Advancement in Provskite Solar Cells

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Mathews, Energy Environ. Sci., 2014, DOI: 10.1039/C4EE00673A.
1

Advancements in Perovskite Solar Cells: Photophysics behind the Photovoltaics
Tze Chien Sum
1
* and Nripan Mathews
2,3,4
*

1
Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang
Technological University, 21 Nanyang Link, Singapore 637371.
2
School of Materials Science and Engineering, Nanyang Technological University, Nanyang Avenue,
Singapore 639798.
3
Energy Research Institute @NTU (ERI@N), Research Techno Plaza, X-Frontier Block, Level 5, 50
Nanyang Drive, Singapore 637553.
4
Singapore-Berkeley Research Initiative for Sustainable Energy, 1 Create Way, Singapore 138602,
Singapore.

*Correspondence to: Tzechien@ntu.edu.sg; Nripan@ntu.edu.sg

Page 1 of 34 Energy & Environmental Science
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Abstract
Solution-processed organic-inorganic perovskite solar cells are hailed as the recent major
breakthrough in low-cost photovoltaics. Power conversion efficiencies approaching that of
crystalline Si solar cells (exceeding 15%) have been reported. Remarkably, such phenomenal
performances were achieved in a matter of 5 years up from ~3.8% back in 2009. Since then,
the field has expanded exponentially. In this perspective, we review the basic working
mechanisms of perovskite solar cells in relation to their intrinsic properties and fundamental
photophysics. The current state-of-the-art and the open questions in this maturing field are also
highlighted.

Keywords: Perovskite Solar Cells, Organic-inorganic lead halides; device performance; charge
dynamics and photophysics

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1. Introduction
Solar power is the world's most abundant energy resource. A year's worth of sunlight contains 1.5
10
18
kWh of energy. By comparison, the known reserves of oil, coal, and gas are 1.75 10
15
kWh, 1.4
10
15
kWh, and 5:5 10
15
kWh, respectively. Thus, a years worth of sunlight provides more than a
hundred times the energy of the world's entire known fossil fuel reserves. Harnessing solar power would
yield a never-ending energy supply.
1
The difficulty has always been converting solar energy in an
efficient and cost-effective way. Photovoltaic cells are the most promising avenue, directly converting the
photons to electricity. For photovoltaic energy to become competitive with fossil fuels and capture a
significant share of the electricity market, it is necessary to reduce the total cost of solar energy. This can
be achieved by either reducing the cost of photovoltaic cells or by increasing their power conversion
efficiency.

The photovoltaic market is currently dominated by crystalline Si solar cells with efficiencies
close to 20%. Alternative third generation technologies such as organic photovoltaics (OPVs), dye
sensitized solar cells (DSCs) and quantum dot solar cells (QDSCs) which are fabricated through solution
based processes such as blade coating, screen printing and spraying, promise low cost solar power while
allowing the utilization of unconventional substrates. Although the utilization of low temperature
processes reduces the energetic costs and the energy payback time, the power conversion efficiencies
(PCEs) of these solar cells still lag significantly behind conventional solar cells. The levelized cost of
energy (LCOE) which allows for the comparison of various electricity generation sources, depends
critically on the efficiency of the solar cells produced.
2
A more efficient module yields more power per
unit area. A significant fraction of a solar cell's cost scales proportional to the installation area, including
the cost of the glass, inverter costs and installation costs, among others. A more efficient solar cell allows
for a reduction in all the costs associated with installation, while requiring much lower numbers of solar
panels to be installed. Thus power conversion efficiency is a primary driver of cost for solar cells.

Organic-inorganic halide perovskite solar cells has been the most significant development in the
field of photovoltaics in the present decade and is the best bet at satisfying the need for high efficiencies
while allowing for low cost solution based manufacturing. Since the first reports of stable solid state solar
cells based on CH
3
NH
3
PbI
3
perovskite in mid-2012, the PCEs of the solar cells have already exceeded
15%, leapfrogging every other solution-processed solar cell technology. The wide range of efficient
perovskite solar cell device architectures demonstrated point towards a remarkable semiconducting
material with excellent electrical and optical properties. Early pioneering work
3, 4
in the area of organic-
inorganic halides has clearly shown that this class of materials can behave as low dimensional electronic
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systems with tunable properties, allowing for the development of newer perovskite solar materials in
addition to CH
3
NH
3
PbI
3
.

This review focuses on the recent developments (i.e., up to Feb 2014) in perovskite solar cells as
well as their photophysical properties and charge dynamics. We first review the intrinsic physical and
electronic properties of this class of organic-inorganic perovskites, followed by its progress as a
photovoltaic material. The review then examines the recent photophysical studies on unraveling the
charge dynamics and transport mechanisms in both perovskite thin films as well as in perovskite solar
cells. Due to the rapid pace of research in this area, this review does not aim to be comprehensive but will
highlight key work and findings. Lastly, we conclude the review with the open questions facing these
classes of solar cells and future directions of research.

2. Intrinsic Properties of Organic-Inorganic Perovskites

(a) Physical Structure
Perovskites is a common nomenclature for compounds with the generic chemical formula of
AMX
3
. In the cubic unit cell, the A-cation resides at the eight corners of the cube, while the M-cation is
located at the body center that is surrounded by 6 X-anions (located at the face centers) in an octahedral
[MX
6
]
4-
cluster. Typical inorganic perovskites include CaTiO
3
and SrTiO
3
. Due to the interplay of the
charge, spin and structural properties, this family of materials is known to exhibit a plethora of novel and
exciting phenomena such as superconductivity, magnetoresistance, ferroelectricity, magnetoelectricity,
anti-ferromagnetism, anti-ferroelectricity etc.
5
In the classes of compounds being discussed here, the A
cations are organic (typically CH
3
NH
3
+
,C
2
H
5
NH
3
+
, HC(NH
2
)
2
+
), the metal cations (M) are typically
divalent metal ions such as Pb
2+
, Sn
2+
, Eu
2+
, Cu
2+
etc, while the X anions are halides (Cl
-
, Br
-
, I
-
).
CH
3
NH
3
PbI
3
belongs to a large family of organic-inorganic perovskites where the [PbI
6
]
4-
octahedral can
form 3-D, two-dimensional (2-D), one-dimensional (1-D) or zero-dimensional (0-D) networks, possessing
the same unit structure Figure 1. The absence of any inhomogenous broadening (arising from size
distribution of the samples) in these 3-D and their low-dimensional counterparts makes these compounds
ideal for investigating quantum confinement effects in semiconductor mesoscopic structures. Pioneering
work in this class of compounds began as early as 1989 where the focus was on the effects of
dimensionality on the excitonic, optical and electronic properties.
4, 6, 7
The optoelectronic properties of
layered organic-inorganic perovskites were also extensively studied because of the novel properties
exhibited by these crystals which include: high mobilities for thin-film transistors
8, 9
; strong excitonic
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properties for light emitting diodes
10, 11
; large nonlinearities with ultrafast response
12, 13
; and even
polariton emission in 2D perovskite-based microcavities.
14-18

