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Materials Chemistry A
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Fundamental physics behind high-efficiency

organo-metal halide perovskite solar cells
Cite this: J. Mater. Chem. A, 2015, 3,
15372
Yu-Che Hsiao, Ting Wu, Mingxing Li, Qing Liu, Wei Qin and Bin Hu*
Published on 12 May 2015. Downloaded by Fudan University on 13/01/2017 09:44:25.

Received 20th February 2015
Accepted 9th May 2015
DOI: 10.1039/c5ta01376c
www.rsc.org/MaterialsA
Organo-metal halide perovskite solar cells have shown remarkable progress in power conversion
efficiencies in the past five years due to some amazing intrinsic properties such as long-range ambipolar
transport characteristics, high dielectric constants, low exciton binding energies, and intrinsic
ferroelectric polarizations. This review article discusses recent results with the focus on fundamental
physics involved in internal photovoltaic processes in perovskite solar cells. The discussion includes
charge transport, photoexcited carriers versus excitons, exciton binding energies, ferroelectric
properties, and magnetic field effects. The objective of this review article is to provide the critical
understanding for materials synthesis and device engineering to further advance photovoltaic actions in
the state-of-the-art organo-metal halide perovskite solar cells.

organo-metal halide perovskites to perovskites. In 2009, the rst

1. Introduction
In the effort of developing a new-generation organic photovol-
taic (PV) cells, organic bulk-heterojunctions (OBHs) and dye
sensitized solar cells (DSSCs) have become an interesting
component with unique facile property-tuning features.
However, the power conversion efficiencies (PCEs) of both
OBHs and DSSCs are largely behind the silicon-based PVs due to
still limited optical absorption and lower carrier mobility. As a
result, new-generation solar cells with higher PCEs have been
pursued for the past decades. Recently, organo-metal halide
perovskites have become extremely attractive photovoltaic
materials to develop new-generation solar cells. Here, we refer
Department of Materials Science and Engineering, University of Tennessee, Knoxville,
37996, Tennessee, USA. E-mail: bhu@utk.edu
perovskite solar cell with a PCE of 3.81% was reported by
Miyasaka et al.1 Two years later, Park et al. further enhanced the
PCE to 6.5%.2 Until 2012, high-efficiency perovskite solar cells
were demonstrated by Snaith et al. with the PCE reaching
10.9%.3 During the past three years, the PCEs of perovskite solar
cells have shown an amazing growth from 10.9% to 20.1%.4
Clearly, the perovskites provide a unique platform to explore
new-generation photovoltaic systems with superior device
performance.
In general, organo-metal halide perovskites can be described
by chemical formula ABX3, where the A, B and X sites are
occupied by an organic cation, metal cation and halide anion,
respectively (Fig. 1). The organic and inorganic components are
responsible for ferroelectric and semiconducting properties,
respectively. We should note that methylammonium lead

Yu-Che Hsiao is currently Ting Wu is currently pursuing

pursuing his PhD under the her PhD under the supervision of
supervision of Prof. Bin Hu in Prof. Bin Hu in the Department
the Department of Material of Material Science and Engi-
Science and Engineering at the neering at the University of
University of Tennessee, Knox- Tennessee, Knoxville, USA. She
ville, USA. He obtained an MS received her BS in polymer
degree in the Department of science (2009) and MS in mate-
Photonics at National Cheng- rials science (2012) at Sichuan
Kung University, Tainan, Tai- University, China. Her current
wan in 2009. His current research interests focus on
research focuses on organic materials processing, device
photovoltaic device engineering engineering and fundamental
and spin-dependent optoelectronic processes in organic semicon- physics in perovskite solar cells.
ducting materials and organo-metal halide perovskite materials.

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Review
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Fig. 1 Schematic crystal structure of organo-metal halide perovskites.
trihalide perovskites (CH3NH3PbX3, X ¼ Cl, Br or I) have shown
great merits for PV application among other members in the
perovskites family.5–9 In addition, the diverse choices of either
Mingxing Li is currently
pursuing his PhD under the
supervision of Prof. Bin Hu in
the Department of Materials
Science of Engineering at the
University of Tennessee, Knox-
ville, USA. He obtained his BS in
Physics and M.S. in Condensed
Matter Physics from Shandong
University, Jinan, China, in
2008 and 2011, respectively. His
current research interests
concern magnetically control-
lable spin-dependent electronic, optical, and optoelectronic
processes in organic semiconducting.
Qing Liu is currently pursuing
her PhD under the supervision of
Prof. Bin Hu in the Department
of Materials Science of Engi-
neering at the University of
Tennessee, Knoxville, USA. She
received her BS and MS in
Polymer Chemistry and Mate-
rials Science and Engineering
from Shanghai Jiaotong Univer-
sity in 2008 and 2011, respec-
tively. She is currently working
on the fundamental study of
thermoelectric effects based on organic polymer materials and
organic/inorganic hybrid structures.
This journal is © The Royal Society of Chemistry 2015
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Journal of Materials Chemistry A
organic cation or halide anion enables development of a series
of perovskites for enhancing PV actions,10–12 light emission,13–16
lasing actions,17–19 and spintronics.20 With the concern of the
toxicity of lead, lead-free perovskites have been developed, such
as tin halide perovskites.21–26
Recently, PCEs of perovskite solar cells have been quickly
increased from 3% up to 20.1% through materials processing
and device engineering efforts.1–5 However, the fundamental
physics involved in internal photovoltaic processes still demand
further investigations to gain in-depth understanding toward
further advancement in light-electricity conversion efficiencies.
In general, the perovskites can demonstrate remarkable long-
range ambipolar charge transport characteristics,27 high dielec-
tric constants,28,29 low exciton binding energies,30,31 intrinsic
ferroelectric polarizations,32,33 and spin-dependent responses.34,35
Clearly, these intrinsic photophysics and spinphysics properties
indicate that perovskites are the most promising candidates for
developing the next-generation PV cells.
In this review article, we focus on the fundamental photo-
physics and spinphysics involved in perovskite solar cells. In
Wei Qin obtained his BS in
physics (2007) and PhD (2013)
from Shandong University.
Then, he joined the University of
Kansas as a postdoc from 2013
to 2015. Since January 2015, he
has joined Prof. Bin Hu's group,
at the University of Tennessee,
as a postdoc. His research
interests focus on design and
self-assembly of organic nano-
materials, organic magneto-
electronic coupling effect of
organic charge-transfer complexes
and perovskite solar cells.
Professor Bin Hu received his
PhD from the Chinese Academy
of Sciences under the supervi-
sion of Professor Xurong Xu in
1991. He then worked as a
postdoc at the Institute of
Molecular Spectroscopy – CNR,
Bologna, Italy with Professor
Carlo Taliani, and as research
scientist at the University of
Massachusetts/Amherst with
Professor Frank Karasz. In 2002,
he joined the faculty in the
Department of Materials Science and Engineering at the University
of Tennessee, Knoxville. His research includes spin-dependent
processes in excited states, magneto-optic studies on photovoltaic
and thermoelectric processes at different length scales, and lasing
actions in ferroelectrically semiconducting materials.
J. Mater. Chem. A, 2015, 3, 15372–15385 | 15373

