PEROVSKITES
A. Fundamental properties of lead halide perovskite
LHPs have the chemical formula of APbX3, where X is a halogen
(Cl, Br, I), and A is a monovalent cation, which can be either organic
like methylammonium (MA) and formamidinium (FA), or inorganic
like Cs. There are three typical crystal structures of most interest,
namely, the a (cubic), b (tetragonal), and c (orthorhombic) phases, as
shown in Fig. 1(a). The basic building block of LHPs is the PbX6 octa-
hedron with one Pb atom at the center and six X atoms at the corners.
The PbX6 octahedra form a 3D network by sharing the corner X
atoms, and different phases of LHPs exhibit different extent of tilting
of the octahedra. The relative stability of different phases changes with
increasing temperature, and phase transition of LHPs from c- to b-
and then to a-phase is often observed.56–59 For example, the a-phase is
usually unstable at 0 K, while it can be stabilized at a finite temperature
[e.g., 330 K for MAPbI359 and 400 K for CsPbBr356]. Compared
with many conventional semiconductors, LHPs have a much softer
lattice,55,60 as indicated by their high density of phonon modes at fre-
quency below 2 THz [Fig. 1(b)]. These phonon modes are mostly con-
tributed by the rotation and distortion of the PbX6 octahedra.61 The
softness of the PbX6 framework leads to strong electron phonon cou-
pling and significant anharmonicity, which could have great impact
on the properties of LHPs.
In general, LHPs have direct bandgap,62–64 although in some
cases spin–orbit coupling (SOC) may induce Rashba slitting and result
in slight mismatch of CBM and VBM in the k-space.65 Depending on
the halogen X, the bandgap of LHPs is in the range of 1.5–3 eV, and
the gap value decreases when X goes from Cl to I.21 In Figs. 1(c) and
1(d) the calculated band structure of c-phase CsPbBr3 and the corre-
sponding projected density of states are presented. There are several
notable features in the electronic structure of LHPs:55,66,67 (i) In con-
trast with conventional semiconductors where the valence band edge
comes from anion p states and the conduction band edge comes from
cation s states, in LHPs the top of the valence band originates from the
Pb s states and X p states, while the bottom of the conduction band is
dominated by Pb p states. The unique orbital character in LHPs results
in enhanced overlap between CBM and VBM and thus enables effi-
cient optical transition. It also contributes to the defect tolerance in
LHPs, as will be discussed later. (ii) The A-site cation has negligible
contribution to the band edges; therefore, the bandgap value is not
quite dependent on its type. Nevertheless, the A-site cation can
indirectly affect the electronic structure of LHPs through Coulomb
interaction or vibrational coupling with the PbX6 octahedral frame-
work.68–70 (iii) Due to the large atomic number of Pb, SOC in LHPs is
quite strong, especially in the conduction band. Typically, the inclu-
sion of SOC in calculation causes a bandgap reduction of
0.5–1 eV,67,71,72 which can be mainly attributed to the downward shift
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(a) Cubic Tetragonal Orthohombic

Pb

(b) 5 (c) 3 (d)

Total

4 2
Frequency (THz)

3 1
Energy (eV)

Br p

DOS
w/ SOC
2 w/o SOC
0

Pb s
1 Pb p
−1

0
−2 −3 −2 −1 0 1 2 3
G X S Y G Z U R T Z G X S Y G Z U R T Z Energy (eV)

FIG. 1. (a) Crystal structures of different phases of APbX3. (b)–(d) Phonon spectrum, band structure, and density of states of c-CsPbBr3. (b)–(d) Reprinted with permission
from Kang et al., J. Phys. Chem. Lett. 8, 489 (2017). Copyright 2017 American Chemical Society.55

of the CBM. Thus, SOC plays a critical role in determining the defect
physics in LHPs, as the defect properties are sensitive to the band edge
position.
B. Formation energy of intrinsic point defects
Point defects in a crystal introduce imperfection around a single
lattice site. If the defect does not involve extra elements other than
those consisted in the host material, it is called intrinsic defect (or
native defect). It is common to refer to intrinsic defect as defect and
extrinsic defect as impurity. In LHPs, there could be three groups of
intrinsic defects as illustrated in Fig. 2(a), namely, vacancy, interstitial,
and antisite. Vacancy defects (VA, VPb, VX) are lattice sites with miss-
ing atoms. Interstitial defects (Ai, Pbi, Xi) are atoms occupying the
interstitial sites of the lattice that are normally unoccupied. Antisite
defects (APb, AX, PbA, PbX, XA, XPb) are atoms on lattice sites that are
occupied by a different type of atom in a perfect crystal.
The formation energy DHf of a defect describes how easily it can
be formed. Under thermodynamic equilibrium conditions, the con-
centration nD of a particular type of defect at temperature T can be cal-
 DH 
culated by nD ¼ Ng exp  kB Tf , where N is the available lattice site
in the host and g is the degeneracy factor, which depends on defect
configuration and charge state. Thus, the defects with lowest formation
energy would have the most abundant defects. DHf is usually not a
constant but depends on the chemical environment during the growth
of the host. In practical calculations, the formation energy DHf ða; qÞ
for a defect a with charge q is determined by43–45
X
DHf ða; qÞ ¼ Eða; qÞ  EðhostÞ þ ni li þ q½EVBM ðhostÞ þ EF :
i
(1)
Here, Eða; qÞ is the total energy of the defective structure, and E(host)
is the total energy of the pristine host material. EVBM ðhostÞ is the
VBM energy, and EF is the Fermi energy referenced to VBM. ni is the
number of atom i exchanged with the reservoirs during defect forma-
tion. The effect of the chemical environment is commonly involved in
the chemical potential li for different elements i. Very often li is refer-
enced to the atomic energy Ei of pure elemental solid/gas of i, i.e.,
li ¼ Ei þ Dli . The thermodynamic equilibrium growth condition
sets a series of limitations on the chemical potential, and Dli is con-
fined in a finite range. First, to avoid the formation of elemental solid/
gas, Dli should be smaller than 0. Second, the formation of competing
compounds (like AX, PbX2, and others) should also be prevented,

Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402 8, 031302-3

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 Applied Physics Reviews
(a)
Vacancy Antisite Interstitial
−3 −2 −1
(b) 0.0
Br2 Gas Molecule
A 300 k, 1 atm
−0.5
PbBr2
mBr (eV)
CsPbBr3
B
−1.0
CsBr
−1.5
Cs Metal
−3 −2 −1
mPb (eV)
FIG. 2. (a) Illustrations of intrinsic point defects in LHPs. (b) Thermodynamic stable range for equilibrium growth of CsPbBr3. Reprinted with permission from Kang et al., J.
Phys. Chem. Lett. 8, 489 (2017). Copyright 2017 American Chemical Society.55 (c) The calculated formation energy of intrinsic point defects in c-CsPbBr3, c-CsPbI3, a-
MAPbI3, and a-FAPbI3, summarized from the literature.32,55,73,74
namely, DlA þ DlX < DHf ðAXÞ and DlPb þ 2DlX < DHf ðPbX2 Þ.
Finally, to maintain a stable APbX3 compound, the chemical potentials
should satisfy: DlA þ DlPb þ 3DlX ¼ DHf ðAPbX3 Þ. Hence, Dli
close to zero corresponds to the i-rich growth condition, as the ele-
ment i is so abundant that it reaches the critical point of forming ele-
mental solid/gas. Accordingly, the situation of lowest possible Dli can
be interpreted as the i-poor condition. The defect charge transition
energy level ðq=q0 Þ is defined as the EF at which the formation energy
DHða; qÞ ¼ DHða; q0 Þ, i.e.,
 
ðq=q0 Þ ¼ Eða; qÞ  Eða; q0 Þ þ ðq  q0 ÞEVBM =ðq0  qÞ: (2)
In Fig. 2(b) the stable region of chemical potential for thermody-
namic equilibrium growth of CsPbBr3 is presented.55 Other LHPs
exhibit similar features.32,73,75 It is seen that the width of the region is
quite small, only 0.25 eV. The narrow region indicates low dissociation
energy of APbX3 into AX and PbX2. Especially for MAPbI3, this
region is extremely narrow76 or even disappears77 (with negative
width), depending on the computational method used. This observa-
tion is consistent with the low stability of LHPs.78,79 Nevertheless, the
region sits across a wide range of chemical potential, allowing effective
control of growth condition to tune defect properties. In Fig. 2(c), the
calculated formation energy of intrinsic point defects in several typical
LHPs is presented, summarized from various literature.32,55,73,74
Although the type of defect with lowest formation energy is material
specified, overall, the vacancies have relatively smaller formation
energy, typically less than 1 eV under appropriate growth condition.
This suggests considerable concentration of vacancies in LHPs.
Meanwhile, many antisites have relatively high formation energy (sev-
eral eV); thus, they are energetically unfavorable. These distinct mag-
nitudes of formation energy contribute to unique defect properties in
LHPs, which are discussed in the next part.
Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402
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(c) X-rich
Pb-rich
6 CsPbBr3
0
6 CsPbI3
Formation Energy (eV)
0 3
0.0
0
6 MAPbI3
−0.5
3
−1.0 0
6 FAPbI3
−1.5 3
0 0
VA VPb VX Ai Pbi Xi APb AX PbA PbX XA XPb
While Eq. (1) works well for bulk materials, it is also worth not-
ing that the formation of defects in nanocrystals (NCs) deserves fur-
ther discussions. Brinck et al. proposed that for NCs prepared in
solution, the chemical potential should be related to molecular ion
pairs in solution (such as CsBr and PbBr2) rather than solid precipi-
tates.80 Moreover, due to the low dielectric environment in the solu-
tion, the formation of a specified defect is always accompanied by its
charge compensating defect, and the neutral molecular ion pair is then
dispersed in the solvent. For example, the creation of a lead vacancy is
accompanied by the removal of two Br ions, and thus a PbBr2 specie is
detached from the NC. Considering such a process, it is suggested to
use the following equation for defect formation energy in NC:80
 