In CH
3
NH
3
PbI
3
, each [PbI
6
]
4-
octahedron is connected with six neighbours at the iodide forming
a 3-D network. The countercation (CH
3
NH
3
+
) is located at the void of the network. For the 2-D case
19

(e.g., (CH
3
NH
3
)
2
PbI
4
, each [PbI
6
]
4-
octahedron is connected with four neighbours at the halide forming a
2-D network layer that is sandwiched between two CH
3
NH
3
+
layers (also not shown in figure). A multiple
quantum well structure results with the stacking of these sandwiched layers via van der Waals interaction
with the 2-D [PbI
6
]
4-
functioning as the quantum well and the CH
3
NH
3
+
layer as the barrier. For the 1-D
case
20
(e.g., (NH
2
C(I) = NH
2
)
3
PbI
5
), each octahedron is connected at two opposite corners with its
neighbour forming separate infinite chains. Lastly, the quantum dot (0-D) analogue manifests as
(CH
3
NH
3
)
4
PbI
6
.2H
2
O, where each [PbI
6
]
4-
complex is neutralized by four CH
3
NH
3
+
ions to form a
molecule. A quantum dot array results when these molecules are isolated by H
2
O molecules to form a
molecular crystal.

Figure 1: Crystal Structures of (a) CH
3
NH
3
PbI
3
,
21
(b) (CH
3
NH
3
)
2
PbI
4
,
19
(c) (C
10
H
21
NH
3
)
2
PbI
4
,
20
and (d)
(CH
3
NH
3
)
4
PbI
6
.2H
2
O,
22
corresponding to 3D, 2D, 1D and 0D networks. The blue polyhedra represent the MX
6
(M =
Pb, Sn and Cu; X = I and Br) octahedra with the halogens represented by orange spheres the building block of
these compounds. The blue, green and red spheres are the N, C and O respectively (the H ions were removed for
clarity). The ID network extends into the plane of the document.

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(b) Electronic Structure
Early studies on the electronic band structures of organic-inorganic (3-D and low-dimensional)
perovskites can be traced to the works by: Koutselas et. al.
7
using band structure calculations by a semi-
empirical method based on the extended Hckel theory and an ab-initio approach based on the Hartree-
Fock theory; T. Umebayashi et. al.
23
using ultraviolet photoelectron spectroscopy and first principles
density functional theory (DFT) band calculations for the room temperature cubic phase; and Chang et.
al.
24
using first principles pseudopotential calculations. DFT calculations for the 3-D CH
3
NH
3
PbI
3
crystal
revealed that the valence band maxima comprises the Pb 6p I 5p -antibonding orbital, while the
conduction band minima consists of Pb 6p I 5s anti-bonding and Pb 6p I 5p anti-bonding orbitals
(See Figure 2 below).
23

Figure 2: Bonding diagram of (a) [PbI
6
]
4-
cluster (0-D), (b) CH
3
NH
3
PbI
3
(3-D) and (b) (C
4
H
9
NH
3
)
2
PbI
4
(2-D) at the
top of the valence band and the bottom of the conduction band. Reproduced with permission from ref. 23 copyright
2003, American Physical Society (APS).

Following the attention garnered by perovskite solar cells, renewed interests in the DFT studies of
3-D perovskites began in earnest with the work of E. Mosconi together with F. De Angelis and their
collaborators.
25
They calculated the band structure for CH
3
NH
3
PbX
3
(cubic phase) and the mixed halide
CH
3
NH
3
PbI
2
X (tetragonal phase) (X = Cl, Br and I) with the surrounding CH
3
NH
3
+
counterions, which
were ignored in the earlier studies. Nevertheless, the organic component had little influence to the
bandgap energy, of which is mainly determined by the [PbI
4
]
6-
network. In addition, the authors highlight
that the close matching of their calculated bandgaps (where spin-orbit coupling (SOC) effect were not
considered) with the experimental data is likely to be fortuitous. These findings are consistent with those
in the later works by T. Baikie et. al.
26
and Y. Wang et. al. (low-temperature orthorhombic phase)
27

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Investigation on the SOC effect on the electronic band structure in 3-D perovskites (low-temperature
orthorhombic phase) was reported by J. Even et. al.
28
, where they found that the SOC dramatically
reduces the energy gap affecting mainly the conduction band.

Having covered the fundamental properties of the large family of organic-inorganic perovskites,
we next focus our attention on CH
3
NH
3
PbI
3
and their photovoltaic applications.

3. Progress in Perovskite Photovoltaics
Initial studies in the area of perovskite solar cells arose as an evolution of the dye sensitized solar
cell
29
architecture. DSCs typically consist of a mesoporous n-type TiO
2
electrode which has been
sensitized by a dye and placed in a liquid electrolyte (typically I
-
/I
3
-
redox couple). Since the grafted dyes
only form a monolayer, the mesoporous electrode must be 10-15 m thick to enable complete light
absorption. The development of alternative semiconducting sensitizers (either in thin film or QD form)
allows for a reduction in the mesoporous TiO
2
layer thickness. Miyasaka and coworkers
30
in 2009
demonstrated the first perovskite sensitized solar cells utilizing CH
3
NH
3
PbI
3
and CH
3
NH
3
PbBr
3
as light
absorbers on TiO
2
mesoporous layers with halide electrolytes. A significant efficiency of 3.81% was
obtained from CH
3
NH
3
PbI
3
with photocurrent onset observed from ~800 nm. An impressive photovoltage
of 0.96V was obtained from CH
3
NH
3
PbBr
3
, attributed to the deeper bromide redox couple used in such
solar cells. Further improvements
31
in such liquid electrolyte solar cells were made by N.G. Park and
coworkers in 2011 through a careful optimization of the mesoporous layer thickness, perovskite
concentration and surface treatment. Surface modification of TiO
2
with Pb(NO
3
)
2
prior to deposition of
perovskite resulted in an efficiency of 6.54% (J
SC
= 15.82 mAcm
-2
, V
OC
= 0.706 V and FF = 0.586).
Despite the efficiencies achieved in such configurations, the overall instability of the solar cells due to the
dissolution of the perovskite in the liquid electrolyte appeared to be a challenge.

A breakthrough in both efficiency and stability was achieved in 2012 through utilization of a
solid-state hole transporter 2,2,7,7-tetrakis(N,N-p-dimethoxy-phenylamino)-9,9-spirobifluorene (spiro-
OMeTAD) with CH
3
NH
3
PbI
3
and CH
3
NH
3
PbI
3-x
Cl
x
light absorbers (Figure 3).
32, 33
N.G. Park, M. Grtzel
and coworkers reported a PCE of 9.7% (J
SC
= 17.6 mAcm
-2
, V
OC
= 0.888 V and FF = 0.62) for
CH
3
NH
3
PbI
3
on 0.6m TiO
2
layers. The use of spiro-OMeTAD dramatically improved the device
stability compared to liquid junction cells with ex-situ long-term stability tests for over 500 h, where the
devices are stored in air at room temperature without encapsulation.
32
H. Snaith and coworkers on the
other hand utilized a mixed halide system - CH
3
NH
3
PbI
3-x
Cl
x
on both TiO
2
and Al
2
O
3
mesoporous layers.
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Incredibly, the highest efficiencies (PCE = 10.9%, J
SC
= 17.8 mAcm
-2
, V
OC
= 0.98 V and FF = 0.63) were
obtained for the mesoporous Al
2
O
3
devices where its acts purely as a scaffold and does not take part in the
electrical processes.
33
These two reports sparked an explosion of research activities where a variety of
device configurations, deposition protocols and material sets have been employed.

