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High-Efficiency Perovskite Solar Cells

Jin Young Kim, Jin-Wook Lee, Hyun Suk Jung,* Hyunjung Shin,* and Nam-Gyu Park*

Cite This: https://dx.doi.org/10.1021/acs.chemrev.0c00107 Read Online

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ABSTRACT: With rapid progress in a power conversion efficiency (PCE) to reach 25%,
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metal halide perovskite-based solar cells became a game-changer in a photovoltaic

performance race. Triggered by the development of the solid-state perovskite solar cell in
2012, intense follow-up research works on structure design, materials chemistry, process
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engineering, and device physics have contributed to the revolutionary evolution of the solid-
state perovskite solar cell to be a strong candidate for a next-generation solar energy
harvester. The high efficiency in combination with the low cost of materials and processes
are the selling points of this cell over commercial silicon or other organic and inorganic solar
cells. The characteristic features of perovskite materials may enable further advancement of
the PCE beyond those afforded by the silicon solar cells, toward the Shockley−Queisser
limit. This review summarizes the fundamentals behind the optoelectronic properties of
perovskite materials, as well as the important approaches to fabricating high-efficiency
perovskite solar cells. Furthermore, possible next-generation strategies for enhancing the
PCE over the Shockley−Queisser limit are discussed.

CONTENTS 3.5.3. Photon Recycling AM

3.5.4. Concentrator Solar Cells AN
1. Introduction A 4. Summary AN
2. Fundamentals of the Organic Lead Halide Author Information AO
Perovskite Required to Achieve High PCE C Corresponding Authors AO
2.1. Electronic and Optical Properties of Perov- Authors AO
skites C Author Contributions AO
2.2. Parameters Affecting Charge Transport, Notes AO
Collection, And Recombination E Biographies AO
2.3. Recombination in Perovskite Materials and Acknowledgments AP
Solar Cells G References AP
3. Key Challenges in Achieving High Efficiency G
3.1. Structure Design G
3.1.1. Crystal Structure G 1. INTRODUCTION
3.1.2. Defect Structure H
3.1.3. Microstructure J The solid-state perovskite solar cell (PSC) was reported in
3.2. Materials Chemistry M 2012,1,2 with a power conversion efficiency (PCE) of
3.2.1. A Site(Cation)-Modified Perovskites N approximately 10% under a simulated 1 sun illumination.
3.2.2. B Site(Cation)-Modified Perovskites Q Furthermore, the solid-state PSC exhibited long-term stability
3.2.3. X Site (Anion)-Modified Perovskites R for 500 h, as confirmed by stability tests conducted using
3.2.4. Low-Dimensional Perovskites T unencapsulated devices under ambient conditions.1 Although
3.3. Processing Engineering T the application of organic−inorganic lead halide perovskite as a
3.3.1. One-Step vs Two-Step Processes V sensitizer in dye-sensitized solar cell (DSSC) structures was
3.3.2. Adduct Intermediated Process Z first attempted in 20093 and improved efficiency, from 3.8% to
3.4. Device Physics AA
3.4.1. Selective Contact AA Received: February 12, 2020
3.4.2. Interface Engineering AD
3.4.3. Defect Passivation AG
3.5. Over Shockley−Queisser Limit AI
3.5.1. Tandem Solar Cells AI
3.5.2. Hot Carrier Device AL

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.chemrev.0c00107

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Figure 1. (a) Chronological evolution of the power conversion efficiency (PCE) of perovskite solar cells (PSCs). The numbers in the plot are
explained in Table 1. (b) PSCs with mesoscopic, normal-planar, and inverted-planar device structures. The mesoscopic structure contains a
mesoporous electron-transporting material (ETM) layer, where the perovskite can either be deposited on the ETM surface or filled in the
mesopores, and a blocking layer is usually required to protect the electron−hole recombination. In the planar configuration, structures are classified
as normal or inverted based on the type of charge collected on the transparent conductive oxide (TCO).

Table 1. PCEs Depicted in Figure 1a, Perovskite Composition, and Device Structuresa
no. PCE (%) perovskite composition device structure (coating procedure) instituted (year) ref
1 3.8 MAPbI3 liquid junction Toin U (2009) 3
2 6.5 MAPbI3 liquid junction SKKU (2011) 4
3 9.7 MAPbI3 solid-state mesoscopic TiO2 SKKU (2012) 1
4 10.9 MAPbI3 solid-state mesoscopic Al2O3 Oxford U (2012) 2
5 12 MAPbI3 mesoscopic TiO2 KRICT (2013) 6
6 14.1b MAPbI3 mesoscopic TiO2 (two-step) EPFL (2013) 11c
7 16 FAPbI3 mesoscopic TiO2 SKKU (2014) 7
8 17 MAPbI3 mesoscopic TiO2 (two-step) SKKU (2014) 8
9 17.9b (FAPbI3)0.85(MAPbBr3)0.15 mesoscopic TiO2 KRICT (2014) 12c
10 19.3 MAPbI3 normal planar, Y:TiO2 ETM UCLA (2014) 9
11 20.1b (FAPbI3)0.95(MAPbBr3)0.05 mesoscopic TiO2 KRICT (2014) 13c
12 20.4 MAPbI3 mesoscopic TiO2 SKKU (2015) 10
13 22.1b (FAPbI3)0.95(MAPbBr3)0.05 mesoscopic TiO2 KRICT (2016) 14c
14 22.7b (FAPbI3)0.95(MAPbBr3)0.05 mesoscopic TiO2, fluorene-terminated HTM KRICT (2017) 15c
15 23.7b FA0.92MA0.08PbI3 normal planar, SnO2 ETM ISCAS (2018) 16c
16 24.2b KRICT/UNIST (2019) 17c
17 25.2b KRICT/MIT (2019) 18c
a
The device structures are displayed in Figure 1b. bCertified value. c“Solar Cell Efficiency Tables” published in Progress in Photovoltaics: Research
and Applications. dInstitutes: SKKU = Sungkyunkwan University; KRICT = Korea Research Institute of Science and Technology; ISCAS =
Institute of Semiconductors, Chinese Academy of Sciences.

6.5%, was reported in 2011,4 the dissolution of the perovskite
dots adsorbed on the TiO2 surface in an iodide/iodine-based
liquid electrolyte remained highly problematic. This drawback
was eventually resolved by replacing the liquid electrolyte with
a solid-state hole-conducting material: spiro-MeOTAD
(2,2′7,7′-tetrakis(N,N-di-p-methoxyphenyl amine)-9,9′-spiro-
bifluorene.1
Perovskite is originally the mineral name of calcium titanate
(CaTiO3), which is often applied to the class of materials
possessing the same type of crystal structure as CaTiO3.5 In
the perovskite structure with the chemical formula, ABX3, the
A-site cation is coordinated to 12 X anions, forming a
cuboctahedron, while the 6-fold-coordinated B-site cation has
an octahedral geometry. The perovskite structure is unique
among the known structures of close-packed oxides because it
can accommodate a very large cation. Therefore, small organic
cations, which are larger than inorganic cations, can participate
in the perovskite structure, leading to organic−inorganic
B https://dx.doi.org/10.1021/acs.chemrev.0c00107
hybridization. The most studied organic−inorganic lead halide
perovskites for PSCs are MAPbI3 (MA = methylammonium;
CH3NH3+) and FAPbI3 (FA = formamidinium; HC(NH2)2+),
where mixed cations in the A site and/or mixed anions in the X
site are also available. Starting with a PCE of 9.7% with pure
MAPbI3 in 2012, a certified PCE of 25.2% was achieved in
2019 using a mixed cation and/or mixed anion composition.
Since 2009, high efficiency has been realized by two main
approaches: effective coating and composition engineering. In
Figure 1, the chronological progress in the PCE of PSCs is
displayed. Noncertified PCE values are collected from the
literature,1−10 and the certified data are collected from “solar
cell efficiency tables” reported in Progress in Photovoltaics.11−18
By examining the PCE data in Figure 1a, it can be observed
that the PCE increases steeply between number 3 and number
11, indicating that this big jump occurred in only three years,
from 2012 to 2014. Most of the achievements are based on a
mesoscopic structure containing mesoporous TiO2 layers (see
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the mesoscopic-filled device structure in Figure 1b). From
2015 to 2019, the PCE increased rather slowly but
continuously and eventually reached 25.2%. Since 2015,
relatively high PCEs have been realized by changing the
material composition from MAPbI3 to FAPbI3 (Table 1),
where small amounts of the MA cation and Br anion are
introduced to FAPbI3 to stabilize the α phase of FAPbI3 at
ambient temperature. A PCE of 24.2% was certified in 2019
(number 16 in Figure 1a) resulting from open-circuit voltage
(Voc) = 1.1948 V, short-circuit current density (Jsc) = 24.16
mA/cm2, and fill factor (FF) = 0.84,17 where Voc and FF are
significantly improved as compared to a PCE of 20.1% certified
in 2014 (Voc = 1.059 V and FF = 0.77).13 In addition to
composition engineering, interface engineering is likely to be
involved in the improvement of Voc and FF, as explained in the
section describing the importance of interface engineering.9 In
addition to perovskite compositional engineering, deposition
(coating) methods play an equally important role in improving
the PCE. In 2013, the first high PCE of 14.1% was achieved by
a two-step coating method,19 which led to the deposition of
organic halide on the predeposited PbI2 film. While the PCE
was improved to 17% by controlling the size of the perovskite
cuboid in the two-step process,8 further improvement in the
PCE was realized by a one-step procedure and perovskite
composition engineering. Although the best PCE of 25.2% was
reported, the cell area of ca. 0.1 cm2 was considered overly
small for classification as an outright record.18 A PCE of 21.6%
was certified with a cell area of 1 cm2, which was measured
based on a “settled power at fixed voltage” (SPFV) method,
where the device voltage was maintained at the nominal
maximum power point voltage of 1.05 V for 5 min.18
As listed in Table 1, the PCEs as high as 22% are mostly
derived from FAPbI3 in the mesoscopic or normal-planar
device structure. Moreover, because of the progress in coating
technologies, PCEs of over 25% can be achieved. Although the
two-step method is still useful for controlling the perovskite
grain size and morphology, the one-step procedure is more
economical. In one-step spin-coating, kinetic control of the
crystal growth is of critical importance and can be achieved via
an intermediate formed by antisolvent dripping20 or Lewis
acid−base adduct formation.21 In Figure 2, two approaches are
schematically illustrated, where the antisolvent method is
Figure 2. Schematic illustration of the formation of high-quality
perovskite films via the (a) antisolvent dripping method and (b)
Lewis acid−base adduct method. An antisolvent is defined as a
solvent in which the perovskite is slightly soluble. The figures are
modified versions of the original figure in ref 21.
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employed primarily to remove the polar aprotic solvents used
for preparing the precursor solution, such as dimethyl sulfoxide
(DMSO) and γ-butyrolactone (GBL), while in the Lewis
acid−base adduct approach, the polar aprotic solvent (DMSO)
is used as the Lewis base instead of using the solvent to form
an adduct, and the solvent, such as dimethylformamide
(DMF), is removed by a selective diethyl ether solvent
(DMF is selectively dissolved without dissolving DMSO).
Currently, these technologies are extended to fabricate high-
quality FAPbI3 films and have contributed to achieving
relatively high PCEs, which will be discussed in detail in
section 3.3.
In this review, the key challenges associated with achieving
high PCE in PSCs are described and discussed. Because a high
PCE is directly related to the device configuration, under-
standing the device physics and device structure engineering is
of critical importance. Nevertheless, the materials and
interfaces in the device are equally important for achieving
maximum Jsc, Voc, and FF. In addition, an optimal fabrication
process must be developed, specifically for high-quality
perovskite films, because the perovskite light absorber is the
key element in PSCs. A brief introduction to the optoelec-
tronic properties of perovskite materials is considered as a
prerequisite to designing the best PCE device.
2. FUNDAMENTALS OF THE ORGANIC LEAD HALIDE
PEROVSKITE REQUIRED TO ACHIEVE HIGH PCE
A solar cell is a device that converts absorbed incident light
into electrical energy. The optical and electronic properties of
light absorbers are fundamental for understanding their
interaction with light, as well as the transport and collection
of photogenerated charges. In addition, the recombination
processes must be adequately understood to maximize the
charge-collection efficiency toward achieving the best PCE.
2.1. Electronic and Optical Properties of Perovskites
Because the optical properties of solids correlate with their
energy band structure, impurity levels, excitons, localized
defects, and lattice vibrations, it is important to study the
optical properties of the organic−inorganic lead halide
perovskite. The exciton binding energy for the iodide-based
perovskite materials commonly utilized in solar cells was
measured to be a few millielectronvolts at room temper-
ature.22,23 Therefore, the excited charge carriers move as free
carriers. As is well-known, a high efficiency of a PSC is related
to a high absorption coefficient and direct bandgap transition,
as well as a low effective mass, long diffusion length, and
relatively high carrier mobility of free electrons and holes. If
the organic lead halide perovskite is regarded as a semi-
conductor, the optical absorption in the perovskite can be
related to its electronic band structure and, thereby, its crystal
structure. First, we construct the molecular orbital of PbI2
based on the linear combination of atomic orbitals (LCAOs)
of Pb and I. Orbital energies can be calculated by
−Z 2
E = 2eff 13.6 eV ,24 where Zeff and n represent the effective
n
nuclear charge and principal quantum number, respectively.
Zeff was reported to be 13.40 and 11.61 for the 5s and 5p
orbitals of I, respectively, and 14.10 and 12.39 for the 6s and
6p orbitals of Pb, respectively; these values were obtained from
the orbital exponent expression: ζ = Zeff/n.25,26 The orbital
energies are, thus, calculated to be E(6p(Pb)) = −57.99 eV >
E(5p(I)) = −73.33 eV > E(6s(Pb)) = −75.10 eV > E(5s(I)) =
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Figure 3. (a) Schematic molecular orbital of PbI2 constructed by the linear combination of atomic orbitals (LCAOs) of Pb and I. The orbital
energies were estimated from the effective nuclear charge and the principal quantum number. (b) Schematic illustration of the valence band (VB)
and conduction band (CB) formed from the molecule (0D) state to the solid (3D) state of PbI2. Total density of states (DOSs) for (c) MAPbI3
and (d) FAPbI3. The patterned DOSs represent the upper part of the VB. (c,d) Reproduced with permission from ref 28. Copyright 2018 Elsevier.

Figure 4. Optical absorption for (a) GaAs and (b) MAPbI3. (c) Joint density of states (JDOSs) for MAPbI3 and GaAs. Reproduced with
permission from ref 30. Copyright, 2015 American Chemical Society. (d) Schematic illustration showing the indirect-to-direct transition, achieved
by applying a pressure of over 325 MPa. The weak indirect-bandgap transition was due to the spin−orbit coupling in the CB. Reproduced with
permission from ref 32. Copyright, 2017 Royal Society of Chemistry.

−97.68 eV. On the basis of the orbital energy diagram and
assuming that the bond angle of I−Pb−I in the gas phase is
90°, an approximate molecular orbital for PbI2 is constructed,
as shown in Figure 3a. The overlap between the Pb 6s and I
5pz orbitals produces σ-bonding and σ*-antibonding orbitals,
and the I 5px and 5py orbitals result in nonbonding orbitals.
The overlap between the Pb 6p and I 5p orbitals produces one
σ-bonding (6pz−5pz) and two π-bonding (6px−5px and 6py−
5py) orbitals along with the corresponding σ*- and π*-
antibonding orbitals, where the π-bonding orbitals are
expected to be more stabilized due to s−p mixing. The
highest occupied molecular orbital (HOMO) is, therefore,
composed of a σ-antibonding (Pb 6s−I 5p)* orbital, and the
lowest unoccupied molecular orbital (LUMO) consists of σ-
antibonding (Pb 6p−I 5p)* and π-antibonding (Pb 6p−I 5p)
orbitals, which are the bases for the valence band (VB)
maximum and conduction band (CB) minimum when gas
species are condensed into the 3D perovskite material (Figure
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3b). The HOMO has more I 5p characteristics, and the
LUMO tends to have more Pb 6p characteristics. According to
ab initio effective core potential calculations,27 the electronic
configuration of PbI2 is (a1)2(b2)2(a1)2(b2)2-
(a1)2(b1)2(a2)2(b2)2(a1)2 based on 4 valence electrons in
(6s)2(6p)2 for Pb and 7 valence electrons in (5s)2(5p)5 for I,
and the HOMO is dominantly a combination of the hybrid 6s
and 6pz(Pb) orbital and the 5pz(I) orbital. A significant Pb → I
charge transfer was expected based on the double-ζ valence
(DZV) population analysis, which resulted in the electronic
configurations of (6s)1.98(6p)1.25 for Pb and (5s)1.98(5p)5.40 for
I due to a strong 6p(Pb)−5p(I) overlap. This eventually
implies a direct transition from the VB to CB upon light
absorption. The density of states (DOSs) of MAPbI3 (Figure
3c) and FAPbI3 (Figure 3d) were calculated based on cubic
perovskite with lattice constants of 6.276 and 6.362 Å for
MAPbI3 and FAPbI3, respectively.28 The upper part of the VB
between 0 eV and ∼−3 eV was confirmed to be mainly
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Chemical Reviews
Table 2. Carrier Transport Properties, Including the Lifetime (τ), Diffusion Length (LD), Mobility (μ), and Carrier
Concentration, Depending on the Electrons (e) and Holes (h), Measured under Illumination Using the Hall Effect
Measurement (the Carrier Type Was Not Resolved)a
LD (μm)
material τ (ns) e h
MAPbI3b 40−10 000 2−8
(FA1−xMAx)Pb(I1−xBrx)3b 44−40 000 1.7−23
a
Reproduced with permission from ref 33. Copyright, 2019 Springer Nature. bPolycrystalline thin film.
composed of the I 5p orbital along with minor contributions
from the Pb 6s orbital, while the Pb 6p orbital contributed
dominantly to the lower part of the CB.
Regarding the origin of the high absorption coefficient (α)
of lead halide perovskite, the optical transition type (direct or
indirect transition) and the time-dependent transition
probability should be considered. Upon light absorption, the
absorption coefficient is proportional to the transition rate
(Wi→f) from the initial state (|i⟩), which is associated with the
VB, to the final state (⟨f |), which is associated with the CB,
according to Fermi’s Golden rule.29 According to this rule, the
transition probability depends on the transition matrix (Mif =
⟨f |H′|i⟩, H′ is Hamiltonian) and the joint density of state
(JDOS) at a given photon energy (hc/λI), which is simplified
in eq 1:
4π 2
Wi → f = |Mif |2 ·JDOS
h (1)
The transition matrix depends on the coupling of the initial
state and the final state, and transition occurs rapidly when the
strength of this coupling increases. The JDOS depends on the
atomic orbitals because it is related to the DOSs of the CB and
the VB.30 As displayed in Figure 4a,b, optical transition occurs
from the (6s(Pb)−5p(I))* antibonding orbital to the (6p-
(Pb)−5p(I))* antibonding orbital. As compared to the optical
transition in direct bandgap GaAs from the As p orbital to the
Ga s orbital, the p → p transition in perovskite is more efficient
because the CB with the p character is less dispersive than that
with the s character from the viewpoint of JDOS, as shown in
Figure 4c.30 The direct bandgap with the p → p transition is
highly suitable for achieving a high absorption coefficient.
When considering that the CB in semiconductors is influenced
by metal cations, elements with lone pair electrons are
expected to deliver the p character at the CB. Thus, In1+,
Ge2+, Sn2+, Pb2+, Sb3+, and Bi3+ are expected to exhibit high
absorption coefficients if the compounds with these metal
cations have an optical direct bandgap. How do we identify
direct- or indirect-bandgap materials? It is well-known that
spectroscopic measurements, such as a simple Tauc plot from a
UV−vis spectrum, together with theoretical calculation, can
provide an answer to this question. Facilitating an indirect-to-
direct transition by material engineering is another approach to
finding new light-absorbing materials with high absorption
coefficients. For instance, Cs2AgBiBr6 perovskite was reported
to have an indirect bandgap, which could be changed to a
direct bandgap when Bi3+ was alloyed with In3+ and/or Sb3+.31
It was reported that a strong spin−orbit coupling (SOC) in
MAPbI3 can influence the optical transition, where a weak
indirect bandgap transition was observed due to Rashba
splitting in the CB.32 The strong absorption and long charge-
carrier lifetime for MAPbI3, which could not be achieved in
conventional semiconductors (where strong absorption with
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μ (cm2/(V s)) carrier conc (cm−3)
e h e h
1.8−12 2−40 10−44 7.6 × 1010
1.8−34 7−26 10−28 8.3 × 1011
short carrier lifetimes is exhibited by direct-bandgap semi-
conductors, and weak absorption with long carrier lifetime is
exhibited by indirect-bandgap semiconductors), could be
explained by the presence of the weak indirect-bandgap
characteristics. An indirect-to-direct bandgap transition was
realized by applying a hydrostatic pressure of over 325 MPa on
MAPbI3 (Figure 4d), resulting in the doubling of the radiative
efficiency and an increase in the carrier lifetime.32
2.2. Parameters Affecting Charge Transport, Collection,
And Recombination
As a working principle in solar cells, photogenerated electrons
and holes (carriers) should be separated, transported, and
collected in electrodes, which result in external quantum
efficiency (EQE). Hence, carrier transport and recombination
are extremely vital in determining the overall photovoltaic
performance. In a solar cell, the majority carriers determine the
overall device architecture, such as the p−n or p−i−n junction,
width of the depletion region, and bulk series resistance, while
the minority carriers directly influence the recombination
lifetime (τ), diffusion length (LD), and recombination
coefficients (kn).33 The conventional standard Hall measure-
ment only provides information on the majority carriers. In
2019, Shin’s research group in KAIST collaborated with IBM
to provide more information on the mobility of electrons and
holes in ambipolar perovskite materials, (FAP-
bI3)1−x(MAPbBr3)x. In Table 2, the carrier transport proper-
ties, including τ, L D , the mobility (μ), and carrier
concentration, are presented based on photo-Hall measure-
ments.33 Because the measurements were carried out under
illumination, the parameters can be applied under the
operational condition. When comparing the highest values of
the transport parameters between MAPbI3 and the cation/
anion mixed perovskite (note that FAPbI3 is dominant in the
mixed perovskite), most of the parameters are similar;
however, τ, LD, and the carrier concentration for the mixed
perovskite are slightly higher than those for MAPbI3 except for
μ, implying that the photovoltaic performance of the FAPbI3-
based mixed perovskite might be better than that of MAPbI3.
Next, we discuss how these parameters affect the photovoltaic
performance. For instance, LD is considered when determining
the device structure, whether mesoscopic or planar (Figure 1).
Because LD is proportional to the diffusion coefficient (D) and
τ, i.e., L D = D τ , the diffusion coefficient for electrons (De)
and holes (Dh) can be estimated from LD and τ. The minimum
required carrier diffusion coefficient (Dm) was derived with the
assumption that the absorbance of the perovskite film is greater
than 1 (more than 90% of the incident light is absorbed), the
charge injection yield is greater than 90%, and the charge
collection yield is 100%. If charge injection is limited by charge
10
diffusion in the perovskite, Dm can be estimated by Dm = α2 τ
(α represents the absorption coefficient).34 According to the
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Figure 5. (a) Grain-size-dependent mobility for MAPbI3. The filled squares with error bars represent the measured data, and the blue solid line
represents the best-fit result obtained using a Kubo relation (see ref 38 for more details). The dotted line represents the fit result with two data
points. Reproduced with permission from ref 38. Copyright, 2016 American Chemical Society. (b) Mobility as a function of the bromide fraction
(x) in FAPb(BrxI1−x)3 and Cs0.17FA0.83Pb(BrxI1−x)3. The arrow indicates that the partial substitution of FA with Cs ions improved the carrier
mobility. Reproduced with permission from ref 35. Copyright 2017 American Chemical Society.