Journal of Materials Chemistry A
Section 2, we summarize the key parameters and effective
methods that control and enable further improvements to
charge transport properties. First, the long-range ambipolar
transport properties are discussed. Second, several methods are
reviewed for further improving transport properties, including
sophisticated chloride doping, morphological development,
electrode interface engineering, and single crystal growth. In
Section 3, we review the recent studies on the formation
processes of photoexcited states towards in-depth under-
standing on the photophysics behind perovskite PV cells. In
particular, excitation-intensity dependent and excitation-wave-
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length dependent branching ratios between free charge carriers
and excitons are discussed. In Section 4, we discuss the key
parameters that are related to exciton binding energies in
perovskite solar cells. In this section, we review three
approaches from recent experimental studies in controlling the
exciton binding energies in perovskite solar cells. In Section 5,
we summarize both the theoretical and experimental studies on
the ferroelectric properties in perovskites. In particular, the
discussion focuses on recent studies of ferroelectric properties
in developing photovoltaic actions under device-operating
conditions. In Section 6, the spinphysics are reviewed for
perovskites. We discuss a recently observed new phenomena:
magnetic eld effects (MFEs). The purpose is to use the MFEs as
a new experimental method to reveal internal useful and non-
useful photovoltaic processes in perovskite solar cells.
2. Superior charge transport
properties
To date, methylammonium lead triiodide perovskite (CH3-
NH3PbI3) and its mixed iodide-chloride analogue (CH3NH3-
PbI3xClx) are considered as most promising candidates for
developing high-efficiency PV cells.36–41 They have demonstrated
superior charge transport properties with ambipolar charac-
teristics. In addition, recent studies have shown that charge
transport properties can be further improved through sophis-
ticated chloride doping, morphological development, electrode-
interface engineering, and single crystal growth.
2.1 Long-range ambipolar charge transport
Ambipolar charge transport. It has been found that perov-
skites have well-balanced electron and hole transports, namely
ambipolar transport properties, based on experimental studies
from time of ight (ToF),42,43 electron beam induced current
(EBIC),44 and thin lm transistors (TFTs)27 measurements. It is
known that most semiconductors oen have unbalanced
transport properties between electrons and holes with different
effective masses (m*e and m*h). However, the rst principle
calculation indicates that the electron effective mass (m*e ¼
0.23m0) is considerably balanced with hole effective mass (m*h ¼
0.29m0) in perovskites.45 This can result in greatly balanced
ambipolar transport properties.46 Balanced ambipolar transport
can affect bulk polarization during charge transport and
collection, consequently changing short-circuit current (Jsc),
open-circuit voltage (Voc), and ll factor (FF) in perovskite solar
15374 | J. Mater. Chem. A, 2015, 3, 15372–15385
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cells. Therefore, ambipolar charge transport is an important
parameter in developing high-efficiency PV materials. It should
be noted that perovskites can demonstrate dual n-type and
p-type properties used in thin-lm devices with different inter-
facial layers.27 It is still a challenging issue to in situ characterize
ambipolar transport properties in thin-lm perovskite solar
cells under device-operating conditions.
Long carrier diffusion lengths. Long carrier diffusion lengths
were demonstrated in solution processed polycrystalline CH3-
NH3PbI3 (100 nm) and CH3NH3PbI3xClx (1 mm).46,47 These
values are dramatically larger than the diffusion lengths in
organic semiconductors (10 nm).47 Normally, short diffusion
lengths can cause severe charge recombination and less charge
collection, leading to poor photovoltaic actions. It is known that
the diffusion length (LD) is essentially determined by the carrier
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
lifetime (s) and mobility (m) according to LD ¼ ðkB Tms=eÞ,
where kB, T and e are the Boltzman constant, temperature and
elementary charge, respectively. All of these parameters are
sensitive to crystallinity, domain size, and defects in the
perovskites.
Predominant p-type character in CH3NH3PbI3. Although
perovskites present ambipolar transport characteristics, CH3-
NH3PbI3 can function as a hole-transporting material towards
developing hole-conductor free solar cells. Etgar et al. reported
for the rst time that a hole-conductor free Au/CH3NH3PbI3/
TiO2 heterojunction solar cell exhibits a PCE of 5.5%.48 Later on,
Laban et al. observed a depletion area between CH3NH3PbI3 and
TiO2, forming a “p–n” like junction, as shown in Fig. 2.49 Clearly,
CH3NH3PbI3 can show p-type behavior due to energy alignment
and majority carriers of holes when the TiO2 interfacial layer is
used. Furthermore, Heo et al.27 measured the transport prop-
erties of CH3NH3PbI3 based on TFT devices. They conrmed
ambipolar characteristics with a predominantly p-type behavior
in CH3NH3PbI3.
2.2 Sophisticated chlorine doping effects
Recent studies have revealed that the CH3NH3PbI3xClx have
longer diffusion lengths as compared to the CH3NH3PbI3.50,51
This feature allows thicker CH3NH3PbI3xClx layers but thinner
Fig. 2 (a) Schematic illustration of a CH3NH3PbI3/TiO2 heterojunction
solar cell. (b) Energy level diagram of the discussed solar cell which
shows the charge separation process. Reprinted with permission from
ref. 49.
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CH3NH3PbI3 layers to fabricate planar heterojunction solar
cells. However, it is found that the introduction of chloride ions
does not change crystalline structures as well as band struc-
tures. Here, we should note that the CH3NH3PbI3xClx
precursor solution is typically prepared by blending CH3NH3I
and PbCl2 with a molar ratio of 3 : 1. Surprisingly, only a small
amount of chloride ions (<5%) can remain in the solution-
processed thin lm. By using angle-resolved X-ray photoelec-
tron spectroscopy and density functional theory modeling,
Colella, et al. have shown that the small amount of chloride ions
is preferentially located in close proximity to the perovskite/
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TiO2 interface.52 It is further found that no chloride ions can be
detected in the perovskite crystals.53,54 As a result, deeper efforts
are needed to explore key functions of chloride ions in perov-
skite solar cells.
Predominant n-type character in CH3NH3PbI3xClx. Lee
et al.3 reported that photovoltaic performance in the CH3NH3-
PbI3xClx based solar cells can be improved by replacing mes-
oporous TiO2 with insulating Al2O3, which indicates that
electron transport can be faster through the CH3NH3PbI3xClx
itself than mesoporous TiO2. Clearly, CH3NH3PbI3xClx can
function as an n-type semiconductor. Meanwhile, You et al.55
observed that the energy difference between the Fermi level and
the valence band edge is about 1.1 eV as compared to the
bandgap of 1.5 eV in the CH3NH3PbI3xClx. This nding
conrms that CH3NH3PbI3xClx can act as an n-type
semiconductor.
Improved crystallization in CH3NH3PbI3xClx. Recent
studies indicated that introduced chloride ions can modify the
crystallization process for increasing crystallinity, improving
lm coverage, and enlarging domain size. Yu et al.51 showed
that chloride ions can reduce the density of CH3NH3+ by
removing the by-product (CH3NH3Cl) during formation of
Fig. 3 Cross-sectional SEM images of (a) thermally annealed (TA) and (b) solvent annealed (SA) perovskite films. (c) Photocurrent decay from TA
and SA perovskite solar cells. Reprinted with permission from ref. 62. (d) Average overall PCE (left) and Jsc (right) as a function of crystalline grain
size. Gray area represents the range of PCE values obtained using the conventional post-annealing processes. (e) With all other parameters
characterized and/or obtained from the literature, the PCE values appear to be correlated to bulk mobility of the absorber (labels correspond to
the average grain size). Reprinted with permission from ref. 63.
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Journal of Materials Chemistry A
perovskite polycrystals. The reduced CH3NH3+ can lead to a
higher order of crystallinity. More recently, Tidhar et al.56
revealed that adding inactive PbCl2 in a perovskite precursor
solution forms heterogeneous nanocrystals which act as a
nucleation center to develop perovskite crystals in solution.
Thermal annealing can be used to remove residual CH3NH3Cl
in perovskite crystals, which can coalesce the dispersed perov-
skite crystals to form larger grain size and well orientated
crystalline domains. Williams et al.57 demonstrated that chlo-
ride ions can enhance the formation rate of a CH3NH3PbCl3
intermediate product. Here, this intermediate product can work
as a nucleation template to grow larger-size polycrystalline
domains, and hence lead to better surface coverage and higher
photovoltaic performance. Clearly, the high crystallinity, larger
domains, and better lm quality induced by chloride ions can
lead to strong light absorption and charge transport towards
generating high PCEs in perovskite solar cells.
2.3 Morphological development
Morphological structures can be conveniently tuned by
controlling materials processing conditions.40,58 In general, the
morphological structures, such as crystalline shape, grain sizes,
grain boundaries and surface areas, can dramatically affect
charge recombination, transport, and collection in bulk perov-
skites during the development of photovoltaic actions.
Grain size effects. CH3NH3PbI3 is likely to form cuboid
polycrystals through either two-step solution processing or a
vapor deposition method.59–61 It is found that photovoltaic
performance signicantly relies on crystalline grain sizes.60,62
Xiao et al.62 demonstrated that the carrier diffusion length can
be increased to 1 micrometer through solvent annealing, which
enlarges the size of cuboids from 260 nm to 1 micrometer
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Fig. 4 Plane-view SEM images of CH3NH3PbI3 formed by a two-strep spin coating method using a solution of CH3NH3I in IPA (35 mg/5 mL) with
(a) 10 mL of DMF, (b) 50 mL of DMF, (c) 100 mL of DMF, and (d) without DMF. Scale bars represent 1 mm (200 nm in insets). (e) DC conductivity of the
in-plane perovskite by evaporating two gold contacts 0.14 mm apart onto a film. Reprinted with permission from ref. 60.