(a) Device Architectures
A common device configuration for CH
3
NH
3
PbI
3
based solar cells consists of infiltrating the
perovskite within an n-type mesoporous layer (Figure 3(a)). The solar cell fabrication process commences
with the deposition of a compact TiO
2
hole-blocking layer on top of the fluorine doped tin oxide (FTO)
substrate. This is typically done through the spray pyrolysis of precursors such as titanium diisopropoxide
bis(acetylacetonate) at ~450
o
C. It is important to ensure that the compact layer is pinhole-free and
uniform to prevent the recombination between carriers from the perovskite layers and FTO. On top of the
compact layer, a mesoporous layer of n-type TiO
2
is formed either by screen printing or spincoating a
nanoparticle TiO
2
paste followed by annealing to remove the polymeric binders. Thickness and porosity
of these layers can be modulated by changing the filler and solvent concentrations in the TiO
2
paste. The
perovskite films are then deposited on top of the n-type mesoporous layer by spincoating it from a solvent
such as -butyrolactone (GBL) or N,N-dimethylformamide (DMF). This is followed by the deposition of
a hole transporting material (HTM) such as spiro-OMeTAD with appropriate dopants to improve
conductivity. Finally, a metal electrode is deposited on top of the HTM to complete the solar cell.

Although TiO
2
nanoparticles are most commonly used,
32, 34-37
there have also been reports of solar
cells employing TiO
2
nanosheets
38
, nanorods
39
, nanofibers
40
as well as other n-type materials such as
ZnO.
41, 42
Despite the wide variety of mesoporous architectures being employed, there has been no clear
evidence that the efficiencies of the perovskite solar cells can be effectively increased by mesoporous
layer modification. The most significant effect of the mesoporous layer that has been noted is how their
thicknesses can affect the power conversion efficiencies. Both in the liquid junction configuration, as well
as in its solid state equivalent, it has been demonstrated that lower mesoporous layer thicknesses perform
better.
31, 32, 39
The highest efficiencies in these kinds of configurations have been obtained with a 350 nm
thick mesoporous TiO
2
layer infiltrated with CH
3
NH
3
PbI
3
.
35
The high efficiencies of these solar cells at
relatively low TiO
2
thicknesses (in contrast to ~3um thickness for solid state DSCs
43
and 10-15 m
thickness for DSCs
44
) can be traced to the high optical absorption coefficient (~10
5
cm
-1
) of
CH
3
NH
3
PbI
3
.
31, 45, 46
The exact dependence of the mesoporous layer thickness on the power conversion
efficiency is determined by the nature of the perovskite distribution within the TiO
2
layers
47
as well as the
perovskite overlayer thickness
34
(which is in turn dependent on the perovskite solution concentration).The
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demonstration of good efficiencies
39
in rutile TiO
2
nanowires which have been shown to perform poorly
in DSCs (due to poor electron transport)
48
, again indicates that the thickness of the mesoporous layer is a
more critical factor. An interesting change in this device configuration stems from the work of Etgar and
coworkers who have demonstrated that such mesoporous TiO
2
based solar cells do not require a HTM to
function.
38, 49
The initial study employed anatase TiO
2
nanosheets as the mesoporous layer
38
, onto which
the perovskite layers were spuncoated and followed by the evaporation of a gold electrode. The solar cells
so fabricated, displayed an efficiency of 5.5% (J
SC
=16.1 mAcm
-2
, V
OC
= 0.63 V and FF= 0.57). Further
optimization of the perovskite layer thickness through consecutive spincoating resulted in an efficiency of
8%.
49
The successful functioning of such devices indicate that CH
3
NH
3
PbI
3
can act as an effective hole
transporter. However, the V
OC
s of such devices are lower than that produced with spiro-OMeTAD
indicating that the lack of electron selection layer results in increased recombination.

Figure 3: (a) Schematic illustrating mesoporous perovskite solar cells. The mesoporous oxide can be an electron
transporting semiconductor such as TiO
2
, ZnO or an insulating layer such as Al
2
O
3
or ZrO
2
(meso-superstructured
solar cell MSSC) (b) Relevant energy levels in the mesoporous TiO
2
perovskite solar cells (c) Schematic
illustrating the charge transfer and charge transport in a perovskite TiO
2
solar cell and a non-injecting Al
2
O
3
based
solar cell (a) and (c) are reproduced from ref. 33 copyright 2012, Science (AAAS) and (b) is reproduced from ref. 32
copyright 2012, Nature Publishing Group.

Another efficient solar cell configuration that has been chiefly employed by Snaith and coworkers
is the meso-superstructured solar cell (MSSC). This device configuration employs an insulating
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mesoporous layer on top of the compact TiO
2
layer as a scaffold to load the perovskite within them. Much
of the reports employing this configuration utilize Al
2
O
3
as the mesoporous layer and the mixed
perovskite CH
3
NH
3
PbI
3-x
Cl
x
as the absorber.
33, 50-52

However, the high efficiencies observed in this device configuration are not specific to this
material combination. Hagfeldt and coworkers have also demonstrated efficient solar cells (PCE= 10.8%,
J
SC
=17.3 mAcm
-2
, V
OC
= 1.07 V and FF= 0.59) by employing CH
3
NH
3
PbI
3
deposited on an insulating
ZrO
2
mesoporous layer
36
. The lack of an n-type mesoporous layer in this device configuration clearly
indicates that efficient electron transport occurs within the perovskite itself (Figure 3 (c)). This also
indicates that the perovskite within the mesoporous layer is continuous, in contrast to previous studies
which had considered them as isolated quantum dots.
30, 31
The contrast between both the views could be
explained by a recent work
47
which indicated that CH
3
NH
3
PbI
3
exists as two components within the
mesoporous TiO
2
, one component with medium range crystalline order (30 atom %) and another with
only local structural coherence (70 atom %). The electron transporting nature of the perovskite is further
highlighted in the work of Ball et.al.
50
By thinning down the Al
2
O
3
scaffold thickness (Figure 4(a)), the
authors were able to form solar cells which appeared more as thin film solar cells. The J
SC
for such solar
cells were 16.91.9 mAcm
-2
for thin alumina scaffold layers (80 nm) indicating that thick perovskite films
could generate sufficient photocurrent. The ability of the perovskites to be employed in such an electron
transporter-free configuration, as well as to perform efficiently in an HTM-free configuration
38, 49
, points
towards the ambipolar nature of transport in them. However, it is important to note that the MSSCs do not
have the reduced V
OC
s associated with the HTM-free solar cells primarily due to the presence of the hole
selective contacts. The effects of carrier accumulation within the perovskite could also be a possible
reason for the enhanced V
OC
s.