Figure 6. (a) Schematic illustration of the recombination process, where the first-order SRH, second-order radiative, and third-order Auger
recombinations are present. The interface recombination is related to the presence of an electron transport layer (ETL). (b) The recombination
rate, dn/dt, is given as a function of the charge density, n, for MAPbI3. Reproduced with permission from ref 41. Copyright 2016 Springer Nature.
(c) Effect of nonradiative recombination on the current−voltage curves, and (d) difference in the quasi-Fermi level between the CB and the VB
depending on the interfaces. Reproduced with permission from ref 42. Copyright 2017 Springer Nature.

estimation, a mesoscopic structure containing mesoporous
TiO2 is recommended for MAPbI3 because De is lower than
Dm, although Dh is higher than Dm. For GaAs, the planar
structure is preferable because De and Dh are much higher than
Dm.32 D can also be evaluated from μ via the following Einstein
relation: μ = eD/(kBT), where kB is the Boltzmann constant,
which indicates that a high mobility can lead to a high LD.
Charge-carrier mobility values depending on the perovskite
compositions and architectures (film, polycrystalline, single
F https://dx.doi.org/10.1021/acs.chemrev.0c00107
crystal, etc.) have been reported,35,36 where a single crystal
exhibited a higher μ than a polycrystalline thin film. This is
reasonable when considering that LD increased with the
perovskite grain size.37 Nevertheless, it cannot be generalized
because of experimental uncertainty. Excluding the intrinsic
factors limiting μ, we investigate the extrinsic factors affecting
μ. Evidently, the grain size influences the carrier mobility, as
mentioned previously.38 Figure 5a shows that the carrier
mobility increases with the grain size; however, it reaches a
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Figure 7. (a) Perovskite crystal structure. For photovoltaically interesting perovskites, the large cation (A) is usually the methylammonium ion
(CH3NH3), the small cation (B) is Pb, and the X anion is a halogen ion (usually I, although both Cl and Br are also receiving attention). For
CH3NH3PbI3, the cubic phase forms only at temperatures above 330 K. Reproduced with permission from ref 48. Copyright 2015 Elsevier.
Schematic structural representation of MAPbI3, where MA = methylammonium in the (b) pseudocubic and (c) tetragonal phases. The thick
dashed lines indicate the unit cell, which contains C (black), N (green), H (white), I (violet), and Pb (light gray) atoms; the highest symmetry
phase for MAPbI3 and its related materials is the cubic (Pm3̅m) lattice phase, with sequential transitions lowering the symmetry typically through
octahedral tilting. The tilting collectively leads to the transition from the cubic to tetragonal phase. Reproduced with permission from ref 50.
Copyright 2013 American Chemical Society.

saturation point at grain sizes larger than 100 nm. Energetic
disorder was reported to change the carrier mobility, where
structural changes with low crystallinity in FAPb(Br1−xIx)3
were observed at x ≈ 0.3−0.5, at which point μ was
significantly reduced.39 This challenge could be overcome by
introducing the Cs ion, which eliminates the mobility gap,40 as
shown in Figure 5b.
2.3. Recombination in Perovskite Materials and Solar Cells
The recombination of charge carriers in semiconductors can be
simply expressed by the following relation: dn/dt = −k1n −
k2n2 − k3n3, where n is the electron charge-carrier density, k1 is
the first-order Shockley−Read−Hall (SRH) trapping (non-
radiative) rate constant (also called monomolecular recombi-
nation), k2 is the second-order band-to-band (radiative)
recombination rate constant (also termed “bimolecular
recombination” due to the reaction of e + h → γ), and k3 is
the third-order Auger (nonradiative) recombination rate
constant.40 Because monomolecular recombination is related
to traps, the SRH recombination is also termed “trap-assisted
recombination”. The recombination rate constants were
estimated to be k1 = ∼107 s−1 (τ = ∼100 ns) for SRH, k2 =
∼10−10 cm3 s−1 for radiative recombination, and k3 = ∼10−28
cm6 s−1 for the Auger recombination, for both MAPbI3 and
FAPbI3.40 The trap-assisted recombination (SRH) was
reported to be accelerated by impurities and crystal disorder.39
In Figure 6a, the recombination process is schematically
displayed from the electron point of view. The dependence of
the recombination rate (dn/dt) on the light intensity,
represented by the charge-carrier density, is displayed in
Figure 6b, where at low light intensities, the recombination
kinetics is dominated by the monomolecular process attributed
to the unfilled trap states, whereas the bimolecular kinetics
dominate at high light intensities because the traps are filled,
and consequently, there is a substantial number of free
electrons and holes.41 At very high light intensities or carrier
densities over 1018 cm−3, Auger recombination appears to be
significant. Here, we discuss the effect of the nonradiative
recombination on the photovoltaic performance. The trap-
assisted SRH recombination tends to decrease both Jsc and Voc,
as compared to an ideal device, which allows only radiative
recombination, as shown in Figure 6c. Voc is expected to
decrease further when interface recombination exists. A PCE of
30.5% can be achieved from an ideal single-junction device
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without nonradiative recombination because the Voc and FF
values approach the Shockley−Queisser limit values of 1.33 V
and 0.91, respectively.42 Because Voc is logarithmically
proportional to the photoluminescence external quantum
yield (EQYPL), i.e., Voc = Voc,rad + kT/q[ln(EQYPL)], Voc
reaches a theoretical value when EQYPL = 1 for only radiative
recombination. For nonradiative recombination, EQYPL will be
<1, and thus Voc is expected to be lower than Voc,rad. For
instance, for EQYPL = 10−3 at 25 °C, Voc will be ca. 173 mV
lower than Voc,rad (kT/q = 25 mV at 25 °C). In Figure 6d, Voc,
represented by the difference in the quasi-Fermi level between
the CB (FCB) and VB (FVB), tends to decrease as EQYPL
decreases, which is caused by the creation of interfaces by the
electron transport layer (ETL) and/or hole transport layer
(HTL). This clearly indicates that interface engineering is of
critical importance in increasing the photovoltaic performance
toward achieving high theoretical efficiency.43,44 As one of the
factors responsible for the nonradiative recombination, the
lattice strain was reported to enhance nonradiative recombi-
nation,45 which highlights that structural modification also
plays an important role in the modulation of the recombina-
tion process.
3. KEY CHALLENGES IN ACHIEVING HIGH
EFFICIENCY
3.1. Structure Design
3.1.1. Crystal Structure. MAPbI3 has a crystal structure of
perovskite with a general chemical formula of ABX3 in a simple
cubic lattice.46 The space group is Pm3̅m. In principle, any
combination of compatible ions can form a stable perovskite
crystal, where the tolerance and octahedral factors are satisfied
within an empirically determined range, depending on the
ionic radii of the constituents (this will be discussed in more
detail in section 3.2.).47 The anion corner-shared 3D network
of the PbI6 octahedra can be viewed in Figure 7a.48 As a simple
cubic lattice, the Pb ions are centered in the octahedral, and
the MA ions are located between the octahedral building
blocks.49 The highest symmetry phase for MAPbI3 and its
related materials is the cubic (Pm3̅m) lattice, with sequential
transitions lowering the symmetry typically through octahedral
tilting. The tilting collectively leads to the phase transition
from cubic to tetragonal. (Figure 7b,c)50 The collective
rotation of the PbI6 octahedra around the c axis results in
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the tetragonal space group, I4/mcm, with relatively close
packing within the ab plane. Further transition to an
orthorhombic phase (space group: Pnma) is accompanied by
a tilting of the PbI6 octahedra out of the ab plane. MAPbI3
transforms from the cubic to the tetragonal phase at
temperatures below 315−330 K, and the tetragonal to the
orthorhombic phase at ∼160 K. These transitions need to be
critically considered when assessing charge-carrier dynamics
because they may alter the electronic band structure and,
consequently, the optoelectronic properties of the material.
The group of hybrid perovskites exhibits crystallographic
phase transitions with varying temperatures and pressures.
Heat capacity measurements along with temperature-depend-
ent X-ray diffraction (XRD) studies revealed a crystallographic
phase transition from cubic to tetragonal at temperatures of
330.8, 236.1, 177.2, 238, and 403 K for MAPbI3, MAPbBr3,
MAPbCl3, FAPbBr3, and CsPbBr3,51 respectively. The cubic
structure contains only one formula unit (Z = 1); therefore, the
noncentrosymmetric MA ions must be randomly oriented to
satisfy the Oh symmetry. As the temperature decreases,
tetragonal and orthorhombic phases are stabilized with
accompanying ordering of MA molecular ions.52 The structural
transition from the cubic to tetragonal phase occurs due to the
reorientation of MA+, as observed by NMR studies, where the
number of disordered states of MA+ was lowered from 24 in
the cubic phase to 8 in the tetragonal phase. This molecular
ordering is completed in the orthorhombic phase such that at
161.8, 149.8, 171.5, 150, and 385 K for MAPbI3, MAPbBr3,
MAPbCl3, FAPbBr3, and CsPbBr3, respectively, an ortho-
rhombic Pnma space group is formed. Some studies have
reported the crystal structure of MAPbX3 (X = I, Br, Cl) to
comprise noncentrosymmetric space groups, such as I4cm and
Pna21 for the tetragonal and orthorhombic phases, respec-
tively. Nandi et al. refined the high-resolution synchrotron
XRD data both in centrosymmetric and noncentrosymmetric
space groups and reported relatively good reliability parameters
in the centrosymmetric structure.53 Irrespective of the
temperature-dependent phase transitions, hybrid perovskites
exhibit crystallographic phase transitions with applied pressure.
Reportedly, in the literature, the crystal structure of MAPbI3 is
tetragonal (I4/mcm) at ambient temperature and pressure and
has a distorted orthorhombic phase with the space group Imm2
when the pressure is above 0.3 GPa. Further, reversible
amorphization was realized for this system when a pressure of
10 GPa was applied.54 However, MAPbBr3 is in the cubic
phase with space group Pm3̅m at ambient pressure, and has a
cubic space group (Im3̅) when a pressure of 1.7 GPa is
applied.55
Many theoretical studies have improved our fundamental
understanding of electronic structures.56,57 In contrast, few
fundamental and experimental studies have been reported.58 In
2014, the electronic structures of TiO2/MAPbI3 interfaces
were investigated using hard X-ray photoelectron spectroscopy.
The simulated DOS of the VB describes the experimental
spectra adequately and shows that the outermost levels consist
of Pb and I orbitals.59
As discussed earlier, MAPbI3 exhibits an inverted band
structure compared with conventional inorganic semiconduc-
tors, and the MA+ ion contribution to the electronic states is
far from the band edges. In other words, occupied molecular
states are found well below the top of the VB, and empty
molecular states are found well above the bottom of the CB.
Consequently, the organic molecules do not play a direct role
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in the formation of the electronic structures; rather, they
stabilize the structure of the perovskite and change the lattice
constant.60,61 As a result, MAPbI3 and its related materials are
direct-bandgap semiconductors with strong band optical
absorption and luminescence. Essentially, the valence band
maximum (VBM) and conduction band minimum (CBM) lie
at the same point in the reciprocal space (k-space). Note that
recent theoretical calculations suggest that there may be subtle
yet important exceptions that arise in noncentrosymmetric
crystal structures in MAPbI3 due to SOC.56,62 The Rashba
spin-splittings with CBM are not located at the same high-
symmetry points of the Brillouin zone (R point); instead, they
are slightly shifted. In other words, the CBM and VBM are not
located at the same points, having different Rashba momentum
offsets.63,64 This result indicates the formation of an indirect
bandgap, which significantly reduces the radiative recombina-
tion rate. Conversely, because the indirect bandgap is generally
only a few tens of millielectronvolts smaller than the direct
optical transition gap, it does not significantly affect the
absorption spectrum.65 Furthermore, the direct bandgap
characters in the strong optical absorption and indirect
bandgap characters in the slow recombination are responsible
for the high efficiencies of MAPbI3 solar cells. Both Pb and I
are heavy ions in MAPbI3, and therefore, both the VB and CB
exert considerable relativistic effects; that is, for a quantitative
treatment of the electronic band structure, the SOC must be
included. SOC causes a decrease in the electronic bandgap due
to the splitting of the gap. Prediction of the bandgap by a state-
of-the-art quasiparticle self-consistent GW with SOC correc-
tions is the only method that can accurately predict the
electronic structure of MAPbI3. The calculated direct bandgap
of MAPbI3 is Eg ∼ 1.67 eV, which is in good agreement with
the measured value of 1.61 eV by room-temperature
photoluminescence (PL). The computed bulk ionization
potential and electron affinity are 5.7 and 4.1 eV,
respectively.66
3.1.2. Defect Structure. Thus far, MAPbI3 and its related
materials have mainly been synthesized by a low-temperature
solution process. This process inevitably produces many
different types of defects, including thermodynamically stable
point defects, interfaces, surfaces, and grain boundaries
(GBs).67 Generally, the Voc deficit arises from a trap-assisted
electron−hole nonradiative recombination. The Voc decrease
in PSCs is rather small compared to that in other inorganic
semiconductors, indicating that defects play a relatively minor
role in PSCs. Nonradiative recombination and carrier
scattering are often caused by defects that generate deep-
level states in the bandgap. Most structural defects, including
surfaces and GBs, occur in deep-level states.68 Unusually, deep-
level defects with high formation energy are rare, whereas
shallow trap states in the bandgap are abundant in MAPbI3,
resulting in defect-tolerant materials. These unique defect
properties are also attributed to the strong Pb lone-pair s−
halogen p antibonding coupling and the ionic characteristics, as
mentioned in the previous section.69,70 Understanding and
controlling defects to suppress nonradiative charge recombi-
nation are essential for further improvement of the PSC
efficiency.69,71
First-principles calculations have been used to study the
point defect properties of MAPbI3 and its related materi-
als.30,72−75 The growth of the MAPbI3 phase can occur only in
a long and narrow range of chemical potential, indicating a
small experimental window in terms of thermodynamic
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Chemical Reviews
variables, e.g., precursors, pressure, and temperature. All
possible intrinsic point defects include three vacancies (VMA,
VPb, VI), three interstitials (MAi, Pbi, Ii), and four antisite
substitutions (MAI, PbI, IMA, IPb). All the vacancy defects and
most interstitial defects, such as MAi, VPb, MAPb, Ii, VI, and
VMA, exhibit rather shallow transition energy levels. The
shallow level defects of both, donors and acceptors, have
comparable low defect formation energies resulting in n- and
p-type electronic systems in MAPbI3.76 Theoretical bipolar
conductivities have already been confirmed by doping
experiments.77 In MAPbI3, the dominant donors, MAi and
VI, and acceptors, VPb and MAPb, have comparable formation
energies; therefore, both p- and n-type dopings are possible.
The shallow acceptors originate from the covalent coupling
between the Pb lone-pair s orbital and I p orbitals, which
increase the VBM so that the acceptors are generally shallower
than those in the cases without strong sp coupling. In contrast,
the shallow donors originate from the high ionicity. The
calculated transition energy levels of the point defects in
MAPbI3 and MAPbBr3 are shown in Figure 8.78 For the
Figure 8. Thermodynamic ionization levels of most stable defects in
MAPbI3 and MAPbBr3. Reproduced with permission from ref 78.
Copyright, 2019 John Wiley and Sons.
simulated MAPbBr3, one can notice quite similar defect
chemistries in the two perovskite materials. The defects that
generate deep levels are IMA, IPb, Pbi, MAi, and Pbi, which are
mostly cation or antisite defects, except for Pbi, having high
formation energies. The most stable defects in both MAPbI3
and MAPbBr3 are MA and halide interstitials, i.e., MAi+ and
Ii−/Bri−. MAi is not covalently bonded to the Pb−I framework
and does not create additional gap states. Thus, MAi defects
are stable only in the positive charged states within the Fermi
level range spanning the perovskite bandgap, and they exhibit a
shallow (+/0) transition close to the CBM. In the physical
image, the cation occupies the interstitial positions on the
facets of the Pb−X6 (X = I, Br) octahedra, with associated
densities of ∼1012 cm−3. Ii+ exhibits relatively high stability, i.e.,
a lower defect formation energy, compared to Bri+, leading to a
sizable defect density of ∼1010 cm−3. The relatively high
stability of positive I interstitials is mainly due to the lower
electronegativity of I compared to Br. Interestingly, an
interstitial I atom introduces deep trap states near the VBM,
and holes are trapped in the states; the trapped holes exhibit
surprisingly long lifetimes. Figure 9 shows the calculated DOSs
of pristine MAPbI3 (top panel) and MAPbI3 with the I
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Figure 9. Total and projected densities of states (DOS) of pristine
MAPbI3 (top panel) and MAPbI3 with the I interstitial defect
(bottom panel). The insets show the charge densities of the (a) VBM
and (b) CBM in pristine MAPbI3, and the (c) VBM, (d) CBM, and
(e) trap state in MAPbI3 with the I interstitial defect. Reproduced
with permission from ref 71. Copyright 2019 American Chemical
Society.
interstitial defect (bottom panel), showing I interstitials near
the VBM. The recombination of the trapped holes with the CB
electrons is several times slower than that of the VB holes with
the CB electrons. These factors can lead to charge reduction
and energy losses in PSCs with I interstitial defects and,
consequently, contribute to the high efficiency of the PSCs.
Pb vacancies, VPb, also contribute to the defect chemistry of
MAPbI3 with a low defect formation energy. VPb is less stable
in MAPbBr3 than in MAPbI3. VPb is stable in the −2 charge
state in MAPbI3, showing comparable defect density with
those of Ii− and MAi+. The oxidation of VPb2− with two holes
leads to the oxidation of lattice halides with the formation of Ii+
and an I vacancy. The effect of VPb on the charge-carrier
dynamics in MAPbI3 was studied using the Redfield theory
formalism, and it was experimentally confirmed that VPb
increases the nonradiative relaxation time of the excited
electrons.79 For FAPbI3, the effect of VPb was also investigated
theoretically and experimentally; it was concluded that the
effect was similar to that in MAPbI3.80,81 Although PSCs based
on FAPbI3 with mixed A-site cations of MA and Cs exhibited
much higher PCEs, only a few first-principles calculation
studies of intrinsic defects in FAPbI3 can be found in the
literature.82 In this study, it was calculated that defects VFA,
FAI, and IFA show much lower formation energies in FAPbI3
than in MAPbI3. Antisites FAI, and IFA create deep-level states
in the bandgap and can act as recombination centers, resulting
in reduced carrier lifetimes and low Voc values in FAPbI3-based
cells. They also found that by mixing the cations of MA and FA
in perovskites, the formation of these defects can be
substantially suppressed, which would lead to enhanced PCEs.
The formed halide vacancies may couple with metal
vacancies through the formation of Schottky defects. As
reported by Walsh et al., these defect couples have low
formation energies and do not introduce electronic disorders.83
The Schottky formation energy of 0.14 eV per defect is
remarkably low and corresponds to an equilibrium vacancy
concentration of 0.4% at room temperature. In comparison,
the reported Schottky formation energy for BaTiO3 is 2.29 eV
per defect, which results in parts-per-million (ppm) levels of
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equilibrium vacancy concentrations. The Sargent group
provides a complete electronic band diagram of a single-crystal
MAPbI3 using the in-gap electronic state spectrum. The high
mobility and long diffusion length of both electrons and holes
are directly measured, as well as the extremely low
concentration (nt(VB) = 3 × 1010 cm−3; nt(CB) = 3 × 1011
cm−3) with ambipolar charge carriers.84 The halide perovskites
show an ultralow density of trap states even at low synthesis
temperatures. The most easily formed defects in perovskites
have little influence on the charge-carrier lifetimes, ration-
alizing the high efficiencies of PSCs.
Conventional semiconductor technologies are centered on
the production of perfect crystals to reduce defects, as
exemplified by single-crystalline Si with remarkably low defect
densities. However, the synthesis of MAPbI3 by solution
processing, at near room temperature, inevitably results in a
high density of defects, which may be detrimental to its
performance. Whereas nonradiative charge recombinations
involving defect states are significant in traditional semi-
conductors, the reported charge-carrier lifetimes are excep-
tionally long in perovskites, ranging from a few nanoseconds to
hundreds of nanoseconds,85 indicating that the defect states in
perovskites are indeed benign electrically. In this context,
defect-tolerant MAPbI3 materials are still not fully understood.
According to the original concept of defect tolerance, the
presence of an antibonding upper VB and a bonding lower CB,
as in MAPbI3, signifies that dangling bond defects would be
repelled quantum mechanically into the continuum bands,
leaving the bandgap clean and allowing for the formation of
shallow defects. The second point to consider is the screening
in the dielectric medium. If charged defects are present in the
host material, their influence should be minimized. The
dielectric constant represents the ability of a material to screen
an electrostatic perturbation. The higher the dielectric constant
of a material, the more effective the screening, and thus, the
higher the defect tolerance of the material. The dielectric
constants of MAPbI3 are approximately three times higher than
those of other thin-film photovoltaic materials, such as CdTe
and Cu2ZnSnS4.86,87 The last factor under consideration is the
carrier effective mass. A low mass favors free charge carriers
and can support high carrier mobility and electrical
conductivity. The spatial localization of electrons and holes
at charged defect sites should be avoided as they retard the
transport of charge carriers and are associated with thermal
energy losses. The effective mass is also a critical factor in
avoiding the formation of small polarons. There is competition
between the kinetic energy of the free carriers and the potential
energy gained by localization in the lattice. Typically, metal
oxides often have a high hole effective mass due to the
localization of the O 2p orbitals that form the VB; this leads to
the formation of small polarons, which make it difficult to find
p-type oxides.
In MAPbI3, the unique electronic structure results from
corner-sharing in the PbI63− octahedral framework with overall
stoichiometric PbI3− and a sublattice of MA+ cations in the
cuboctahedral voids, as discussed earlier. The framework with
the corner-sharing octahedra is overly intrinsically soft and
exhibits structural dynamics. The relatively light electrons and/
or holes in the CB are rapidly protected to form a large polaron
with phonons.88 In addition, the large polaron can screen the
electrostatic potential drastically and, thus, reduces its
scattering with charged defect sites.89 Consequently, the high
polarizability in the soft and ionic lattice can enable adequate
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screening and compensation of the charged defects in the
MAPbI3 lattice. The traps are energetically shallow and