(Fig. 3a–c). Also, Nie et al.63 demonstrated a solution-based hot-
casting technique to grow continuous and pinhole-free thin
lms of perovskites with millimeter-scale crystalline grains,
which show a PCE of 18%. Fig. 3d and e illustrate that photo-
voltaic performance can be enhanced by increasing the grain
size. This is essentially correlated with improved charge carrier
mobility.
Low dimension effects. Recently, Im et al.60 prepared CH3-
NH3PbI3 nanowires-based solar cells with the best PCE of
14.71% by using a modied two-step spin coating method
(Fig. 4a–d). Meanwhile, they demonstrated that in-plane low-
dimensional nanowires can exhibit better transport properties
than three-dimensional (3D) nanocuboid polycrystals (Fig. 4e).
It is noted that the carrier transport in 3D perovskite thin lms
may be limited by random walks through grain boundaries in
nano-crystalline systems.64
2.4 Electrode interface engineering
Photovoltaic action in perovskite solar cells heavily relies on
electrode interfaces which are controlled by an electron trans-
port layer (ETL) and a hole transport layer (HTL). In general, the
electrode interlayers can largely affect the charge transport
through a built-in eld required to dri photogenerated carriers
under device-operating conditions. You et al.55 studied the
electrode-interface effects on charge transport properties in
polycrystalline CH3NH3PbI3xClx by using steady-state
photoluminescence (PL) and time-resolved PL (TRPL). They
observed signicant quenching on both PL intensity and PL
lifetime when the CH3NH3PbI3xClx layer is in contact with
either the PEDOT:PSS or the PCBM layers (Fig. 5). These results
indicate that the electrode interlayer can affect bulk dissocia-
tion and recombination through a built-in eld that drives the
photogenerated carriers to the respective electrodes. Further-
more, it has been proposed that the ambipolar charge transport
characteristics allow perovskites to act as both n- and p-type
conductors, depending on the type of junction formed with the
neighboring semiconductor.27 Therefore, the charge carriers
can be transferred at both the ETL/perovskites and perovskites/
HTL interfaces.
2.5 Single crystal growth
In general, perovskites can be prepared in polycrystalline and
single-crystalline forms. Polycrystalline perovskite lms inevi-
tably exist with defects. There are two main types of defects: (i)
point defects, exist with intrinsic doping to determine the n- or
p-type characters and (ii) grain boundaries, which act as trap
states or recombination centers. Normally, the trap states are
too shallow to create in-gap states.65,66 Therefore, trap-assisted
recombination due to in-gap deep states can be extremely
suppressed in perovskite lms. Perovskite single crystals have
demonstrated interesting optic and electric properties with
trap-free high quality lms (Fig. 6a and b).42,43,67 As shown in