Figure 4: (a) Cross-sectional SEM view of a pseudo-thin film architecture employing a thin Al
2
O
3
mesoporous
layer with a significantly thick perovskite film over it (b) Cross-sectional view of a planar perovskite solar cell
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illustrating the typical organic charge transport layers employed. (a) is reproduced from ref. 50 copyright 2013,
Royal Society of Chemistry. (b) is reproduced from ref.
53

The success of the pseudo-thin film MSSC solar cells drove explorations into planar thin film
configurations of the perovskite solar cells. Thin film solar cells allow for a simpler processing route. One
approach to realizing such thin film solar cells is to avoid the use of any mesoporous layer and deposit the
films directly on the TiO
2
compact layer. The initial report on MSSC had included results from a planar
configuration (FTO /compact TiO
2
/ CH
3
NH
3
PbI
3-x
Cl
x
/ spiro-OMeTAD / Ag), but with a relatively low
efficiency of 1.8%.
33
The difficulties associated with the fabrication of a thin film solar cell stem from the
challenges of depositing a homogenous pin-hole free perovskite layer through solution based processes.
Poor coverage results in poor light absorption as well as shunting paths through the light absorber layer
which reduces efficiency. Unlike polymeric films which are mostly amorphous when deposited by
spincoating, the perovskites are crystalline. Even mild heating to remove solvent residues can result in
dewetting and roughening of the as deposited perovskite film. Eperon et.al. have carefully studied the
morphological effects of the underlying substrate, annealing time, temperature and initial
perovskite(CH
3
NH
3
PbI
3-x
Cl
x
) film thickness. Through a control of the various factors involved, the
authors have achieved an efficiency of 11.4% (J
SC
=20.3 mAcm
-2
, V
OC
= 0.89 V and FF= 0.64).
54
A much
simpler approach
55
involved the vapour deposition of the perovskite films onto the TiO
2
films which
yielded a short-circuit photocurrent of 21.5mAcm
2
, an open-circuit voltage of 1.07V and a fill factor of
0.68, and an efficiency of 15.4%. An interesting vapor assisted approach to form efficient planar solar
cells has also been demonstrated by Yang Yang and coworkers.
56
A 350 nm thick CH
3
NH
3
PbI
3
film
formed on the compact TiO
2
layer, yielded an efficiency of 12.1%, despite the relatively thick HTM layer
employed in the devices. A similar planar solar cell approach, but which allows for low temperature
processing involves the utilization of ZnO as the blocking layer. The first approach by Kumar et.al
employed electrodeposited ZnO on both rigid FTO and flexible ITO on top of which CH
3
NH
3
PbI
3
was
spuncoated.
41
The second approach utilized spuncoated films from a solution of 5nm ZnO nanoparticles
suspended in a butanol/chloroform mixture requiring no calcination or sintering. The authors argue that
the lack of a constricting mesoporous layer allows for unconstrained CH
3
NH
3
PbI
3
perovskite crystal
growth yielding an impressive efficiency of 15.7% on FTO and 10.2% on flexible ITO substrates.
57

Another growing area of research involves the use of electron and hole transport layers
commonly utilized by the organic photovoltaic community in the implementation of the planar solar cell
configuration. The first work in this direction was performed by Chen and coworkers who employed a
device architecture consisting of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid)
(PEDOT:PSS) as the hole transport layer and C
60
derivatives including (6,6)-phenyl C61-butyric acid
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methyl ester (PCBM) and indene-C
60
bisadduct (ICBA) as the electron transporter in a planar
configuration.
58
As with forming perovskite on top of TiO
2
thin films, the authors faced challenges in
forming a uniform CH
3
NH
3
PbI
3
coating on top of the PEDOT:PSS layer. This restricted the total
thickness of the CH
3
NH
3
PbI
3
utilized, hence limiting the efficiencies to 3.9%. Sun et.al employed a
similar device configuration but succeeded in making a thicker CH
3
NH
3
PbI
3
(110 5 nm) film through
the utilization of a two-step conversion approach. The highest efficiency reported in such a device was
7.41%.
45
Snaith and coworkers
53
screened a wider material set employed in OPVs, including NiO and
V
2
O
5
hole transport layers and poly[(9,9-bis(30-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9
dioctylfluorene)] (PFN) as an electron selective contact with CH
3
NH
3
Pb1
3-x
Cl
x
. However, the most
efficient device configuration still employed PC
61
BM and PEDOT:PSS as the two previous reports
covered above. A ~300 nm thick CH
3
NH
3
Pb1
3-x
Cl
x
layer (Figure 4(b)), yielded an efficiency of 9.8%
while flexible solar cells were also fabricated on ITO coated glass yielding 6.3%. Crucially, the lower
efficiencies on the flexible devices were attributed to the smoother surface of the ITO layer which affects
the uniformity of the perovskite coating. However, even higher efficiencies have been demonstrated for
flexible CH
3
NH
3
Pb1
3-x
Cl
x
solar cells on ITO by Yang Yang and coworkers (9.2%).
59

(b) Deposition Processes
Much of the initial work on CH
3
NH
3
PbI
3
and CH
3
NH
3
PbI
3-x
Cl
x
solar cells utilized spin-coating to
deposit the light absorbers from a single precursor solution. CH
3
NH
3
PbI
3
films were formed by dissolving
stoichiometric quantities of CH
3
NH
3
I and PbI
2
in polar solvents such as GBL or DMF.
32, 34
CH
3
NH
3
PbI
3-
x
Cl
x
is typically formed from a solution in DMF where the PbCl
2
and CH
3
NH
3
I are in a molar ratio of
1:3.
33, 50
With appropriate optimization of the precursor concentration and spincoating conditions, the
perovskite can be deposited within the pores of the mesoporous layers or be used to form compact layers
for planar solar cells. As described previously, the formation of a uniform perovskite layer for planar
devices through spincoating requires the optimization of multiple parameters including post deposition
processes.
45, 54, 58
Due to wettability differences, the perovskite would need to be separately optimized for
each underlying layer. When spincoating on mesoporous layers, conditions similar to the deposition of
HTMs within the mesoporous TiO
2
layers of a solid state DSC could be expected to occur.
60
In such a
case, the excess solution on top of the film can act as a reservoir during the spincoating process. The
amount of infiltration within the mesoporous layer could deposit critically on solution concentration,
spincoating speed and the solvent utilized. The tendency of the perovskite films to crystallise, could lead
to rough surface morphologies
34
which could introduce shunts into the solar cells.