electrostatically screened, which minimize their roles in
nonradiative recombination processes.90,91
3.1.3. Microstructure. Highly efficient PSCs are generally
produced by simple solution processes. The simple solution
method guarantees low-cost photovoltaic devices. Spinning of
the precursor solution often results in polycrystalline thin films
on transparent, conducting substrates. Polycrystalline Si,
Cu(In1−xGax)Se2 (CIGS), CdTe, and PSCs are all parts of
polycrystalline thin-film solar cells. The PCE and other solar-
cell performance parameters, such as stability, are largely
dependent on the microstructure of the thin films.
A GB is a critical defect in polycrystalline functional
materials. GBs can affect the mechanical, chemical, and
electrical properties of a material. The latter is important for
solar cells because GBs modify the charge-carrier transport
properties and, thus, the performance.92 In GBs, a lattice
discontinuity, incomplete and/or broken bonds resulting in
dangling bonds, and depletion and/or segregation of impurities
can be expected. The defects, dislocations, misplaced atoms
(interstitials), vacancies, distorted bond angles, and bond
distances at GBs can act as recombination centers and/or trap-
states for the charge carriers. Depending on their trap states
and/or centers, the GBs in a polycrystalline thin-film
photovoltaic material play an important role that could be
either benign or detrimental to the cell performance. In
polycrystalline Si thin-film solar cells, the dangling bonds at the
GBs create deep-level states within the bandgap and act as a
nonradiative recombination center. Reducing the density of
dangling bonds in a polycrystalline Si absorber by hydrogen
passivation is a critical microstructure engineering solution for
GBs.93 Meanwhile, deep-level states are not found at the GBs
of CuInSe2 absorber films. GBs are calculated to be electrically
benign.94 Many experimental studies have also demonstrated
the beneficial effects of the GBs in CZTS, CZTSSe, CIGS, and
CdTe films, toward enhancing minority carrier collections. The
GBs in these solar absorbers are electrically charged by
impurities or different types of vacancies, and they create a
downward band bending toward the GBs in mostly p-type
absorbers. Thus, the photogenerated electrons and holes near
the GBs will be easily separated by the built-in field at the GBs,
and the recombination rate of these carriers will be lower at the
GBs.95 GB engineering is, therefore, inevitable for high-
efficiency solar cells.96
Many studies on the GB in polycrystalline semiconducting
organic−inorganic metal halides for PSCs have been reported;
however, the exact role of GBs is yet to be clarified.97 One
aspect is clear though, that the trap density at perovskite
surfaces and GBs is much higher than in bulk because the
observed carrier diffusion length is much greater in single
crystals than in polycrystalline MAPbI3 films. Numerous
theoretical as well as experimental studies have reported
controversial results regarding the effect of GBs on the
perovskite photovoltaic performances.98 First-principles calcu-
lations predicted that the GBs in MAPbI3 are benign simply
because no deep trap states were found. Haruyama et al.
systematically studied the thermodynamic properties of
MAPbI3 surfaces and concluded that the PbI2-terminated
surface does not introduce subgap states.99,100 Yin et al.
reported GBs with intrinsically benign properties by first-
principles calculation. GBs such as Σ5 (310) and Σ3 (111) do
not generate deep states in the bandgap, making polycrystalline
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Figure 10. HOMO and LUMO charge density in (a) pristine MAPbI3, (b) Σ5 (012) GB, and (c) Cl-doped Σ5 (012) GB; the VBM and CBM are
delocalized in (a), and become localized in inorganic atoms in the vicinity of the GB in (b) and (c). Doping with Cl atoms pushes the charge
density away from the GB. DOSs of the (d) pristine MAPbI3, (e) Σ5 (012) GB, and (f) Cl-doped Σ5 (012) GB obtained using optimized zero-
temperature geometries. The zero energy is set to the Fermi level. Reproduced with permission from ref 103. Copyright 2019 American Chemical
Society.
halide perovskite thin films behave single-crystal-like.101 The
same research group further studied and reported that the Σ5
(310) GB forms shallow defects states close to the VBM. They
also showed that the structural disorder at GBs, which induces
the formation of Pb−Pb bonds, creates no subgap states
because of the relatively large distance between the two Pb2+
ions. The shallow trap states are not as critical as the deep
levels; possibly, the states may increase the effective mass of
holes and/or trap the holes to decrease the hole mobility,
thereby inducing nonradiative SRH recombination.102 These
benign GBs can, in part, explain the long carrier diffusion
length and high efficiency reported with lead halide perov-
skites.
Meanwhile, another theoretical study involving a time-
domain atomistic simulation via nonadiabatic molecular
dynamics combined with the density functional theory
(DFT) showed that while GBs may act as major recombina-
tion sites in a pure iodide material, they can be
passivated.103−105 By breaking the perovskite crystalline
periodicity, GBs create localized states, which overlap less
than the CBM and VBM in the pristine perovskite (Figure
10).103 These studies demonstrated that GBs strongly
accelerate the electron−hole recombination relative to the
bulk MAPbI3, while the introduction of substitutional Cl
dopants at the boundary reduces the recombination. Once
relatively light Cl ions substitute relatively heavy I ions at the
GB, they introduce high-frequency vibrations and accelerate
the quantum coherence loss. Furthermore, in contrast to I, the
Cl dopants do not contribute to the hole wave function;
consequently, they eliminate some of the wave function
overlap, reduce the nonadiabatic electron−phonon coupling,
and restore the value of the material close to that of the
pristine MAPbI3. It is suggested that charge recombination
depends on the type of GBs created and that annealing of
perovskite films can cure GB defects, which would, in turn,
eliminate midgap states and stabilize the GBs, thereby
prolonging the charge-carrier lifetime.106
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Many scanning probe techniques have been employed to
investigate the local properties of perovskite microstructure
conjunctions. In particular, atomic force microscopy (AFM)
and Kelvin probe force microscopy (KPFM) have been
employed to explore the local electronic structures of
perovskite photovoltaic absorbers. Both techniques typically
provide information based on the measurement of the surface
potential differences and local conductivity. Yun et al.
investigated the effect of high-density GBs in the presence of
a MAPbI3 absorber by KPFM and conductive-AFM (c-AFM).
Their KPFM results showed a relatively low contact potential
difference (CPD) at the GBs under the dark condition,
implying that a downward band bending occurred in the GBs.
The higher current collection observed by c-AFM near the
GBs is consistent with the KPFM results, which indicates that
photogenerated carriers are more efficiently separated and
transported along the GBs.107 Chen et al. also employed
KPFM to study the CPD between and near the GBs. They
found that the band bending near the GBs and the band
bending of the grains to the GBs switched from downward to
upward when the organic species were released to form PbI2.
This indicates that PbI2 could effectively passivate the GBs and
prevent charge recombination at the GBs.108 Scanning
tunneling microscopy (STM) combined with scanning
tunneling spectroscopy (STS) was also employed to provide
the local electronic DOSs with spatial resolution at the
nanometer scale or even atomic scale. M.-C. Shih et al. utilized
a light-modulated STM technique to reveal the correlation
between the nanoscale compositional distribution and the
interfacial electronic structures of the heterointerfaces in PbI2-
passivated MAPbI3 films. They revealed the important role of
the optimum PbI2 passivation layers in charge separation and
recombination at the perovskite crystal grains.109 In contrast,
Chu et al. conducted the quantitative nanoscale photo-
conductivity imaging of MAPbI3 thin films by light-stimulated
microwave impedance microscopy. The microwave signals
were largely uniform across grains and GBs, suggesting that the
microstructures do not cause strong spatial variations in the
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Figure 11. I−V curves for a series of different voltage scanning rates measured on the (a) grain of a MAPbI3/TiO2/FTO/glass sample by AFM and
(b) an Au/MAPbI3/TiO2/FTO/glass structure using macroscopic probes in the nonilluminated state. (c) Topography and (d) corresponding
current image of the MAPbI3 thin films obtained by applying −1.5 V to the AFM tip. (e) Current image overlaid on a 3D topography image of the
white boxed region, as indicated in (c) and (d). (f) Schematic representation of the origins of I−V hysteresis, i.e., ionically active GBs. Reproduced
with permission from ref 111. Copyright 2017 John Wiley and Sons.
photoresponse. The measured photoconductivity and lifetime
are strongly affected by bulk properties, such as the
crystallinity.110 Using temperature-dependent PFM and scan-
rate-dependent nano/macroscopic I−V measurement, ion
migration through GBs was determined as the primary origin
of the I−V hysteresis. The relatively high current passing
through the grains was measured as the voltage scan rates were
increased, by local I−V measurement using a c-AFM, and
opposite I−V behaviors were observed through the GBs, as
shown in Figure 11.111 Further investigations are required to
elucidate the local intrinsic properties of GBs.
The consensus is that charge-carrier trapping is the
dominant recombination pathway under typical operating
conditions owing to the slow recombination of free charge
carriers despite the low trap density. None of the spectroscopic
techniques have provided information on the spatial locations
of the trap states or their associated chemical/physical
nature.112 Spatially resolved measurements, mostly based on
PL imaging, combined with microstructural characterization
techniques, such as confocal microscopy, scanning electron
microscopy (SEM), and AFM, are required to study the
microstructural contribution in highly efficient PSCs. M. J.
Simpson et al., in their early work, utilized a combination of PL
and femtosecond transient absorption microscopic techniques
to map the trap states by spatial resolution.113 The localized
optical response of the MAPbI3 films, obtained by spatial
resolution and correlated emission/absorption measurements,
was used.114 Their results strongly implied the existence of
other factors, beyond GB-related nonradiative recombination
channels, which led to significant intrafilm optical hetero-
geneities in the perovskite films. The effect of the significant
morphological heterogeneity of the polycrystalline perovskite
films on their photovoltaic performance, determined by PL
microscopy, was also reported by W. Tian et al.115 They
studied the carrier lifetime, intra- and intergrain carrier
diffusion length, and carrier extraction efficiency with
submicrometer spatial resolution. Contrary to the common
belief concerning the deleterious effect of the morphological
heterogeneity on the carrier lifetimes and diffusivities, in neat
MAPbI3(Cl) polycrystalline films, the local carrier diffusivities
in different grains are all surprisingly high. Furthermore, the
local carrier lifetimes are long and surprisingly homogeneous
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among grains and uniform across the GBs and interiors.
Confocal fluorescence microscopy was suggested as a powerful
tool to investigate the spatially as well as the temporally
resolved charge-carrier recombination dynamics, providing
insight into the potential sources of nonradiative loss in
perovskite. M. Yang et al. examined GBs in high-quality
micrometer-sized MAPbI3 thin films using high-resolution
confocal fluorescence-lifetime imaging microscopy with kinetic
modeling of the charge-transport and recombination processes.
They found that the GBs generally display lower luminescence
intensities than the grain surfaces and/or grain interiors;
additionally, the lifetimes at GBs are not poorer than those of
the grain surfaces/interiors, suggesting that the GBs do not
dominate nonradiative recombination.116 Through transient
reflection spectroscopy, the same group also observed that the
charge-carrier lifetime is mainly limited by surface recombina-
tion.117 Moreover, Snaider et al. employed transient absorption
microscopy (TAM) to directly measure the carrier transport
across GBs in hybrid organic−inorganic perovskite thin films
with 50 nm spatial as well as 300 fs temporal resolutions.118
While carrier transport across GBs is limited to some extent,
the carrier diffusion constants are only reduced by approx-
imately a factor of 2 when the grain sizes are >1 μm. For a film
with a grain size on the order of 200 nm, carrier transports
across multiple GBs have been observed within a time window
of 5 ns, although they were not spatially uniform. Their results
demonstrated how grains oriented between grains affect carrier
transport. Adequately large grains, arranged in the depth
direction of the film, can also play a critical role in high-
performance PSCs. The preferential orientation of tetragonal
perovskite grains can thus enhance the charge-carrier lifetime,
resulting in superior photocurrent and high electric potentials
in PSCs.119,120 Kim et al. fabricated highly preferred-oriented
and enlarged perovskite grains by pressure-induced crystal-
lization with low-angle GBs, which led to improved solar cell
performance.121
In contrast, de Quilettes et al. observed PL quenching in the
GBs of nonstoichiometric organic−inorganic perovskites,
MAPbI3(Cl), by confocal fluorescence microscopy in con-
junction with SEM to spatially resolve the PL decay dynamics.
Although the PL intensities and lifetime varied between
different grains in the same film, the GBs were relatively dim
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Figure 12. (a) ABX3 cubic perovskite crystal structure and the corresponding lengths expressed by the ionic radius. (b) Band structure of
CH3NH3PbI3. (c) Total DOS (top panel) and contributions from CH3NH3+, Pb, and I partial DOSs (bottom panels), respectively. The zero in
DOS refers to the VBM. The Pb partial DOS is enlarged by five times for a clear indication of the s orbital contribution. Reproduced with
permission from ref 72. Copyright 2014 American Institute of Physics.
and exhibited fast nonradiative decay.122,123 The GBs in their
study are not benign, as has been suggested previously.
Chemical treatment with pyridine could activate previously
dark grains. Ham et al. also reported the acceleration of charge-
carrier recombination at the GBs of MAPbI3 films prepared
from both stoichiometric and nonstoichiometric precursor
solutions. The average charge PL lifetime is relatively longer at
the grain interiors than at the GBs. The relatively short PL
lifetime was found to be due to trap-assisted nonradiative
recombination, which is dominant at the GBs.124 By removing
these nonradiative recombination pathways to obtain more
uniform brightness with high emissivity across all the grains
and GBs, efficiencies close to the theoretical efficiency of PSCs
can be achieved. Although many investigations have
demonstrated that GBs could enhance the photovoltaic
performances by acting as charge-carrier dissociation sites,
thus leading to an increase in the photocurrent density, the
passivation of GBs, which can prevent negative behaviors such
as nonradiative recombination, has been conducted by many
researchers.
3.2. Materials Chemistry
As briefly mentioned in section 3.1, the structural formability
of the 3D ABX3 perovskite can be estimated by considering the
tolerance factor. The tolerance factor defines the geometrical
criteria for the formation of an ideal cubic perovskite structure.
From Figure 12a, the hypothetical cubic crystal structure
displays the lengths of all the yellow lines as identical and equal
to 1 of the length of the blue line. With the assumption that
2
the distance between two ions is the same as the sum of the
ionic radii, we can derive an expression for the tolerance factor
(t), as follows:
rA + rX
t=
2 (rB + rX) (2)
where rA, rB, and rX are the ionic radii of A, B, and X ions,
respectively. In principle, when the tolerance factor is 1, the
ideal cubic perovskite crystal structure is formed. Empirically,
material compositions with tolerance factors ranging from 0.8
to 1.0 were found to be able to crystallize into perovskite-
structured materials at room temperature.125 Below 0.80, other
structures, such as ilmenite-type (FeTiO3), are stable, whereas
at tolerance factors greater than 1, hexagonal structures with
face-sharing octahedra are formed. Although the tolerance
factor only considers the geometrical criteria of the materials
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and not the physicochemical interactions between the
constitutive ions, it provides useful insights for estimating the
structural formability and intrinsic stability of oxide perovskite
materials. For hybrid perovskite materials, in fact, the
application of the tolerance factor is relatively challenging. A
conventional concept concerning ionic radii assumes that the
ion is a solid sphere, which is reasonable in the case of
inorganic oxide perovskite materials with high bond ionicity.
Unfortunately, the organic cations in perovskite are not
spherically symmetric, and they form hydrogen bonds with
the BX6 octahedra. Furthermore, typical perovskite materials
based on the large-sized iodide would have lower bond ionicity
than conventional oxide perovskites, making it challenging to
estimate the effective ionic radius of the constitutive ions. In
fact, we noted that in published studies (including our study),
different ionic radii of organic cations were utilized to estimate
the tolerance factor. Consequently, intensive efforts have been
devoted to revising the ionic radii to obtain a more realistic
tolerance factor.125−127 In this review, we adopt the effective
ionic radii of organic cations estimated by Kieslich et al.125
They hypothesized the rotational freedom of the organic
cations around the center of mass to apply the rigid sphere
model, which appears to be reasonable based on the
experimental observation. The effective ionic radius is
estimated by the following equation:
rAeff = rmass + rion (3)
where rmass is the distance between the center of mass of the
molecule and the atom with the largest distance to the center
of mass, excluding the hydrogen atom; rion is the corresponding
ionic radius of this atom. For inorganic ions, we utilized the
Shannon effective radii for the discussion.128 The ionic radii of
common ions are summarized in Table 3.
The optoelectronic properties of semiconductor materials
are generally dependent on the electronic structure of the band
edges. The band edge state of ABX3 perovskite materials
mainly originates from the orbitals of B and X ions. For the
APbI3 perovskite, as mentioned previously, the CB edge of the
perovskite material mainly originates from a Pb 6p orbital with
negligible coupling with I, whereas the VB edge of these
materials originates from a strong antibonding coupling
between a fully occupied 6s orbital of Pb2+ and a I 5p orbital
(Figure 12b,c).72 The A-site cations were found to contribute
to the deep energy levels in the CB and VB; thus, they do not
directly contribute to the optoelectronic properties of the
perovskite materials. Different from conventional semiconduc-
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Table 3. Ionic Radii of Commonly Used Ions in ABX3 PbI6 octahedra is relatively weak; therefore, it undergoes
Halide Perovskites125,128 degradation at relatively low temperatures (<200 °C), which
can cause the thermal degradation of the materials and devices.
radius B radius X radius
A cations (pm) cations (pm) anions (pm) Therefore, compositional engineering and, thus, modifica-
tion of the chemical bonding nature critically impact not only
ammonium [NH4]+ 146 Pb2+ 119 Cl− 181
the optoelectronic properties of the materials and the PCE of
methylammonium 217 Sn2+ 69 Br− 196
[(CH3)NH3]+ the devices but also their thermodynamic and environmental
azetidinium 250 I− 220 stability. In this section, we review the critical roles of each
[(CH2)3NH2]+ constitutive ion in this regard and summarize the successful
formamidinium 253 strategies developed to date.
[NH2(CH)NH2]+
3.2.1. A Site(Cation)-Modified Perovskites. Although
dimethylammonium 272
[(CH3)2NH2]+ the A-site cation does not directly contribute to the band edge
ethylammonium 274 states of perovskite materials, it serves as a geometrical spacer
[(C2H5)NH3]+ for the corner-sharing PbI6 octahedra in a 3D perovskite to
guanidinium [C(NH2)3]+ 278 prevent distortion. Therefore, depending on the size and
tetramethylammonium 292 symmetry of the A cation, the bond distance and angle
[(CH3)4N]+ between the Pb2+ and halide ions can be changed to ultimately
Cs+ 167 affect the distribution of the band edge state.129 In fact, the
Rb+ 152 bandgap of APbI3 perovskite was found to vary from ∼1.7 to
K+ 137 1.5 eV depending on the size of the A cation. Nevertheless,
compared to the cases of the B- and X-site ions, the
tors, such as cadmium chalcogenides, whose bandgap is formed compositional engineering of the A cation does not
between the bonding (σ) and antibonding (σ*) orbitals, the significantly affect the optoelectronic properties of the
bandgap of perovskite materials is formed between the perovskite materials; this provides an opportunity to fine-
antibonding states; therefore, the majority of the structural tune the crystal structure of the materials.
defect states are formed inside the energy band, or they only 3.2.1.1. MAPbI3. Historically, the MA-based perovskite
constitute the shallow trap states, which do not significantly material was first explored for photovoltaic applications. With
deteriorate the charge-carrier transport properties. This defect- an ionic radius of 217 pm and a corresponding tolerance factor
tolerant property of perovskite materials was found to promote of 0.91 (Tables 3 and 4),125 it crystallized as a tetragonal
the optoelectronic properties of low-temperature-solution- perovskite at room temperature, whose octahedra were slightly
derived perovskite thin films compared to conventional highly distorted from the cubic structure (Figure 13a,c).46 At elevated
crystalline inorganic semiconductors obtained by delicate high- temperatures (54−57 °C), the MA-based perovskite material
temperature vacuum processes. was found to undergo a phase transition to a cubic structure.
The chemical bonding nature of perovskite materials is The bandgap of the single-crystal MAPbI3 was measured to be
found to be considerably more ionic than that of conventional 1.51 eV. The effective masses of the charge carriers in MAPbI3
semiconductors. This characteristic ionic bonding property have been obtained either using first-principles calculations of
enables the easy dissolution of perovskite materials in a variety the band curvature or by magneto-absorption measurements,
of polar aprotic solvents for further processing via solution- where the low effective masses for both electrons (me*) and
based coating methods at low temperatures. However, the holes (mh*) (around 0.1−0.2 m0) were correlated with the
highly polar ionic nature of the bonding, in turn, causes it to be high charge-carrier mobility (1−70 cm2/(V s) for polycrystal-
easily degraded by moisture, oxygen, and polar solvents, line films).23,35,130 The organic MA cations in the octahedral
resulting in relatively low environmental stability of the cage were found to reorient dynamically within a very short
materials compared to conventional inorganic semiconductors. time. At room temperature, dipolar MA cations reorient
The low stability of the perovskite materials in liquid between the faces, corners, or edges of the pseudocubic lattice
electrolytes posed a serious hindrance to further development cages of corner-sharing octahedra with a residence time of ∼14
until the introduction of solid-state PSCs.4 Furthermore, the ps.131 The dynamic reorientation of the organic cation is
secondary hydrogen bonding between the organic A cation and suggested to stabilize the energetic charge carriers by the