Fig. 5 (a) Steady-state PL spectra and (b) time-resolved PL from CH3NH3PbI3xClx single layer, PEDOT:PSS/CH3NH3PbI3xClx, CH3NH3-
PbI3xClx/PCBM, and PEDOT:PSS/CH3NH3PbI3xClx/PCBM. Reprinted with permission from ref. 55.

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Fig. 6 Photograph of CH3NH3PbI3 single crystals prepared by (a) A. Poglitsch and D. Weber's method and (b) anti-solvent vapor assisted
crystallization. (c) Steady-state absorbance and photoluminescence of a CH3NH3PbI3 single crystal. (d) Current–voltage traces and trap density
characteristics of a CH3NH3PbI3 single crystal. Reprinted with permission from ref. 42 and 43.
Fig. 6c, CH3NH3PbI3 single crystals present a sharp band-edge
absorption and narrow PL spectrum with respect to poly-
crystalline thin lms. This indicates that the single crystals
possess exceptionally low trap-state densities, which are on the
order of 1010 cm3 (Fig. 6d). Most importantly, the extremely low
trap-states enable crystal growth with much higher long-range
structural ordering, and hence dramatically improving the
carrier mobility. Shi42 and Dong43 reported extremely long
diffusion lengths up to 10 micrometers and 175 micrometers in
large-size crystals, respectively. Moreover, Dong et al. also
demonstrated that the long diffusion lengths enable use of
CH3NH3PbI3 in radiation sensing devices through gamma-
voltaic effect with an efficiency of 3.9% measured with an
intense cesium-137 source. These ndings pave the way for
extending the applications of perovskite single crystals to other
optoelectronic devices in the future.
3. Dual photoexcited states: carriers
versus excitons
Photoexcited states in organo-metal halide perovskites have
been signicantly studied since 1990s. Hirasawa, et al.
demonstrated that the photoexcited states are Wannier-type
excitons with large radii.30 These Wannier-type excitons have
low binding energies ranging from 20 meV to 98 meV.30,31,39,68,69
In contrast, Frenkel excitons in organic semiconductors have
much higher binding energies (>100 meV). Clearly, the low
binding energies can lead to a large amount of free charge
carriers through quick dissociation at room temperature.
However, recent studies have observed the presence of excitons
(or electron–hole pairs) in perovskite materials and perovskite
solar cells.34,35,70,71 These ndings raise an open question on the
branching ratio between free charge carriers and excitons that
determines the photovoltaic performance.
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Journal of Materials Chemistry A
Theoretically, a photoexcitation can excite the electrons from
a valence band to the conduction band, forming conduction
electrons when the photon energy exceeds the bandgap in
semiconductors. The conduction electrons can undergo two
processes: (i) transport towards generating free charge carriers
driven by a built-in eld and (ii) relaxation towards forming
excitons through a multiphoton process. As a consequence, the
carrier/exciton ratio can be largely affected by changing the
built-in eld and multiphoton process. Nevertheless, control-
ling the carrier/exciton ratio is a key procedure to improve
photovoltaic and light-emitting properties in perovskite lms.
3.1 Excitation intensity-dependent carrier/excitons ratio
D'Innocenzo et al.39 studied the carrier/exciton ratio (nfc/nex) as a
function of excitation intensity in CH3NH3PbI3xClx (Eb z 55 
20 meV) by combining temperature-dependent absorption with
theoretical modeling based on the Saha–Langmuir equation. As
shown in Fig. 7, the modeling based on the law of mass action
for Wannier–Mott excitons suggests that free charge carriers are
predominate (nfc/n z 1) in perovskite solar cells at room
temperature. This is because the perovskite solar cells possess
large built-in elds which can effectively dri photogenerated
carriers to respective electrodes to avoid charge recombination
aer quick dissociation of photogenerated excitons. Moreover,
D'Innocenzo et al. demonstrated that further increasing
photoexcitation density (n  1021 cm3) enables the formation
of excitons and consequently decreases the carrier/excitons
ratio (nfc/n  1). However, it is still unclear whether the excitons
are directly generated aer light absorption or recombined
from electron–hole pairs during charge recombination. Never-
theless, the formation of excitons at high excitation intensities
poses a serious challenge to develop concentrated perovskite
solar cells.
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Fig. 7 (a) Modeling of the fraction of free charges over the total density of states (nfc/n) at thermal equilibrium. (b) Simulation of the temperature
dependent fraction of free charges over the total photoexcitation. Reprinted with permission from ref. 39.