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A significant development for solution based deposition has been the application of the sequential
deposition process (originally developed by Mitzi and coworkers
61
) to the fabrication of perovskite solar
cells by Grtzel and coworkers.
35
The process consists of first spincoating PbI
2
on the TiO
2
layer from a
solution with concentrations and spincoating speed set to enable infiltration within the mesoporous layer
(Figure 5(a)). Subsequently, the yellow substrates are dipped in a CH
3
NH
3
PbI
3
solution in 2-propanol
solvent. During the dipping, the yellow PbI
2
converts to form the dark brown CH
3
NH
3
PbI
3
in a few
seconds (Figure 5(b)). It is important to note that the conversion time can vary between the different PbI
2

conditions. A 20 minute conversion time has been reported for perovskite solar cells
40
, while the initial
work by Mitzi and coworkers indicated that the conversion required 1-3h
61
. It is likely that the PbI
2
layer
deposited on top of mesoporous substrates has increased roughness that allows the conversion reaction to
proceed faster.
35
Due to the volume expansion
56
(~75%) occurring due to the conversion of PbI
2
into
CH
3
NH
3
PbI
3
, it can be expected that the mesoporous layer would be better infiltrated through the
sequential deposition process. The top view of the sequentially deposited samples reveals a highly
crystalline film with complete coverage (Figure 5(c)).

Figure 5: (a) Cross-sectional SEM of a mesoporous TiO
2
film infiltrated with PbI
2
. (b) Change in absorbance at
550 nm of such a film monitored during the transformation from PbI
2
to CH
3
NH
3
PbI
3
. (c) Top view of CH
3
NH
3
PbI
3

film obtained using the sequential deposition method. (d) An illustration of the vapour assisted transformation of
PbI
2
to CH
3
NH
3
PbI
3
by exposure to CH
3
NH
3
I vapour. (e) Dual-source thermal evaporation system for depositing the
perovskite absorbers; the organic source was methylammonium iodide and the inorganic source PbCl
2
. (a) - (c) are
reproduced from ref. 35 copyright 2013, Nature Publishing Group; (d) is reproduced from ref.
56
copyright 2013,
American Chemical Society and (e) is reproduced from ref.
55

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Apart from the widely utilised solution-based deposition processes, vapour deposition has also
been employed to form perovskite solar cells. Snaith and coworkers
55
demonstrated efficient planar solar
cells (15.4%) of CH
3
NH
3
PbI
3-x
Cl
x
formed by dual source evaporation of PbCl
2
and CH
3
NH
3
I (Figure 5(e)).
The evaporated film was sandwiched between a compact TiO
2
layer and a spuncoated Spiro-OMeTAD
layer acting as electron and hole transporters respectively. The vapour-deposited films are extremely
uniform, with crystalline features on the length scale of hundreds of nanometres. Another example of
vapor deposition was demonstrated by Bolink and coworkers
62
who deposited thin films of CH
3
NH
3
PbI
3

from the dual source evaporation of PbI
2
and CH
3
NH
3
I. The authors employed organic electron and hole
transport layers such as PCBM and PEDOT:PSS to form solar cells with 12.04% efficiency. Both the dual
source evaporation examples described above required careful optimization to yield the desired perovskite
layers and efficient solar cells. An interesting approach which employs both solution based deposition
and vapor phase transformation has been reported by Chen et.al.
56
In the vapor-assisted solution process
(VASP), PbI
2
was first deposited from solution on to a compact TiO
2
substrate. Subsequently, the films
were exposed to a vapour of CH
3
NH
3
I at 150
o
C in N
2
for 2h (Figure 5(d)). The slow rate of conversion
resulted in CH
3
NH
3
PbI
3
films which exhibited micron sized grains with very low surface roughness of
~20 nm. Solar cells made from such films exhibited an efficiency of 12.1%.
In conjunction with these exciting device-centric advancements, fundamental studies into the
photoexcited species and their photogeneration and recombination dynamics in perovskites also began in
earnest. The next section traces these early studies to the latest findings of the fundamental photophysical
mechanisms in this system.

4. Photophysical Mechanisms in CH
3
NH
3
PbI
3
Thin Films
The early photophysical studies in this class of organic-inorganic perovskites are mainly centered
on the excitonic properties of layered perovskites such as the optical non-linearity around the excitonic
resonances
63
and the exciton-exciton interactions
64
. Coherent transient spectroscopy such as four wave
mixing has been used to investigate the exciton and bi-exciton dynamics
65
and temperature dependent
TRPL spectroscopy for the exciton recombination dynamics
66
in these 2D perovskites. Depending on the
exciton binding energy E
b
, the fundamental excited species following photoexcitation could exist as
bound electron-hole pairs or as free carriers. Hence, E
b
have also been extensively investigated for
CH
3
NH
3
PbI
3
, the photovoltaic material of choice. Table 1 shows the E
b
, of selected 3-D perovskites with
low-dimension perovskites included for comparison. These E
b
are estimated using optical absorption
7
and
magneto-absorption spectra
67, 68
as well as from temperature-dependent photoluminescence (PL)
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intensities
45, 69
. The excitons in CH
3
NH
3
PbI
3
are expected to be of the more delocalized Wannier-type
with exciton Bohr radius, r
B
~30 .
7, 70
Larger binding energies for CH
3
NH
3
PbBr
3
and the mixed halide
CH
3
NH
3
PbI
3-x
Cl
x
system indicates a more tightly bound nature of the excitons resulting from the halogen
substitution. In contrast, for 2-D layered perovskites, the excitons are the Frenkel type and their large
binding energies are ascribed to dielectric modulation between the organic and inorganic layers and the
two dimensionality of the inorganic structure.
71
With decreasing dimensionality to 1-D and 0-D, the
exciton binding energies increase in accordance to the quantum confinement effects.
70

Table 1: Exciton binding energies E
b
of the 3-D CH
3
NH
3
PbI
3
and CH
3
NH
3
PbI
3-x
Cl
x
perovskites and selected low-
dimension perovskites.
Compound Dimensionality E
b
(meV) Method
CH
3
NH
3
PbI
3
3D
30
37
45
50
193
optical absorption
7