Table 4. Crystal Structures, Along with Optoelectronic and Physical Properties of MAPbI3, FAPbI3, and CsPbI3 Perovskites

mobility diffusion length

effective mass129 (cm2/V s)33 [μm]33
ionic activation
radius of energy for
the A the first cation
cation tolerance crystal structure bandgap mass loss reorientation
[pm]125,128 factor (300 K) (eV) e h e h e h (kJ/mol)143 rate (ps)142
MAPbI3 217 0.91 tetragonal 1.55 0.19me 0.25mh 2−40 10−44 2−8 1.8−12 93 ± 8 108 ± 18
(cubic, (300 K)
>330 K)
FAPbI3 253 0.99 hexagonal/cubic 1.48 0.18me 0.23mh 35 6.6 115 ± 3 8.7 ± 0.5
(metastable)
CsPbI3 167 0.84 orthorhombic 1.73 650 ± 90
cubic
(metastable)

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Figure 13. Crystal structure of (a) tetragonal MAPbI3 and (b) cubic FAPbI3 perovskites. (c) molecular structure and ionic radii of the MA+ and
FA+ ions. (d) DOS and (e) absorption coefficients of the MAPbI3 and FAPbI3 perovskites. Reproduced with permission from ref 129. Copyright
2014 American Chemical Society. Reproduced with permission from ref 7. Copyright, 2014 John Wiley and Sons.
formation of a large polaron, which, in turn, enhances the
lifetime of hot carriers as well as band edge carriers.132,133
However, this dynamic disorder of the A cation highlights the
relatively weak bond between the A cation and PbX6
octahedra. Consequently, the degradation of MAPbI3 under
illumination or at elevated temperatures is typically triggered
by the volatilization of the MA cation.
3.2.1.2. FAPbI3. Crystal growth and defect engineering,
which will be discussed in a later section, have enabled the
formation of high-quality MAPbI3 films to achieve PCEs
exceeding 20%.10 However, the high PCE of MAPbI3 PSCs is
limited by the relatively large bandgap and low charge-carrier
mobility, which limit the photocurrent and photovoltage of the
devices. After a few years of study, an FA cation-based FAPbI3
perovskite material was proposed as an alternative to overcome
the drawbacks of the MAPbI3 perovskite. FAPbI3 crystallizes
into a nonperovskite hexagonal phase at room temperature
with a bandgap of 2.43 eV.134 The hexagonal phase is
converted to a pure cubic phase upon annealing at temper-
atures above 150 °C, and the cubic perovskite phase is
maintained after cooling to room temperature (Figure
13b).7,135−137 The spontaneous crystallization of the non-
perovskite hexagonal phase at room temperature is probably
related to the larger ionic radius of the FA cation (253 pm,
tolerance factor = 0.99) compared to that of the MA cation
(Figure 13c, Tables 3 and 4),125 resulting in intrinsic lattice
strain, which induces the distortion of the corner-sharing
octahedra constituting the cubic perovskite lattice to the face-
sharing octahedra. Although the cubic perovskite phase was
formed upon annealing at relatively high temperatures, the
phase was found to be metastable at room temperature with an
activation energy barrier of approximately 0.6 eV for reverse-
phase conversion to the hexagonal phase.138 Owing to the
relatively high potential barrier, the as-formed cubic FAPbI3
film was stable under inert atmosphere conditions. However,
the reverse-phase conversion was found to be significantly
accelerated upon exposure to moisture.139 Because of the
highly polar ionic bonding, water vapor can attack the crystal
surface of the perovskite phase and induce a significant number
of surface defects, which reduce the energy barrier for
nucleation of the nonperovskite phase.140 Consequently, the
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cubic FAPbI3 film tends to undergo an accelerated phase
transition to the nonperovskite phase in humid environments.
Nevertheless, the cubic FAPbI3 phase film was found to have a
relatively lower bandgap of 1.48 eV compared to that of the
MAPbI3 thin film (1.57 eV), while the electronic band
structure and, thus, the absorption coefficient are comparable
(Figures 13d,e).136 Furthermore, the charge-carrier lifetime
and diffusion length in the FAPbI3 thin film were found to be
much longer than those in the MAPbI3 film. Through solid-
state NMR measurements, the reorientation rate of the FA
cation in the lattice was found to be much higher (8.7 ± 0.5
ps) than that of the MA cation (108 ± 18 ps), enabling a
superior charge-carrier stabilization capability.141,142 However,
the low phase stability of the FAPbI3 perovskite limits the
further enhancement of the PCE in devices based on pure
FAPbI3 perovskite films (PCEs exceeding 19% were rarely
achieved).
3.2.1.3. CsPbI3. As a replacement for the volatile organic A
cations, the pure inorganic CsPbI3 perovskite has also been
explored. Different from organic cations exhibiting weak
secondary hydrogen bonding with the perovskite lattice, Cs
forms a strong primary chemical bond with the perovskite
lattice. The strong chemical bond between the Cs cation and
perovskite lattice is supported by the considerably high
activation energy required for the initiation of the thermal
degradation (650 ± 90 kJ/mol) of CsPbI3.143 However, the
relatively small ionic radius of the Cs cation (167 pm) results
in a tolerance factor of 0.81, effectuating the low thermody-
namic stability of the perovskite phase at room temperature. In
fact, the CsPbI3 film formed by solution processes was found
to exist in a nonperovskite orthorhombic phase with a wide
bandgap (2.82 eV) at room temperature; this phase trans-
formed into a cubic perovskite phase at temperatures above
300 °C.144 However, the cubic CsPbI3 film is very unstable
under ambient conditions.145 Consequently, it tends to
undergo a phase transition to the orthorhombic phase after a
few minutes. The thermodynamic stability of the cubic phase
was found to be improved by additive engineering. Eperon et
al. found that the addition of hydroiodic acid (HI) into the
precursor solution could facilitate the formation of the cubic
perovskite phase at 100 °C with a bandgap of 1.73 eV.144 The
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Figure 14. (a) Absorbance at 630 nm and (b) X-ray diffraction (XRD) patterns of the FA1−xCsxPbI3 films coated on glass. The film was dried in a
vacuum without heat treatment. Insets of (a) show the photographs of the films depending on the Cs content. (c) Differential scanning calorimetry
(DSC) curves for x = 0 and 0.10 in FA1−xCsxPbI3. Reproduced with permission from ref 139. Copyright 2014 John Wiley and Sons.
addition of HI into the precursor solution was found to induce
the formation of relatively small grains with a slightly strained
lattice, which enables the stabilization of the cubic phase at
lower temperatures (approximately 100 °C). The enhanced
thermodynamic stability with reduced crystal size was also
observed for CsPbI3 quantum dots, which enabled the
achievement of stable CsPbI3 quantum dot solar cells with
efficiencies exceeding 13%.146,147 The surface and strain
energies were found to be the origin of the enhanced
thermodynamic stability with the reduced crystal size. A
similar approach was also applied to fabricate stable FAPbI3
quantum dot solar cells.148 Recently, the development of
various additives has enabled noticeable improvement in the
PCE. Both zwitterion and 2D perovskite additives induce small
grains to stabilize the cubic phase, resulting in efficiencies
higher than 11%.149,150 Furthermore, the passivation of the
crystal surface by organic-halide treatment significantly
improves the optoelectronic properties of CsPbI3 films,
which results in efficiencies as high as 18%.151,152 However,
the PCE of CsPbI3 PSCs is still limited due to its relatively
high bandgap of ∼1.7 eV. It can possibly be applied to the top
subcell of tandem solar cells with appropriate bandgap
engineering.
3.2.1.4. Mixed A-Cation Perovskites. Because the low
environmental stability of FAPbI3 is attributed to the overly
large FA cation, which needs to be fitted into the
cuboctahedral site, the partial replacement of the FA cation
with the relatively small MA cation was found to stabilize the
cubic perovskite phase at room temperature. 153 The
incorporation of the MA cation (<50 mol %) enables the
formation of the cubic perovskite phase at room temperature
and significantly enhances the PL lifetime of the perovskite
films, resulting in improved photovoltaic performance.153,154
The significantly enhanced PL lifetime might be related to the
enhanced crystallinity of the films, as a consequence of the
released intrinsic strain, enabling long-range ordering of the
crystals.155 Although the incorporation of the MA cation
enhances the phase stability of the perovskite film, it causes the
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degradation of the photo and thermal stabilities of the film.
The FA cation possesses an additional proton (4) compared to
the MA cation (3), which enables the formation of enhanced
hydrogen bonding with the perovskite lattice,129 and the
resonance characteristics of the C−N bonds in the FA cation
further stabilize the proton to avoid the generation of HI.139 In
fact, a relatively high activation energy for the initiation of the
thermal degradation was observed for FAPbI3 (115 ± 3 kJ/
mol) compared to that for MAPbI3 (93 ± 8 kJ/mol).143
However, the partial replacement of the FA cation with the
MA cation led to the degradation of the beneficial photo and
thermal stabilities of the FAPbI3 perovskite films. For example,
the FA0.5MA0.5PbI3 film undergoes much-accelerated degrada-
tion (complete bleaching after about 8 h of illumination) under
1 sun illumination compared to the FAPbI3 film (complete
bleaching after about 16 h).139
This problem was overcome by the incorporation of the
relatively small Cs cation instead of the MA cation.128 Owing
to the strong primary chemical bond with the perovskite
lattice, the incorporation of the Cs cation does not degrade the
stability of the FAPbI3 films. Lee et al. first incorporated the Cs
cation in FAPbI3 films and observed the formation of the cubic
perovskite phase at room temperature.139 By replacing 10% of
the FA cation with the Cs cation (FA0.9Cs0.1PbI3), seeds of the
cubic FAPbI3 perovskite phase were formed at room
temperature,139 promoting the formation of the cubic
perovskite film at relatively low temperatures.156 The
contraction of the unit cell volume with the addition of the
Cs cation indicates the successful incorporation of the cation
into the lattice, resulting in the effective tuning of the tolerance
factor, which would facilitate the formation of the cubic
perovskite phase at room temperature (Figure 14a,b).139,157
Consequently, the endothermic peak observed for pure
FAPbI3, which corresponded to the phase transition at 106.5
°C, disappeared upon addition of the 10 mol % Cs cation
(Figure 14c). Similar to the FA/MA mixed-cation perovskite,
enhanced crystallinity was also observed with the substituted
cation, which resulted in reduced defect density and enhanced
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photovoltaic performance. Contrary to the FA/MA case, the
incorporation of the Cs cation was found to also be beneficial
for the environmental stability of the films. Enhanced stability
under moisture and illumination was achieved with the Cs
cation, which contributed to enhancing the stability and
reproducibility of the solar cells.136,139,157,158
With the development of alternative cations, complex
multication systems have also been explored to enhance the
performance and stability of the films and devices. In addition
to the improved structural formability achieved by tuning the
tolerance factor, it was suggested that increasing the perovskite
complexity by the addition of inorganic elements can enhance
the entropy of mixing to stabilize the perovskite phase.158 In
fact, Park et al. fabricated MAPbI3 perovskite films with
enhanced quality using the relatively small Rb cation (ionic
radius = 152 pm),128 which reduced the tolerance factor to a
value further away from 1.0.159 Saliba et al. incorporated Cs
cations into MA/FA systems to fabricate a triple-cation
system.160 The addition of the Cs cation enhanced the phase
purity as well as the thermal stability of the perovskite film. As
a result, a stabilized PCE of over 21% was achieved with an
enhanced operational lifetime of the device. They further
extended their approach by adding the Rb cation with an ionic
radius of 166 Å (the composition of the A-site cation is
RbxCsyMAzFA1−x−y−z). The addition of Rb further reduced the
defect density and charge-transporting capability of the films,
resulting in a stabilized PCE of 21.6% with a Voc of 1.24 V,
corresponding to a potential loss of 0.39 V, considering the
bandgap of 1.63 eV.161 Furthermore, the device demonstrated
excellent thermal stability, where over 95% of the initial PCE
was maintained after 500 h of operation at 85 °C under
continuous light illumination.
Recently, more diverse organic cations are being explored as
alternative constituents for the A site. The utilization of a
guanidinium (GA) cation was first suggested by De Marco et
al.162 GA has a much larger ionic radius of 2.78 Å than MA and
FA cations (corresponding to a tolerance factor of 1.04);125
therefore, pure GAPbI3 cannot form the perovskite phase.
They incorporated GA cations into the MAPbI3 perovskite to
partially replace MA cations; the GA cations were found to
drastically enhance the PL lifetime of the perovskite film. The
enhanced charge-carrier lifetime was also observed in the
corresponding devices, resulting in the enhancement of the
photovoltage, which, in turn, improved the device perform-
ance. Through solid-state NMR measurements, it was found
that the reorientation rate for the GA cation in the
GA1−xMAxPbI3 system is much higher (≤18 ± 8 ps) than
that for the MA cation (113 ± 25 ps) at 300 K,141,142 which
probably helps to stabilize the charge carriers for enhancing the
PL lifetime. In addition to the improved tolerance factor of
MAPbI3 due to the incorporation of the relatively large GA
cation, the GA cation forms larger number of hydrogen bonds
with the PbI6 octahedral cage, which contribute to the reduced
formation enthalpy (ΔH), which, in turn, stabilizes the
perovskite phase.163 Because of the enhanced optoelectronic
properties and stability, Jodlowski et al. achieved the maximum
PCE of 19.21% with a significantly improved operational
lifetime in a solar cell device based on MA0.86GA0.14PbI3.
Similarly, Chen et al. replaced the MA cation with the
dimethylammonium (DMA) cation (ionic radius = 272 Å,
tolerance factor = 1.03).164 The incorporation of DMA
allowed the MAPbI3 lattice to expand and, thus, form the
cubic phase, probably due to the increased tolerance factor.
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Additionally, DMA enhanced the moisture stability of the film
by hindering the penetration of water molecules toward the
perovskite lattice, and impeded the migration of ionic species
in the film. Ferdani et al. investigated the ion transport
properties in a variety of mixed-cation systems. They found
that the activation energy for ion transport in a mixed-cation
system increases due to the modified bonding nature and steric
inhibition of ion transport.165 In fact, with the incorporation of
5 mol % of a variety of different cations (Rb, Cs, azetidinium,
FA, DMA, and GA) in MAPbI3, the activation energy for ion
transport was increased. Notably, ion transport is critical to the
operational stability of the PSC;166 this indicates that the
mixed-cation system is probably beneficial for enhancing not
only the environmental and intrinsic stability of the perovskite
materials but also the operational stability of the solar cell
devices.
Notably, most of the certified record PCEs were achieved
using devices based on mixed MA/FA-based perovskite
materials (Table 1). Nonetheless, there is a recent publication
on high certified PCEs over 22% achieved using devices based
on MA/FA/Cs-based perovskite materials.167 While the
utilization of organic A cations was reported to be advanta-
geous in terms of polaron formation,132 it was also recently
reported that the utilization of the multication system
incorporating Cs is beneficial for preventing carrier reflection
at GBs.168 Furthermore, the A cation composition can affect
the local strain and, consequently, the crystallization and
stability of the thin films.165,169 Therefore, in-depth and
systematic studies are required to unravel the effects of the A
cation composition on the photovoltaic performance of the
films.
3.2.2. B Site(Cation)-Modified Perovskites. Most
reported high-efficiency solar cells incorporate Pb-based
perovskite materials. Because of the toxicity issue associated
with Pb, however, intensive efforts have been devoted to the
development of alternative B-site cations. Thus, far, only Sn-
based perovskites have demonstrated the potential to replace
Pb-based perovskites to some degree. Sn has a valence-shell
electron configuration identical to that of Pb (4 valence
electrons in its s and p orbitals, s2p2); this probably allows the
Sn-based perovskites to render optoelectronic properties
comparable to those of Pb-based perovskites.145 Sn2+ has a
much smaller ionic radius of 69 pm compared with that of Pb2+
(119 pm), resulting in different band structures and
corresponding bandgaps of the materials. The bandgap of
Sn-based iodide perovskites was found to be smaller than that
of Pb-based iodide perovskites. For example, the bandgaps of
CsSnI3, MASnI3, and FASnI3 were measured to be 1.3−1.4
eV.170−172 Although Sn-based perovskite materials have more
ideal bandgaps for single-junction solar cells than Pb-based
perovskite materials, the reported PCEs of solar cells based on
pure Sn-based perovskites is still much lower than those of the
devices based on Pb-based perovskite materials (PCE <
12%).173 The poor performance of Sn-based PSCs is attributed
to the instability of Sn2+ due to its intrinsically low redox
potential (E0), i.e., Sn2+/Sn4+ (E0 = +0.15 V), compared to that
of Pb2+, i.e., Pb2+/Pb4+ (E0 = +1.67). Consequently, a
significant proportion of Sn2+ ions is oxidized to Sn4+ during
the fabrication of Sn-based perovskite films, resulting in a high
defect density and undesired p-type doping. Hence, intensive
studies have been conducted to stabilize pure Sn-based
perovskites considering that the low stability of Sn2+ hinders
the progress of Sn-based PSCs.
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Figure 15. Photographs and UV−vis absorption spectra of MAPb(I1−xBrx)3. (a) UV−vis absorption spectra of the FTO/bl-TiO2/mp-TiO2/
MAPb(I1−xBrx)3/Au cells measured using an integral sphere. (b) Photographs of 3D TiO2/MAPb(I1−xBrx)3 bilayer nanocomposites on FTO glass
substrates. Reproduced with permission from ref 183. Copyright, 2013 American Chemical Society. (c) UV−vis absorbance spectra of the
FAPb(I1−xBrx)3 (top panel) and FA0.83Cs0.17PbI(1−xBrx)3 films (bottom panel). a.u.: arbitrary units. Reproduced with permission from ref 189.
Copyright, 2016 American Association for the Advancement of Science.
Perovskite materials with a partial substitution of Pb with Sn
were found to possess superior stability than pure Sn-based
perovskite materials. Mixed Sn−Pb perovskite materials have
low bandgaps around 1.25 eV, which is ideal for the bottom
subcell of tandem solar cells. The suppression of Sn4+ and the
reduction of the defect density enabled PSCs based on Sn−Pb
mixed compositions to deliver markedly enhanced PCEs. For
example, Zhao et al. achieved a PCE of 18.4% by incorporating
2.5% Cl into a thick (FASnI3)0.6(MAPbI3)0.4 perovskite
film.174,175 Tong et al. utilized a GuaSCN additive to further
enhance the charge-carrier lifetime in the (FAS-
nI3)0.6(MAPbI3)0.4 film and achieved a PCE of 20.2%.176
Yang et al. achieved a PCE of 20.3% using a device based on
FA0.5MA0.45Cs0.05Pb0.5Sn0.5I3, attributed to the low trap density
and long electron diffusion length (2.72 ± 0.15 μm), with the
addition of 0.03 mol % Cd2+.177 Recently, Lin et al. achieve a
PCE as high as 21.1% with a device based on a
MA0.3FA0.7Pb0.5Sn0.5I3 perovskite by adding metallic Sn into
the precursor solution to suppress the formation of Sn4+.178
The highly efficient Sn−Pb PSCs were successfully applied to
all-perovskite tandem solar cells, and a PCE of 24.8% was
obtained. Owing to the extended bandgap tunability toward
the lower end, mixed Sn−Pb-based PSCs have the potential to
surpass pure Pb-based PSCs in terms of the PCE, if an effective
methodology for crystal growth and defect engineering is
established.
3.2.3. X Site (Anion)-Modified Perovskites. Because X-
site anions directly contribute to the band edge states of
perovskite materials, the substitution of the X-site anion can
significantly alter the optoelectronic properties of perovskite
materials. The tolerance factor determines whether or not the
A cation can fit into the cuboctahedral site formed in the
corner-sharing BX6 octahedra, and another factor needs to be
considered for the structural formability of the BX6 octahedra.
The octahedral factor is devised for this purpose. The radius of
the octahedral hole (rhole) within the six closely packed X ions
is approximately 0.41rhole; hence, a B-site cation smaller than
0.41rhole cannot coordinate octahedrally without overlapping
the surrounding anions. From this relationship, the octahedral
factor is expressed as
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rB
μ=
rX (4)
where rB and rX are the ionic radii of the B-site cation and X-
site anion, respectively. The BX6 composition with μ > 0.41
can form stable BX6 octahedra. The most common X anions
are halide anions, including Cl−, Br−, and I−. With 8 valence
electrons, the ionic radii of Cl−, Br−, and I− are 181, 196, and
220 pm, respectively. With the ionic radius of Pb2+ (119 pm),
the octahedral factors of APbCl3, APbBr3, and APbI3 are
calculated to be 0.66, 0.61, and 0.54, respectively.
As the ionic radius of the halide anion decreases, the bond
length between the Pb and halide anion decreases;
consequently, the overlap of the wave function increases to
enhance the coupling of atomic orbitals, which, in turn,
increases the bandgap of the material.56 For example, the
bandgap of MAPbX3 increases from 1.58 eV (MAPbI3) to 2.28
eV (MAPbBr3) to 2.88 eV (MAPbCl3) in accordance with the
substituted halide anion.179,180 In terms of photovoltaic
application, iodide-based perovskite materials are desirable
because they have the lowest bandgap, which corresponds to a
broad light-absorption range. In terms of structural stability
and chemical bonding nature, MAPbI3 is the least stable
material because of the following: (i) the tolerance factor of
MAPbI3 (t = 0.91) deviates further away from 1.0 compared to
those of MAPbBr3 (t = 0.93) and MAPbCl3 (t = 0.94), and (ii)
the relatively low electronegativity (χ) of I− (χ = 2.66)
compared to those of Br− (χ = 2.96) and Cl− (χ = 3.16), which
corresponds to a relatively weak bond with the Pb2+ ion.181,182
Accordingly, the formation enthalpy of MAPbI3 was higher
than those of MAPbBr3 and MAPbCl3 as per calorimetric
measurements and DFT calculations. The partial substitution
of I− with Br− or Cl− was, therefore, utilized to fine-tune either
the optoelectronic properties or the chemical stability of the
perovskite films.
3.2.3.1. Br/I Mixed Perovskites. The partial substitution of
I− with the relatively small Br− ion to fabricate MAPb-
(I1−xBrx)3, changed the average Pb−X bond distance and,
consequently, the bandgap of the perovskite thin films (Figures
15a,b).56 The bandgap of the films increases with respect to x
according to the following equation:183
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Eg (x) = 1.57 + 0.39x + 0.33x 2 (5)
Because of the relatively small ionic radius of Br−, the tolerance
factor of MAPb(I1−xBrx)3 increases with x; consequently, the
tetragonal crystal structure of MAPbI3 changes to a cubic or
pseudocubic structure when x is greater than 0.2.183 Because of
the substantial increase in the bandgap with the incorporation
of the Br− ion (approximately 6 mol %), only a small amount
of Br can enhance the PCEs owing to the improved FF and
Voc. However, a further increase in the Br content will reduce
the short-circuit current density and, consequently, the PCE of
the devices due to the relatively high bandgap. The improved
FF was attributed to the reduced series resistance of the
perovskite layer, which might be related to the crystallinity of
the film. The more ideal tolerance factor possibly improved the
long-range ordered growth of the perovskite crystals, thereby
promoting the charge-carrier transport properties. Regardless
of the PCE drop, the improved ambient stability of the device
with a high Br content was noticeable. The device with a high
Br content (x = 0.20, 0.29) was considerably more stable than
those with low Br contents (x = 0, 0.06) under ambient
conditions, with the relative humidity exceeding 50%. This is
probably related to the high electronegativity of the Br− ion,
which enables a stronger bond with the Pb and MA ions,
compared to the case with the I− ion.
Despite the beneficial effects of Br incorporation into the
MAPbI3 perovskite, the phase homogeneity of the mixed halide
perovskite was found to be degraded under light illumination.
In halide perovskite materials, the formation enthalpies of
point defects were estimated to be much lower (<0.3 eV per
defect) than those of conventional oxide perovskite materials
(2.29 eV per defect for BaTiO3).83 In particular, the formation
enthalpy of halide vacancies was calculated to be as low as 0.08
eV per defect (iodide vacancy in MAPbI3, VI•), indicating the
presence of a substantially high density of halide vacancies in
the film (estimated to be 2 × 10 20 cm −3 at room
temperature).83 Furthermore, these defects tended to migrate
inside the lattice, and the activation energy for the migration
was 0.58 eV for VI•,184 which further reduces under light
illumination.185 Because of active halide migration in mixed
halide perovskites, the segregation of different crystalline
phases was observed under illumination, which hindered
effective charge-collection efficiency and operational stability of
the devices.186−188
The phase segregation in the MA-based mixed halide
perovskite was mitigated by replacing the MA cation with an
FA or Cs cation. As discussed in the previous section, FA and
Cs cations have relatively strong interactions with the
surrounding PbX6 octahedra cage; therefore, they can be
expected to suppress the migration of halide ions.143
Furthermore, regarding the tolerance factor, the incorporation
of the relatively small Cs cation would compensate for the
increased tolerance factor due to Br incorporation (t = 0.99 for
FAPbI3, and t = 1.01 for FAPbBr3), which will help in
maintaining the structural stability of the cubic perovskite
phase. Indeed, the incorporation of the Cs cation (17 mol %)
enables diverse Br incorporation without the formation of a
secondary phase. Consequently, a continuous blue-shift of the
absorption onset was observed with the incorporation of Cs in
FAPb(I1−xBrx)3 (Figure 15c).189 Owing to the stronger
interaction of FA and Cs with the PbX6 octahedra compared
to the case with MA, the FA1−xCsxPb(I1−yBry)3 perovskite thin
films did not exhibit phase segregation; therefore, the shift in
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the PL spectrum under prolonged illumination was not
observed. Conversely, the PL spectrum of the MAPb(I1−yBry)3
films exhibited a red-shift due to the segregation of the I-rich
phases.189 The perovskite film with an optimized composition
(FA0.83Cs0.17Pb(Br0.4I0.6)3 exhibited a charge-carrier mobility
(μ) of 21 cm2 V−1 s−1 and diffusion length of 2.9 μm. Owing to
the high bandgap (1.74 eV), the perovskite film with this
composition is suitable for the top subcell in a tandem solar
cell (tandem devices are discussed in more detail in later
sections).189 Rehman et al. investigated the correlation
between the composition-dependent crystallinity, optoelec-
tronic properties, and photostability.190 They found that the
evolution of the charge-carrier mobility and lifetime in mixed-
cation and mixed-halide perovskite films closely correlated with
the crystallinity of the films, indicating that composition-
dependent crystal growth behaviors have crucial effects on the
optoelectronic properties of the films. This is probably related
to the composition-dependent structural stability of perovskite,
which will ultimately affect the energetics of crystal nucleation
and growth (discussed in more detail in the later section).
3.2.3.2. Cl-Incorporated Perovskites. At the initial stage of
the development, incorporating Cl− ions into an iodide-based
perovskite materials has been under debate for quite some
time. Although the ionic radius of the Cl− ion (181 pm) is
smaller than that of the I− (220 pm) ion, MAPbI3−xClx
perovskite thin films fabricated from precursor solutions
incorporating Cl− showed an absorption onset comparable
with that of MAPbI3 films (i.e., no noticeable change in the
bandgap of the film was observed). For example, MAPbI3−xClx
perovskite films fabricated from a solution containing 3 mmol
of MAI and 1 mmol of PbCl2 showed an absorption onset
around 800 nm, which is almost identical to that of MAPbI3
films.2 Despite the identical absorption properties, however,
the significant difference in the electrical properties of the films
indicated that Cl− plays a crucial role in the determination of
the charge-carrier behaviors. For instance, both the electron
and hole diffusion lengths in the MAPbI3−xClx film (L = 1069
± 204 nm for electrons, and L = 1213 ± 243 nm for holes)
were almost 10 times those in the MAPbI3 films (L = 129 ± 41
nm for electrons, and L = 105 ± 32 nm for holes).85
Consequently, the roles of the Cl− ion in iodide-based
perovskite films have been intensively investigated.
The added Cl− ions were found to influence the
crystallization of the perovskite films. During the formation
of the MAPbI3 perovskite, the Cl− ion in the solution forms
intermediate MAPbI3‑xClx phases, which are finally converted
to MAPbI3 via the volatilization of MACl from the film. The
formation of the intermediate phase promotes the growth of
large grains with relatively high crystallinity, thereby enhancing
the optoelectronic quality of the films.191,192 de Quilettes et al.
observed the correlation between a high Cl content and a high
PL emission at a local site (few micrometers scale).122 They
suggested that Cl might be present at the surface, interstitial
site, or crystal lattice after aiding the crystallization of the
perovskite film. It was also suggested that the residual Cl− in
the film (∼2 wt % or less) has beneficial effects on the
optoelectronic properties of the film. From first-principles
calculations, it was suggested that doping lead iodide
perovskites with the Cl atom inherently reduces the
recombination velocity of the photoexcited charge carriers in
the bulk and GB regions by reducing the electron−phonon
coupling and lifetime of quantum coherence for the charge
recombination processes.103,104
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Figure 16. (a) Schematics of the device incorporating a polycrystalline 3D perovskite film with 2D perovskite at the GBs. Reproduced with
permission from ref 201. Copyright, 2018 Springer Nature. (b) Proposed electronic band alignment between 2D and 3D perovskites. (c) Current
density−voltage (J−V) curves of the devices without (control) and with 2D perovskite (target). Stability measurement of (d) perovskite films and
(f) devices. Reproduced with permission from ref 201. Copyright, 2018 Springer Nature.
3.2.4. Low-Dimensional Perovskites. If the size of the
A-site cation becomes larger than the volume of the
cuboctahedral site formed by the corner-sharing PbX6 network,
the PbX6 octahedra would not be able to maintain their corner-
sharing geometry of the ABX3 3D perovskite, initiating the
formation of a layered 2D A′2BX4 structure. These crystalline
materials are classified under the 2D perovskite family. 2D
perovskite materials typically incorporate large organic cations
with long alkyl chains or aromatic rings; hence, they are
relatively less hygroscopic compared to 3D perovskite
materials.193,194 However, the bulky organic cations form
potential barriers to the charge-carrier transport inorganic
network; consequently, their charge-carrier transport proper-
ties are inferior to those of 3D perovskite materials. Quasi-2D
perovskite materials have been utilized as light-absorbing layers
in an attempt to exploit their excellent stability. Upon mixing
2D and 3D perovskite materials, the A′2An−1BnX3n+1 quasi-2D
perovskite is formed, where the n layers of the 3D perovskite
are separated by a bilayer of bulky A′ cations.195 Although the
quasi-2D perovskite materials exhibited outstanding environ-
mental and operational stability, they compromised the PCE of
the devices due to the presence of insulating organic layers in
their bulk crystals. The maximum PCE barely exceed
15%.195−200
A strategy to overcome the poor charge-transport properties
of quasi-2D perovskite materials has been developed. It was
found that if the concentration of the 2D perovskite is below a
certain threshold (<5 mol%), the added 2D perovskite is
preferentially formed at the GB region due to its low surface
energy and the high activation energy required for
nucleation.201,202 The formation of the 2D perovskite at the
localized GB region does not degrade the bulk charge-
transporting properties; however, the 2D perovskite forms a
type-I band alignment with the grain interior of the 3D
perovskite to repel photogenerated charge carriers from the
defective GB region (Figure 16a,b).201,203 Consequently, the
PL lifetime of the film incorporating the 2D perovskite was
significantly enhanced compared to that of bare 3D perovskite.
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Owing to the improved charge-carrier lifetime, Wang et al.
reported an improved stabilized PCE of 19.5% obtained with a
butylammonium (BA)-based 2D perovskite compared to that
achieved with the pure mixed-cation-halide perovskite
(FA0.83Cs0.17PbI2.4Br0.6) (17.5%).203 Lee et al. utilized the
low bandgap FA0.98Cs0.02PbI3 perovskite incorporated with
1.67 mol % of 2D PEA2PbI4 perovskite and achieved a
stabilized PCE of 20.64% compared to 14.91% achieved with
the device based on a pure 3D perovskite (Figure 16c,d).201
With the improvement in the PCE, the added 2D perovskite
was found to also be beneficial to the environmental and
operational stabilities of the film and device (Figure 16e,f).
The defective GB region is typically more vulnerable to
degradation by moisture due to its relatively high surface
energy. The relatively hydrophobic 2D perovskite can protect
the GBs from moisture and, thus, improve the environmental
stability of the perovskite film.201 Furthermore, the defective
GBs act as a major pathway for ion migration, which is
regarded as the main factor causing the degradation of the
solar cells under operational conditions. While the 2D
perovskite itself has a relatively high activation energy for ion
migration, it probably passivates the defective GBs of the 3D
perovskite, which, in turn, enhances the activation energy for
ion migration.201 Consequently, the device based on the film
with 2D perovskite showed significantly improved operational
stability compared to that based on the pure 3D perovskite
film. Recently, a similar approach was adopted to stabilize
CsPbI3 perovskite, where both the PCE and stability of the
CsPbI3 solar cell were improved.150 This approach involving
the utilization of a 2D perovskite material might be promising
for achieving both high efficiency and long-term stability of the
devices.
3.3. Processing Engineering
The performance of PSCs is determined by film qualities such
as crystallinity and morphology, which are dependent upon the
film fabrication process. For example, highly efficient PSCs
possess a dense microstructure without any voids. In this
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Figure 17. (a) LaMer model for nucleation and growth of perovskite thin films. Cs is the supersaturation concentration of a precursor solution. (b)
Free energy diagram of nucleation. ΔGs, surface free energy; ΔGν, bulk free energy; ΔG, total free energy, ΔGc; critical free energy; and rc, critical
radius of nucleus. (c) A correction term for heterogeneous (⌀) nucleation as a function of contact angle of the solution on a substrate. (d) A
schematic illustration of the nucleation and growth of perovskite films at each stage. Reproduced with permission from ref 206. Copyright 2019
John Wiley and Sons.
section, we introduce many proposed fabrication processes for
obtaining high efficiency when fabricating perovskite layers. In
typical PSC fabrication, the perovskite thin films are formed by
low-temperature solution processes. The low formation
enthalpy of metal halide perovskite materials and the high
ionic nature of their chemical bonding enable the utilization of
cost-effective solution processes at low temperatures. However,
during the solution processes, the crystallization of the
perovskite films is completed within few seconds, limiting
effective control over the crystallinity and orientation of the
film. In solution processes, intermolecular interactions between
the perovskite precursor and solvent molecules, as well as
fabrication protocols, were found to have critical influences on
the crystallization kinetics of the perovskite films.
To understand the crystallization processes of the perovskite
films, the La Mer mechanism can be applied. In Figure 17,
three different stages of the crystallization processes of
perovskite films are demonstrated according to the La Mer
mechanism. In stage I, the perovskite precursors exist as ions
and molecules in the precursor solution until the concentration
of the solution increases to a supersaturation level (Cs) owing
to the evaporation of the solvents during the spin coating and
heat treatment of the film. As the concentration reaches Cs, in
stage II, perovskite crystal nuclei start to form and grow with a
supply of solute owing to a diffusion process. The nucleation
continues until the concentration of the solution decreases
below Cs, as the consumption of the solutes becomes faster
than the evaporation of the solutes in stage III. In stage III,
nucleation does not occur, and only the growth of the formed
nuclei progresses until the precursor solution is depleted.
The crystallization of perovskite thin films can be modulated
by tuning the rate of nucleation and growth. According to the
classical theory, the rate of homogeneous nucleation is
described as a function of the critical free energy (ΔGc in
Figure 17b), representing the free energy required for the
formed nuclei to be stable without being redissolved in the
precursor solution. This critical free energy is defined as the
activation energy for nucleation, which is used to describe the
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nucleation rate using an Arrhenius type equation, expressed in
eq 6:204,205
ij ΔG yz
= A expjjj− c zzz
j kBT z
dN
k {
dt (6)
where t is time, N is the number of nuclei, A is the pre-
exponential factor, kB is the Boltzmann constant, and T is the
temperature. The crystal free energy (ΔGc) can be written as a
function of the surface energy γ, molar volume ν, and
supersaturation of solution S, which yields eq 7:204,205
ij 16πγ 3ν 2 yzz
= A expjjj− 3 3 z
j 3k T (ln S)2 zz
dN
k {
dt (7)
B
When a substrate is used in device fabrication, the interface
between the precursor solution and substrate can act as a
heterogeneous nucleation site. Heterogeneous nucleation can
be described by introducing the correction term ⌀,204,205
ΔGchetero = ⌀ΔGchomo (8)
(2 + cos θ )(1 − cos θ )2
⌀=
4 (9)
where θ is the contact angle of the solution on the substrate. As
shown in Figure 17c, ⌀ significantly varies depending on θ;
hence, the nucleation kinetics largely depend on the substrate
used for film fabrication. For example, considering the good
wettability of the perovskite solution on typical metal oxide
transporting layers for an n-i-p structured device (e.g., θ = 15−
20° for SnO2), ΔGc is expected to be significantly lower at the
interface between the solution and substrate. Therefore,
nucleation is likely to dominantly occur at the interface
between the solution and substrate (the situation can change
with different substrate materials and processes).
During nucleation, growth occurs because of the diffusion of
the precursor molecules and subsequent surface reaction. If the
surface reaction is the rate-determining process, the growth
rate can be expressed using the following equation,
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Figure 18. Schematic diagrams displaying procedure for one-step spin-coating of perovskite thin films using (a) conventional antisolvents and (b)
anisole. Reproduced with permission from ref 212. Copyright 2018 John Wiley and Sons. (c) Photograph of the 10 cm × 10 cm perovskite solar
module. Reproduced with permission from ref 213. Copyright 2019 American Chemical Society. (d) J−V curves of 0.14 and 1.08 cm2 PSC devices
fabricated by anisole as an antisolvent. Reproduced with permission from ref 212. Copyright 2018 John Wiley and Sons.
dr
= kv(C b − Cr)
dt (10)
where r is the radius of the particle, k is the surface reaction
rate constant, and Cb and Cr are the concentrations of the
solution at the bulk and at the surface of the particle,
respectively. If the diffusion of precursor molecules is the rate-
limiting process, the growth rate is given by
dr Dv
= (C b − Cr)
dt r (11)
where D is the diffusion coefficient of the precursor molecules.
3.3.1. One-Step vs Two-Step Processes. The fabrication
processes of perovskite films can be classified as one-step and
two-step. The one-step process involves the formation of a
perovskite layer via nucleation and growth from a solution
containing all precursors that constitute perovskite halide
compounds. The two-step process indicates a perovskite film
fabrication procedure that yields a perovskite layer through the
step-by-step deposition of each precursor layer, followed by a
thermal interdiffusion process.207 Thus far, the understanding
of perovskite formation behavior has been restricted because of
limited characterization tools, making it difficult to arrive at an
exact theory for perovskite formation.
3.3.1.1. One-Step Process. In the one-step process,
perovskite films are formed via the evaporation of the solvent
from undried films that are deposited from a homogeneous
solution containing all components. Various methods have
been proposed to improve photovoltaic performance via the
fabrication of uniform, well-crystallized, and void-free perov-
skite layers. The one-step process was first proposed by Kojima
et al. in 2009.3 The raw precursors, including PbI2 and
methylammonium iodide (MAI), are dissolved in a polar
aprotic solvent such as DMF, DMSO, and GBL, following
which the solution is directly cast onto the substrate using
spin-coating. During spinning, the solvent evaporates;
concurrently, the concentration of the dissolved precursor
reaches the supersaturation state, thereby inducing the
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nucleation of perovskite or preperovskite materials. The as-
dried films are then annealed at a low temperature in the range
of 100−150 °C for controlling the nucleation and growth of
the perovskite phase.
At an early stage, the conventional one-step process
presented some critical issues that prevented the attainment
of high efficiency, such as difficulty in fully covering the
substrate surface with the perovskite layer and irregular grain
growth due to the unsuccessful control of nucleation and
growth. For example, in a well-used DMF solvent system,
irregular rod or needle-like structures with poor coverage on
the substrate have been frequently observed.208 The high
boiling point and low vapor pressure of DMF retard
evaporation, leading to slow nucleation and rapid growth,
thereby preventing the generation of a uniform grain structure.
Therefore, research on the one-step process has focused on
methods to quickly remove the solvent for control over the
rapid and uniform nucleation of perovskite mediates. Rapid
solvent removal has been attained through various methods,
such as solvent engineering, substrate heating, gas blowing, and
vacuum treatment.
The solvent engineering method, also known as the
antisolvent extraction method, was first reported by Cheng et
al.209 The antisolvent should be miscible with the polar aprotic
solvent but should not dissolve perovskite ingredients such as
PbI2 and MAI. They dripped chlorobenzene as an antisolvent,
which rapidly extracted solvent from the cast film,
consequently facilitating uniform nucleation. Thus far, many
antisolvents, including toluene,20 hexane,210 ethyl acetate,211
and diethyl ether,21 have been explored. Many high-efficiency
solar cells have been fabricated using this antisolvent extraction
method. Moreover, antisolvent extraction can be applied to
fabricate mixed halide compositions, such as
[CsPbI3]0.05[(FAPbI3)0.85(MAPbBr3)0.15]0.95.212 However, un-
like MAPbI3, the diffusivity of other ions such as Br is different
from that of I, and relatively high, which induces the formation
of pinholes in the mixed halide perovskite. Furthermore, a
molecular interaction between the perovskite precursor ions
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Figure 19. (a) Schematic procedure for the gas-blowing spin-coating method and (b) J−V curve of PSC fabricated by gas-blowing. Reproduced
with permission from ref 225. Copyright 2014 Elsevier. (c) Schematic description of cryocontrolled nucleation for perovskite synthesis and (d) J−V
curve of PSC fabricated by cryogenic process. Reproduced with permission from ref 227. Copyright 2018 John Wiley and Sons. (e) Schematic
illustration of nucleation and crystallization procedures during the formation of a perovskite film via vacuum flash-assisted solution processing
(VASP) and (f) J−V curves for the best-performing devices using perovskite films prepared by the conventional process (black) or VASP (red)
method. Reproduced with permission from ref 228. Copyright 2016 American Association for the Advancement of Science.