Fig. 8 (a) Transient PM spectra of a CH3NH3PbI3 thin film excited at 400 nm at ambient condition (the inset shows the absorption spectrum); (b)
decay dynamics of PB and PA1 bands up to 500 ps and 10 ps (inset); (c) transient PM spectra excited at 800 nm at ambient condition. Reprinted
with permission from ref. 70.

3.2 Excitation wavelength-dependent carrier/exciton ratio
CH3NH3PbI3 presents a broad absorption spectrum from the
ultraviolet regime to the near infrared regime. Therefore, the
wavelength-dependent carrier/exciton ratio becomes a critical
issue in developing photovoltaic actions. Sheng et al.70 studied
the carrier/excitons ratio (nfc/nex) in CH3NH3PbI3 lms with
both above-gap excitation and below-gap excitation through
polarized pump-probe photomodulation (PM) spectroscopy.
They detected both free charge carriers (PB and PA2, 1.65 eV)
and excitons (PA1, 0.8 eV) with above-gap excitation (400 nm)
(Fig. 8a). Those two species are found to present remarkably
different dynamics (Fig. 8b): excitons (PA1) are generated
instantaneously, whereas PB generation is delayed for 1 ps.
Furthermore, they found that only PB and PA2 bands (1.65 eV)
can be detected when the below-gap excitation (800 nm) is
applied, which indicates exciton generation is negligible in this
situation.
3.3 Coulomb-correlated electron–hole pairs
Whether photoexcited states can be considered as charge-
neutral excitons or ionized electron–hole pairs in ferroelectri-
cally semiconducting perovskites where both organic and
inorganic components co-exist has been an issue. Addressing
this critical issue is important for developing photovoltaic,
light-emitting, and lasing devices. Saba et al.71 observed that a
photoexcitation can generate conducting plasma under
different excitation intensities in perovskites. This experimental
observation indicates that photogenerated electrons and holes
can form coherent electron–hole pairs through non-geminate
recombination due to a Coulomb interaction. In general, the
electron–hole pairs can generate three different outcomes: (i)
dissociation into free carriers, (ii) spontaneous recombination,
and (iii) coherent recombination. Under the inuence of
intrinsic ferroelectric polarization, the electron–hole pairs can
be effectively dissociated into free carriers at low excitation
intensities due to their strong ionic properties and low binding
energies. However, at high excitation intensities, electron–hole
pairs can experience mutual Coulomb interactions, leading to
Coulomb-correlated electron–hole pairs. This can give rise to a
coherent light-emitting behavior with low threshold excitation
intensity in perovskites. Therefore, investigating the dynamic
behaviors of electron–hole pairs can deepen the understanding
to advance photovoltaic, light-emitting, and lasing actions in
perovskites.
3.4 Charge-transfer states
K. G. Stamplecoskie et al. observed a 480 nm band transition in
CH3NH3PbI3 in addition to a 760 nm band edge transition by
using a time-resolved absorption measurement (as shown in
Fig. 9).72 The two band transitions were initially assigned to two
valence bands (VB1 and VB2) and common conduction band
minimum (CB).73 However, the dual valence-band model cannot
account for the discrepancy in recovery kinetics at the two
spectral positions. With further studies they attributed the
760 nm and 480 nm transitions to charge separated states (free
charge carriers) and charge-transfer states, respectively.