magneto-absorption
67

temperature dependent PL
69

magneto-absorption
68

temperature dependent PL
45

CH
3
NH
3
PbBr
3
3D
76
150
magneto-absorption
68

optical absorption
7

CH
3
NH
3
PbI
3-x
Cl
x
3D 98 temperature dependent PL
72

(C
9
H
19
NH
3
)
2
PbI
4
2D 330 temperature dependent PL
69

(NH
2
C(I)=NH
2
)
3
PbI
5
1D 410 optical absorption
7

(CH
3
NH
3
)
4
PbI
6
.2H
2
O 0D 545 optical absorption
7

Absorption of photons creates electron-hole pairs in the perovskite. Following carrier
thermalization, these carriers could either continue to exist as free carriers or form excitons depending on
the excitons binding energy. Presently, it is still unclear whether these species at room temperature exist
as excitons or free charges which gave rise to the 3-D perovskites exceptional properties of long
diffusion lengths. This uncertainty stems from the low exciton binding energies E
b
ranging from 19 meV
to 50 meV, which are comparable to the room temperature thermal energies of k
B
T ~25 meV. Given the
uncertainties and the assumptions involved with the estimation/extraction of the values for E
b
based on
the various methods employed (optical absorption
73, 74
, magneto-absorption
68
and temperature dependent
PL
75
), it is reasonable from Table 1 that the E
b
for CH
3
NH
3
PbI
3
is comparable to the thermal energies of
k
B
T ~ 25 meV at room temperature. As an illustration, even for an E
b
~19 meV, the faction of the excitons
with energy greater than E
b
at ~300K can be calculated from statistical physics to yield: ~57% of the
photo-generated excitons dissociating spontaneously and ~43% remaining as excitons. It is an open
question on how the co-existence of free carriers and excitons, whose dynamic populations could vary
over their lifetimes, will affect the carrier dynamics in perovskite solar cells.
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To the best of our knowledge, there have been no reported studies on the charge dynamics in 3D
perovskites until the advent of the 9.7% perovskite solar cells in 2012
32
. Despite the rapid progress in
organic-inorganic perovskite solar cells, the fundamental photophysical processes driving the high
performance of these devices is still severely lacking. The bulk of the research efforts to date are
predominantly focused on device development, with limited studies on charge carrier dynamics in the
CH
3
NH
3
PbI
3
perovskite materials.
32, 33, 46, 76-78
Nevertheless, the efforts into applying ultrafast optical
spectroscopy (UOS) techniques to investigate the structure-function relations in perovskite solar cells are
on the rise. UOS techniques are powerful probes of the carrier dynamics and the charge transfer
mechanisms in materials. A clear understanding of the charge generation and transport mechanisms in
perovskites solar cells will provide valuable feedback to guide the materials design and device
engineering. Here, we first examine the intrinsic charge dynamics in the bare perovskite thin films. The
charge transfer processes in a typical perovskite solar cell will be examined in the next section.

Long Electron-Hole Diffusion Lengths and Hot Hole Cooling Dynamics: In tandem with the
developments of increasing perovskite solar cell efficiencies, indications of ambipolar charge transport in
perovskites become apparent when efficient perovskite-based devices in a broad range of device
architectures are reported. The perovskite material functions well as an absorber in a configuration used
by Kim et. al.
32
and Heo et. al.
34
that sandwiches the thin perovskite layer between a mesoporous TiO
2

photoanode and a HTM layer (Spiro-OMeTAD). Lee et. al.
33
demonstrated that the perovskite material
can work effectively as both an absorber and an electron transporter by fabricating solar cells with an
insulating Al
2
O
3
scaffold instead of the TiO
2
photoanode. Surprisingly, Etgar et. al.
38
fabricated devices
with appreciable performance in a configuration without the HTM layer indicating that the perovskite
material can work as an absorber and a hole transporter.

These reports provide us with a compelling case to devise quenching experiments utilizing
femtosecond transient optical spectroscopy (i.e., TAS and time-resolved PL (TRPL) spectroscopy) of
CH
3
NH
3
PbI
3
heterojunctions with selective electron or hole extraction to decouple the electron and hole
dynamics in this material.
46
Our findings revealed clear evidence of balanced and long-range electron-
hole diffusion lengths of at least 100 nm in the solution processed CH
3
NH
3
PbI
3
(Figure 6). Concurrently,
using the same PL quenching approach, H. J. Snaith and coworkers
77
also performed diffusion length
measurements on CH
3
NH
3
PbI
3
and the mixed halide CH
3
NH
3
PbI
3-x
Cl
x
. Their findings of the electron-hole
diffusion lengths in CH
3
NH
3
PbI
3
concur with ours. Amazingly, the mixed halide CH
3
NH
3
PbI
3-x
Cl
x

possesses diffusion lengths one order longer (i.e., >1 m) than CH
3
NH
3
PbI
3
, although no clear reason was
identified for this difference. Nevertheless, these two works clearly show that the electron-hole diffusion
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lengths in perovskites are much longer than those for most solution processed materials (typically ~10
nm). Most recently, G. Giorgi et. al.s spin-polarized DFT calculations determined the effective masses of
both the electron and hole in CH
3
NH
3
PbI
3
to be small, (i.e., m
e
* = 0.23 m
0
and m
h
* = 0.29), thus
providing further validation of their long-range ambipolar charge transport property
46, 77
.

Figure 6: (A) Time-integrated PL spectra and (B) Time-resolved PL decay transients measured at 760 10 nm for
quartz/CH
3
NH
3
PbI
3
(65 nm) (black), quartz/CH
3
NH
3
PbI
3
(65 nm)/PCBM (red), quartz/CH
3
NH
3
PbI
3
(65 nm)/Spiro-
OMeTAD (blue) films in vacuum after excitation at 600 nm (1 KHz, 150 fs, 1.3 J/cm
2
). The solid lines in (B) are
the single-exponential fits of the PL decay transients. a.u., arbitrary units. (C) A plot of exciton diffusion length
versus PL lifetime quenching ratios. Diffusion length is scaled in multiples of CH
3
NH
3
PbI
3
layer thickness (L = 65
nm). Reproduced with permission from ref. 46, Copyright 2013, Science (AAAS).

In this same work, we also examined the early time relaxation dynamics in the CH
3
NH
3
PbI
3

system. It is important to note that the carrier dynamics in the perovskite system are strongly pump
fluence dependent due to their large light absorption coefficients and the long charge diffusion lengths.
Multi-particle Auger (third order) recombination processes becomes dominant for pump fluence >2.6
J/cm
2
. In fact, we recently discovered that at pump fluence >12 J/cm
2
, amplified spontaneous emission
(ASE) prevails and even out-competes the Auger processes.
79
Therefore, careful control of the pump
fluence in ultrafast optical spectroscopy of perovskites is absolutely essential for uncovering their
intrinsic photophysical properties. Femtosecond TAS measurements with selective 400 nm and 600 nm
pump excitation (fluence <1.3 J/cm
2
) and WLC probe uncovered a slow 0.4 ps hot hole cooling process
from a deeper valence band level (VB2) to the valence bandedge (VB1) see Figure 7. With careful
tailoring of the HTMs energy levels, one could efficiently extract these hot hole energies before they
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cool down to VB1. Potentially, this could be utilized in perovskite solar cells to exceed the theoretical
Shockley-Queisser limit.
80
Further investigations into this area should be conducted.

Figure 7: Normalized bleaching kinetics at 480 and 760 nm in a short time range show the intervalence band hot
hole cooling for CH
3
NH
3
PbI
3
film (in vacuum) after excitation at (A) 400 nm (1 J/cm
2
) and (B) 600 nm (1.3
J/cm
2
). (C) A schematic illustrating the hot-hole cooling and charge recombination within CH
3
NH
3
PbI
3
and charge
separation at the CH
3
NH
3
PbI
3
/PCBM and CH
3
NH
3
PbI
3
/Spiro-OMeTAD interfaces. The approximate positions of
VB1 and VB2 were obtained from the TA measurements. Reproduced with permission from ref. 46, Copyright 2013,
Science (AAAS).