and solvent molecules in the solution is dependent on the
composition of the added precursors. Therefore, a change in
the composition of the perovskite results in variations in the
precursor solubility and the solvent evaporation rate, inducing
differences in the optimized antisolvent timing. The process
window for the mixed halide perovskite was found to be fairly
narrow for conventional one-step fabrication using a
chlorobenzene antisolvent. Recently, anisole has been intro-
duced as an antisolvent.212 Owing to a low evaporation rate
and intermolecular interaction between the anisole and DMF/
DMSO, anisole has an ultrawide processing window for the
one-step fabrication of efficient PSCs, for which the small-cell
efficiency (0.14 cm2) is 19.76% (Figure 18c).213 Further, the
application of anisole enables the fabrication of uniform large-
area perovskite films as large as 100 cm2. The module
efficiency of the anisole-derived PSC (100 cm2) was 14%.213
Therefore, antisolvent extraction ensures a reproducible
fabrication process for highly efficient PSCs as well as large-
area devices, if one can identify a suitable antisolvent.
In the antisolvent method, modification of the solvent and
the addition of additives have been attempted to improve
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efficiency. For example, the use of a saturated mixture of
methylamine in acetonitrile (ACN) can improve the perovskite
microstructure.214 This modified solution allows the formation
of a liquid “melt” of MAPbI3·xCH3NH2, which results in the
direct crystallization of the perovskite during spin coating. The
perovskite layer prepared by this method possessed fewer
defects as well as a compact microstructure, yielding over 18%
PCE. The addition of the cyclic urea compound 1,3-dimethyl-
2-imidazolidinone (DMI) in the precursor solution of MAPbI3
induced weak coordination with PbI2 and formed a MAPbI3
film with no intermediate phase.215 The resultant perovskite
film showed smooth grain structure with an average crystal size
of 1 μm and reduced the number of defect sites. The solar cells
based on these films exhibited a PCE of 17.6%. The
incorporation of Bpy (2,2′-bipyridine) and Tpy (2,2′:6′,2″-
terpyridine) additives increased the grain size and crystallinity
of the perovskite films and reduced the defect density, which
improved the PCE and operational stability of the device.216
Compared to the controlled bare film cell, the Bpy-and Tpy-
added cells showed higher PCEs of 19.02% and 18.68% in the
reverse and forward scans, respectively. This work highlights
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Figure 20. Schematic depicting the stages of the reaction in sequential deposition. Dashed arrows indicate mass transfer. (a) Nucleation and
growth of PbI2. (b) Intercalation of MAI and structural reorganization to form CH3NH3PbI3 perovskite. (c) Ostwald ripening, in which the
perovskite from the mesoporous layer is transported to the capping layer. (d) Further Ostwald ripening at longer dipping times in which the
perovskite from the small crystals in the capping layer is transported to larger crystals. (e) Gibbs free energy as a function of the reaction coordinate.
Reproduced with permission from ref 230. Copyright 2018 American Association for the Advancement of Science.

the importance of additive engineering for morphology and
defect passivation improvement in highly efficient and stable
PSCs. The addition of a polymeric Lewis base, such as ethylene
carbonate (EC), propylene carbonate (PC), and poly
propylene carbonate (PPC), increased the activation energy
for the nucleation and diffusion of the precursor molecules,
leading to the formation of perovskite films with high
crystallinity and significantly enlarged grains.217 Moreover,
this polymer enabled the formation of polymer−perovskite
composites between grains, which improved the stability of the
PSCs. The highest PCE for these cells was 20.06%. Most
methods for achieving high efficiency over 20% have been
solvent engineering processes, which include a formation step
for organic halide−Pb halide−DMSO intermediates and an
antisolvent extraction step.160,161,218−222
The simplest way to quickly evaporate solvents is to apply
heat rapidly. Nie et al.223 developed the so-named hot casting
method. They dripped a 70 °C mixture of PbI2 and MACl
solution onto a 180 °C heated substrate with spinning. This
process yielded exceptionally large millimeter-scale grains with
reduced trap sites, leading to a high PCE of 18%. The heat
energy enabled efficient evaporation of the solvent in the as-
deposited film, which induced rapid nucleation. Moreover, the
heat energy enhanced the diffusivity of ions, which is one of
the reasons this process yielded large-sized grains. As a
derivative of the hot casting method, Deng et al. used a hot-
blade coating process and achieved a high efficiency of
20.3%.224 A gas-blowing or gas-quenching method can
evaporate out the solvent from the as-deposited film by
blowing a nonreactive gas, such as N2 or Ar, onto it. This
process also promotes a high degree of supersaturation and
consequent rapid and homogeneous nucleation. Huang et
al.225 employed an Ar gas blowing method and successfully
produced highly uniform perovskite thin films consisting of
densely packed single-crystalline grains (Figure 19a). They
achieved a high PCE of 17%, which was a fairly high efficiency
in 2014 (Figure 19b). Recently, a facile and scalable air-knife-
assisted meniscus coating technique has been demonstrated.226
A N2 gas air knife quickly blows out the solvent, leading to a
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high PCE of 20.26%. Because this gas-blowing method does
not use toxic antisolvents such as toluene, chlorobenzene, and
diethyl ether, this process is an environmentally friendly
fabrication method. Recently, a cryogenic process was used to
control the crystallization of perovskite films. This process
enabled the decoupling of nucleation and crystallization phases
by inhibiting chemical reactions in as-deposited films that were
rapidly cooled by immersion in liquid nitrogen (Figure
19c).227 The cooling was followed by conventional gas-
blowing. This process initiated the formation of a uniform
precursor seed layer, resulting in increased grain size,
crystallinity, and low defect density. The best-performing cell
attained a PCE of 21.4% (Figure 19d).
Another effective method for evaporating the solvent is to
use a vacuum. Li et al.228 devised vacuum flash-assisted
solution processing (VASP), which could yield smooth
perovskite films of high electronic quality over large areas
(Figure 19e). The flash evaporation of a solvent produced a
burst of perovskite precursor crystals and prevented dewetting,
yielding homogeneous films without pinholes. The resultant
PCE was 20.5% owing to good crystallinity with reduced trap
sites. Further, a combination of the gas blowing and vacuum
process, termed the gas-flow-induced gas pump (GGPM)
method, was developed. The maximum efficiency of a GGPM-
manufactured cell was 20.44%.229
3.3.1.2. Two-Step Process. The two-step process, or
sequential deposition method, for the fabrication of PSCs
involves (i) the deposition of Pb precursors, such as a Pb
halide or Pb-based adduct, on a substrate, (ii) exposure to a
liquid, vapor, or solid of an organic salt, and (iii) a diffusion-
driven formation of perovskite materials that is usually enabled
by heat treatment. This process is beneficial for the moderate
control of reactions between the Pb halide and organic salt,
which induces the crystallization of perovskite materials.
Recently, a detailed path for the two-step process for
MAPbI3 formation has been proposed by Ummadisingu et
al.230 As shown in Figure 20, the formation behavior adopts a
sequential path involving (i) the nucleation and growth of
PbI2, (ii) the intercalation of MAI and structural reorganization
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Figure 21. (a) Schematics of FAPbI3 perovskite crystallization involving direct intramolecular exchange of DMSO molecules intercalated in PbI2
with formamidinium iodide (FAI). The DMSO molecules are intercalated between edge-sharing [PbI6] octahedral layers, as shown in the field-
emission scanning electron microscopy surface images of a FAPbI3-based layer formed on mp-TiO2 by the (b) intramolecular exchange process
(IEP) and (c) conventional method, (d) J−V curves of best device measured with a 40 ms scanning delay in reverse (from 1.2 to 0 V) and forward
(from 0 to 1.2 V) modes under standard AM 1.5G illumination, and (d) EQE spectra for best device and integrated Jsc. Reproduced with
permission from ref 233. Copyright 2015 American Association for the Advancement of Science.

to form MAPbI3, (iii) Ostwald ripening, in which the
perovskite from the mesoporous TiO2 is transported to the
capping layer, and (iv) further Ostwald ripening over dipping
times in which the perovskite from the small crystals in the
capping layer is transported to large crystals. Severe Ostwald
ripening is detrimental to a high PCE. Each step should be
carefully controlled to obtain a highly crystalline and dense
morphology for attaining high efficiency. This section reviews
the efforts invested toward obtaining high-efficiency PSCs
prepared using the two-step process.
The two-step method was first proposed by Liang et al.231
They fabricated MAPbI3 films through the deposition of PbI2
on a glass or quartz substrate and subsequent dipping into a
MAI solution. In PSCs, Burschka et al.19 applied this two-step
method using nanoporous TiO2 films. In their report, they
employed slightly modified conditions for the deposition of
PbI2 as well as the formation reaction for increasing the loading
of the perovskite absorber on the mesoporous TiO2 film. The
spinning time for PbI2 casting was short at 5 s, and
subsequently, the PbI2 films were prewetted by dipping them
in 2-propanol for 1−2 s before dipping in a solution of MAI
and 2-propanol. This process led to a PCE of 15.0% with good
reproducibility. The PCE was further increased to 17.01% by
adopting the size-controlled cuboidal MAPbI3 proposed by Im
et al.8 The cuboid MAPbI3 was prepared using the two-step
method, and its size was controlled by changing the
concentration of MAI and the exposure time of PbI2 to the
MAI solution before spin-coating. The average cuboid size
decreased with the concentration of MAI and was determined
to be ∼720 nm for 0.038 M, ∼360 nm for 0.044 M, ∼190 nm
for 0.050 M, ∼130 nm for 0.057 M, and ∼90 nm for 0.063 M.
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The light-harvesting efficiency and charge carrier extraction
were found to strongly depend on the cuboid size. High
average PCEs were obtained using MAI concentrations higher
than 0.038 M and lower than 0.050 M.
Substrate preheating for PbI2 deposition is another strategy
for improving the PCE.232 During spin coating, the preheated
substrate enabled full coverage of the mesoporous TiO2 film
with PbI2, induced by better infiltration of PbI2 into the
mesopores. The optimized preheating temperature was 50 °C,
exhibiting a high PCE of 15.76%. Beyond 50 °C, the
crystallinity of deposited PbI2 increased, which retarded the
formation reaction of MAPbI3 with MAI. Without preheating,
the average PCE was 10−11%, which demonstrates that
preheating during PbI2 coating is critical for producing high-
quality MAPbI3.
Mixed halide materials, such as a mixture of FA and MA
cation-based perovskite materials, were successfully synthe-
sized using the two-step process, which extended the optical
absorption onset further into the red region for the
enhancement of light harvesting. The mixed cation
MA0.6FA0.4PbI3 PSC yielded a PCE of 14.9% by virtue of
superior light harvesting and charge-collection efficiency.154 A
highly efficient PSC was realized by exploiting the intra-
molecular exchange process (IEP), wherein the PbI2·DMSO
film was deposited as a first step, followed by the deposition of
FAI and postannealing.233 During annealing, DMSO was
exchanged with FAI, consequently forming FAPbI3 with large-
grained dense microstructures and flat surfaces without
residual PbI2 (Figure 21). In addition, mixed FAPbI3/
MAPbBr3 was synthesized by IEP. The resultant cell efficiency
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Figure 22. Schematic illustration of the stamping method comprising two steps: (a) preannealing and (b) bifacial stamping, in which each
perovskite film was prepared at a low temperature with a short annealing time in the preannealing step. Two perovskite films were bifacially
contacted at 100 °C for 9 min without pressure during the stamping step. (b) Perovskite printing technology based on bifacial stamping, in which
(c) the letters “SKKU” were printed by inserting a mask between the MAPbI3 and yellow d-FAPbI3 via the delta−alpha phase transition of FAPbI3,
and (d) a portrait image using an EAPbI3 film was produced by inserting a mask between the MAPbI3 and the yellow EAPbI3 via the reduction of
the bandgap. Reproduced with permission from ref 237. Copyright 2019 Royal Society of Chemistry.

was 20.1%, certified by the standardized method in a PV
calibration laboratory.
3.3.2. Adduct Intermediated Process. Although exten-
sive efforts have been invested to improve the efficiency of
PSCs, the standard deviation of the average PCE is fairly large,
which indicates that the reproducibility of high-efficiency PSCs
is a persisting challenge. The presence of the intermediate
phase was initially observed by Jeon et al.,20 which was later
found to be a Lewis acid−base adduct composed of perovskite
precursors and Lewis base solvent molecules.21 The Lewis base
adduct of MAI·PbI2·DMSO was formed by spin-casting an
equimolar MAI, PbI2, and DMSO solution dissolved in DMF
solvent.21 The diethyl ether quickly extracted the DMF
solvent, which formed the adduct of MAI·PbI2·DMSO. The
adduct film converted into MAPbI3 by simple postannealing.
The resultant perovskite film showed more uniform morphol-
ogy compared with the perovskite film fabricated using
conventional PbI2. Chiefly, the adduct method yielded a high
reproducibility, i.e., a narrow standard deviation with average
PCE of 18.3% from 41 cells and the best PCE of 19.7%.
Another adduct compound, MA2Pb3I8·2(DMSO), was
prepared by changing the DMF/DMSO solvent ratio.234 The
perovskite film fabricated from the adduct showed a dense
structure with large grains. When no DMSO was added, the
resultant perovskite film exhibited a high density of pinholes
and voids at the interface between the perovskite and NiO film
substrate. These results suggested that the crystallization of the
perovskite was initiated from the top surface of the film rather
than from the substrate. This top-surface crystallization is the
origin of the poor contact with the NiO surface. For the
intermediate adduct compound, the perovskite film crystallized
from the bottom surface during annealing, enabling facile
contact with the NiO film. Moreover, the similar densities of
(MA)2Pb3I8·2DMSO and MAPbI3 induced less strain during
the formation of the perovskite, preventing interfacial
delamination. The improved stability of the (MA)2Pb3I8·
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2DMSO adduct enabled the broadening of the antisolvent
dropping window for obtaining good-quality perovskite films.
Another benefit of this adduct compound is the improved
mobility of the grain-boundary motion, which is favorable for
forming a dense grain morphology. During the decomposition
of (MA)2Pb3I8·2DMSO, the evolution of DMSO vapor
induced the local dissolution of MAPbI3, similar to solvent
annealing. As a result, the p-i-n planar structured PSC
employing the NiO hole conducting layer exhibited a PCE
of 18.4%. Further, this adduct method was adopted to fabricate
FAPbI3 perovskite materials.235 FAPbI3, with large grains, high
crystallinity, and long carrier lifetime, was obtained using an
adduct of PbI2 with sulfur-donor thiourea as the Lewis base.
For FAPbI3, thiourea was more suitable compared to DMSO
because of the difference in their chemical interaction natures.
The FAPbI3 prepared by the adduct method exhibited superior
photovoltaic performance because of its faster charge transport
and reduced trap sites. The Lewis base NMP made it possible
to fabricate a PSC with better photovoltaic performance via
forming a stable intermediate FAI·PbI2·NMP adduct.236 DFT
calculations showed a higher interaction energy of the NMP
with the FA cation, supporting the experimental results on the
formation of a strong coordinative bond with FAI and NMP.
Owing to the excellent uniformity and reproducibility of
FAPbI3, the resulting PSC attained a high PCE of 20.19%.
Moreover, in this report, criteria for selecting Lewis bases were
suggested: (1) a high hydrogen bond-accepting ability and low
hydrogen bond-donating ability, (2) a sterically accessible
electron-donating atom, and (3) matching the hardness and
softness of the Lewis acid and base.
Recently, a new fabrication method for perovskite layers
based on an adduct compound has been reported. Simple face-
to-face contact without pressure, termed the bifacial stamping
process, enabled the low-temperature phase transition of
FAPbI3 and the effective interface modification of MAPbI3,
yielding superior photovoltaic performances for both perov-
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Table 5. Efficiencies of PSCs Fabricated by One-Step and Two-Step Processes