DHfNC ða þ a0 Þ ¼ E NCða þ a0 Þ  EðNCÞ6EðsÞ; (3)
where a and a0 are charge compensating defect pairs, E½NCða þ a0 Þ;
EðNCÞ, and E(s) are the total energy of the defective NC, pristine NC,
and charge neutral molecular species, respectively. The formation
energy is dependent on the location of a and a0 , e.g., either in the core
or at the surface of the NC.
C. Defect tolerance and its origins
LHPs are usually synthesized through simple and cost-efficient
solution-based processes, during which various defects could be easily
introduced. The abundance of defects in LHPs is also expected accord-
ing to the low formation energy. For conventional semiconductors,
defects can greatly reduce the performance. In contrast, LHPs exhibit
excellent optical and electronic properties (long carrier lifetime, high
quantum yield, etc.) as if carrier trap and excessive doping barely
exist,81 despite the fact that structural and other characterization tech-
niques found there are high density structural defects up to a few
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atomic percent.33,82 However, in situ XPS measurements reveal that Therefore, the energy of atomic Pb p orbital is higher than the CBM.
the electronic structure of MAPbI3 remains intact even when the I/Pb As a result of the unique band structure, the DLS of vacancies and
ratio drops to 2.5 (which indicates 17% deficient of I).33 The physical many interstitials, which come from the dangling bonds of cations or
origin for the defect tolerance in LHPs is under active investigation, anions, reside inside either the VB or CB, and they only create shallow
and several possible mechanisms are proposed. defect levels close to the band edge. However, for some types of defects
such as antisites, due to the formation of Pb–Pb or X–X wrong bonds,
1. Defect tolerant band structure the DLS enter the bandgap, resulting in deep levels. These features are
clearly seen in the calculated density of states and defect transition lev-
The first attempts to understand the defect tolerance in LHPs els of LHPs [Fig. 3(b)].32,55,73,74,84 As the vacancies in general have
paid attention to their band structures.32,55,83 For conventional cova- lower formation energy, the majority of defects in LHPs are expected
lent semiconductors that are defect intolerant due to the strong bon- to be shallow and do not significantly affect the performance of LHPs.
ding–antibonding interaction between cation and anion, the CB and Although there could be deep-level defects, most of them have high
VB are higher and lower than the atomic orbital levels. Such a property formation energy and low concentration. Based on these arguments,
leads to deep defect localized states (DLS) inside the bandgap when the unique band structure of LHPs is regarded as an important mecha-
atoms are removed or displaced, as illustrated in the left panel of nism responsible for their defect tolerance.
Fig. 3(a). The situation in LHPs is quite different. In the right panel of
Fig. 3(a), an illustration of electronic structure of LHPs is presented. 2. Polaron effect
As aforementioned, the A sites have no contribution to the band edges.
The top of VB stems from the strong s–p repulsion between Pb and X, Formation of polarons is another mechanism suggested to explain
leading to antibonding character of the VBM. This makes the VBM the defect tolerance. In an ionic material with strong electron-phonon
higher in energy than the X p orbital. The CB of LHPs consists of coupling like LHP, an excess carrier may be self-trapped to form a
empty Pb p states. Due to the ionic character of the Pb–X bond, the polaron, which refers to the electron (hole) dressed by the deformation-
covalent bonding–antibonding interaction between the p states of Pb induced nuclear polarization (phonon cloud).86 Depending on the effec-
and X is weak. Moreover, the strong SOC interaction due to the heavy tive range of the driving force, the size of a polaron can be either small
Pb ion greatly broadens the width of CB and lowers the CBM. (comparable to a unitcell) or large (across multiple unitcells). The
attractive Coulomb interaction between carrier and the deformed lattice
is proportional to ½1=eð1Þ  1=eð0Þ, where eð1Þ and eð0Þ are the
(a) Defect intolerant Defect tolerant high-frequency and static dielectric constant, respectively. A significant
difference in eð1Þ and eð0Þ facilitates the formation of large polaron.86
Pb p Pb p For LHPs, eð0Þ is >20 whereas eð1Þ is 5,87 which is likely to cause
CBM DLS
the formation of large polaron. Zhu proposed that the carrier in LHPs
DLS is protected as large polarons.86 The polaron transport coherently. The
CBM nuclear polarization would follow the movement of the localized charge
Cation Deep Shallow levels carriers, thus the carriers are dynamically screened by the lattice defor-
levels mation. However, on the one hand, the efficient screening diminishes
VBM the Coulomb potential of the polaron, thus greatly reducing its scatter-
Anion Br p
DLS ing with trapped charge on defects; on the other hand, it significantly
DLS
increases the effective mass of the polaron compared to free band edge
Pb s
VBM carriers.88,89 For example, the estimated effective mass of polaron in
MAPbI3 is 10–300 m0.86 As a result, a heavy polaron moves with large
momentum and is only weakly scattered by defect-induced phonons or
LO phonons which have relatively small momentum.89 In addition, the
(b) 2.5 “protective” shield (nuclear deformation) needs to be removed to allow
0/1+ 0/1+ 0/1+ 0/1+
CBM the recombination of two large polarons with opposite charge, which
2.0 1+/2+ 0/1+ 0/1+
introduces a barrier90 and slows down the carrier recombination. The
1+/2+ 1+/2+
1.5 2+/3+ 2−/3−
formation of large polaron in LHPs is supported by theoretical calcula-
Energy (eV)

tions as shown in Fig. 4, with predicted formation energy of

1.0
1−/2−
55–140 meV.85,91 Signatures of large polaron are also observed experi-
mentally.85,92 Besides the large polaron, formation of small polaron in
0.5
0/1− 0/1− 0/2−
LHPs is also predicted.93,94 Moreover, the electron and hole polarons
0.0 VBM
1−/2− 0/1− 0/1− are found to localize in spatially distinct regions.95 Such localization
0/1− minimizes the overlap between electrons and holes and could reduce
CsBr Csi Pbi PbBr PbCs VBr BrCs BrPb CsPb Bri VCs VPb their recombination.

FIG. 3. (a) Schematic representation of electronic band structure of typical defect-

3. Self-inhibition of deep traps
intolerant semiconductors and LHPs. (b) Defect charge-transition levels of
CsPbBr3. Reprinted with permission from Kang et al., J. Phys. Chem. Lett. 8, 489 Although theoretical studies reveal that, in general, the formation
(2017). Copyright 2017 American Chemical Society.55
energy of deep-level defects is relatively high, many calculations also

Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402 8, 031302-5

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in either relative level position to the band edges or kinetic barrier),

2.97
then inefficient channels would be the bottleneck of the overall recom-
Pb-Br distance (Å)

2.94
2.91
2.89
–25 –20 –15 –10 –5 0 5 10
Distance (Å)
FIG. 4. Illustration of large polaron formation in CsPbBr3. Reprinted with permission
from Miyatae et al., Sci. Adv. 3, e1701217 (2017). Copyright 2017 AAAS.85
point out this trend is not always followed, especially when defects are
charged. For instance, the formation energy of charged Ii in MAPbI397
and PbI in CsPbI396 could have formation energy below 1 eV, resulting
in non-negligible amounts of deep traps. Experimentally, the existence
of considerable deep traps (1016 cm3) is also observed.28,98 Why do
these deep traps not cause efficient nonradiative recombination? Based
on a multiphonon transition model, it is showed that deep trap
induced recombination rates strongly depend on the defect level posi-
tion, due to the low phonon energies of LHPs.99,100 While the recom-
bination is most efficient when the defect level is at mid-gap, it
becomes orders of magnitude slower when the defect level is just a few
100 meV away from mid-gap. Since most of the deep defect levels do
not locate right at the mid-gap, the overall trap-assisted recombination
rate is expected to be low. Besides the low phonon energy, a self-
inhibition mechanism for deep defects with multiple charged states is
proposed by several works to rationalize the inactive deep
traps.96,101,102 In LHPs, a deep defect can often have many different
charged states, introducing multiple levels inside the bandgap, as well
as multiple recombination channels. If the nonradiative recombination
rates for different channels are extremely imbalanced (e.g., some are
efficient and some are inefficient, which may be caused by differences
bination cycle, and the efficient channels are thus deactivated. The
defect would be stuck in the charged state with low recombination
rates, being an inactive deep trap.
Zhang et al. have studied the self-inhibition of PbI in CsPbI3,96 as
presented in Fig. 5. PbI has three stable charged states þ1, þ2, and
3þ
15 20 25 þ3. By capturing an electron (C3þ n ), PbI transitions to Pb2þ I . The
þ
capturing of another electron (C2þ n ) induces Pb2þI to PbI transition.
The reverse transitions from Pbþ I to PbI
2þ
and then to Pb3þ I occur
þ 2þ
through capturing holes (Cp and Cp , respectively). First-principles
calculations on the carrier capturing coefficients reveal that while the
C3þ 2þ 2þ
n and Cn processes are fast, the rate of Cp process is moderate,
and the Cp process is extremely slow. The slow Cþ
þ
p is attributed to the
strong anharmonicity-induced high kinetic barrier.96 Consequently,
Cþp is the rate limiting process of the overall recombination cycle, and
most of the defects stay at the 1þ charged state. Although other
charged states can capture carriers more efficiently, their concentration
is low, leading to minimal overall recombination rate.
4. Self-regulation of defects
The predicted high concentration of shallow defects in LHPs is
expected to introduce considerable unintentional doping. However, a
notable feature of defect tolerance in LHPs is that excessive doping
concentration is unusually low (109–1010 cm3).103,104 Several studies
proposed that the formation of Schottky defect (combination of anion
and cation vacancies) results in a self-regulation mechanism,84,105,106
which is responsible for the low carrier concentration. The formation
energy of Schottky defect in LHPs is found to be extremely low (e.g.,
0.08–0.22 eV in MAPbI3), which is attributed to the reduced electro-
static potential on lattice sites.105 Yang et al. further showed that the
formation energy of the Schottky defects can be independent of atomic
chemical potentials due to the entanglement of atomic chemical
potentials and Fermi energy, thus the defect compensation is self-regu-
lated.106 As a consequence, the formation of a certain type of point
vacancies is likely to trigger the formation of the corresponding
charge-compensating vacancies. For instance, a VMA will be compen-
sated by a VI, and a VPb will be compensated by two VI. The resulting