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Fig. 9 (A) Transient absorption spectra recorded following 387 nm excitation of annealed CH3NH3PbI3 on a mesoporous alumina support at
various pump-probe delay times. (B) Difference absorption-time profiles recorded at 480 (blue trace), 600 (grey trace), and 760 nm (red trace).
Reprinted with permission from ref. 72.
Specically, the charge-transfer states are related to I2-like
species (CH3NH3PbI3 + hn / [CH3NH3PbI/I2]), which do not
present free carrier kinetics. Considering the nature of charge-
transfer states, the methylammonium ions are possibly aligned
under an external electric eld to further enhance photovoltaic
performance.74
4. Exciton binding energy in
perovskites
Exciton binding energy (Eb) is a key parameter to generate
photovoltaic actions in perovskite solar cells. The exciton
binding energy has been estimated by theoretical calculation,75
optical absorption,76 magneto-absorption,30 or temperature-
dependent PL.31,77 In the 1990s, theoretical studies reported the
exciton binding energy to be around 37 meV in CH3NH3PbI3.30
This low binding energy suggests that the excitons are Mott–
Wannier type with a Bohr radius of about 30 Å.30,76,78 It is noted
that the exciton binding energy in perovskites is much lower
than that in organic materials which is usually in the range of
0.2 eV to 1 eV.79 The low binding energy, together with long
diffusion length, can account for the high PECs in perovskite
solar cells. In contrast, organic solar cells require effective
donor: acceptor interfaces to dissociate the Frenkel excitons
with high binding energy into free charge carriers towards the
generation of photocurrent.80,81 Here, the large difference in
exciton binding energy between perovskites and organics can be
attributed to different dielectric constants. Recently, Hu et al.28
observed a high dielectric constant (32) in perovskites under
dark conditions. Furthermore, Juarez-Perez et al.29 showed that
the dielectric constant can be largely enhanced (1000) under
photoexcitation. More recently, Lin et al.75 found that this high
dielectric constant can lead to an ultralow binding energy
(<10 meV) in low light illumination. In contrast, organic mate-
rials only show a dielectric constant of about 3.82,83 The high and
low dielectric constants can lead to strong and weak dielectric
screening effects.84,85 Clearly, the dielectric constant is an
important parameter in controlling the binding energy towards
generation of photocurrent in solar cells. Alternatively, the
This journal is © The Royal Society of Chemistry 2015
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Journal of Materials Chemistry A
binding energy can be modied by local polarizations induced
by built-in elds, plasmonic effects, and doping. Recent studies
demonstrated that binding energy can be indeed changed by
using (i) different interfacial layers,86–88 (ii) plasmonic effects by
doping core–shell metal nanoparticles into perovskites,9 and
(iii) different halogen elements (I or Cl).14,89,90 These three
methods are discussed in the following sections.
4.1 Interfacial layer effects on binding energy
Interfacial layers play a crucial role in improving the PCEs of PV
cells.91,92 Recently, Wu et al.93 showed that interfacial layers can
affect exciton binding energy in organic solar cells by intro-
ducing strong interfacial dipoles between the interfacial layer
and organic active layer. The interfacial dipoles can modulate
the built-in eld across the photovoltaic layer and consequently
decreases the exciton binding energy. Similarly, we have
observed that perovskite lms with and without an interlayer
present different photoluminescence quenching as a function
of external reversed bias (as shown in Fig. 10). This experi-
mental observation shows that interfacial dipoles formed at a
perovskite/interlayer interface can also decrease the exciton
binding energy, leading to an enhanced charge dissociation in
perovskite solar cells. Roiati et al.87 discussed the observation
that interfacial dipoles can be formed when the perovskites
Fig. 10 (a) Photoluminescence as a function of excitation intensity
from a CH3NH3PbI3 single layer and CH3NH3PbI3/PCBM double layer
under the photoexcitation of a xenon lamp at 530 nm. (b) Photo-
luminescence change as a function of applied electric field for both
single-layer and double-layer devices under photoexcitation of a
xenon lamp at 530 nm.
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Fig. 11 (a) Schematics of calculated ground and excited state
permanent dipole moments at the interface of TiO2 and perovskites.
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Reprinted with permission from ref. 87. (b) Absorptance spectra of bulk
crystalline MAPbI3 (black), meso-MAPbI3 (blue), and mesoporous TiO2
(red) samples. Photoluminescence spectrum of meso-MAPbI3 (cyan).
Reprinted with permission from ref. 88.
active layer contacts with a metal oxide interfacial layer, as
shown in Fig. 11a. In this study, they used Stark spectroscopy to
conrm the oriented permanent dipoles formed at the interface
in perovskite solar cells. On the other hand, Choi et al.88 found
that the optical properties can be signicantly modulated when
a perovskite lm is prepared on a mesoporous titanium dioxide
(TiO2) layer. Fig. 11b shows that the absorption tail can be
signicantly changed by the TiO2 layer. This spectral change
can be attributed to the connement effects caused by nano-
scale grains in perovskite polycrystals. In addition, the spectral
shi in optical absorption induced by a TiO2 interfacial layer
suggests that the interfacial dipoles can affect the bandgap of
perovskite samples.
4.2 Plasmonic effects on exciton binding energy
Doping has been demonstrated as an effective approach to
enhance electrical conductivity94 and optical absorption in
organic materials.95 Recently, Zhang et al.31 found that doping
Au@SiO2 (a core–shell nano-particle) into mesoporous perov-
skite solar cells causes a decrease of exciton binding energy due
to the plasmonic effect. In addition, the plasmonic effect can
also inuence the dipole–dipole interaction between photoex-
cited states. Fig. 12a and b show the time-integrated PL as a
function of temperature for perovskite lms with and without
doping Au@SiO2 nanoparticles. Here, curve tting indicates
that doping with nanoparticles leads to a reduction of binding
energy from 98.0 meV to 34.3 meV. In addition, doping with
Au@SiO2 nanoparticles shows a higher PCE in the perovskite
solar cell (Fig. 12c).
4.3 Halogens effects on exciton binding energy
The exciton binding energies in CH3NH3PbI3 and CH3NH3-
PbI3xClx have been reported as 37–50 meV (ref. 30) and
98 meV,31 respectively. There are two possible mechanisms
accounting for controlling these exciton binding energies based
on halogen effects. First, using different halogen elements with
different ionic sizes can modulate the bandgap by shiing the
valence band to higher energy in the perovskites.89,90 Changing
the bandgap can consequently modify the exciton binding
15380 | J. Mater. Chem. A, 2015, 3, 15372–15385
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Review
Fig. 12 Time-integrated PL spectra as a function of temperature for
perovskite films on (a) Al2O3-only (control) and (b) Al2O3 films mixed
with Au@SiO2 NPs. (c) I–V curves of Al2O3 mesoporous perovskite
solar cells with and without doping Au@SiO2 nanoparticles, the
measurement is done under AM1.5 simulated sunlight (100 mW cm2
irradiance). Reprinted with permission from ref. 31.
energy by changing the Bohr radius. Second, different halogen
elements can cause different dielectric screening effects,
leading to changes in the binding energy. It should be noted
that additional studies are required to further clarify these two
possible mechanisms in order to understand the effects of
halogens on binding energy in perovskites.
5. Ferroelectric properties
Perovskites can be prepared in both polycrystalline and single
crystalline forms.22,42,43,96 In general, ferroelectric properties can
be theoretically expected due to the breaking of crystal center
symmetry caused by a structural transition from orthorhombic
phase to tetragonal phase.96,97 In particular, intrinsic ferroelec-
tric polarizations provide additional mechanisms to control key
photovoltaic parameters, including Jsc, Voc, and FF in perovskite
solar cells.
5.1 Theoretical calculations of ferroelectric properties
Computational studies involving electronic structure, ab initio
molecular dynamics, and density function theory have been
carried out to understand ferroelectric properties in perov-
skites.32,33,98 Organic CH3NH3+ molecules in perovskites are
apart with each other around 6 Å. Together with their large
permanent electric dipoles, the dipole–dipole interaction
energy has been estimated to be 25 meV.33 It should be noted
that this relatively low dipole–dipole interaction energy is
comparable to thermal energy at room temperature, therefore, a
complex ferroelectric behavior is expected by the rotation of
these dipoles. Frost et al.32 predicted a transition from an
antiferroelectric alignment of dipoles at low temperature to a
paraelectric alignment at high temperature by using Monte
Carlo simulations. More importantly, they also proposed an
equilibrium ferroelectric domain structure and polarizability
arising from CH3NH3+ molecular rotation in perovskites.
Furthermore, the ferroelectric domains are conjectured to vary
as a function of temperature and applied electric eld due to
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Fig. 13 AFM topography images (top row) and corresponding PFM
images of a single 2.5  2.5 mm2 area b-CH3NH3PbI3 thin film.
Reversible ferroelectric domain switching is observed. Reprinted with
permission from ref. 99.
rotation of the organic cations. As a consequence, it can be
theoretically expected that perovskites can exhibit intrinsic
ferroelectric properties.
5.2 Experimental results of ferroelectric properties
Recent works reported ferroelectricity in perovskites based on
direct or indirect experimental measurements. Kutes et al.
observed direct evidence for ferroelectric domains in b-CH3-
NH3PbI3 by using piezoforce microscopy (PFM).99 The ferro-
electric domains were determined to be  100 nm, which can be
reversely switched by a DC bias with b-CH3NH3PbI3 (Fig. 13).
Furthermore, Juarez-Perez et al. found an intrinsic giant
dielectric constant in the order of 30 ¼ 1000, which can be
further increased by a factor of 1000 under photoexcitation,
with CH3NH3PbI3xClx (Fig. 14).29 This giant dielectric constant
Fig. 14 Photo-induced increase of real permittivity from dark to 1 sun
for CH3NH3PbI3xClx perovskite. Inset, linear regression of dielectric
constant vs. illumination intensity at f ¼ 50 MHz. Reprinted with
permission from ref. 29.
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Journal of Materials Chemistry A
Fig. 15 Room temperature I–V characteristics of single-crystals of an
annealed pellet of CH3NH3PbI3 obtained from the grinding method
under dark conditions. Reprinted with permission from ref. 22.
corresponds to the modication of local unit cells mediated by
photo-induced carriers and the change of polarizations with the
assistance of organic cations rotations. Stoumpos et al.22
observed a non-ohmic hysteresis behavior from CH3NH3PbI3
upon changing the current polarity in dark conditions (Fig. 15).
The non-ohmic hysteretic behavior originates from the reor-
ientation of permanent dipoles of CH3NH3+ on application of
an external electric eld. Therefore, it is possible to align the
permanent dipoles in organic cations with an external electric
eld, leading to ferroelectric domains and ultimately the
ferroelectricity in perovskites. In addition, Xiao et al.100 reported
a switchable photocurrent by applying a low electric eld in
perovskite photovoltaic devices. This electric eld-switchable
photocurrent can be related to the ferroelectric properties in
perovskite solar cells. Consequently, the experimental studies
showed that the permanent dipoles from organic cations can be
conveniently modied by an external eld, such as photoexci-
tation or electric eld, and consequently lead to ferroelectric
properties in perovskites.
5.3 Tuning ferroelectric properties
In general, ferroelectric properties can be tuned by manipu-
lating organic cations in perovskites. Frost et al.32 predicted that
the molecular dipoles can be changed by using organic mole-
cules with different electronegativity, which can lead to
different polarizations in perovskites. Wu et al.101 found that
changing the organic molecular structure from CH3NH3+ to
NH2CHNH2+ can largely affect dielectric properties due to
different organic molecular dipoles. In addition, they also
indicated that changing the metal atoms from Pb to Sn can
inuence the dielectric properties because of different ionic
polarizabilities of Pb2+ and Sn2+. Clearly, ferroelectric properties
can be easily tuned by modifying the components due to
different dipole strengths.
5.4 Ferroelectric effects on photovoltaic actions
In general, ferroelectric polarization can affect charge transport,
recombination, and collection in the development of photo-
voltaic actions in solar cells. Frost et al.102 and Liu et al.32
reported that ferroelectric polarization can enhance charge
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Journal of Materials Chemistry A Review