ref materials planar/mesoscopic type method PCE (%) year
207 MAPb(I1−xBrx)3 mesoscopic 1-step solvent engineering 16.2 2014
210 MAPbI3 mesoscopic 1-step solvent engineering 17.08 2017
211 MAPbI3 planar 1-step solvent engineering 15.58 2016
212 [CsPbI3]0.05[(FAPbI3)0.85(MAPbBr3)0.15]0.95 mesoscopic 1-step solvent engineering 19.76 2018
213 [CsPbI3]0.05[(FAPbI3)0.85(MAPbBr3)0.15]0.95 mesoscopic 1-step solvent engineering 19.4 2019
214 MAPbI3 planar 1-step solvent engineering 19.0 2017
215 MAPbI3 mesoscopic 1-step solvent engineering 17.6 2018
216 MAPbI3 mesoscopic 1-step solvent engineering 19.02 2019
217 MAPbI3 planar 1-step solvent engineering 20.06 2019
161 RbCsMAFA mesoscopic 1-step solvent engineering 21.6 2016
218 MAPbI3 mesoscopic 1-step solvent engineering 21.2 2017
219 FA1−xMAxPb(I1−yBry)3 mesoscopic 1-step solvent engineering 20.8 2016
220 FA0.81MA0.15Pb(I0.836Br0.15)3 mesoscopic 1-step solvent engineering 20.6 2017
221 (FAPbI3)0.95(MAPbBr3)0.05 mesoscopic 1-step solvent engineering 22.85 2018
222 (FAPbI3)0.85(MAPbBr3)0.15 mesoscopic 1-step solvent engineering 20.3 2017
160 Csx(MA0.17FA0.83)(1‑x)Pb(I0.83Br0.17)3 mesoscopic 1-step solvent engineering 21.1 2016
223 MAPb(I1−xClx)3 planar 1-step heating substrate 18 2015
224 MAPbI3 planar 1-step heating substrate 20.3 2018
225 MAPbI3 planar 1-step gas blowing 17 2014
226 Cs0.05FA0.81MA0.14PbI2.55Br0.45 planar 1-step gas blowing 20.26 2019
227 Cs0.05(MA0.17FA0.83)0.95 Pb(I0.84Br0.16)3 planar 1-step gas blowing 21.4 2018
228 FA0.81MA0.15PbI2.51Br0.45 mesoscopic 1-step vacuum treatment 20.5 2016
229 FA0.1MA0.9PbI3 planar 1-step vacuum treatment 20.44 2017
21 MAPbI3 mesoscopic 1-step adduct intermediate 19.7 2015
234 MAPbI3 planar 1-step adduct intermediate 18.4 2017
236 FAPbI3 mesoscopic 1-step Adduct intermediate 20.19 2018
237 MAPbI3 mesoscopic 1-step Adduct intermediate 20.18 2019
19 MAPbI3 mesoscopic 2-step 15.0 2013
8 MAPbI3 mesoscopic 2-step 17.01 2014
232 MAPbI3 mesoscopic 2-step 15.76 2015
154 MA0.6FA0.4PbI3 mesoscopic 2-step 14.9 2014
233 (FAPbI3)0.95(MAPbBr3)0.05 mesoscopic 2-step 20.1 2015

skites (Figure 22).237 This result was explained in terms of the
content of the DMSO reservoir in the MAPbI3 adduct film,
which induced the phase transition of FAPbI3 and high-quality
MAPbI3. During the bifacial stamping, a DMSO-mediated ion
exchange reaction took place, which facilitated ion transport
from the Lewis base reservoir in the MAPbI3 adduct film,
consequently resulting in the fast phase transition of FAPbI3 at
a low temperature. The adduct-intermediate process is
promising for preparing dense perovskite films with large
grains, which is among the requirements for achieving high
efficiency.
In Table 5, the efficiencies of PSCs fabricated by one-step
and two-step processes are summarized. Thus, far, champion
cell has employed a mixed-halide perovskite layer prepared by
the one-step process.
3.4. Device Physics
In terms of the device geometry, PSCs can be classified in two
different ways. First, they can be classified either as a
mesoscopic structure or as a planar structure depending on
the existence of the mesoporous nanoparticle layer. Meso-
scopic devices have a structural similarity to DSSCs, but the
mesoporous charge-transporting layer in PSCs is much thinner
than the sensitized solar cells, and the perovskite layer
generally fills the pores in the mesoporous nanoparticle layer
and forms an overlayer on top of it. In contrast, planar devices
consist of stacked multiple thin layers, such as selective
contacts, light-absorbing layers, and window layers, which have
AA
a structural similarity to organic photovoltaics or thin-film solar
cells (e.g., CdTe, CIGS, and CZTS). Mesoscopic devices
generally require higher processing temperatures to sinter the
nanoparticle layer, whereas planar devices can be prepared at
lower temperatures, especially when the device contains carbon
or organic charge-transporting layers. Therefore, planar devices
are preferred when fabricating flexible solar cells with plastic
substrates or tandem devices, although the best single-junction
PSC still has a mesoscopic structure. Second, PSCs can be
classified as either n-i-p type or p-i-n type, depending on the
direction of charge collection. For n-i-p type devices, electrons
are collected to the substrate through which the incident light
enters, whereas for p-i-n type devices, holes are collected
through the substrate.
3.4.1. Selective Contact. 3.4.1.1. Inorganic Electron
Transport Layer (ETL). Titanium dioxide (TiO2) has been
mostly used as an ETL in PSCs because the first PSC
constructed using the current device structure originates from
solid-state DSSCs.1 TiO2 offers several advantages as an ETL,
including a wide bandgap to minimize parasitic absorption, an
appropriate conduction band alignment with the perovskite for
efficient electron injection, and good electron-transport
capability. Therefore, many record efficiencies have been
obtained using TiO2 ETLs. However, TiO2 does present some
disadvantages as an ETL in PSCs, such as UV-induced
photocatalytic activity, which causes degradation in the device
performance, capacitance issues that create I−V hysteresis and
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Chemical Reviews
Figure 23. (a) I−V hysteresis in n-i-p devices constructed using a TiO2 ETL and their relevant capacitance spectra. Reproduced with permission
from ref 246. Copyright 2015 American Chemical Society. (b) Mechanisms of I−V hysteresis. Reproduced with permission from ref 248.
Copyright 2016 American Chemical Society. (c) J−V curves of the n-i-p device constructed using a SnO2 ETL. Reproduced with permission from
ref 254. Copyright 2017 Royal Society of Chemistry.
high processing temperatures (>450 °C). Because of the
limited compatibility of their processing, most TiO2 ETLs are
deposited directly onto a TCO substrate and applied in n-i-p
type devices. It should also be noted that most high-efficiency
devices incorporate a mesoporous ETL consisting of TiO2
nanoparticles due to the severe I−V hysteresis observed in
planar devices constructed using a thin-film TiO2 ETL. At the
early stage of perovskite research, most TiO2-related research
studies conducted toward improving the photovoltaic perform-
ance involved the modification of TiO2, including the
crystalline phase (i.e., anatase vs rutile),238,239 morphology of
its nanoparticles (i.e., size and shape), 238,240,241 and
doping.9,242,243 The lesson learned from these early studies
was that a thin mesoporous TiO2 nanoparticle layer was the
optimal form of a TiO2 ETL; the conversion efficiencies
obtained for PSCs constructed using a TiO2 ETL have
continuously increased since then, to >23%.221 However,
issues such as UV-instability, I−V hysteresis, and high
processing temperature still need to be resolved. With regard
to the photocatalytic degradation observed under UV
irradiation, Ito et al. introduced a Sb2S3 layer between the
TiO2 and perovskite layers as a blocking layer, which resulted
in significantly improved stability under visible-light and UV
irradiation.244 Optical modulations such as UV down-
conversion can also be applied to avoid photocatalysis,245
but the only way to completely mitigate this issue is to use
another ETL material without any photocatalytic activity. I−V
hysteresis is another fundamental issue for TiO2 ETLs. This
hysteresis is mainly ascribed to the capacitance of the TiO2
layer (Figure 23a).246 The relatively high dielectric constants
observed for TiO2 materials (∼40 for anatase and ∼100 for
rutile)247 are primarily responsible for the capacitance. Other
potential causes include charge accumulation due to
unbalanced charge extraction/transport between the ETL
and HTL, and interfacial defects/traps (Figure 23b).248
Successful attempts to circumvent the issues related to
interfacial charge extraction and traps include the incorpo-
ration of a PCBM for efficient electron extraction,249,250
complete crystallization to reduce the interfacial trap
density,251 and Cl treatment on the TiO2 surface.243
SnO2 ETLs have also been extensively investigated as an
alternative to conventional TiO2 ETLs because SnO2 exhibits
good conduction band alignment with perovskites, high
electron mobility, a wide bandgap, high transmittance, good
stability, and offers easy processing.252 More importantly, SnO2
possesses some critical advantages over TiO2, such as lower
processing temperatures, less I−V hysteresis, and improved
pubs.acs.org/CR Review
photostability. SnO2 ETLs have been prepared via various
synthetic approaches, such as spin-coating of nanopar-
ticles213,253 or precursor solutions,254,255 atomic layer deposi-
tion (ALD),256,257 and chemical bath deposition (CBD);257
among the ETLs prepared by these methods, most high-
performance SnO2 ETLs reported to date have been prepared
at temperatures below 200 °C. The conversion efficiency of
PSCs constructed using SnO2-based ETLs has continuously
increased using various optimization processes, such as bilayer
formation,258 interfacial cross-linking,259 and EDTA complex-
ation,260 leading to the highest certified efficiency of >23%.261
In contrast to TiO2-based ETLs, most highly efficient PSCs
constructed using SnO2-based ETLs reported to date have
been prepared with a planar n-i-p geometry incorporating a
SnO2 thin film because SnO2-based PSCs usually exhibit
insignificant I−V hysteresis (Figure 23c). The origin of the
reduced I−V hysteresis in SnO2 ETLs when compared to their
TiO2-based counterparts remains largely unclear, but fast
charge extraction due to the deeper conduction band edge and
low interfacial charge accumulation due to high conductivity
(or electron mobility) have been proposed as possible
causes.252 Like other oxide materials, SnO2 is stable under a
variety of environments, such as oxygen-rich and humid
conditions, which helps to improve the long-term stability of
the PSC when compared to its organic counterparts. In
addition, PSCs constructed using SnO2-based ETLs are very
stable under visible-light illumination, especially in the
presence of UV light262 because SnO2, unlike TiO2, does not
exhibit any photocatalytic activity. There have been several
approaches using an SnO2 ETL in p-i-n type devices, which are
much more beneficial toward the stability of the device because
the inorganic ETL on top of the perovskite layer effectively
blocks the permeation of water and/or oxygen molecules by
acting as an encapsulation layer. To date, SnO2 ETLs can only
be deposited on an additional ETL, such as C60263 and
PCBM,264 due to technical difficulties, but devices constructed
using top-layer SnO2 ETLs exhibit significantly improved long-
term stability. Besides the two most popular inorganic ETL
materials (i.e., TiO2 and SnO2), various oxide materials with
desirable electrical/optical properties (e.g., ZnO, 265
Zn2SnO4,266,267 and BaSnO3218) have been investigated as
potential alternatives, but their ETL performances have yet to
be improved to compete with those of TiO2 and SnO2.
3.4.1.2. Organic ETLs. Fullerene (C60) and its derivatives,
such as PCBM, are the most popular organic ETLs, especially
for p-i-n type and/or flexible PSCs, due to their appropriate
electrical properties and physical softness. PSCs constructed
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Figure 24. (a) J−V curves obtained for highly efficient NiO-based p-i-n perovskite solar cells. Reproduced with permission from ref 269. Copyright
2017 American Chemical Society. (b) Operational stability of NiO-based perovskite solar cells. Reproduced with permission from ref 159.
Copyright 2017 John Wiley and Sons. (c) Operational stability of highly efficient CuSCN-based n-i-p perovskite solar cells. Reproduced with
permission from ref 293. Copyright 2017 American Association for the Advancement of Science. (d) SEM image and (e) J−V curves obtained for
the n-i-p device constructed using a CuGaO2 HTL. Reproduced with permission from ref 301. Copyright 2017 John Wiley and Sons.

from C60 or PCBM exhibit high FF values and negligible I−V
hysteresis due to their high electron mobility and excellent
electron-extracting capabilities. In addition, their processing
conditions using either vacuum deposition or solution
deposition are well-established because they have been widely
used in organic solar cells. In particular, they can be dissolved
in a nonpolar solvent that is orthogonal to the perovskite layer,
and hence, can be deposited directly on top of the perovskite
layer during the solution-phase process. One of the drawbacks
of fullerene-based ETLs is that stable noble metals such as Ag
cannot be used due to their inappropriate energy alignment.
The energy barrier for electron transfer from PCBM (or C60)
to the Ag metal electrode can be successfully reduced by
introducing interfacial layers including bathocuproine
(BCP),268 polyethyleneimine ethoxylated (PEIE),269,270 and
other small-271/macro-molecules272 between PCBM (or C60)
and the metal electrode, leading to the significantly improved
FF values observed for p-i-n type PSCs.
3.4.1.3. Organic Hole Transport Layer (HTL). Similar to
TiO2 ETLs, the HTL used for the first PSC was also adopted
from solid-state DSSCs. Spiro-OMeTAD, which has been used
as a hole-transport material in solid-state DSSCs,273 was used
as the first HTL in PSCs1 and is still the most commonly used
HTL, especially in n-i-p type devices. State-of-the-art spiro-
OMeTAD or related small molecules require the addition of
dopants and/or additives such as lithium bis(trifluoro-
methane)sulfonimide (Li-TFSI) and 4-tert-butylpyridine
(tBP) due to the low conductivity (∼10−5 mS/cm) and low
hole mobility (10−5−10−4 cm2/(V s)) of pristine spiro-
OMeTAD. However, essential additives such as Li-TFSI are
known to cause significant instability due to their hygroscopic
nature.274 Therefore, there have been various approaches
toward the development of new dopants with good efficiency/
stability275 and new dopant-free HTLs.276
AC
For p-i-n devices, on the other hand, poly(3,4-ethyl-
enedioxythiophene)−poly(styrenesulfonate) (PEDOT:PSS)
was initially used as the HTL because it has been used in
organic bulk heterojunction solar cells.277 This polymeric
material presents many advantages such as an appropriate
HOMO energy level (−5.5 eV), good conductivity, and low-
temperature processing but also presents the catastrophic
disadvantage of low stability resulting from its hygroscopic and
acidic nature.278 Despite these drawbacks, PEDOT:PSS HTLs
are still commonly used in small-bandgap PSCs (∼1.2 eV)
incorporating Sn ions, particularly with the p-i-n geometry
designed for tandem solar cells.279,280
Another widely used polymeric HTL based on poly[bis(4-
phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) shows higher
intrinsic hole mobility (10−3−10−2 cm2/(V s)) and enhanced
stability when compared to other small molecules and
PEDOT:PSS. Interestingly, PTAA HTLs have been applied
to both n-i-p183 and p-i-n281 type devices, resulting in high
conversion efficiencies regardless of doping282 and work very
well in p-i-n type wide-bandgap PSCs.283 Recently, the use of
poly(3-hexylthiophene) (P3HT) as a HTL in highly efficient
(22.7%) n-i-p type PSCs without doping has also been
reported, where successful defect passivation at the P3HT/
perovskite interface not only increases the Voc (more than 200
mV) and FF (10%) values but also minimizes I−V
hysteresis.284
3.4.1.4. Inorganic HTLs. To overcome the instability issues
presented by organic HTLs, various inorganic p-type semi-
conducting materials have been investigated as HTLs in PSCs.
Among them, NiO is one of the most extensively investigated
p-type materials because of its large bandgap, high trans-
mittance, and deep valence band (Figure 24a,b).285 In
addition, it can be easily deposited using various fabrication
methods, such as spin-coating,278 electrodeposition,269 sputter-
ing,286 e-beam evaporation,287 and ALD.288 However, NiO
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Table 6. Various Materials Used for Electron/Hole-Selective Contact Layers
classification materials device type
inorganic ETL TiO2 mesoscopic/planar n-i-p
SnO2 planar n-i-p
organic ETL C60 planar n-i-p/p-i-n
PCBM planar p-i-n
inorganic HTL NiO planar p-i-n
CuSCN mesoscopic/planar n-i-p/p-i-n
CuOx planar n-i-p/p-i-n
delafossite mesoscopic/planar n-i-p/p-i-n
organic HTL spiro-OMeTAD mesoscopic/planar n-i-p
PEDOT:PSS planar p-i-n
PTAA mesoscopic/planar n-i-p/p-i-n
HTLs also suffer from some drawbacks, such as low hole
conductivity and poor electrical/physical contact with the
perovskite layer, which have been successfully improved upon
doping with monovalent acceptor ions such as Li+289 and
Cu+,290 interfacial treatment with PEDOT:PSS,278 and the
introduction of nanoscale roughness on the surface of the NiO
HTL.269 It should be noted that NiO HTLs have been mostly
used in p-i-n type devices due to the relatively harsh processing
conditions of oxide materials.
Copper thiocyanate (CuSCN) is another widely used
inorganic HTL material with a deep valence band, high carrier
mobility, good thermal stability, and high transparency.291 It
readily dissolves in a variety of solvents and does not need a
postannealing process for crystallization; hence, it has been
used in both p-i-n and n-i-p type devices. However, in p-i-n
devices, the underlying CuSCN HTL was found to react with
the perovskite layer during the annealing conducted to
crystallize the perovskite layer, resulting in the degradation of
the device performance.292 Therefore, higher efficiencies and
improved stability have been reported for n-i-p devices. For
example, a high conversion efficiency of 20.4% can be achieved
for n-i-p devices by forming a highly compact and conformal
CuSCN layer using a dynamic drop-casting method, in which
the device showed excellent long-term operational stability
over 1000 h even at an elevated temperature of 60 °C, with a
spacer layer consisting of reduced graphene oxide (rGO)
between CuSCN and Au (Figure 24c).293 The role of the rGO
layer was described as an encapsulation layer for the CuSCN/
perovskite layers and a protection layer for the potential-
induced reaction that occurs between the CuSCN and Au
layers.
Copper oxide (CuOx) has also been investigated as a HTL
material in PSCs due to its deep valence band and high carrier
mobility. CuOx HTLs have been prepared using a variety of
synthetic methods such as solution-phase,294 evaporation,295
and sputtering processes.296 However, the relatively low
bandgap energy of CuOx (1.2 eV for cupric oxide, CuO; 2.1
eV for cuprous oxide, Cu2O) causes significant optical loss,
especially in p-i-n devices where the incident light should enter
via the HTL. n-i-p devices are free from the issue of optical
loss, but only a limited number of synthetic approaches (e.g.,
evaporation) are available due to the degradation of the
perovskite layer during the processing. Therefore, research
efforts have been invested toward increasing the bandgap
energy of CuOx by forming new p-type delafossite oxides with
AD
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process
nanoparticle1,221
213,253
nanoparticle, solution,254,255 ALD,256,257 CBD257
evaporation302
solution303
solution,278 electrodeposition,269 sputtering,286 evaporation,287 ALD288
solution293
solution, evaporation,295 sputtering296
294
nanoparticle299,301
solution1
solution278
solution183,281
higher bandgap energies, such as CuCrO2 (3.0 eV)297 and
CuGaO2 (3.6 eV).298 Delafossite-based HTLs generally
require doping to improve the hole conductivity and have
been mostly prepared using nanoparticle-based spin-coating
deposition at low temperature, which can be used for both p-i-
n and n-i-p devices. The p-i-n and n-i-p devices constructed
using CuCrO2-based HTLs show high conversion efficiencies
of 20.54%299 and 16.25%,300 respectively. It is noteworthy that
the n-i-p device in which the undoped CuCrO2 HTL was
directly deposited onto the perovskite layer exhibits a high
conversion efficiency of 16.25% and significantly improved
long-term stability, indicating that the device performance can
be further improved via an appropriate doping strategy during
the synthesis of the nanoparticles. CuGaO2-based HTLs have
also exhibited good performance (20.15%) in the p-i-n device
with a Zn-doping and bilayered structure, and NiO HTL.298
The corresponding n-i-p device constructed using an undoped
CuGaO2 HTL directly deposited onto the perovskite layer
showed excellent ambient long-term stability and a conversion
efficiency of 18.51% (Figure 24d,e).301 The various contact
materials discussed in this section are summarized in Table 6.
3.4.2. Interface Engineering. A PSC is typically
constructed from stacked multiple layers consisting of the
perovskite active layer, charge-transporting layers for electrons
and holes, and current-collecting electrodes; consequently,
there exist four major interfaces between the layers (i.e.,
electrode/ETL/perovskite/HTL/electrode). The properties of
the interfaces are very important for achieving good device
performance because they directly influence charge extraction/
transport/recombination as well as photon transmission. The
interfaces can be further classified into two simplified groups
(i.e., one between the charge-transporting layer and the
current-collecting electrode and another between the perov-
skite layer and charge-transporting layer). Some of the
representative studies used to improve the solar cell perform-
ance by modifying each interface are described below.
3.4.2.1. Electrode/ETL and Electrode/HTL Interfaces. The
work function of the metallic electrode is an important
parameter governing the charge transfer observed at the
interface with the charge-transporting layer. For example, metal
electrodes for collecting electrons generally require a relatively
low work function (e.g., Al, 4.1 eV) that matches the CB (or
LUMO level) of the ETL (below CBperovskite, −3.9 eV),
whereas the electrodes for hole transfer require a relatively high
work function (e.g., Ag, 4.2−4.7 eV; Au, 5.3 eV) due to the VB
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Figure 25. (a) Illustration of the dipole in PEIE and (b) work function shift observed using PEIE. Reproduced with permission from ref 304.
Copyright 2012 American Association for the Advancement of Science. Effects of the PEIE layer on the J−V curves obtained for the (c) n-i-p
device9 and (d) p-i-n device (unpublished results). Reproduced with permission from ref 9. Copyright 2014 American Association for the
Advancement of Science. (e) PEDOT-treated NiO HTL. Reproduced with permission from ref 278. Copyright 2015 American Chemical Society.
(f) An SnO2-based n-i-p device constructed using an ionic liquid (ImAcHCl). Reproduced with permission from ref 259. Copyright 2019 John
Wiley and Sons.