(a) (b) 10−5

Cn3+
Cn2+
Capture coefficient (cm3s−1)

PbI2+ 10−10
Cp2+
FIG. 5. (a) The four carrier capture pro-
Cp+ Cn3+ cesses mediated by PbI in CsPbI3, and
PbI+ PbI3+ (b) the calculated nonradiative capture
CB 10−15 coefficients. Reprinted with permission
Cn2+ Cp2+ from Zhang et al., J. Phys. Chem. C 124,
e– 6022 (2020). Copyright 2020 American
Chemical Society.96
10−20 Cp+ Ctot
slow
h+
VB
100 200 300 400 500
Temperature (K)

Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402 8, 031302-6

Published under an exclusive license by AIP Publishing
 Applied Physics Reviews
700
600
PbI2 vacancy
MAI vacancy
Density of states
500 Bulk
400
300
200
100
0 the prediction of band edge position.
−2 −1 0 1 2 3
Energy (eV)
(a) (b)
FIG. 6. (a) PbI2 Schottky defect in MAPbI3. Vacant Pb and I are denoted by yellow
and green, respectively. (b) Density of states of pristine MAPbI3 and defective ones
with VMAI or VPBI2 . Reprinted with permission from Kim et al., J. Phys. Chem. Lett.
5, 1312 (2014). Copyright 2014 American Chemical Society.84
Schottky defect is stoichiometric, so it does not contribute free carrier
nor in-gap states, as shown in Fig. 6, and the overall charge neutrality
of the system is maintained.84 The benign nature of the Schottky defect
is further demonstrated by experimental evidence, which showed
intact electronic structure of MAPbI3 upon creating high concentra-
tion of VMAI by x-ray irradiation.33
Despite the above-mentioned progress already made, a clear and
complete understanding of the origin of the defect tolerance has not
yet been reached. Theoretically, due to the complicated structure and
electronic properties of LHPs, the results could strongly depend on the
choice of computational schemes, and sometimes conflicting conclu-
sions were reported in the literature. Experimentally it is challenging
to reliably probe atomic-scale details of the defects, thus bringing diffi-
culty in providing a series of controlled and direct experiments to ver-
ify different proposed mechanisms. To date, the origin of defect
tolerance in LHPs remains an open question. Intensive investigations
and lively debates on this topic are ongoing.107–110 For example,
recently Chu et al. carried out non-adiabatic molecular dynamic stud-
ies for defective MAPbI3 and CsPbI3.107,108 They concluded that due
to the soft lattice and defect covalency, the presence of native defects
does not accelerate (and sometimes suppresses) the nonradiative
recombination compared to the case of perfect host. Walsh et al. ques-
tioned this conclusion and commented that there could be flaws in the
computational setup, resulting in exaggerated non-radiative recombi-
nation for pristine LHPs.109 Further studies are still needed toward a
full understanding of the mystery of defect tolerance in LHPs.
D. The effects of band edge position on calculated
defect properties
The defect properties in LHPs have been under extensive study.
However, very often one sees discrepancies in the reported results
from different published sources, and sometimes the difference can be
qualitative. Taking the most studied MAPbI3 as an example, some
studies proposed VI to be an effective DX-like recombination center
with negative-U character (acceptor level lower than donor level) due
to the formation of Pb–Pb dimer when negatively charged,112,114,115
whereas others predicted that Pb–Pb dimer is not stable and VI is shal-
low with positive-U character.111 There are also disagreements on
Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402
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whether VPb introduces deep levels inside the bandgap101 or not.32,116
Ii was predicted to be shallow32,114 and suppression of nonradiative
recombination by Ii was reported,117 but this defect was also suggested
to be a cause of nonradiative recombination in MAPbI3.97,101 In the
latter case, different conclusions on whether the rate limiting process
of the nonradiative recombination is electron capture97 or hole cap-
ture101 are obtained. Dispersed results for defect related properties of
other LHPs, such as defect level,74,118 migration barrier,119,120 and
recombination rate,96,107 are also seen. The origin of these discrepan-
cies can be complicated, but an important contribution comes from
4
For defect calculations, it is essential to obtain correct bandgap
and band edge positions.45,121 As an example, the position of individ-
ual band edges plays critical roles in reproducing the self-doping
behavior of PbTe.122 The semi-local exchange functionals used in
bare-DFT calculations, such as the Perdew-Burke-Ernzerhof (PBE)
functional,123 usually underestimate the bandgap and lead to incorrect
band edge positions. Higher-level schemes like the hybrid-DFT,124
which includes exact exchange potential, can significantly improve the
results due to the correction of self-interaction. In addition, when
heavy elements like Pb are involved, spin–orbit coupling (SOC) intro-
duces large splitting of energy bands, thus the bandgap and band edge
positions can be significantly affected. For LHPs, several works dem-
onstrated that the bandgap underestimation and SOC splitting have
similar magnitude of 1 eV [Fig. 7(a)].62,111,112,125,126 Neglecting SOC
shifts the CBM upward, and the bandgap error shifts the VBM
upward.
In defect calculations, there are usually two steps: structural relax-
ation (SR) to obtain equilibrium geometries, and single-point calcula-
tion (SPC) to get the electronic structure. The usage of different levels
of DFT (semi-local or hybrid functionals, with or without SOC) in the
calculations can greatly contribute to the discrepancies on reported
defect properties in the literature. As a result of error cancelation, acci-
dental “agreement” on calculated and experimental bandgap value of
LHPs is often achieved when bare-DFT without SOC is employed. A
large number of defect calculations on LHPs thus adopt bare-DFT for
both SR and SPC,32,84,114 with the expectation that the inclusion of
exact exchange or SOC would not qualitatively change the results as
long as the bandgap value is reasonable. However, this expectation
does not always come true, especially when there are deep defects.
Because of the overestimation of both CBM and VBM energy, it is
possible that bare-DFT fails to predict some deep levels near the VBM
and incorrectly predicts some deep levels near the CBM [Fig. 7(b)].
This effect is already significant even if hybirdþSOC calculations are
performed only for the SPC step, as shown by Du.112 With this insight
and because of the high computational cost of hybrid-DFT, a mixed
scheme for defect calculations in LHPs is often employed, using bare-
DFT for SR and hybridþSOC for SPC. The assumption is that
bandgap error and SOC have minor influence on the structural prop-
erties of defects, and all their effects can be included in the SPC
step.127–129 While the mixed scheme leads to much improved results
compared with bare-DFT,130 there could still be cases in which it fails.
SOC and exact exchange may not only affect the electronic structure,
but also modify the equilibrium geometry and potential energy surface
in case the occupation on the defect state is changed.
The Br vacancy in CsPbBr3 is a demonstrative example to show
the effects of band edge positions. Using the mixed scheme, the VBr is
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2
(a) (c)

Conduction band
SR: SR: SR: SR: SR:

SR: PBE SPC: PBE

CB PBE PBE-SOC HSE-SOC PBE PBE-SOC 0.6
Eg=1.56
3.0 0.0
SPC: SPC: SPC: SPC: SPC:
Eg=1.68 Eg=1.64 PBE PBE-SOC HSE-SOC HSE-SOC HSE-SOC
Eg=1.58 –0.6
1 Eg=1.10
2.5
Energy (eV)

Eg=0.55 –1.2
(+/0)
(+/–) –1.8
(+/0)
2.0 –2.4
(0/–) (+/–)

Energy (eV)
0.19 (0/–) (0/–)
0 (0/–) G U
–0.23 (+/0) (+/0)
–0.53 1.5 (0/–)
–0.51

SR: PBE SPC: HSE-SOC

(+/0)
0.8
0.5 VBr–

Valence band
a = 0.25 VB 0.0

Energy (eV)
a = 0.43
−1
PBE PBE* HSE06* PBE0* HSE06* GW* –0.8
0.0
–1.6

–0.5 –2.4

(b) GGA-non-SOC HSE-SOC (d) G U

SR: HSE-SOC SPC: HSE-SOC

0.6 0.2 0.6 0.0
VBr0 V +
Br VBr–
PBE VBr–
Donor level Donor level 0.4 PBE-SOC 0.4 –0.8
CBM
Energy (eV)

HSE-SOC
0.1
–1.6
0.2 0.2
–2.4
Acceptor level Acceptor level
0.0 0.0 0.0
–3.2
4 5 6 5.5 6.0 6.5 3 4 5 6
VBM dPb-Pb (Å) dPb-Pb (Å) G
dPb-Pb (Å) U