separation and improve carrier lifetime due to transportation of

carriers through the “ferroelectric highways” established by
ferroelectric domains. Furthermore, Grinberg et al.103 observed
that the photovoltage can be larger than the bandgap in
perovskite oxides: [KNbO3]1x[BaNi1/2Nb1/2O3- d]x(KBNNO).
Clearly, ferroelectric polarization can function as a promising
mechanism to tune open-circuit voltage (Voc) by promoting
desirable charge dissociation in perovskite solar cells. In addi-
tion, perovskite solar cells can exhibit hysteresis phenomena in Fig. 16 (a) Scheme of tunability of recombination by magnetic field.
device performance which can be related to ferroelectric (b) Magnetic field dependent photocurrent and PL. Reprinted with
permission from ref. 35.
polarization, charge trapping, and moving ions during device
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operation.32,33,104,105 Nevertheless, we can see from recent studies

that ferroelectric polarization can play an important role in
developing advanced photovoltaic actions in perovskite solar
cells. In addition, it should be mentioned that ferroelectric
properties can present a potential application in spintronics.
Rashba effects have been theoretically predicted by considering
coexisted ferroelectric polarization and strong spin–orbital
coupling.106,107 This presents a new approach to develop spin-
tronics devices by using ferroelectrically semiconducting
perovskites. Clearly, perovskite solar cells can provide a plat-
form to explore new magneto-optic and magneto-electric
phenomena based on Rashba effects.