energy level (or HOMO level) of the HTLs (above VBperovskite,
−5.4 eV). In terms of the long-term stability, noble metals with
better resistance to chemical reactions are considered as better
candidates for the current-collecting electrode despite their
high cost. Noble metals function suitably with most HTLs
reported to date, but their work functions are generally too
high to collect electrons efficiently from the ETL. A universal
method to reduce the work function of the electrodes using
polymer modifiers has been reported by Zhou and Kippelen et
al.304 The work functions of various conducting electrodes can
be significantly reduced by the physical adsorption of an
ultrathin layer (1−10 nm) of an amine-containing polymer,
such as polyethylenimine ethoxylated (PEIE) and branched
PEI, on the surface of the electrodes, leading to a significant
increase in the FF of their corresponding organic solar cells.
The intrinsic molecular dipole moments associated with the
neutral amine groups contained in the insulating polymer layer
along with the charge-transfer characteristics of their
interaction with the conductor surface reduce the work
function of a wide range of conductors (Figure 25a,b).304
Later, Zhou and Yang et al. adopted this approach to n-i-p type
PSCs, where PEIE treatment of the ITO substrate resulted in a
reduced shunt conductance, decreased series resistance, and
increased FF, which can be ascribed to the facilitated electron
extraction at the ETL/electrode interface (Figure 25c).9 This
approach cannot be directly applied to p-i-n devices because
the metal electrodes are deposited on top of the ETL layers.
Park et al. have shown that the PEIE layer deposited on the
surface of the PCBM ETL also reduces the work function of
the Ag electrode deposited on top of the PEIE layer and FF of
the p-i-n type PSC significantly increases upon the addition of
the PEIE layer (Figure 25d).159,269 A thin layer of bath-
ocuproine (BCP) between PCBM and Ag is also known to
AE
increase the FF value of p-i-n type devices. Although its
working mechanism has not been fully elucidated, Shibayama
et al. reported that the thin BCP layer (<5 nm) facilitates
electron collection by changing the Schottky contact at the
PCBM/Ag interface into an ohmic contact.268
3.4.2.2. Perovskite/ETL and Perovskite/HTL Interfaces. The
interface formed between the perovskite and charge-trans-
porting layers has been mostly investigated toward improving
the photovoltaic performance of PSCs regardless of their type
because several major phenomena, including the charge
extraction/recombination and degradation of materials, occur
at the interface. Most of these studies have focused on oxide-
based ETLs and HTLs because the heterogeneous interface
formed between the perovskite and oxide charge-transporting
layers generally exhibits poorer physical/electrical contact
properties when compared with their organic counterparts.
NiO HTLs, for example, often exhibit lower FF values than
organic HTLs due to their inefficient hole extraction
capabilities.269,278,288 Park et al. first demonstrated that the
surface treatment of an NiO HTL using a dilute solution of
PEDOT:PSS drastically improves hole extraction, which was
confirmed by the enhanced PL quenching and significantly
reduced total series resistance obtained in the presence of an
extremely thin interlayer (Figure 25e).278 As a consequence, a
high FF of 0.72 and conversion efficiency of 15.1% without I−
V hysteresis can be achieved, which was one of the best
performances observed for NiO-based p-i-n type PSCs at that
time. As mentioned earlier in this chapter, some TiO2 ETLs
also show sluggish electron transfer from the perovskite layer,
resulting in charge accumulation and significant I−V hysteresis.
As with NiO HTLs, it has been reported that electron transfer
from the perovskite to the TiO2 ETL can be effectively
facilitated upon inserting carbon-based materials.250,305,306 Li
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Figure 26. (a,b) Effect of Cl− on the quality of the TiO2/perovskite interface. The (c) charge extraction/transport, (d) charge recombination, (e)
I−V hysteresis, and (f) J−V curves obtained for the optimum device constructed using the TiO2−Cl ETL. Reproduced with permission from ref
243. Copyright 2017 American Association for the Advancement of Science.
et al. reported that the modification of the TiO2 surface using a
triblock fullerene derivative (PCBB-2CN-2C8) improves
charge extraction from the perovskite layer, leading to
drastically increased Voc and FF values along with reduced
I−V hysteresis.305 Passivation of the deep trap states of TiO2
along with facilitated charge extraction have also been
proposed to be responsible for the enhanced device perform-
ance, in which the long-term stability increased 4-fold in the
presence of the fullerene-based interlayer. Kim et al. also
reported similar phenomena upon forming a hybrid ETL layer
consisting of PCBM and ALD-deposited amorphous TiO2 for
use in flexible PSCs.250 In the hybrid ETL, the PCBM layer
reduces I−V hysteresis by facilitating charge extraction and
reducing interfacial charge accumulation, and the amorphous
TiO2 layer deposited using plasma-enhanced ALD suppresses
the dark current and shunt conductance of PCBM ETLs.
Graphene and related two-dimensional materials are also often
introduced into the perovskite/TiO2 interface.307 Agresti et al.
have reported that the light intensity dependency of Jsc in n-i-p
devices becomes more linear in the presence of an interlayer
consisting of graphene flakes and/or lithium-neutralized
graphene flakes, which indicates the absence of energy barriers
and improved charge extraction.284 Most approaches employed
for interface engineering of the TiO2 ETLs such as fullerene,308
PCBM,309 and graphene quantum dots,310 have also been
applied to SnO2 ETLs, and their effects have been discussed in
a similar manner (i.e., facilitated charge extraction and reduced
energy barrier). One recent and new approach toward
improving the performance of PSCs constructed using oxide
ETLs is to incorporate an ionic liquid.311 Bai et al. introduced
1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4)
into a variety of NiO-based p-i-n devices, in which the
improved device performance was ascribed to the improved
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interaction between the perovskite and NiO formed at the
interface, and the excellent long-term stability was discussed in
terms of the greatly suppressed ion migration process.303 Chen
et al. introduced an ionic-liquid-based multifunctional chemical
linker between the perovskite and SnO2 ETL (Figure 25f).259
4-Imidazoleacetic acid hydrochloride (ImAcHCl) provided a
chemical bridge between SnO2 and the perovskite using an
ester bond with SnO2 formed via an esterification reaction and
an electrostatic interaction with the perovskite (i.e., between
the imidazolium cation in ImAcHCl and an iodide anion in the
perovskite). The n-i-p device constructed using the ionic liquid
exhibited significantly improved charge extraction and reduced
charge recombination, leading to a high Voc of 1.14 V and high
efficiency of 21% with good long-term stability and negligible
I−V hysteresis.
Atomic doping or treatment of the oxide charge-transporting
layer was also found to improve the interfacial contact
properties with the perovskite layer, especially for TiO2
ETLs.9,304,243 Zhou et al. reported the use of Y-doped TiO2
(Y-TiO2) as an ETL in an n-i-p device, where the Y-TiO2 ETL
showed improved charge-extraction capability when compared
to its undoped counterpart due to the slight upward shift in the
Fermi level of the Y-TiO2 layer.9 The increased donor
concentration of the Y-TiO2 layer and the reduced depletion
width at the interface with the perovskite layer was also
proposed to be responsible for the lower contact resistance and
facilitated charge extraction. Tan et al. reported an interfacial
engineering strategy involving the use of Cl-capped TiO2
(TiO2−Cl) colloidal nanocrystals in the ETL, which mitigated
interfacial recombination and improved interfacial binding in
low-temperature planar solar cells (Figure 26).243 The band
alignment between TiO 2 −Cl and the perovskite was
determined using ultraviolet photoelectron spectroscopy
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Figure 27. (a) Effect of adding K+ ions on the I−V hysteresis of a n-i-p device (up/left). Reproduced with permission from ref.313 Copyright 2018
American Chemical Society. Effect of adding Rb+ ions on (b) J−V curves and (c) conductivity and tDOS of a p-i-n device (up/right). Reproduced
with permission from ref 159. Copyright 2017 American Chemical Society. Effect of adding divalent MDACl2 on (d) carrier lifetime, (e) XPS
results, and (f) TOF-SIMS profiles of pure α-FAPbI3. Reproduced by permission from ref 316. Copyright 2019 American Association for the
Advancement of Science.
(UPS), and the absorption measurements showed an excellent
match in the CB minimum, which allowed efficient electron
transfer to TiO2−Cl, whereas the high offset in the VB
maximum provided efficient hole blocking. Therefore, the
TiO2−Cl device showed a high conversion efficiency of 21.4%
with negligible I−V hysteresis. DFT calculations also reveal the
stronger chemical binding at the TiO2−Cl/perovskite interface
as opposed to the relatively weak binding observed between
the bare TiO2 and perovskite, indicating that the TiO2−Cl
device was likely to undergo stronger electronic coupling at the
ETL/perovskite interface and exhibit enhanced long-term
stability. Inorganic materials have been proposed by some
research groups as interface modifiers for TiO2 ETLs. Han et
al. introduced a thin layer of MgO between TiO2 and the
perovskite, where the MgO layer was found to increase the Voc
and FF due to the retarded charge recombination.312 However,
it should be noted that a thicker MgO layer blocks charge
extraction from the perovskite to TiO2. Therefore, maintaining
a sufficiently low thickness is essential in this approach. Ito et
al. deposited a thin Sb2S3 layer between perovskite and TiO2 in
an n-i-p device constructed using the CuSCN HTL.244 The
device showed an improved Jsc and conversion efficiency in the
presence of the Sb2S3 layer and, more importantly, significant
improvement in the durability of the solar cell.
3.4.3. Defect Passivation. As discussed in earlier chapters,
highly efficient PSCs are based on a polycrystalline film and
contain a significant amount of defects with various origins,
including vacancies, interstitials, GBs, interfaces, impurities,
and atomic clustering/segregation. The density of defects and
their properties directly influence the device performance of
solar cells, especially the Voc and FF, because these defects are
generally nonradiative recombination centers. Several success-
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ful strategies for passivating point defects and interfacial defects
of the PSC, including various additive-based and non-
stoichiometric approaches will be summarized below.
3.4.3.1. Passivation of Bulk Defects. The bulk defects in
perovskites are mostly point defects, such as cation/anion
vacancies, interstitials, and substituted ions, which are known
to act as nonradiative recombination centers with shallow
energy levels. Son et al. systematically studied the effect of
alkali metal ions (i.e., Li+, Na+, K+, Rb+, and Cs+) on the I−V
hysteresis of PSCs (Figure 27a).313 It was found that the I−V
hysteresis strongly depends on the size of the alkali metal ions,
and the addition of potassium ions, which have an intermediate
ionic radius, completely eliminate I−V hysteresis unlike smaller
(i.e., Li+ and Na+) or larger (i.e., Rb+ and Cs+) metal ions.
Theoretical calculations revealed that the reduced I−V
hysteresis observed upon the addition of potassium ions was
associated with the reduced number of Frenkel defects. The
potassium doping effect is much more pronounced for mixed-
cation perovskites because the potassium interstitials can be
energetically more stabilized. Saidaminov et al. reported that
the formation energy of the atomic vacancies increases, and
thus, the formation of vacancies can be successfully suppressed
upon the addition of isovalent small ions, such as Cd2+ and
Cl−.314 Although the device performance was barely affected,
the addition of isovalent ions greatly improved the long-term
stability due to the reduced number of vacancies, which are
prone to react with water and oxygen molecules. Rb ions are
often added to stabilize α-FAPbI3,315 but this strategy has
rarely been reported for MAPbI3. Park et al. have reported that
Rb ions can also be incorporated into MAPbI3 at levels up to 5
at% (i.e., Rb0.05MA0.95PbI3) for a p-i-n devices (Figure
27b,c).159 The addition of Rb+ effectively reduces the density
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Figure 28. (a) Formation mechanism and TEM images of the (quasi-)2D/3D structure constructed using PEAI and Pb(SCN)2 as additives.
Reproduced with permission from ref 283. Copyright 2019 Cell Press. (b) Cross-linking mechanism using TMTA molecules. Reproduced with
permission from ref 319. Copyright 2018 Springer Nature.
of the deep-level trap states and increases the electrical
conductivity of the perovskite layer, leading to improved Voc
and Jsc, respectively. Min et al. introduced the divalent cation,
methylene diammonium (+H3N−CH2−NH3+; MDA), to pure
α-FAPbI3 by adding MDACl2 molecules into the perovskite
coating solution (Figure 27d−f).316 The addition of ∼5% of
MDACl2 successfully stabilized the α-FAPbI3 phase due to the
stronger ionic interactions of the divalent state, leading to a
high conversion efficiency of 23.7% and excellent thermal
stability over 20 h at 150 °C under an ambient atmosphere. It
should be noted that the existence of the divalent cation allows
Cl− interstitials in the lattice of the perovskite, which enables
increased charge-carrier lifetime. The existence of Cl− ions in
the perovskite layer was confirmed using TOF-SIMS and XPS
analysis.
3.4.3.2. Passivation of Grain-Boundary/Surface Defects.
The most popular additives used to passivate GBs or surface
defects are alkylammonium halides because they can passivate
both cation and anion defects and may enable enhanced
passivation via hydrogen/ionic bonding. Using a nonstoichio-
metric approach, Son et al. first reported that an excess of
methylammonium iodide (MAI) is precipitated at GBs, where
the MAI layer suppresses nonradiative recombination and
improves hole and electron extraction at the GBs by forming
highly ionic conducting pathways.10 The MAPbI3-based n-i-p
device constructed using the MAI passivation layer exhibited a
high conversion efficiency of >20% without I−V hysteresis.
Alkylammonium halides bearing long alkyl chains such as
AH
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ethylammonium (EA+), n-butylammonium (BA+), isobutyl
ammonium (iso-BA+), and GA+ have also been used to
passivate the interface/surface, most of which improve the
device performance and carrier lifetime by forming two-
dimensional (2D) perovskite layers as mentioned in section
3.2, with the exception of those with longer alkyl chains, such
as octyl ammonium (OA+), which directly act as passivation
molecules rather than forming the 2D perovskite.317 Recently,
alkylammonium halides bearing benzene moieties have been
shown to exhibit good passivation properties, among which
phenethylammonium iodide (PEAI) is the most promising
additive used in highly efficient PSCs. Jiang et al. reported a
highly efficient (23.2%) SnO2-based planar p-i-n device
constructed using a PEAI passivation layer, where the best
passivation effect was achieved without annealing due to the
transformation of PEAI into the 2D perovskite (i.e., PEA2PbI4)
at elevated temperature.261 The proposed passivation mecha-
nism of PEAI involves the synergetic effect of the π-conjugated
structure of the benzene ring, which promotes charge transport
and reduces the neutral defects, the amine groups which form
hydrogen bonds with the iodide ions and coordinate with the
Pb2+ interstitials, and the iodide ions that fill the iodine
vacancies. However, the amount of PEAI added is limited by
its insulating properties. Kim et al. introduced the PEAI
additive together with Pb(SCN)2 into a wide-bandgap PSC
(1.68 eV), where the reduced defect density and energetic
disorder as well as the improved charge carrier mobility and
lifetime led to a high conversion efficiency of 19.8% (Figure
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28a).283 The simultaneous use of PEA+ (from PEAI) and
SCN− (from Pb(SCN)2) was crucial for the formation of
(quasi-)2D/3D structures at the GBs and good device
performance.
Cross-linking grains with functional organic molecules has
been shown to enable passivation of the defects/imperfections
located at the GBs of a perovskite layer. Li and Grätzel et al.
introduced a bifunctional molecule, butylphosphonic acid 4-
ammonium chloride (4-ABPACl), which cross-linked the
MAPbI3 grains via the formation of hydrogen bonds (O−
H···I and N−H···I).318 Supramolecular hydrogen bonds were
found to be formed between 4-ABPACl and MAPbI3 in the
precursor solution, and the conversion efficiency increased
from 8.8 to 16.5% in the presence of these cross-linking
molecules. Li and Fang et al. employed trimethylolpropane
triacrylate (TMTA) in the MAPbI3 layer, in which the TMTA
molecules were chemically anchored to the GBs and then
cross-linked in situ to form a robust continuous polymeric
network after thermal annealing (Figure 28b).319 The addition
of TMTA improved the Voc and conversion efficiency, which
was attributed to the passivation of the defects. More
interestingly, the cross-links formed by the TMTA molecules
greatly improved the stability of the device against UV,
temperature, and moisture. The operational stability of the
MAPbI3-based device was improved 590-fold upon TMTA
addition and the subsequent cross-linking process. Another
powerful approach to passivate both positively and negatively
charged ionic defects is to use zwitterions that possess both
positively and negatively charged functional groups. Zheng et
al. first reported choline zwitterions, such as L-α-phosphati-
dylcholine, choline chloride, and choline iodide, which can
passivate both types of charged defects in halide perovskites.320
Theoretical analysis suggested that these zwitterions can
passivate two typical deep surface defects consisting of anionic
Pb−I antisites and cationic Pb clusters. Upon the addition of
choline chloride, the conversion efficiency of the MAPbI3 and
mixed-cation/anion perovskite devices increased from 17.1 to
20.0% and 19.2 to 21.0%, respectively. The improvement in
the efficiency was mainly attributed to the increased Voc, and
the Voc deficit of the optimal device constructed using the
mixed cations/anions was as low as 0.39 V.
3.5. Over Shockley−Queisser Limit
3.5.1. Tandem Solar Cells. The formation of a tandem
configuration, in which two or more photosystems with
different bandgap energies are combined in series or parallel, is
the only feasible approach to achieve conversion efficiencies
above the Shockley−Queisser limit. This has been proven by
the high efficiencies observed in multijunction solar cells.321 In
a double-junction solar cell (or tandem solar cell with two
photosystems), for example, the top cell with a higher bandgap
energy absorbs high-energy photons, whereas the bottom cell
with a lower bandgap energy absorbs low-energy photons
which have transmitted through the top cell.322 In the tandem
configuration, a wide range of solar radiation can be effectively
shared by the two photosystems while minimizing the
thermalization loss of the photons’ excess energy. Therefore,
one can expect much higher conversion efficiencies for tandem
solar cells when compared with their single-junction counter-
parts.
In terms of the device structure, tandem solar cells can be
classified as monolithic two-terminal,323,302 mechanical four-
terminal,324 and optical four-terminal devices.325 In a two-
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terminal monolithic tandem solar cell, two subcells are directly
connected in series with a tunnel junction326 or recombination
layer,302 in which the overall tandem current is limited by the
subcell exhibiting the lowest photocurrent. Therefore, it is very
important that each subcell generates the same photocurrent
by efficiently sharing the incident photons in order to obtain a
high matching photocurrent of the tandem solar cell. The
photocurrent in the subcells can be successfully matched by
controlling the optical properties, such as the bandgap/
transmittance of the layers,176,280 light scattering,327 and up/
down-conversion of incident light.328 Most perovskite-based
tandem solar cells including the champion device are prepared
using a crystalline Si bottom cell. The optimum bandgap
energy of the perovskite top cell that perfectly matches that of
Si (1.12 eV) is 1.68 eV, which is somewhat higher than that for
an optimal PSC and requires a mixed halide system
incorporating Br. To improve the photovoltage of tandem
solar cells, the photovoltage of each subcell has to be improved
independently. Therefore, numerous approaches that have
been applied toward improving the photovoltage of single-
junction PSCs can be applied to large-bandgap perovskites,
such as the passivation of defects using additives.261,283
However, the relatively large Voc-deficit (i.e., Eg−Voc) and
low photostability of mixed halides (e.g., phase segregation)
have yet to be addressed.329,330 The FF values of tandem solar
cells can be increased by either reducing the dark current and/
or shunt conductance or by reducing the series resistance of
the multiple layers and the interfacial charge transfer resistance
between them.331 In addition, developing more reliable
characterization methods including EQE/J−V measurements
and electron dynamics for tandem solar cells and their subcells
are important areas of research.302,332
The first successful demonstration of a perovskite/Si tandem
solar cell with a certified conversion efficiency of 23.6% was
provided by Bush et al. A perovskite top cell with an Eg of 1.63
eV (Cs0.17FA0.83Pb(Br0.17I0.83)3) was directly deposited onto a
polished Si heterojunction bottom cell with a textured
backside.323 A number of additional interfacial layers were
deposited to fabricate the functioning tandem solar cell, such
as the SnO2/ZTO layer used to protect the perovskite cell
from the plasma damage that occurs during the deposition of
the ITO window layer and the silicon nanoparticle layer on the
textured backside used to improve the near IR photoresponse
of the Si bottom cell. More important to note than the high
conversion efficiency is that the tandem solar cell passed a
damp heat test designed for crystalline silicon modules (IEC
61215), suggesting that the stability of perovskite-based
tandem solar cells can be significantly improved with the aid
of an appropriate encapsulation agent, such as an inorganic
TCO layer, EVA film, and the glass cover sheet. One can
expect significantly higher photoresponses with textures on
both sides of the Si bottom cell, especially toward the near-IR
region; however, directly fabricating a perovskite top cell on
top of a textured Si bottom cell is quite challenging. Sahli et al.
reported a vacuum-solution hybrid approach used to fabricate
a monolithic perovskite/Si tandem solar cell with a fully
textured Si bottom cell.333 Because of the effective light
scattering of the textured top surface, a very high overall
tandem current density close to 20 mA/cm2 and high
conversion efficiency of >25% could be achieved. As a result
of the continued research efforts of several research groups, the
highest efficiency of perovskite/Si tandem solar cells has
recently reached 29.1%.321 Very recently, several notable
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Figure 29. (a) Triple-halide perovskites with enhanced stability. Reproduced with permission from ref 335. Copyright 2020 American Association
for the Advancement of Science. (b) Microscopy/performance of a perovskite top cell with anion-engineered 2D additives and a corresponding
tandem device. Reproduced with permission from ref 336. Copyright 2020 American Association for the Advancement of Science.

Figure 30. (left) Structure of the monolithic two-terminal perovskite/CIGS tandem solar cell and its photovoltaic properties. Reproduced with
permission from ref 337. Copyright 2018 American Association for the Advancement of Science. (right) TEM image of the GuaSCN passivated
perovskite grains and photovoltaic properties of the GuaSCN-passivated monolithic two-terminal perovskite/perovskite tandem solar cell.
Reproduced with permission from ref 280. Copyright 2019 American Association for the Advancement of Science.

papers on highly efficient and stable perovskite−Si tandem
solar cells have been published. Hou et al. demonstrated that
solution processes can be used to prepare perovskite top cells
on textured Si bottom cells and reported a certified efficiency
of 25.7% with good device stability.334 Xu et al. reported that
the phase segregation observed in perovskite top cells using
mixed-halide (i.e., Br/I) compositions can be successfully
suppressed by the incorporation of Cl− ions and, thus, by the
formation of triple-halide compositions (Figure 29a).335 A
perovskite-Si tandem solar cell constructed using the triple-
halide perovskite showed a conversion efficiency of 27.04% (its
maximum power point tracking was not certified). Kim et al.
proposed the concept of anion-engineered additives to
AJ
improve the solar cell performance and stability of the
perovskite top cell, and reported a highly efficient and stable
perovskite-Si tandem solar cell with an operational efficiency of
26.7% and certified efficiency of 26.2% (Figure 29b).336
Perovskite-based tandem solar cells constructed using thin-
film-based bottom cells have also been actively investigated
because of the various materials available with low bandgap
energies of 1.0−1.2 eV as well as their potential applications,
which are not possible with Si bottom cells, such as flexible
solar cells. A mechanically stacked four-terminal tandem solar
cell constructed from perovskite and CIGS subcells with an
optimal efficiency of 22.1% has been reported by Fu et al.,324 in
which the perovskite top cell exhibited a low temperature
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Figure 31. (a) Efficiency contour map obtained for an ideal double-junction tandem solar cell. Reproduced with permission from ref 322.
Copyright 2017 Elsevier. (b) Efficiency contour map obtained for a triple-junction tandem solar cell, where the first and second cells refer to the
top and middle cells, respectively and the bandgap of the bottom cell was fixed at 1.1 eV. Reproduced with permission from ref 340. Copyright
2015 Elsevier. (c) Schematic representation of the three-terminal measurement platform and (d) EQE curves and (e) Nyquist plots obtained for
the subcells using the three-terminal platform. Reproduced with permission from ref 302. Copyright 2018 Elsevier. (f) FF as a function of the
current mismatching between subcells. Reproduced with permission from ref 332. Copyright 2019 Royal Society of Chemistry.