FIG. 7. (a) Band edge positions of MAPbI3 calculated at different levels of theories. The  denotes calculations including spin–orbit coupling. Reprinted with permission from
Meggiolaro et al., ACS Energy Lett. 3, 2206 (2018). Copyright 2018 American Chemical Society.111 (b) Scheme of band edge effects on the calculated defect level. Reprinted
with permission from Du, J. Phys. Chem. Lett. 6, 1461 (2015). Copyright 2015 American Chemical Society.112 (c) Calculated charge transition levels for VBr in CsPbBr3 using
different schemes for structural relaxation (SR) and single-point calculation (SPC). (d) The total energy as a function of Pb–Pb distance for V0Br , V þ
Br , and VBr in CsPbBr3, with
the structural relaxation done with PBE, PBE–SOC, and HSE–SOC. (e) The band structure and the charge density of the electronically active states for V Br in CsPbBr3.
(c)–(e) Reprinted with permission from Kang, Phys. Rev. Mater. 4, 085405 (2020). Copyright 2020 American Physical Society.113

predicted to be a negative-U center, and the formation of Pb–Pb dimer lead-free halide perovskites, namely, tin halide perovskite (THP)
is expected to be favored when the defect is negatively charged,128 as ASnX3 and double perovskite A2BB0 X6 (where B and B0 are monova-
seen in Fig. 7(e). However, if hybrid-DFT (HSE) with SOC is used for lent and trivalent metal ions, respectively). A number of calculations
both SR and SPC, VBr exhibits a normal shallow level feature instead showed that the defect properties of THPs have much similarity to
of the negative-U character, and the Pb dimer becomes unstable, as those in LHPs.132–136 This is not surprising given the similarity
shown in Fig. 7(c).113 Configuration diagrams on the Pb–Pb distance between Sn and Pb. Most of the defects are predicted to be shallow,
clearly shows that the potential energy surface is changed when and vacancies in THPs are found to be dominant.132,134,135 Especially,
HSE–SOC is adopted instead of bare-DFT [Fig. 7(d)]. Moreover, the Sn vacancy under Sn-poor condition has very small formation
highly dynamic defect level of VBr predicted from bare-DFT–based energy133 (or even negative at the LDA/PBE level132,134–136) because of
molecular dynamic simulations131 is absent once SOC is included.113 the tendency of Sn to be in 4þ valence state. The abundance of VSn
For other systems such as VI and Ii in MAPbI3, different equilibrium could cause high structural instability. In contrast, Sn-rich condition is
geometries are also observed for calculations with bare-DFT and predicted to increase the formation energy of VSn and many other
HSE–SOC, leading to qualitative differences in defect level and carrier defects.134,136 With these understood, theory-guided synthesis of
capture rates.97,101,111,114 These works demonstrate that it is critical to highly luminescent THPs under Sn-rich condition is achieved.136
correctly describe the band edge position for accurate modeling of For double perovskite A2BB0 X6, there could be many choices for
defects in LHPs. Careful hybrid-SOC tests on top of bare-DFT calcula- B and B0 . Two typical combinations are Ag–In and Ag–Bi, which has
tions are advised, and structural relaxation with hybrid-SOC should be been realized experimentally.137,138 In terms of defect level depth, the
performed if necessary, especially when occupation change on deep (Ag,In)- and (Ag,Bi)-based double perovskites are not as defect toler-
defect states is observed. ant as LHPs. In these materials, the VBM is mainly contributed by the
coupling between Ag 4d states and anion p states, whereas the s states
from In and Bi have very small contribution, especially for In.139,140 As
E. Intrinsic point defects in lead-free halide perovskites a result, the VAg remains a shallow defect but VIn and VBi become
While the focus of this review is LHP, for comprehensiveness, deep defects.139–141 Several other defects with low formation energy in
here we would also like to briefly discuss intrinsic point defects in these materials are identified as deep traps, e.g., BiAg and halogen
nontoxic lead-free halide perovskites. There are two representative vacancies in Cs2AgBiCl6 and Cs2AgBiBr6 as well as InAg in

Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402 8, 031302-8

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 Applied Physics Reviews
Cs2AgInCl6.139 Again, careful control of growth conditions is impor-
tant to suppress the formation of these detrimental defects.139,140
III. IMPACTS OF INTRINSIC POINT DEFECTS
Although LHPs exhibit better defect tolerance than many other
semiconductors, it never means that their properties are not affected
by defects. For surfaces80 and grain boundaries,142 there could be more
defects leading to the trapping of carriers. Moreover, the defect toler-
ance is merely associated with certain electronic and optical properties.
The abundant defects in LHPs can have significant structural effects.
In this section, current knowledge about the impact of intrinsic point
defects on the properties of LHPs is presented.
A. Defect assisted degradation
While LHPs possess excellent optical and electronic properties,
their long-term operational stability is not satisfactory for practical
applications.77–79 Degradation of LHPs due to many factors like heat,
moisture, light, and oxygen often occurs in a few tens of hours.146 On
the one hand, the instability can be attributed to the low decomposi-
tion energy of APbX3 into AX and PbX2. On the other hand, due to
their high concentration in LHPs, the degradation can be greatly accel-
erated by intrinsic defects. Besides experimental efforts, atomistic ori-
gins of defect assisted degradation have been widely investigated
through theoretical calculations. These studies reveal that both vacan-
cies and interstitials associated with the halogen X in LHPs can accel-
erate the degradation.
Vacancy-accelerated degradation is usually induced by enhanced
interaction of water or oxygen molecules with the defect sites.147 For
example, it is reported that a humid environment promotes the forma-
tion of Br vacancy on the (010) surface of MAPbBr3.148 The formation
energy of VBr decreases from 2.39 eV to 1.05 eV before and after,
including the solvent effect of water. The adsorption of a series of mol-
ecules and atoms (including H2O, O2, CH3CN, and H) on pristine
(010) surface is found to be either weak (with 0.1–0.3 eV adsorption
energy) or endothermic. In contrast, on a defective surface containing
VBr, the adsorption energy is significantly increased due to the stronger
hydrogen bond.148 Therefore, defective surfaces with vacancies are
more active than the pristine ones, and the vacancy sites can serve as
the starting point of the degradation. Combined experimental and the-
oretical investigations on oxygen-induced degradation of MAPBI3
were carried out by Aristidou et al.143 Through isothermal gravimetric
analysis and mass spectrometry, fast oxygen diffusion in MAPbI3 was
identified. However, the enthalpy of the degradation reaction caused
by neutral O2 molecule and in the absence of light is found to be high.
Further ab initio calculations indicated that the iodide vacancies are
favorable sites to capture the diffusing O2 and mediate the formation
of superoxide (O 
2 ) with the presence of a photoelectron. The O2 spe-
cie is highly active and results in negative enthalpy of the reaction of
degradation: 4MAPbI3 þ O 2 ! 4PbI2 þ 2I2 þ 2H2O þ 4CH3NH2
(the symbol  stands for photo-oxidization). A scheme of this VI
assisted degradation is shown in Fig. 8(a). This mechanism is also sup-
ported by Ouyang et al.’s calculations, and they concluded that the
presence of water further promotes this process.149 Molecule dynamics
simulations by Mosconi et al. on an MAPbI3/water interface showed
that the strong Pb–I bonds on a PbI2-terminated surface protect it
from degradation. However, once PbI2 vacancies are introduced on
the surface, dissolution of the exposed facet is observed within a few
Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402
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picoseconds, through the formation of solvated complexes
[PbI2(H2O)4] and [PbI(H2O)5]þ by surface Pb atoms,144 as shown in
Fig. 8(b). Besides, the formation of HI vacancy through thermody-
namic process is proposed to be responsible for the MAPbI3 degrada-
tion to PbI2 in vacuum without the involvement of water and
oxygen.150
Interstitial defects formed by halogen atoms or atomic clusters
can also boost the degradation of LHPs. Tan et al. experimentally
observed degradation of cubic a-FAPbI3 without the formation of
PbI2. This is explained by the transition from the a phase to the c
phase with the assistance of shallow iodine interstitials.145 According
to their calculations, the barrier for the phase transition is reduced
from 0.69 eV to 0.35 eV after introducing the Ii, as seen in Fig. 8(c).
The lowering of the barrier is possibly caused by the participation of Ii
into the bond breaking and reconstruction during the phase transition;
see Figs. 8(d)–8(e). Zhang et al. demonstrated that iodine interstitials
in MAPbI3 make the Pb–Pb distance closer to that in the PbI2 frame-
work, thus easing the formation of local PbI2 structure.151 Motti et al.
showed that the highly diffusive Ii in LHPs can form I2 molecules, and
the I2 molecules are stabilized on the surface rather than in the bulk by
0.4 eV.152 The surface coordinated I2 can then trigger a set of auto-
catalytic chain reactions, leading to an intrinsic degradation pathway
to PbI2.153
B. Ion migration
Because of high defect concentration and weak ionic bonding, it
is likely that the defect-associated ions (i.e., originated from vacancies
or interstitials) in LHPs are mobile. In an early study in 1983, migrat-
ing halide-ion vacancies in CsPbCI3 and CsPbBr3 have been recog-
nized.154 During the past few years, with state-of-the-art experimental
and theoretical techniques, various phenomena related to defect/ion
migration in LHPs were observed, and atomistic mechanisms of the
migration were explored.155–157
1. Migrating species and activation energy
There have been numerous theoretical studies investigating the
migration of different defects, usually combining DFT calculations
and NEB methods.158,159,161,162,164 The migration is considered as hop-
ping of ions from one site to another and can be either vacancy
assisted or through the interstiticaly mechanism, as illustrated in Figs.
9(a) and 9(b). A kinetic barrier Ea is thus needed to be overcome for
the migration. The migration rate rm is affected by Ea through an
Arrhenius relation rm  expðEa =kB TÞ. Due to different computa-
tional setups in different studies (such as supercell size, phase of struc-
tural model, orientation of A site molecules, level of theory, etc.), there
are large variations among the reported values of migration barrier, as
summarized in Table I. For example, the calculated barrier for the
migration of VPb ranges from 0.8 eV119 to 2.31 eV.158 Nevertheless,
these studies consistently showed the trend that halide anions have
lower migration barrier than A-site cations (but somewhat compara-
ble), while the migration barrier of Pb is significantly higher.
Therefore, the halide anions and A-site cations are considered to be
the major source of ion migration,159,161 with typical migration barrier
of 0.1–0.6 eV. For MAPbI3, vacancy-assisted migration is suggested to
be dominant by VI due to low formation energy and barrier.161 Studies
also revealed that while VI and Ii have similar diffusion barrier, the
8, 031302-9
 Applied Physics Reviews
(a)
O2 Vacancy Pb2+ I−
(c)
800 Defect-free
Relative energy (meV)
w/Ii
600
689 meV
400
200 354 meV
0
−200
−400
Cubic Hexagonal
FIG. 8. (a) Defect assisted photo-degradation of MAPbI3 by O2 adsorption. From left to right: oxygen adsorption on vacancy site; generation of photo-carriers; superoxide for-
mation from O2; reaction and degradation. Reproduced with permission from Aristidou et al., Nat. Commun. 8, 15218 (2017). Copyright 2017 Springer Nature.143 (b)
Interaction of undercoordinated Pb with H2O on the surface of MAPbI3, and formation of [PbI2(H2O)4] (upper panels) and [PbI(H2O)5]þ (bottom panels). Reprinted with permis-
sion from Mosconi et al., Chem. Mater. 27, 4885 (2015). Copyright 2015 American Chemical Society.144 (c) Energy barrier of cubic-to-hexagonal phase transition of FAPbI3
with or without Ii defect. (d)–(e) Evolution of the atomic arrangements during the a-FAPbI3-to-d-FAPbI3 transformation with (d) and without (e) the Ii defect. (c)–(e) Reprinted
with permission from Tan et al., Joule 4, 2426 (2020). Copyright 2020 Elsevier.145
diffusion barrier of MAi is much reduced compared with VMA.159
Therefore, both MA and iodine ion could significantly contribute to
the interstitial migration. In addition, it is also proposed that the
migration of a proton (Hþ) in MAPbI3 also has a low barrier of
0.29 eV.166 However, since methylammonium is a weak acid with high
dissociation energy,167 the concentration of (Hþ) in MAPbI3 is small,
and the Hþ diffusion effect is expected to be minor.168
Experimentally, the activation energy of the ion migration is
often measured by Arrhenius fitting of conductivity data.154 Mobile A-
site cations and halide anions were identified. The measured activation
energy is typically below 1 eV, and scattered values from 0.1–1 eV
were reported.158,169–172 Despite the general agreement on the magni-
tude of experimental activation energy and calculated migration bar-
rier, a quantitative comparison should be made with caution. Several
works pointed out that the conductivity r depends on both the migra-
tion rate rm and the ion concentration nD.154,161,164 nD is determined
DH
by the defect formation energy DHf through nD ¼ Ng expð kB Tf Þ.
Thus, the fitted activation energy from r is actually the sum of the
defect formation energy and the migration barrier. Based on this argu-
ment, Meggiolaro et al. proposed a model of defect formation and ion
migration at the surfaces/grain boundaries to explain the experimen-
tally observed grain size–dependent activation energy of MAPbI3.164
They found that while there is only a minor difference in migration
barriers between iodine ions in bulk and on surfaces, their formation
energy is much reduced on the surface. As a result, for smaller grain
Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402
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(b) 0.0 ps 2.5 ps 6.0 ps
0.0 ps 3.0 ps 8.0 ps
h+ e− H2O CH3NH2
(d)
(e)
Cubic Transition state Hexagonal
size with larger surface/volume ratio, the averaged defect formation
energy is smaller, leading to a lower overall activation energy.
Another factor that can enhance ion migration is light illumina-
tion,173 probably due to reduced migration barrier with the presence
of photo-excited carriers.174 In addition, the polar A-site cation is pro-
spected to be critical in determining the activation energy of migration.
It is shown that the positively charged (MAþ, Pb2þ) and negatively
charged (I) ions prefer to migrate along and against the intrinsic
dipole direction of MA, respectively. The migration energy is strongly
dependent on the MA orientation, e.g., ranging from 0.06 to 0.65 eV
for I, and it is suggested that an antiferroelectric order of MA
arrangement can suppresses the ionic migration.175 Mosconi et al.
found that the ion migration and the A-site cation is dynamically cou-
pled and advised that less polarity may slow down the migration.176
Contrastingly, Pazoki et al. reported that stronger dipole of the A cat-
ion impedes ion migration.165 Further studies are needed to clarify the
role of A-site polarity in the ion migration in LHPs.
2. Ion migration–related phenomena
Hysteresis in photovoltaics. LHP-based solar-cell devices often
exhibit anomalous hysteretic current-voltage (I-V) characteris-
tic,177–179 namely, there is a mismatch of I-V curves for forward
(short-circuit to open-circuit) and reverse (open-circuit to short-cir-
cuit) voltage sweeping, as shown in Fig. 9(c). The timescale of the
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(a) Pb −I plane
(b)
VI V˝Pb