Origins of the Long Electron-Hole Diffusion Lengths: The mechanism of the long electron-hole diffusion
lengths in CH
3
NH
3
PbI
3-x
Cl
x
and CH
3
NH
3
PbI
3
and their charge carrier mobilities were elucidated by L. M.
Herz in collaboration with H. J. Snaith and coworkers
78
using transient THz spectroscopy. Their findings
show that both the monomolecular (first order, i.e., from germinate recombination of excitons and/or from
trap- or impurity-assisted recombination) and bimolecular (second order) charge carrier recombination
rates are extremely low, with the latter defying the Langevin limit by at least four orders of magnitude.
However, the Auger (third order) recombination rates, were found to be high ~10
-29
cm
6
s
-1
comparable
to those of strongly confined colloidal quantum dots.
81
Comparatively, the Auger recombination in
highly-doped bulk Si wafers is ~2 orders smaller.
82
The lower bound values of the charge carrier
mobilities for CH
3
NH
3
PbI
3-x
Cl
x
and CH
3
NH
3
PbI
3
were determined to be 11.6 cm
2
V
-1
s
-1
and ~8 cm
2
V
-1
s
-1
,
respectively, which are extremely high for the solution-processed perovskites. Comparatively, these
values are >20 times larger than that of mesoporous TiO
2
and several orders larger than those of typical -
conjugated molecular semiconductors. The origins of the long electron-hole diffusion lengths stems from
the exotic combination of low charge carrier recombination rates and high charge carrier mobilities in
these perovskites.
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Figure 8: A schematic of the photophysical processes and loss mechanisms in perovskites following photoexcitation.
Efficient paths (black lines) and suppressed paths (grey lines). Monomolecular recombination is charge carrier
density independent, while bi-molecular and Auger recombination are charge carrier density dependent processes
that would typically be present under strong photoexcitation. In fact, under even higher photoexcitation densities,
amplified spontaneous emission (ASE) will out-compete Auger recombination. However, under solar light
intensities (weak excitation), these latter processes will be strongly suppressed.

Summary of Photophysical Processes in Pristine Films: A generalized scheme of the dynamic interplay of
the various photophysical processes and loss mechanisms in bare perovskite thin films following
photoexcitation is shown in Figure 8. Absorption of photons results in the generation of electron-hole
pairs that evolve towards the formation of highly delocalized Waniner excitons after thermalization. A
faction of which would dissociate spontaneously back into free carriers. The excitons and free carriers
coexist and their dynamic populations continue to vary over their lifetimes. Germinate recombination of
the excitons, or the recombination involving an electron and a hole generated from the quenching of a
single exciton is inefficient. Likewise, trap-assisted recombination, another monomolecular process, is
also suppressed in these CH
3
NH
3
PbX
3
perovskites. At stronger light intensities, non-germinate
recombination originating from the recombination of two free charges (i.e., bi-molecular in nature) is
extremely low defying the traditional Langevin limit by at least four orders of magnitude. Auger
recombination (involving a three particle process) on the other hand is dominant in CH
3
NH
3
PbX
3

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perovskites and surprisingly, ASE even occurs at higher pump excitations out-competing the Auger
processes in CH
3
NH
3
PbI
3
.
79
Eventually, in these bare perovskite films without HTM and in the absence of
any charge extraction, the photoexcited species (excitons and free carriers) undergo radiative
(luminescence) or non-radiative processes within the perovskite. It is also important to note that under
solar light intensities (weak excitation), Auger recombination or ASE would be strongly suppressed. With
the non-radiative pathways (germinate recombination, trap-assisted recombination and Auger
recombination) weak or inactive under solar light intensities, it is therefore understandable that these
perovskites make excellent photovoltaic materials.

5. Charge Transfer Mechanisms in Perovskite Solar Cells
As described previously, various configurations of perovskite solar cells have been explored.
These include the configurations where perovskite has been interfaced with mesoporous TiO
2
,
mesoporous Al
2
O
3
(MSSC) as well as other organic electron and hole transport layers. Ultrafast
measurements have clearly indicated that CH
3
NH
3
PbI
3
and CH
3
NH
3
PbI
3-x
Cl
x
, both have long and
balanced electron-hole transport lengths.
46, 77
It has also been clearly shown that injection into electron
acceptors such as PCBM and hole transporters such as PEDOT:PSS and Spiro-OMeTAD is efficient.
46, 53,
59, 77
Thus, planar configurations of perovskite solar cells can be expected to function as thus: under
photoexcitation, a mixture of weakly bound excitons and direct electron, hole generation occurs. Due to
the crystalline nature of the perovskite as well as low trap densities, the recombination within the
perovskites is limited. The long-lived nature of electrons and holes allows them to be collected by
electron and hole acceptor layers, before making their way out of the solar cells as photocurrent. The high
open circuit voltages noted in such planar configurations also point to a scenario where energetic costs
associated with exciton splitting is not prevalent. Light intensity dependent measurements on a
PEDOT:PSS/CH
3
NH
3
PbI
3-x
Cl
x
/ PCBM solar cell indicate that the main recombination mechanism is free
carrier recombination.
59
The meso-superstructured solar cells
33, 36, 50, 51
which utilize an insulating
mesoporous layer as a scaffold for the perovskite can be expected to work in a similar manner. Here the
primary charge separation phase is probably the hole transporting layer (Spiro-OMeTAD) into which hole
injection occurs efficiently. The good electron transport properties of the perovskite layer ensure that
electrons are collected through the compact TiO
2
layer below the insulating mesoporous layer. Thus, a
connected perovskite layer within the mesoporous layer is critical. The exact working principle behind
solar cells fabricated by depositing perovskite on a mesoporous TiO
2
layer is still not clearly established.
The pertinent questions when considering this architecture are: (a) Is there injection of electrons from the
perovskite into mesoporous TiO
2
; (b) Is the more efficient path for electron collection through the
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mesoporous TiO
2
or within the perovskite itself? (c) Which pathway results in higher extraction
efficiency in perovskite solar cell?

Figure 9: (a) Schematic diagram of energy levels and electron transfer processes in an HTM/perovskite/TiO
2
cell.
(1): Electron Injection; (2): Hole injection; (3): Radiative exciton recombination; (4) Non-radiative exciton
recombination; (5) Back electron transfer at the TiO
2
surface; (6) Back charge transfer at the HTM surface; (7)
Charge recombination at the TiO
2
/HTM interface. (b) Transient absorption signals were measured at a probe
wavelength of 1.4 m following femtosecond- laser pulsed excitation at 580 nm: CH
3
NH
3
PbI
3
on TiO
2
(black);
CH
3
NH
3
PbI
3
on Al
2
O
3
(blue); CH
3
NH
3
PbI
3
and spiro-OMeTAD on TiO
2
(red); CH
3
NH
3
PbI
3
and spiro-OMeTAD
on Al
2
O
3
(green). Thick solid lines represent bi-exponential ts of experimental points starting at t = 1 ps. A
2

represents the normalized absorbance change at 25 ps, used as a metric to compare the various samples. (c) Samples
with HTM. Signals mainly reflect the decay of the h
+
(HTM) population. CH
3
NH
3
PbI
3
and spiro-OMeTAD on TiO
2

(red); CH
3
NH
3
PbI
3
and spiro-OMeTAD on Al
2
O
3
(green). Thick lines represent stretched exponential fit of data.
Reproduced with permission from ref.
83
, copyright 2014, Nature Publishing Group.