coefficient of −0.18%/°C (25−65 °C) and a reversible light-
soaking effect due to the photoconductivity of ZnO nano-
particles. Later, Kim et al. reported a higher efficiency of 25.9%
for a four-terminal device by using bimolecular additives283
and Han et al. reported a certified conversion efficiency of
22.43% for a monolithic two-terminal perovskite/CIGS
tandem solar cell constructed using a PTAA HTL, PCBM
ETL, and ZnO nanoparticle protection layer (Figure 30a).337
The top ITO layer of the CIGS bottom cell was polished using
a chemical mechanical polishing method, which was found to
be critical for the fabrication of highly efficient perovskite/
CIGS tandem solar cells. Low-bandgap (∼1.2 eV) PSCs are
also good candidates for the bottom cell of perovskite tandem
solar cells, where the bandgap of the perovskite top cell must
be increased up to 1.8 eV. The first perovskite/perovskite
tandem solar cell was reported by Eperon et al., in which a
conversion efficiency of 17.0% was reported using a
FA 0.83 Cs 0.17 Pb(I 0.5 Br 0.5 ) 3 bottom cell (1.8 eV) and
FA0.75Cs0.25Pb0.5Sn0.5I3 bottom cell (1.2 eV).279 A combination
of high bandgap energies was also reported by Forgács et al.,
where the wide bandgaps of the MAPbI3 bottom cell (1.55 eV)
and the Cs0.15FA0.85Pb(I0.3Br0.7)3 top cell (2 eV) led to a high
tandem photovoltage of 2.1 V.338 It is notable that all the layers
were deposited using thermal evaporation except for the
solution-processed wide-bandgap layer. Further improvements
to these perovskite/perovskite tandem solar cells were realized
by improving the Sn-incorporating bottom cell with an Eg of
1.25 eV.175,280,339 Zhao et al. reported that the thickness of the
Sn−Pb perovskite layer should be greater than that of the other
perovskite layer (>1000 nm)174 and also showed that the
addition of Cl− ions further improved the device performance
by increasing the grain size and suppressing charge
AK
recombination.175 Tong et al. reported that the addition of
GASCN to the Sn−Pb perovskite effectively reduces the defect
density, leading to a carrier lifetime of >1 μs and diffusion
length of >2.5 μm for the bottom cell (Figure 30b).280 As a
result, the resulting all-perovskite-based tandem solar cells
exhibit high conversion efficiencies of 23.1 and 25% in the two-
terminal and four-terminal devices, respectively. More recently,
Lin et al. reported a simple but effective approach to suppress
the oxidation of Sn2+ to Sn4+ in the precursor solution by
incorporating metallic Sn in the precursor solution.178 The
suppression of Sn oxidation was found to successfully passivate
the defects, reduce the charge recombination losses, and
improve the near IR photoresponse, leading to a high
conversion efficiency of 24.8%.
Given the rapidly increasing conversion efficiencies of
perovskite-based tandem solar cells, it is reasonable to expect
ultrahigh efficiencies of >30% in the near future. Then, what
are the key scientific issues or the technical challenges?
Bandgap engineering is probably one of the most important
issues, which not only involves tuning the bandgap to the
desired value but also optimization of the single-junction
device performance with a specific bandgap energy. The typical
bandgap energies of perovskite required for tandem solar cells
are 1.2−1.25 eV for the bottom cell of perovskite/perovskite
tandem devices, 1.4−1.5 eV for the middle cell of triple
junction devices, 1.65−1.7 eV for the top cell of perovskite/
Si(CIGS) tandem devices, 1.75−1.8 eV for the top cell of
perovskite−perovskite tandem devices, and 1.9−2.0 eV for the
top cell of triple junction devices (Figure 31a,b). The biggest
challenge for small-bandgap perovskites (i.e., 1.2−1.25 eV) is
to prevent the oxidation of Sn2+ to Sn4+ so that the device can
exhibit high conversion efficiency for a longer time, whereas
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that for wide-bandgap perovskites (i.e., 1.65−2.0 eV) is the
large Voc deficit and light-induced halide segregation. As
described in the earlier sections of this review, various additives
have been investigated toward improving the Voc and FF via
defect passivation as well as enhancing the long-term stability
by suppressing Sn2+ oxidation or halide segregation. Increasing
the bandgap without mixing halide ions or minimizing them
may be another good approach toward enhancing the
photostability of perovskites, especially for top-cell applications
with a Si bottom cell. In addition, preserving the top surface
texture of the Si bottom cell or developing a fabrication
process for perovskite top cells on textured Si substrates is also
important to further increase the matching current of tandem
solar cells by improving the NIR photoresponse of the Si
bottom cell. Another important issue related to the efficiency
of perovskite-based tandem solar cells is the accurate
measurement of the device performance. It is known that
several commercial solar simulators use xenon lamps as the
light source, and the strong NIR spikes observed in the
simulated solar spectrum often cause spectral mismatch issues.
Spectral mismatch issues can easily be avoided for single-
junction solar cells by adjusting the light intensity using a
certified reference cell with or without auxiliary cutoff filters, so
that the total number of electrons coming out of the solar cell
can be calibrated. However, these calibration methods are not
effective for tandem solar cells because the NIR photons are
only absorbed by the bottom cells. Theoretically, the Jsc values
of tandem solar cells and their subcells can be calculated using
EQE curves without being disrupted by spectral mismatch
issues, but measuring accurate subcell EQE curves is also quite
challenging. Park et al. reported a three-terminal measurement
platform for monolithic perovskite/Si tandem solar cells, in
which the EQE curves of each subcell and the tandem device
can be accurately measured without any external bias light or
bias potential (Figure 31c−e).302 With this measurement
platform, one can easily measure the actual Jsc that the tandem
solar cell can produce under 1 sun/AM1.5 irradiation
conditions, which can also be used to investigate the electron
dynamics of each subcell without being disturbed by the other
subcell. However, it should be noted that the device is likely to
show some current mismatching between the subcells during
the J−V measurements, even if an accurately matched current
density can be obtained from the EQE measurements. It has
been reported that the current mismatching observed between
the subcells causes an over/underestimation of the FF
obtained for tandem solar cells (Figure 31f).303,312
3.5.2. Hot Carrier Device. In addition to tandem devices,
another feasible approach to reducing the energy loss from the
thermalization of photoexcited charge carriers is the utilization
of hot carriers. The concept of hot carrier solar cells was
proposed in the 1980s.341 In single-junction solar cells,
photons with energies higher than the bandgap generate
excited charge carriers populated above the band edge states
(electrons at states above the CB minimum and holes below
the VB maximum). These excited charge carriers are referred
to as “hot carriers” and rapidly relax to the band edge state
(typically in picoseconds) upon interaction with the lattice
vibrations. The energy loss during the relaxation of charge
carriers is significant, constituting the major portion of the
energy losses that set the thermodynamic limit of solar cells. In
hot carrier solar cells, the hot carriers with excess energy are
extracted to energy-selective contacts (ESCs) with a narrow
DOS prior to relaxation.322 Because of the narrow DOSs in the
AL
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contacts, the extracted charge carriers cannot relax to their
lower energy states. Because this increases the overall chemical
potential (quasi Fermi-level splitting) from Δμ for conven-
tional solar cells to μceh for hot carrier solar cells, the open
circuit voltage of the device can be enhanced, as shown by the
following equation,342
ij T yz
eVOC = μceh = ΔEehjjj1 − L zzz + Δμ L
j z
T
k Teh {
Teh (12)
where μceh and Δμ are the quasi Fermi-level splitting in the hot
carrier solar cells and conventional solar cells, respectively,
ΔEeh is the energy difference between the ESCs of the
electrons and holes, and Teh and TL are the temperatures of the
hot carriers and electrode lattice, respectively. For hot carrier
solar cells, a maximum efficiency of 66% under 1 sun
illumination (up to 85% under concentrated light) was
estimated with a bandgap of 0.7−0.9 eV.341,342
Although the theoretical modeling predicted the strong
potential for hot carrier solar cells to overcome the
thermodynamic efficiency limit of single-junction solar cells,
it has been challenging to experimentally demonstrate hot
carrier devices ideally working with efficiencies higher than
those of conventional single-junction solar cells. To fabricate
hot carrier solar cells, a suitable absorber as well as ESC
materials are necessary. For the absorber material, the hot
carrier cooling time should be sufficiently long to allow for the
extraction of the hot carriers prior to relaxation, while the ESC
materials should have a narrow DOS at an appropriate energy
level to extract the hot carriers from the absorber layer.
Previously, group III−V semiconductor compounds have been
actively investigated for application as an absorbing layer in hot
carrier solar cells. Well-established epitaxial growth techniques
enable the growth of high-quality crystals with low defect
density and desirable nanostructures, minimizing the inter-
actions between the charge carriers and phonons. For example,
a carrier cooling lifetime of 5.8 ± 0.1 ns has been reported for a
GaAsP/InGaAs quantum well structure with a steady-state
carrier population temperature of >100 K above the lattice
temperature under 1000 sun.343 In addition, a hot carrier
lifetime close to 1 ns with a carrier temperature exceeding 1000
K has been reported for InAs/GaAs quantum dots.344
Encouragingly, an increase in the current density and voltage
in a InGaAsP-based quantum well heterostructure due to the
contribution from the hot carriers has been reported.345
However, it is still challenging to demonstrate the efficiency
gain over a conventional single-junction device because of the
difficulty in achieving a long hot carrier lifetime with all the
desirable properties to be used as an absorber material in solar
cells (e.g., bandgap, high absorption coefficient, long carrier
diffusion lengths, high mobility, etc.).
Recently, halide perovskite materials have attracted increas-
ing attention in this field after a relatively long carrier cooling
lifetime (>100 ps) was reported by several groups when
compared to classical semiconductors (typically <1 ps).346,347
From transient absorption and PL measurements, two
pronounced cooling stages were observed. The primary
temperature cooling step occurred during the first stage with
a time scale in the range of subpicoseconds to 2 ps, while the
second step extended to several hundreds of picoseconds to
nanoseconds.132,346,348,349 Upon the development of strategies
used to enhance the crystal quality and tailor nanostructures,
further improvements in the hot carrier lifetime may be
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Figure 32. Spatial mapping of the emission and photon spectra. (a) Graphical representation of the microscope setup and measurement geometry.
(b) Experimentally measured light emission map obtained for different separation distances between the excitation and collection points (a.u.,
arbitrary units). (c) Comparison of the normalized PL with PL excitation (PLE) and photothermal deflection spectra. (d) Predicted spatial light
emission spectra obtained from the cylindrically decaying Beer−Lambert law. (e) Comparison between the experimental (solid lines) and
theoretical decay (dashed lines) data obtained from the Beer−Lambert law at 765 and 800 nm. The experimental data are not in agreement with
simple linear absorption, which suggests that additional processes, such as photon recycling, maintain a substantial photon intensity at large
distances. Reproduced with permission from ref 353. Copyright 2016 American Association for the Advancement of Science. (f) Theoretical open-
circuit voltage (Voc) obtained for various Schottky−Read−Hall (SRH) lifetimes (τSRH) for the case assuming Lambert−Beer-like absorption
(planar structure, top panel) and assuming a textured structure with Lambertian light trapping (mid panel). In each case, we show the situation
with and without photon recycling, whereby the case without photon recycling is unphysical but serves as a reference point. The bottom panel
shows the difference (ΔVocPR) between the cases with and without photon recycling. Note that the calculation of the internal generation rate due to
photon recycling for the Lambert−Beer case was limited to 104 reflections. Reproduced with permission from ref 354. Copyright 2016 American
Chemical Society.

possible. However, the exact mechanism for the extended
carrier cooling lifetime still appears to be lacking general
consent. Several different mechanisms such as the hot-phonon
bottleneck, acoustical-optical phonon up-conversion, Auger
heating, and large polarons have been suggested, but some of
the results contradict one another.132,346,349 Therefore, further
investigations are required to unravel the mechanism of hot
carrier cooling in halide perovskite materials. Understanding
the exact origin of the long hot carrier lifetime will allow the
design of customized perovskite materials and nanostructures
for use in hot carrier solar cells. Although still at the initial
stage of investigations, an encouraging observation is that hot
carrier transport in halide perovskite thin films is superior to
that in conventional semiconductors.350 Quasi-ballistic trans-
port of the hot carriers driven by excess kinetic energy in a few
hundreds of femtoseconds has been measured to be as long as
∼230 nm, and their subsequent nonequilibrium transport over
tens of picoseconds persists over ∼600 nm. The quasi-ballistic
transport lengths are much greater than those observed for
GaAs (∼85 nm), Si (∼20 nm), and GaN (∼14 nm), indicating
that the possibility of harvesting the hot carriers from realistic
devices is much higher than that from conventional solar
cells.350 However, despite the promising hot carrier lifetime of
perovskite materials, the development of ESC materials with
suitable energy states is necessary to extract the hot carriers
without losing energy. Only a few studies published to date
AM
have attempted to explore the possibility of extracting hot
carriers with existing contact materials.351 Therefore, intensive
research effort is required to demonstrate efficient hot carrier
PSCs.
3.5.3. Photon Recycling. Inspired from contradictory
observations such as the coexistence of long charge carrier
diffusion paths and the high density of crystalline disorder, the
possibility of an active photon recycling process in perovskite
thin films has been investigated. Effective recycling of the
photons can prolong the charge carrier lifetime beyond their
diffusion lengths where energy transport occurs via multiple
cycles of charge recombination and reabsorption. This photon
recycling process can enhance the charge carrier density in the
active layer of solar cells and, thus, the quasi-Fermi level
splitting, increasing the Voc of the devices toward the
Shockley−Queisser limit. In GaAs solar cells, photon recycling
was found to play a central role in enhancing the PCE of these
devices.352
Pazos-Outón et al. designed an experimental setup to probe
the photon recycling processes in perovskite thin films (Figure
32a).353 Using photophysical studies, the charge carrier
diffusion lengths in perovskite thin films were measured to
be on a scale of ∼1 μm, implying that the PL generated by
bimolecular recombination should be mostly observed near the
excitation spot. However, the research group observed that the
PL emission intensity away from the excitation spot was
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significantly higher than that calculated theoretically (Figure
32b−e). As shown in Figure 32b,d, upon increasing the
distance from the excitation spot to the detection spot, the
decay of the measured PL emission became significantly slower
than that calculated theoretically based on the Beer−Lambert
law. The enhanced PL emission was observed up to 50 μm,
which is far greater than the measured charge carrier diffusion
lengths (Figure 32b,e). They attributed the retarded PL decay
to the recycling of photons generated from the recombination
of excited charge carriers. Using a bottom contact lateral
device, the recycled photons were found to contribute to the
photocurrent of the devices. On the basis of the measured
parameters, they suggested that the internal photon density
under 1 sun illumination can be doubled using nonquenching
electrodes and can be further enhanced by minimizing the
nonradiative decay channels. Kirchartz et al. estimated that the
voltage gain by photon recycling is in the range of 50−100 mV
for planar devices and 10−50 mV for textured devices (Figure
32f).354
While Pazos-Outón et al. suggested the significant
contribution from the photon recycling process to the
photovoltaic performance of these devices under 1 sun
illumination, contradictory results have still been reported.
Fang et al. have developed an experimental setup to measure
the photon recycling efficiency of perovskite single crystals.355
By utilizing a polarized excitation light source, they were able
to differentiate the recycled PL emission from the transmitted
PL. They estimated the photon recycling efficiency in a
MAPbBr3 single crystal to be <0.5% under 1 sun illumination
regardless of its strong reabsorption probability exceeding 70%.
They also suggested that the observed PL emission in the
longer-wavelength region originates from the PL filtered by the
crystal itself after self-absorption and multiple reflections. The
measured low photon recycling efficiency was ascribed to the
poor PL quantum yield of the perovskite under 1 sun
illumination. As a result, only a 0.5% increase in the PL
lifetime, corresponding to a 0.26 mV enhancement in the Voc,
was estimated, whereas the 4−6-fold enhancement in the PL
lifetime was attributed to photon recycling in GaAs.355,356
Because the experiment was conducted based on single
crystals, further studies may be required to characterize and
realize photon recycling in thin film-based PSC devices.
3.5.4. Concentrator Solar Cells. Typically, the concen-
trator solar cell architecture is incorporated in a device when
the fabrication cost of the active material is greater than that of
a concentrator mirror. For example, the fabrication processes
used for single- or multijunction GaAs solar cells based on
epitaxial growth are very complex and thus, expensive;
consequently, a photovoltaic concentrator array is often used.
In concentrator solar cells, solar irradiation is concentrated on
a small active area in the device.
The photocurrent density is almost linearly proportional to
the irradiation intensity at low concentrations (<100 sun) with
a reasonably approximated charge extraction rate (∼108
s−1),357 while an additional enhancement in the Voc via
enhanced quasi-Fermi level splitting contributes to the PCE of
the device. The Voc enhancement can be estimated from the
ÄÅ ÉÑ
following diode equation,
nkT ÅÅÅÅ JSC ÑÑ
Ñ
+ 1ÑÑÑ
lnÅÅ
ÅÅ J ÑÑ
ÇÅ 0 ÖÑ
Voc =
e (13)
AN
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where n is an ideality factor, k is the Boltzmann constant, T is
temperature, e is the elementary charge, and J0 is the reverse
saturation current. With an X-fold enhancement in the
irradiation intensity, the Voc is expected to increase because
ÄÅ ÉÑ
the Jsc is enhanced X-fold (XJsc), as shown in eq 14.
nkT ÅÅÅÅ XJSC ÑÑÑ
+ 1ÑÑÑ ≈ Voc(1sun) +
lnÅÅ
ÅÅ J ÑÑ
ÅÇ 0 ÑÖ
nkT
Voc = ln X
e e (14)
ji zy
PCE ∝ jjj1 + ln X zzz
j z
nkT
k {
eVoc(1) (15)
Therefore, the PCE enhancement is dependent on an ideality
factor, the Voc under 1 sun (Voc(1)) and light intensity (X), as
shown in eq 15. Because the dominant charge recombination
mechanism is dependent on the carrier density in the active
layer, n varies as the irradiation intensity increases. At a low
carrier concentration, monomolecular recombination is dom-
inant (n = 2), while as the carrier concentration increases, the
dominant recombination process changes to bimolecular
radiative (n = 1) and Auger recombination (n < 1). While
eq 15 does not consider the resistance effect with the
assumption of low irradiation intensity, the effect of the
resistance becomes pronounced under a high irradiation
intensity and, thus, photocurrent density. As the current
density increases, the potential drop at the series resistance
originating from the selective contacts and electrode becomes
significant, which causes a deviation in the VOC, FF, and JSC
values from those in the ideal case.
The performance of PSCs under concentrated light has been
recently investigated.357,358 Wang et al. studied the perform-
ance evolution of a planar PSC based on FA0.83Cs0.17Pb2.7Br0.3
upon increasing the light irradiation intensity from 0.1 sun to
128 sun.337 Under 1 sun illumination, the device showed a
PCE of 21.1% (Jsc = 23.2 mA/cm2, Voc = 1.14 V, and FF =
0.80). Notably, with a linear increase in the Jsc, the Voc of the
device semilogarithmically increases to enhance the PCE up to
23.6% under 14 sun and 22.9% under 31 sun. The Voc reaches
1.26 V at 53 sun, while the FF starts to deteriorate when the
irradiation intensity exceeded 10 sun. Upon consideration of
the charge carrier recombination constant and consequent
estimation of the charge-carrier diffusion lengths in the
perovskite absorber under concentrated light, they suggested
that the decrease in the FF originates from the resistance in the
charge extraction layers, contact resistance between the
internal layers, or parasitic resistance in the fluorine-doped
tin oxide (FTO) electrode. According to their calculations, the
device performance should not be limited by charge-carrier
recombination up to 1000 sun, where the estimated charge
carrier diffusion lengths are still >1 μm. However, with the
development of appropriate contact layers and device
architectures, the enhancement in the photostability of
perovskite materials may be a prerequisite for their application
in concentrator solar cell applications.
4. SUMMARY
Because the development of solid-state PSCs in 2012, the PCE
of PSCs has presented an unprecedentedly rapid enhancement
from 9.7% to 25.2% in less than 10 years. The high
performance of these devices was found to be due to their
superior optoelectronic properties, such as high absorption
coefficient, long charge carrier lifetimes and diffusion lengths,
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Chemical Reviews
and high defect tolerance, which originate from the character-
istic chemical bonding nature, crystal structure, and resulting
electronic band structures of metal halide perovskite materials.
Many unique features of perovskites have also been studied
to explain the optoelectronic properties of perovskite materials
but still require further study to understand properties such as
Rashba splitting, large polaron formation, and GB effects. In
particular, understanding the nature of the defects in perovskite
materials appears to be key to further enhancing the
performance of PSCs. In terms of materials chemistry, the
composition of perovskite materials has evolved from simple
MAPbI3 to more complex mixed compositions or FA-based
perovskite materials. Recently, various organic cations have
also been developed to broaden the compositional window of
perovskite materials. However, most of these fundamental
studies have still focused on MAPbI3 and, therefore, further
studies on their extended systems will be required to design
more ideal perovskite materials. The development of various
process techniques has enabled the formation of high-quality
perovskite films with compact morphologies and low defect
densities. Control over the nucleation and growth has been
found to be critical toward the formation of uniform and highly
crystalline perovskite films, which has been enabled using
antisolvent-assisted one-step, two-step, and adduct methods.
However, the density of the defects in solution-processed films
is still high, and thus, the development of effective methods to
passivate the defects in the bulk and surface/GBs has been
essential to achieve high efficiencies of >20%. Understanding
the nature of the defects in state-of-the-art perovskite materials
will facilitate the development of effective strategies to
passivate detrimental defects. In full devices, the ETL and
HTL, and their interfaces with the perovskite layer, are equally
important to achieve high efficiency. Although various charge
transporting materials have been adopted in the device, a
mesoporous TiO2 or planar SnO2 layer for the ETL and spiro-
MeOTAD for the HTL are still widely used in high-efficiency
devices. Recently, interface engineering to improve the energy
level alignment and electrical coupling has also been actively
studied. Not only achieving high efficiency but also resolving
the stability issue is of critical importance to enable the
practical use of high-efficiency PSCs. All the issues covered in
this review, including the structural design, materials chemistry,
process engineering, and device physics, are closely related to
the operational stability of the device. While working toward
the enhancement of the efficiency of these devices, it is
necessary to simultaneously consider the durability of the PCE.
For example, the durability of defect passivation agents and
interface engineering layers under prolonged operational
conditions should be considered. Such an approach will
ultimately contribute to the development of commercially
viable perovskite photovoltaic devices.
The unique features of perovskite materials enable the use of
other approaches to further enhance the PCE toward and
beyond the Shockley−Queisser limit. Owing to the tunable
bandgap and low-temperature fabrication processes of PSCs,
their application as the top subcell in tandem devices is easily
achievable. At an initial stage, however, tandem devices were
not able to surpass the PCE of their corresponding single-
junction devices, but intense research efforts on the develop-
ment of interconnecting layers and high-bandgap perovskite
materials have allowed a rapid enhancement in the PCE to
reach 29.1% based on a perovskite/silicon tandem structure.
Furthermore, the development of low-bandgap perovskite
AO
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materials based on a Sn/Pb mixed composition has made it
possible to fabricate perovskite/perovskite tandem solar cells.
Adjusting the bandgap of these materials, while minimizing the
potential loss, will facilitate further enhancements in the PCE
to >30%. However, accurate measurement techniques used to
characterize tandem devices also need to be developed. To
reduce the thermalization loss, the possibility of utilizing hot
carriers has also been explored. While promising hot carrier
lifetimes have been observed, the design of the device used to
extract the hot carriers is still challenging. The photon
recycling effect is another approach used to reduce the
potential loss due to charge recombination; however, there still
persists an active debate on the occurrence of the photon
recycling effect in PSCs. Recently, PSCs have also been tested
under concentrated sunlight, where an enhancement in the
PCE was observed. However, an improvement in the
photostability of perovskite materials seems to be a
prerequisite for application in concentrator solar cell
applications.
AUTHOR INFORMATION
Corresponding Authors
Nam-Gyu Park − School of Chemical Engineering,
Sungkyunkwan University, Suwon 16419, Republic of Korea;
orcid.org/0000-0003-2368-6300; Phone: 821095841386;
Email: npark@skku.edu
Hyun Suk Jung − School of Advanced Materials Science and
Engineering, Sungkyunkwan University, Suwon 16419, Republic
of Korea; orcid.org/0000-0002-7803-6930;
Email: hsjung1@skku.edu
Hyunjung Shin − Department of Energy Science, Sungkyunkwan
University, Suwon 16419, Republic of Korea; orcid.org/
0000-0003-1284-9098; Email: hshin@skku.edu
Authors
Jin Young Kim − Department of Materials Science and
Engineering, Seoul National University, Seoul 08826, Republic
of Korea; orcid.org/0000-0001-7746-9972
Jin-Wook Lee − SKKU Advanced Institute of Nanotechnology
(SAINT) and Department of Nanoengineering, Sungkyunkwan
University, Suwon 16419, Republic of Korea
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.chemrev.0c00107
Author Contributions
J. Y. K. and J.-W.L. contributed equally to this work.
Notes
The authors declare no competing financial interest.
Biographies
Jin Young Kim is an Associate Professor in the Department of
Materials Science and Engineering at Seoul National University
(SNU), Korea. He received his B.S. (2000), M.S. (2002), and Ph.D.
(2006) in Materials Science at Seoul National University. Before
joining SNU, he worked at the National Renewable Energy
Laboratory (NREL), USA (2007−2011), and Korea Institute of
Science and Technology (KIST), Korea (2011−2015), on next-
generation thin film solar cells. His current research interests include
the fabrication of nanostructured electrodes via various approaches
including electrochemical approaches and their applications in solar
energy utilization including thin-film solar cells (e.g., CIGS, CZTS,
https://dx.doi.org/10.1021/acs.chemrev.0c00107
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews
perovskite, and tandem solar cells) and solar fuel generation (e.g., H2
production and CO2 reduction).
Jin-Wook Lee is an Assistant Professor at Sungkyunkwan University
(SKKU) Advanced Institute of Nanotechnology (SAINT) and
Department of Nanoengineering. He received his B.S. in Electronic
and Electrical Engineering and Ph.D. in Energy Science from SKKU
in 2011 and 2016, respectively. From 2016 to 2019, he worked as a
Postdoctoral Researcher at the University of California at Los Angeles
(UCLA) before joining SKKU as an Assistant Professor in 2019. His
research has been focused on the development of highly efficient and
stable perovskite optoelectronics (solar cells, light emitting diodes,
and photodetectors) based on material design, crystal growth, and
defect engineering.
Hyun Suk Jung is a SKKU Young Fellow Professor at the School of
Advanced Materials Science and Engineering, Sungkyunkwan
University (SKKU). He received his B.S., M.S., and Ph.D. in
Materials Science and Engineering from Seoul National University
(SNU) in 1997, 1999, and 2004, respectively. He joined Los Alamos
National Laboratory (LANL) as a Director’s Postdoctoral Fellow in
2005. He has published over 200 peer-reviewed papers and holds
more than 50 patents on the synthesis of inorganic nanomaterials and
solar energy conversion devices such as photovoltaic and photo-
electrochemical devices. His current research interests include
perovskite solar cells and flexible solar cells.
Hyunjung Shin is currently a Professor in the Department of Energy
Science at Sungkyunkwan University (SKKU), Korea. He received his
B.S. degree at YonSei University, Korea in 1991. He then received his
M.S. and Ph.D. at Case Western Reserve University, Cleveland, Ohio,
in 1994 and 1996, respectively. He was an Alexander von Humboldt
Research Fellow at the Max-Planck-Institut für Metallforschung in
Stuttgart, Germany (1996−1997). He started his professional career
as a Member of Research Staff in Samsung Advanced Institute of
Technology, Suwon, Korea (1997−2002), and as an Assistant,
Associated, and Full Professor at Kookmin University, Seoul, Korea
(2002−2012). He moved to SKKU in 2012 as a Tenured Full
Professor. His research interests include renewable energy conversion
and storage devices.
Nam-Gyu Park is a Professor and SKKU-Fellow at the School of
Chemical Engineering, Sungkyunkwan University (SKKU). He
received his B.S., M.S., and Ph.D. degrees from Seoul National
University (SNU) in 1988, 1992, and 1995, respectively. He worked
at ICMCB-CNRS, France, and National Renewable Energy
Laboratory (NREL), USA, from 1996 to 1999 as a Postdoctoral
Researcher. He worked as the Director of Solar Cell Research Center
at the Korea Institute of Science and Technology (KIST) in Korea
before joining SKKU as a Full Professor in 2009. He is the pioneer of
the solid-state perovskite solar cell, discovered in 2012. He received
the Clarivate Citation Laureates in Chemistry in 2017 and was
selected as a Highly Cited Researcher in 2017, 2018, and 2019.
ACKNOWLEDGMENTS
This work was supported by National Research Foundation of
Korea (NRF) grants funded by the Ministry of Science, ICT
Future Planning (MSIP) of Korea under contracts NRF-
2012M3A6A7054861 (Global Frontier R&D Program on
Center for Multiscale Energy System), NRF-
2016M3D1A1027663 and NRF-2016M3D1A1027664 (Future
Materials Discovery Program), and NRF-2015M1A2A2053004
(Climate Change Management Program). J.Y.K. is grateful for
the financial support from the Korea Institute of Energy
Technology Evaluation and Planning (KETEP) and Research
AP
pubs.acs.org/CR Review
Institute of Advanced Materials (RIAM) under contract no.
20193091010310. H.S.J. and H.S. are grateful to the MISP for
financial support under contracts NRF-2019M3D1A2104108
and NRF-2019R1A2C3009157.
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