MA MA MA

MA −I plane

MA
V'MA

(c) 25 (d) Built-in Built-in field

(a) electric field screened in bulk
Current density (mA/cm2)

20
qVbi
Band energy

EC EC
15
Normal structure
10 Ag
spiro-MeOTAD
d+ EV d−
MAPbI3
5
cp-TiO2 −
I− Vacancy drift I redistributed
FTO MA aligned
MA rotation
0 perovskite p perovskite n
0.0 0.2 0.4 0.6 0.8 1.0 p n

Voltage (V)

FIG. 9. (a) Schematic illustration of the vacancy-assisted ionic transport mechanisms. Reprinted with permission from Eames et al., Nat. Commun. 6, 7497 (2015). Copyright
2015 Springer Nature.158 (b) Schematic illustration of the interstiticaly mechanism for ionic migration. Reproduced with permission from Yang et al., J. Mater. Chem. A 4,
13105 (2016). Copyright 2016 The Royal Society of Chemistry.159 (c) Hysteresis curves in a MAPbI3 based photovoltaic device. Reprinted with permission from Kim et al., J.
Phys. Chem. Lett. 6, 4633 (2015). Copyright 2015 American Chemical Society.160 (d) Schematics of ion migration in perovskite under external electric field. Reprinted with per-
mission from Eames et al., Nat. Commun. 6, 7497 (2015). Copyright 2015 Springer Nature.158

hysteresis is 100 sec.180,181 Several mechanisms are proposed to be
responsible for the hysteresis in LHPs, such as ferroelectricity182–184
and charge trapping-detrapping.185,186 Under an external electric field,
ion migration results in charge redistribution and, thus, band bending
in LHPs, which can also contribute to the hysteresis, as illustrated in
Fig. 9(d).158,179,187,188 Moreover, giving the coinciding timescale and
activation energy of ion migration and hysteresis, the mobile ion is
considered to be an important origin for the hysteresis.187,189
Ion conduction. The mobile ions in LHPs introduce a large frac-
tion of ion conduction.154 The conductivity data are thus often used to
determine the activation energy of ion migration. Domination of ionic
conductivity in LHPs is experimentally observed.190,191 In mixed-
cation MA1-xFAxPbI3, it is reported that the ion conductivity by iodine
is 106 S/cm, being one order of magnitude higher than the electron
conductivity.191 In addition, the ion conduction can be enhanced by
orders of magnitude under light illumination.192
Phase segregation. Continuous bandgap modulation can be
achieved in mixed-halide LHP alloys by controlling the concentration
of different constitutes to reach an optimal bandgap for solar cells.5,21
However, the mobile halide ion can cause phase segregation in mixed-
halide LHPs. Under light illumination, I-rich domains are formed in
MAPb(IxBr1x)3 films, inducing sub-bandgap PL at 1.68 eV (known
as the Hoke effect),193 and it disappears in dark conditions. The under-
lying mechanism is that, since light-induced carrier facilitates ion
migration, the halide ions will move away from the illuminated sur-
face. Any difference in the migration rate between Br and I would
result in a vertical gradient of Br/I ratio and create I-rich domains.194
Light-induced phase segregation in all-inorganic CsPbBr1.2I1.8 nano-
crystal is also observed. Interestingly, the segregation leads to a blue
shift of PL instead of the red shift in MAPb(IxBr1x)3 films. This is
attributed to the migration of iodide ions among neighboring nano-
crystals leaving the bromide-rich region.195
Emission quenching. Wang et al. observed illumination-induced
emission quenching in CsPbBr1.2I1.8 nanocrystals and its recovery in
the dark. They proposed that the quenching is due to migration of
iodide ions to the surface, which introduces large lattice distortion and
possible surface defects.196
Healing of trapping centers. When a highly defective domain with
carrier traps exists in an LHP crystal, it is possible that the migrating
ions from the crystallized region can fill the defects and heal the traps.

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TABLE I. Summarized migration barrier for LHPs predicted by DFT calculations. recombination) is still considered to be one of the main carrier loss
mechanisms in LHPs,200–202 and its typical lifetime is on the order of
Migration 107 s.203,204 Theoretical understanding of the defect-assisted non-radia-
Migrating barrier tive recombination is thus important to the design and optimize of
DFT functional Material defect (eV) Ref. LHP-based devices. Although one can get qualitative information about
possible effective recombination center from the defect transition level,
PBEsol Pseudocubic MAPbI3 VI 0.58 158
it does not provide quantitative prediction on the recombination rate.
VPb 2.31 While the recombination lifetime is reproduced by parameterized model
VMA 0.84 calculations based on a multiphonon transition scenario,99 first-
PBE Tetragonal MAPbI3 VI 0.26, 0.34 161 principles calculations that provide atomistic details are highly desirable.
VMA 0.62, 0.89 Recently, there have been efforts combining first-principles elec-
Ii 0.19, 0.33 tronic structure calculations with advanced techniques, such as
MAi 0.38, 0.48 electron–phonon coupling theory and non-adiabatic molecule dynam-
vdWDF2-B86R Tetragonal MAPbI3 VI 0.32, 0.44 162 ics, to investigate defect-assisted non-radiative recombination in
VMA 0.57, 0.89 LHPs.97,117,198 Based on carrier capture coefficients determined from
Trigonal FAPbI3 VI 0.55, 0.48 first-principles calculation and multiphonon emission theory, iodine
VFA 0.61 interstitial was identified as a possible cause of non-radiative recombi-
PBE Pseudocubic MAPbI3 VI 0.08 119 nation in MAPbI3.97 Using structures relaxed by hybrid functional
and with spin–orbit coupling, the (0/–) and (þ/0) transition levels of Ii
VMA 0.46
are calculated to be 0.78 eV above VBM and 0.48 eV below CBM,
VPb 0.80 respectively. Electron-phonon coupling matrix elements were derived,
Ii 0.08 and the capture coefficients for the four processes involved in the non-
Pseudocubic MAPbBr3 VBr 0.09 radiative recombination were then computed, namely, I 0 
i to Ii (Cp ),
VMA 0.56 I0i to Iþi (C0
p ), I þ
i to I0
i (Cþ
n ), and I 0
i to I 
i (C 0
n ), as presented in Figs.
PBE Orthorhombic CsPbBr3 VBr 0.51 163 10(a) and 10(b). Despite that the (þ/0) level is much closer to CBM
VCs 0.80 than to VBM, the hole capture rate at this level is found to be much
VPb 1.88 higher than that of electron capture. This is understood by the strong
HSE-SOCþD3 Tetragonal MAPbI3 Ii 0.12 164 anharmonicity of the lattice and large structural difference between I0i
VI 0.17 and Iþ i , which lead to a nearly zero kinetic barrier for the Cp process
0