6. Magnetic field effects

In general, magnetic eld effects can provide unique experi-
mental measurements to reveal internal photovoltaic processes
in solar cells under device-operating conditions.108,109 Two
decades ago, Hirasawa et al.30 reported the rst magnetic eld
effects at low temperature (4.2 K) and high eld (>20 Tesla) in
CH3NH3PbI3. However, at room temperature and low eld it has
been a challenge to develop magnetic eld effects in perov-
skites. Recently, magnetic eld effects were shown at room
temperature and low eld (<200 mT) in photoluminescence and
photocurrent in perovskites, leading to magneto-photo-
luminescence and magneto-photocurrent.34,35 The experimental
studies proposed that the magnetic eld effects originate from
electron–hole pairs generated by photoexcitation or electrical
excitation. In principle, the electron–hole pairs are formed with
spin-antiparallel and spin-parallel states. Formation rates for
spin-antiparallel and spin-parallel states are essentially deter-
mined by spin-conserving, from spin-exchange interaction, and
spin mixing, from hyperne and spin–orbital coupling. Before
applying a magnetic eld, the competition between spin-
conserving and spin-mixing reaches an equilibrium, leading to
certain populations on spin-antiparallel and spin-parallel states
in electron–hole pairs. Applying a magnetic eld can disturb
spin-conserving and spin-mixing by introducing in-phase and
out-phase spin precessions, modifying the formation rates in
spin-antiparallel and spin-parallel states. When the electron–
hole pairs relax into excitons, modifying formation rates in
spin-antiparallel and spin-parallel states can change the pop-
ulations of singlet and triplet excitons, leading to a change on
photoluminescence intensity, namely magneto-photo-
luminescence (Fig. 16a). Simultaneously, this can change the
density of electron–hole pairs available for charge dissociation,
Fig. 17 Magneto-photocurrent excited at 3.1 eV. The blue line
through the data points is a Lorentzian function fit with HWHM (B1/2) as
indicated. Reprinted with permission from ref. 34.
generating a modication on photocurrent (Fig. 16a). As a
consequence, magneto-photocurrent can be observed in
perovskite solar cells. Clearly, recently observed magnetic eld
effects indicate that both photocurrent and photoluminescence
are a spin-dependent process. Therefore, manipulating spins
can provide a new approach to control photovoltaic and light-
emitting properties in perovskites.
In the recent studies on magnetic eld effects, Zhang et al.34
showed a negative magneto-photocurrent in perovskite solar
cells (Fig. 17). The observed magnetic eld effects were
described by a Dg mechanism. Due to the different g factors of
electron and hole,110,111 spin precessions can essentially change
the populations on spin-antiparallel and spin-parallel states in
electron–hole pairs. Furthermore, Hsiao et al. reported that, only
when photoexcitation exceeds critical intensity, negative
magneto-photoluminescence and positive magneto-photocur-
rent can be observed at room temperature and low eld
(<200 mT) in perovskite solar cells (Fig. 16b).35 Below the critical
excitation intensity, both magneto-photoluminescence and
magneto-photocurrent become negligible. This experimental
observation provided information to support the hypothesis that
the magnetic eld effects originate from electron–hole pairs.
However, further investigations are necessary to understand how
the spin-dependent electron–hole pairs are still operative in
perovskites where strong spin-orbital coupling exists.

15382 | J. Mater. Chem. A, 2015, 3, 15372–15385 This journal is © The Royal Society of Chemistry 2015

Review
Nevertheless, recent studies indicate that photovoltaic actions
and light emission are a spin-dependent process in perovskites.
7. Conclusions and prospects
In summary, this review article discussed the fundamental
physics involved in photovoltaic processes in perovskite solar
cells. The discussion focused on ambipolar transport charac-
teristics, photoexcited carriers versus excitons, exciton binding
energies, ferroelectric properties, and magnetic eld effects to
provide critical understanding for further advancing device
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performance in perovskite solar cells. In the rst section, we
reviewed ambipolar transport characteristics. In particular, the
ambipolar transport properties can lead to both n-type and
p-type behaviors, depending on differently selected interfacial
layers. In the second section, we discussed the dual types of
photoexcited states: photoexcited carriers versus photoexcited
excitons. The discussion focused on the effects of excitation
intensity and wavelength on the carrier/exciton ratio. In the
third section, we analyzed exciton binding energy in relation-
ship with dielectric constant, doping, halogen elements, and
interfacial layers. In the fourth section, we discussed ferro-
electric properties with a focus on theoretical and experimental
results. In the last section, we reviewed recent studies on
magnetic eld effects in perovskites. The discussion considered
two basic processes to generate magnetic eld effects by intro-
ducing (i) in-phase spin precessions and (ii) out-phase spin
precessions in electron–hole pairs. Clearly, magnetic eld
effects indicate that photovoltaic and light-emitting actions are
a spin-dependent process in perovskites. Overall, this review
article discussed the photophysics and spinphysics involved in
photovoltaic processes in perovskite solar cells.
Acknowledgements
This research was supported by the nancial supports from the
Air Force Office of Scientic Research (AFOSR) under the grant
number FA 9550-15-1-0064 and National Science Foundation
(CBET-1438181). The authors also acknowledge the support
from the Sustainable Energy Education and Research Center and
Center for Materials Processing at the University of Tennessee.
This research was partially conducted at the Center for Nano-
phase Materials Sciences based on user project (CNMS2012-106,
CNMS2012-107, CNMS-2012-108), which is sponsored at Oak
Ridge National Laboratory by the Division of Scientic User
Facilities, U.S. Department of Energy. The authors also
acknowledge the project support from National Signicant
Program of China (2014CB643506, 2013CB922104). The authors
also acknowledge the support from Tennessee Solar Conversion
and Storage using Outreach, Research and Education (TN-
SCORE) with a grant number of NSF EPS 1004083.
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