PBE Tetragonal MAPbI3 VMA 1.14 165 [Fig. 10(a)]. The rate-limiting process is Cþ n , but still with considerable
VPb 1.37 magnitude, leading to a overall recombination coefficient of 108
cm3s1 at 300 K. At typical defect concentration of 1015 cm3, the
VI 0.37
resulting non-radiative recombination lifetime is 107 s, which agrees
Tetragonal FAPbI3 VFA 0.63
with experiments. Another studying employing NAMD yielded a sim-
VPb >1.2 ilar trend that hole trapping is much faster than electron trapping for
VI 0.26 Ii. The computed lifetime for hole and electron capturing is 0.03 ns
Tetragonal CsPbI3 VCs 0.61 and 449.2 ns,117 respectively, in qualitative agreement with the first-
VPb 1.40 principles multiphonon transition calculations. Furthermore, NAMD
VI 0.21 calculations also discovered that migration of I vacancy in MAPbI3
PBE Tetragonal MAPbI3 VMA 0.66 159 can greatly accelerate non-radiative recombination by at least one
MAi 0.24 order of magnitude [Fig. 10(c)].198 The enhanced carrier loss is attrib-
VI 0.26 uted to lattice distortion, increased wavefunction overlap, and deep
Ii 0.21 defect states, which are all caused by ion migration.
For organic-inorganic hybrid LHPs, defects on the organic mole-
cules could also play important roles in carrier capture, which are
often overlooked. Zhang et al. demonstrated that hydrogen vacancies
Such an effect is reported by Goash et al. in MAPbBr3. They observed
on nitrogen side of the MA molecules [VH(N)] in MAPbI3 can form
that defect-related emission is suppressed by illumination activated
easily in case both iodine and hydrogen are extremely deficient, with a
ion migration, leaving only band-to-band emission.197
formation energy of 0.72 eV.205 The VH(N) introduces a deep acceptor
level located at 0.4 eV above the VBM, and act as an efficient carrier
C. Carrier trapping and dynamics recombination center. The calculated capture coefficient is 0.8  104
As mentioned in Sec. II C, LHPs exhibit good defect tolerance. In cm3s1 at 300 K, which is able to cause substantial non-radiative
contrast to conventional covalent semiconductors, the electronic and recombination even at small defect concentration. The high carrier
optical properties of LHPs are less sensitive to defects. Nevertheless, trap capture efficiency is understood by two factors that reduces the capture
centers induced by defects do exist in LHPs, with measured density as barrier: (i) the large structure relaxation when the defect charge state
high as 1016 cm3.28,98 Despite its relatively low rate compared to other changes, which drives the system to the Marcus inverted region,206
semiconductors, defect-assisted non-radiative recombination (SRH and (ii) the strong lattice anharmonicity. In contrast, the hydrogen

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(a) 8 (b) 8 10−4

Cp0

Capture coefficients (cm3S−1)

6 6 10−6 Cn0
DQ DQ
Cp−
Energy (eV)

Energy (eV)
4 4 10−8
0
Ii+ + e− + h+ Ii + e− + h+ Cn+
Cn+ −10 Ctot
Cn0 10
2 2
Ii0 + h+ Ii− + h+
DEn+ Cp− DE 0
Cp0 DEp− n
Ii+ Ii0 10−12
0 0

−10 0 10 20 30 −10 0 10 20 30 10−14

100 200 300 400 500
Q (amu1/2 Å) Q (amu1/2 Å)
Temperature (K)

(c) I−-migrated Pristine (d) 0.0

CBM
e− e−

−0.2
P

−0.4

Population
V
−0.6
fast slow
MAPbI3
−0.8
h+ h+ MAPbI3.5
VBM Restricted MA@MAPbI3
= Iodine e− = electron h+ = hole −1.00 200 400 600 800 1000120014001600
Decay Time (fs)

FIG. 10. (a) Configuration coordinate diagram for the four processes involved in the non-radiative recombination in MAPbI3 mediated by Ii. (b) The calculated nonradiative cap-
ture coefficients for the four processes in (a). (a)–(b) Reprinted with permission from Zhang et al., Phys. Rev. B 101, 140101 (2020). Copyright 2020 the American Physical
Society.97 (c) Schematic diagram of electron–hole recombination in Ii-migrated and pristine perovskites. Reprinted with permission from Tong et al., J. Am. Chem. Soc. 142,
3060 (2020). Copyright 2020 American Chemical Society.198 (d) Slowdown of hot hole cooling in MAPbI3 with high concentration of Ii. Reprinted from Banerjee et al., J. Chem.
Phys. 152, 091102 (2020), with the permission of AIP Publishing.199

vacancies in FAPbI3 were found to have much higher formation D. Defect-induced photoluminescence
energy and lower capture rate compared to VH(N). This rationalizes Defects can not only act as non-radiative recombination centers
experimental observations that the domination of FA at the A site is but also induce photoluminescence. Many works have been shown the
essential for achieving high efficiency LHP solar cells.207,208 possibility of point defects in LHPs serving as radiative recombination
Besides carrier recombination, Ii can also have pronounced effect centers, especially in zero-dimensional and two-dimensional layered
on hot carrier relaxation. Experiments and NAMD studies revealed LHPs. For example, experimentally synthesized zero-dimensional
that hot carriers in MAPbI3 relax to the band edge in a timescale of Cs4PbBr6 often exhibits strong narrow-band green emission corre-
0.1–0.6 ps under low-excitation intensity.199,209–211 A recent work sponding to 2.4 eV.212 However, the intrinsic bandgap of Cs4PbBr6
showed that with the appearance of Ii, the hot-hole cooling time is found to be 3.9 eV.213 The origin of the green emission is thus
remains unchanged, whereas the hot-electron cooling time is signifi- under extensive study. One possible explanation is that the emission
cantly increased, from 0.6 ps to 1.5–2.5 ps, as shown in Fig. 10(d).199 originates from intrinsic defect centers. Based on excited-state calcula-
This occurs because Ii causes charge localization, which reduces the tions, Jung et al. predicted that the green PL comes from the polybro-
overlap between CBM and higher energy bands, and the electron- mide (Br3) species resulted from the low-energy BrCs antisite.214 In
phonon coupling strength is weakened. contrast, Yin et al.’s calculation suggested that VBr is responsible for
So far, studies on the carrier trapping and dynamics in LHPs the green emission for the following reasons:215 (i) its small formation
from first-principles calculations are still in the early stage. Recent energy under Br-poor condition, (ii) the match between the defect
progress clearly demonstrated the possibility of sophisticated first- level and emission energy, and (iii) the localized nature of the defect
principles calculation methods to quantitatively simulate carrier- state. This is consistent with their experiments showing that the PL
related processes in LHPs and provide atomistic details. It could thus intensity of Cs4PbBr6 synthesized under Br-poor condition is stronger
be expected that systematic studies among different defects would than under Br-rich condition. Cha et al. revealed lattice contraction,
greatly benefit the identification of critical defects affecting carrier Cs atomic charge change, and electronic state shift by comparing syn-
recombination and dynamics in LHPs. thesized Cs4PbBr6 samples with and without green emission, and their

Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402 8, 031302-13

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 Applied Physics Reviews
simulation results using the Br vacancy model agree with these experi-
mental observations.216 Nevertheless, opposing evidence against the
defect center argument are also reported (e.g., the pressure response of
the luminescence center217,218). There have been several other mecha-
nisms proposed for the green PL,219 including formation of CsPbBr3
nanodomains in the Cs4PbBr6 host and structural distortion induced
self-trapped excitons, and the origin of luminescence center in
Cs4PbBr6 remains an open question.
Besides their band edge luminescence, a very broad emission
band and large Stokes shifted photoluminescence is often observed
in 2D layered hybrid LHPs. For example, the band edge PL of
(PEA)2PbI4 is at 533 nm, while it also exhibits a broadband emission
in the range of 550 to 800 nm (centered at 690 nm). Combined theo-
retical and experimental studies on the mechanism were carried out
by Yin et al.220 Calculations showed that the in-plane I vacancies
have a low formation energy of 0.84 eV, and it introduces a defect
transition level that is 1.73 eV above the VBM and matches the
broadband emission center (1.80 eV). Moreover, iodine-deficient
edge of (PEA)2PbI4 also creates localized defect states at 0.34 eV
below the CBM and is suggested to be another possible radiative
channel. Excess PEAI treatment can significantly reduce the intensity
of the broadband emission. This is interpreted by the effective passiv-
ation of I vacancies due to the low in-plane migration barrier
(0.49 eV) of iodine. Halide vacancies were also proposed to be
responsible for the broad emission in other 2D LHPs such as
[NH3(CH2)8NH3]PbBr4 and HA2PbI4.221,222 In another work, red-
shifted broadband emission is observed in (EDBE)PbI4, and its origin
is attributed to the VPb triggered formation of I 3 trimer, which acts
as a color center.223 It is worth mentioning that the strong electron-
phonon coupling in 2D LHPs can mediate excited-state lattice distor-
tions and induce self-trapped exciton. This is considered to be
another source of the sub-gap broadband emission.224–226
IV. CONTROL OF INTRINSIC POINT DEFECTS
Despite the defect tolerance of LHPs, defects remain a major fac-
tor limiting the efficiency of LHP-based optoelectronic and photovol-
taic devices. Many advanced strategies have been adopted toward
defect engineering to reduce the defect density and minimize non-
radiative recombination loss. Meanwhile, numerous theoretical studies
were stimulated to understand the mechanisms of defect control.
A. Growth condition
The formation energy of defects strongly depends on the chemi-
cal potentials of constitute elements in LHPs, which are determined by
the growth condition. For example, as seen in Fig. 2(c), halide-rich/
Pb-poor condition facilitates the formation of halide-involved and/or
Pb-deficient defects like halide interstitials, Pb vacancies, and halide-
on-Pb antisites, whereas it suppresses the formation of Pb-involved
and/or halide-deficient defects like Pb interstitials, halide vacancies,
and Pb-on-halide antisites. The chemical potential can be controlled
by adjusting precursor compositions during the growth of LHPs. Very
often, the optimal performance is not achieved at stoichiometric ratio
of precursors. It is thus possible to suppress the formation of harmful
defects by choosing proper growth condition. Calculations by Buin
et al.116 showed that under I-rich condition, the formation energy of
PbI deep traps in MAPbI3 is less than 0.2 eV, whereas under I-poor
condition, the formation energies of all deep defects exceeds 0.38 eV.
Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402
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Defect formation on the surface of MAPbI3 is also found to be favored
under I-rich condition.227 Thus, it is suggested that I-poor growth con-
dition can help to improve the performance of MAPbI3. This is sup-
ported by experimental observations that using a Pb(Ac)2 precursor
instead of PbI2 increases the carrier diffusion length from 200 nm to
600 nm.116 Another experiment reported that when the I/Pb ratio
decreases from 2.69 to 2.57, the trap density in MAPbI3 decreases
from 6.12  1016 cm3 to 3.38  1016 cm3, and the power conversion
efficiency increases from 17.61% to 19.55%.228 These results are con-
sistent with recent theoretical predictions that Ii is a major cause of
non-radiative recombination in MAPbI3, which can possibly be sup-
pressed under I-poor condition.97
Although the growth condition can effectively control the defect
concentration, the optimal growth condition for different LHPs is not
unified but case dependent. Yang et al. found that adding excess iodide
ions into the precursor (I-rich condition) increases the carrier lifetime
of FAPbI3 from 228 ns to 1105 ns, and remarkable power conversion
efficiency is realized.229 The underlying mechanism remains to be
explored, and there have been theoretical attempts230 associating the
improvement with the formation of shallow Pb vacancies, which are
proposed to be able to slow down carrier recombination. In addition,
improvement of PL quantum yield in CsPbBr3 nanocrystals under Br-
rich condition has been observed.231 The different optimal growth
conditions for different LHPs imply different types of critical defects.
Comprehensive studies to identify the critical defects from first-
principles calculations would provide helpful guidance to optimize the
growth condition to achieve better performance of LHPs.
B. Passivation by functional groups
The defect concentration on the surface or grain boundaries of
LHPs can be higher than in bulk due to lower formation energy.236
Theoretical and experimental studies suggested two categories of det-
rimental surface defects as the major source of deep traps:127,186,233
under-coordinated Pb associated defects (like VX and Pbi), and
excess halide associated defects (like Xi and XPb induced PbX3). A
variety of molecules with different functional groups (such as fuller-
ene,185,186 pyridine groups,237 thiophene groups,237 ammonium
groups,238 carboxyl and carboxylate groups,233 aromatic struc-
tures,234 and halide salts239,240) were used to passivate these surface
defects. Comprehensive summarizations on various passivation mol-
ecules and the corresponding target defects can be found in Refs.
39,41. Due to the ionic character of LHPs, the defects are charged,
and the passivation mechanisms are different from that for covalent
bonding semiconductors.
The ionic nature of LHPs enables one to consider the passivation
strategy from the Lewis acid-base chemistry.232,233 Under-
coordination of Pb atom leads to positively charged Pb2þ, and it can
be viewed as a Lewis acid trap that attracts electrons. Similarly, under-
coordination of halide atom results in the formation of negative charge
on the atom (X), and it can be regarded as a Lewis base trap that
donates electrons. The addition of molecules with Lewis base (acid)
functional groups can effectively interact with the Lewis acid (base)
traps to form Lewis adducts through the Lewis acid–base reaction,
resulting in coordinate bond formation, charge neutralization, and
shallowing of defect states, as illustrated in Fig. 11(a). This concept is
validated by numerous studies combining both theoretical calculations
and experiments. For instance, it was shown that electron-acceptor
8, 031302-14
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(a) (b) (e)

1.18
CB N (E ) Pb I
1.16
E Pb-I antisite
Grain boundary
A 1.14
E Passivated surface
acid 1.12
As-cast surface

Voltage (V)
:B 1.10
base
1.08
AB
adduct VB 1.06

1.04

DOS (a.u.)
Trap state
1.02

0.3 0.4 0.5 0.6 0.7 0.8 0.9

Binding energy (eV)

Ev Ec
(c) (d)
X-type Ligand

Vx
−
Passivation

+
VA
VCI Defect VBM (h+) CBM (e−)
D-4-tert-butyl-phe (D4TBP)

FIG. 11. (a) Formation of Lewis adducts with coordinate bond through the Lewis acid–base reaction, and the corresponding passivation effect on defect states. Reprinted with
permission from Lin et al., Adv. Mater. 29, 1604545 (2017). Copyright 2017 John Wiley and Sons.232 (b) PCBM passivation of PbI 3 anti-site defects in MAPbI3. Reprinted with
permission from Xu et al., Nat. Commun. 6, 7081 (2015). Copyright 2015 Springer Nature.186 (c) Removal of localized VCl defect state on CsPbCl3 surface through R-COO
passivation. Reprinted with permission from Nenon et al., J. Am. Chem. Soc. 140, 17760 (2018). Copyright 2018 American Chemical Society.233 (d) Multiple functional group
passivation. Reprinted with permission from Yang et al., J. Am. Chem. Soc. 141, 5781 (2019). Copyright 2018 American Chemical Society.234 (e) Correlation between the VOC
and binding energy of passivators in MAPbI3 photovoltaic devices. Reprinted with permission from Xie et al., Sci. Bull. 65, 1726 (2020). Copyright 2020 Elsevier.235

PCBM (phenyl-C61-butyric acid methyl ester, which can be considered
a Lewis acid) can successfully passivate the key PbI 3 anti-site defects
in MAPbI3.186 The binding of PCBM to PbI 3 is thermodynamically
favored, and the electronic states of PCBM strongly hybridize with the
perovskite surface, leading to significantly shallower trap state [Fig.
11(b)]. The PCBM passivated devices exhibit suppressed hysteresis and
enhanced photovoltaic performance exceeding 14.4%, which is 1.5
times of that of unpassivated devices.186 For under-coordinated Pb2þ,
Lewis bases like R-COO and R-PO(OH)O functional groups can be
used for passivation. DFT calculations found that, on the surface of
CsPbCl3, Cl vacancy creates strongly localized trap state inside the
bandgap, while the R-COO group effectively removes the deep state
and restore the clean bandgap,233 as seen in Fig. 11(c). The passivation
effect is also observed for hexylphosphonate-treated CsPbBr3, resulting
a 98% PL quantum yield.233 Besides passivating a single type of defect,
the synergistic effects of passivating both types of positively and nega-
tively charged defects have attracted much attention.241 Single passiva-
tors with multiple functional groups on one molecule for passivation of
different defects were also proposed and realized [Fig. 11(d)].234,242,243
In the study of Ref. 233, harder Lewis bases (e.g., alkylcarboxylate)
are found to be less effective in defect passivation than softer ones (e.g.,
hexylphosphonate), rationalized by the soft nature of the under-
coordinated Pb2þ and the resulting hard-soft mismatch. This implies the
important role of molecule–host interaction strength in the passivation.
An insight gained with the help of theoretical calculation is that the pas-
sivation performance is correlated with the binding energy of the passi-
vator with the defect site. A larger binding energy suggests stronger
coordinate bonding between the defect and the passivator, which thus
more effectively pushes the deep states closer to the band edge. Zhao
et al. studied the passivation effects of three Lewis bases: 2-
aminoethylphosphonic acid (PA), hypotaurine (SA), and b-alanine
(CA), on FAPbI3.244 The calculated binding energies on the surface VI
(PbI) site were found to be 1.09 (1.34), 0.66 (0.69), and 0.53 (0.43) eV,
respectively. The trends in the defect density and opto-electronic proper-
ties (PL lifetime, open-circuit voltage, power conversion efficiency) fol-
low the same order as the binding energy, with the best passivation
performance achieved with PA. Similar results were also reported for the
power conversion efficiency of perovskites passivated by theophylline,
caffeine, and theobromine.236 Xie et al. compared the passivation effects
among 12 types of functional groups on para-tert-butylbenzene for
MAPbI3 solar cell, and they found positive correlation between the bind-
ing energy of the molecules to perovskite and the open-circuit voltage
[Fig. 11(e)].235 Xu et al. revealed by DFT calculations that introducing O
atoms on the alkyl chain of the passivator while keeping the functional
group (-NH2) unchanged reduces its binding with the pristine perovskite
surface but enhances its binding with the defective surface. Thus, the
interaction of the passivator with defect sites can be enhanced by weak-
ening the hydrogen bonding between the passivator and the organic cat-
ion, and the passivation performance is improved.245 Suppressed ion
migration due to enhanced binding of passivator realized by increasing
alkyl chain length is also reported.246 These studies indicates that one
can optimize defect passivation in LHPs through modifying not only the
functional groups but also other moieties of the passivator molecule.
C. Doping
Doping technology is widely applied to tune the electronic and
optical properties of semiconductors, such as bandgap and carrier

Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402 8, 031302-15

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 Applied Physics Reviews
concentration.250 In addition, demonstrated by a great number of
studies, doping is an effective strategy for suppressing defects in LHPs.
1. Defect suppression through doping induced strain
relaxation
As introduced in Sec. II B, the weak stability of LHPs facilitates
the formation of defects, especially vacancies which can either act as
carrier traps or trigger structural degradation. The stability issue is a
result of ionic size mismatch between the A-site cation and the PbX6
octahedra cage. Commonly the radii of the A cation are too small to
stabilize the cubic perovskite structure at 0 K. The mismatch causes an
inherent lattice strain and leads to tilting and distortion of the PbX6
octahedra. This effect is most significant in iodine-based LHPs. The
formation of vacancies partly releases the strain and therefore has a
low formation energy. Alternatively, the strain relaxation can be also
achieved by incorporating smaller ions into the lattice of LHPs; thus,
the octahedra distortion is suppressed, the stability is improved, and
the formation of vacancies can be reduced.247,251 For this purpose, iso-
valent doping is often considered, and the doping concentration is typ-
ically a few percent. The doping can be either on the Pb sites with
divalent metal ions as dopants [Mn2þ, Zn2þ, Cd2þ, Mg2þ, Sr2þ, etc.,
as presented in Fig. 12(b)],12,248,252–255 or on the X sites with smaller
sized halide ions X’251 (e.g., substituting I with Cl). DFT calculations
revealed that for 2.08 mol. % doped cubic CsPbBr3 with various diva-
lent metal ions, the formation energy per Pb site increased 0.3–0.5 eV
compared with the undoped case, indicating enhanced stability and
strain relaxation.256 For Sr and Mg doped MAPbI3 with a concentra-
tion of 6%, the formation energy of V2 Pb is increased by 0.24 and
(a) Octahedra
No tilting of
tilting octahedra
Doping smaller
cation at B-site
Cs+ Pb2+ M2+ I−
(b) Alloyed with Zn2+ 5V
Unalloyed
5V
Cs+ Pb2+ Zn2+ I− Alloyed
FIG. 12. (a) Scheme of strain relaxation by introducing small size ion to suppress octahedra distortion. Reprinted with permission from Swarnkar et al., ACS Energy Lett. 3,
286 (2018). Copyright 2018 American Chemical Society.247 (b) Zn doping in CsPbI3 nanocrystals and improved PL. Reprinted with permission from Shen et al., Nano Lett. 19,
1552 (2019). Copyright 2018 American Chemical Society.248 (c) Suppression of lattice distortion by Cl doping in MAPbI3. Reprinted with permission from Nan et al., Adv.
Energy Mater. 8, 1702754 (2018). Copyright 2018 John Wiley and Sons.249 (d) Wave functions of perovskites with the IPb defect. From left to right: CsFA perovskite; CsMAFA
perovskite with MA orientated at 0 ; CsMAFA perovskite with MA orientated at 180 . Reprinted with permission from Tan et al., Nat. Commun. 9, 3100 (2018). Copyright 2015
Springer Nature.98
Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402
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0.36 eV, respectively, compared with the pristine structure. The sup-
pression of VPb by the doping is further supported by hard x-ray pho-
toelectron spectroscopy.257 Near-unity PLQY in Ni-doped CsPbCl3 is
achieved, and it is proposed Ni doping does not introduce deep trap
states and meanwhile notably increases the formation energy of VCl,
VPb, and VCs under Cl-rich condition by 0.8–1.5 eV.258 The doping
effects of Cl and Cd in CsMAFA perovskite (Cs0.05MA0.15FA0.8
PbI2.55Br0.45) were investigated by Saidaminov et al.251 Both Cl doping
and Cd doping is able to release the strain as indicated by the decreas-
ing in Pb-X bond length and Pb-X-Pb bond angle distortion. The for-
mation energy of I vacancy is increased by over 0.3 eV for 3.1% Cl
doping, and over 0.5 eV for 5.7% Cd doping. The suppressed vacancy
formation reduces degradation. As a result, the ambient-air maximum
power point operational stability of the doped devices is enhanced by
an order of magnitude. Calculations by Nan et al. showed that a small
amount of Cl doping (3%) in MAPbI3 can already suppress the local
structural distortion around the lowest excited Pb vacancy site, and
the defect is healed by a localized-to-delocalized transition of the
excited-state charge densities249 [Fig. 12(c)]. Their experiments further
confirmed that 5% Cl doping decreases the trap state density from
4.7  1016 cm3 to 7  1015 cm3.
There have been also a number of works investigating the effects
of small trivalent dopants on the Pb site, e.g., Bi3þ, Ce3þ and Y3þ.
High level HSEþSOC calculations revealed that Bi substitution of Pb
in the bulk or on the surface creates deep trap states inside the
bandgap, which serves as nonradiative recombination center and
quenches the PL in CsPbBr3.259 Such Bi-induced PL quenching was
experimentally observed.260 A recent work261 demonstrated that the
BiPb in Br-based LHPs is actually a donor-yielded complex center (DY
(c)
CI
Delocalized ES
Localized ES
(MAPbI3) (MAPbI3−mCIm)
(d)
IPb CsFA IPb CsMAFA at 0° IPb CsMAFA at 180°
8, 031302-16
 Applied Physics Reviews
center) which is an analogy to the DX center in tetrahedral coordi-
nated semiconductors. The localized DY defect state originates from
the interaction between the Bi 6p states and anion valence p states. For
Ce3þ and Y3þ whose p orbitals are irrelevant, their doping on the Pb
site enhances the lattice order through the strain relaxation and does
not create deep mid-gap state. Thus, the PL efficiency can be signifi-
cantly improved.259,262,263
2. Defect healing through doping of dipolar cation
Besides Pb/X site doping, A-site doping/alloying is also proposed
for reduction of deep traps in LHPs, but through a different mecha-
nism. Deep trap healing by MA doping in CsFA perovskite
[Cs0.2FA0.8Pb(I0.75Br0.25)3] was observed by Tan et al.98 Cs and FA are
both nonpolar, while MA has a strong intrinsic dipole moment.
Formation energy calculations suggest that introducing MA into CsFA
does not suppress the formation of defects. However, the dynamic
motion of the MA near the defect site can greatly affect the electronic
structure through the strong dipole field. For deep defects such as PbI,
BrPb, Pbi and IPb, when the nearby MA molecule rotates into the ener-
getically favored orientation, namely, the dipole moment is aligned to
the local field induced by the defect, the defect state is significantly
shallowed, and a localized-to-delocalized transition of the defect states
occurs [Fig. 12(d)]. The MA doped devices showed improved power
conversion efficiency and reduced recombination loss. This defect
healing effect due to the dynamic nature of dipolar MA is also
observed in Nan et al.’s calculations.249
Although much progress was made in defect control of LHPs,
current understanding of the underlying mechanism is mostly qualita-
tive and merely supported by indirect experimental evidence. A full
knowledge of defect control in LHPs has yet to be acquired. To go a
step further, an accurate prediction of the types of critical defects, their
concentration, and their energy level is a key issue to be addressed,
since this provides targeting information to support reasonable and
quantitative modeling of defect control.
V. CONCLUSIONS AND OUTLOOK
Defect property is a central topic in the research field of LHPs.
LHPs exhibit strong ionic character and unique electronic structure;
thus, their defect properties are quite different from conventional
covalent bond semiconductors. State-of-the-art first-principles calcula-
tion methods enable one to explore atomistic mechanisms of various
defect-related processes in LHPs. Tremendous efforts from theoretical
simulations have provided invaluable insights toward performance
optimization of LHP-based devices. In this review, recent advances in
the physics, impacts, and engineering of intrinsic point defects in
LHPs have been presented. An important reason that LHPs exhibit
excellent power conversion efficiency and quantum yield is their toler-
ance to defects despite the considerable defect concentration.
Nevertheless, defects in LHPs can have significant structural effects,
causing degradation and ion migration. Moreover, defect-mediated
non-radiative recombination remains a major factor responsible for
energy and efficiency loss in LHPs. Advanced strategies, such as
growth condition optimization, functional group passivation, and dop-
ing, have been applied to effectively reduce the defect density and min-
imize non-radiative recombination loss. The underlying mechanisms
were intensively studied by theoretical simulations.
Appl. Phys. Rev. 8, 031302 (2021); doi: 10.1063/5.0052402
Published under an exclusive license by AIP Publishing
REVIEW scitation.org/journal/are
Although theoretical modeling of defects in LHPs based on first-
principles calculations already provided valuable insights into the
atomistic mechanisms of various defect-related processes, a complete
understanding of the defect physics is not yet achieved. Inconsistencies
do exist among different simulations carried out by different works,
and sometimes not only quantitatively but also quantitatively. LHPs
exhibit complicated structure and electronic properties, such as strong
SOC, multiple structure phases, dynamic A-site cations, and distortion
of the octahedra. The results of defect calculations could strongly
depend on the choice of computational schemes like the level of DFT
method (bare-DFT, hybrid, SOC etc.), the choice of phase, the mole-
cule orientation, and the supercell size. Therefore, calculations should
be performed with great care to accurately model defects in LHPs.
While a good discussion on relevant issues for defects in MAPbI3 is
provided by Meggiolaro et al.,111 further works with systematical and
detailed comparison on different computational schemes and model
setups across different LHPs are needed to clarify the controversy.
Moreover, the identity of critical defects as well as their concentration
and energy level is a key problem in understanding defect tolerance,
defect impacts, and defect control in LHPs. Relevant simulations call
for a combination of high-level DFT, well-tested model setup, and
sophisticated technology dealing with defect-carrier interaction. In
short, a detailed and comprehensive understanding at atomic scale on
the defect science and engineering of LHPs is crucial for further
improvement of their device performance. Deeper insights into this
field are highly expected with rapid development of theoretical and
experimental techniques.
ACKNOWLEDGMENTS
The authors acknowledge support from NSFC (Grant Nos.
12074029, 11991060, 11634003, 12088101, and U1930402) and “The
Pearl River Talent Recruitment Program” (Grant No. 2019ZT08X639).
DATA AVAILABILITY
Data sharing is not applicable to this article as no new data were
created or analyzed in this study.
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