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N. G. Park in collaboration with M. Grtzel and coworkers
32
published the earliest study on the
dynamics of the charge separation processes in CH
3
NH
3
PbI
3
/TiO
2
solar cells probed using femtosecond
transient absorption spectroscopy (fs-TAS). However, clear evidence of efficient electron injection into
TiO
2
could not be observed due to the overlapping signals from the stimulated emission from the
perovskite. Although the question on whether perovskite can inject an electron into the mesoporous TiO
2

has more or less been answered by photoinduced absorption spectroscopy (PIA) from the evidence of a
broad absorption feature in the region ~1.1 m attributed to free electrons in the titania from
CH
3
NH
3
PbI
3-x
Cl
x

33, 84
, clear evidence of the efficient injection remain elusive. Most recently, J.-E. Moser
in collaboration with M. Grtzel and coworkers unravelled the mechanism of the charge transfer
processes in perovskite solar cells (Figure 9(a)) and presented clear evidence of not only efficient electron
injection from the photoexcited CH
3
NH
3
PbI
3
into TiO
2
, but also efficient hole injection from photoexcited
CH
3
NH
3
PbI
3
into the HTM (spiro-OMeTAD) occurring simultaneously over comparable ultrafast
timescales ( 3ps).
83
They had overcome the challenges of spectral overlap encountered in the earlier
study
32
by probing in the infrared (1.4 m) which allows direct observation of only the carriers
population decay within the perovskite itself (Figure 9(b)).

The second and third questions on whether electron collection is more efficient through the
mesoporous TiO
2
or within the perovskite itself; and which pathway results in higher extraction efficiency
in perovskite solar cells remain open. H. J. Snaith in collaboration with T. N. Murakami and T. Miyaska
and coworkers
33
, showed using transient photocurrent measurements that the charge collection in the
insulating Al
2
O
3
-based devices is faster than the TiO
2
-based devices indicating the perovskite material
itself is more efficient in transporting negative charge than the mesoporous TiO
2
. However, recent
findings by Marchioro et. al. using transient absorption spectroscopy showed that the amount of long-
lived charges in the TiO
2
/CH
3
NH
3
PbI
3
/HTM samples is higher than that in the Al
2
O
3
/CH
3
NH
3
PbI
3
/HTM
samples (Figure 9(b)) indicating a more efficient charge separation in the former. Furthermore, charge
recombination with oxidized HTM species was also found to be slower on TiO
2
films compared to Al
2
O
3

films (Figure 9(c)). The efficiency of charge extraction in a perovskite solar cell also depends on the ratio
between charge recombination and charge separation rates. Nevertheless, Marchioro et. al.s findings
showed that it is advantages to use TiO
2
as the electron acceptor and transporter, together with HTM in
perovskite solar cells providing only partial answers to question 3.

Impedance spectroscopy measurements have also been applied to perovskite solar cells in a bid to
understand the electrical processes occurring in them. Bisquert and coworkers analysed perovskite solar
cells on TiO
2
and ZrO
2
and proposed that carrier accumulation occurs in the perovskite layers.
85
This
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indicates that the working principle of the perovskite solar cells is different from that of a pure DSSC
where instantaneous injection from the dye into the TiO
2
occurs and no charge accumulation is
observable in the light absorber. Dualeh et.al. in their impedance spectroscopy analysis have argued that
the observation of the mesoporous TiO
2
s chemical capacitance in perovskite solar cells indicates that the
electron transport is channeled through the mesoporous TiO
2
.
86
The capacitance of TiO
2
in perovskite
solar cells has also been observed by Abrusci et. al in their differential capacitance measurements when
employing a C
60
-self assembled monolayer on top of the TiO
2
surface.
84
Zhu and coworkers also point to
a similar working mechanism in solid state DSCs and perovskite solar cells dominated by electron
transport within the mesoporous TiO
2
layer itself, from intensity modulated photocurrent/photovoltage
spectroscopy (IMPS/IMVS) measurements.
87
However Bisquert and coworkers have reported a similar
impedance spectral shape in planar CH
3
NH
3
PbI
3-x
Cl
x
and nanostructured CH
3
NH
3
PbI
3
solar cells. Since
there is an absence of the TiO
2
mesoporous layer in one of the devices, they attribute the features in the
impedance spectra to charge transport and recombination processes occurring within the perovskite layer
solely. The authors have also noted that more complicated impedance spectra pattern can be observed in
other cases which necessitate the development of a complete model.

The unclear view of the exact working principles of perovskite-mesoporous TiO
2
solar cells could
stem from the variations in the solar cell structures studied and their ensuing interfacial charge transfer
dynamics. The impact of the degree of coverage of the mesoporous TiO
2
by the perovskite is unclear. The
presence or absence of a perovskite overlayer on the mesoporous TiO
2
will modulate the recombination at
the perovskite/TiO
2
/HTM interfaces. Additionally the distribution of the perovskite within the TiO
2
pores
may also play a defining role in what mechanism of electron transport dominates. For example, charge
transport time in CH
3
NH
3
PbI
3
formed from sequential deposition process was found to be 3 times longer
than that obtained from the single precursor spincoating process.
36
From spectroscopic evidence, it is
clear that charge injection from perovskite into mesoporous TiO
2
is possible
33, 83, 84
; however the exact
ratio between electrons being transported through the mesoporous TiO
2
and that transported through the
perovskite is unknown. Possibly, spectroscopic measurements in working solar cells at different applied
voltages may unravel this question.

6. Future Directions and Open Questions in the Field
In the wake of the rapidly expanding field, several pressing open questions remain. They have
been largely swept aside in the initial surge for high efficiencies. As the perovskite photovoltaic field
matures, these gaps in our understanding need to be progressively tackled and filled:

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Interfacial Charge Transfer Dynamics: For any given material system, factors such as device processing
and the ensuing morphology and coverage can strongly affect the carrier dynamics and the device
performance. Systematic studies into understanding the morphology effects arising from the single
precursor vs sequential deposition solution-processed approach or thermal evaporation approach on the
charge dynamics in the pristine and heterojunctions perovskite films are urgently needed. Given that the
100 nm e-h diffusion lengths estimated from the single step processed CH
3
NH
3
PbI
3
are minimum values
46
,
further work is urgently needed to carefully examine the e-h diffusion lengths in sequential deposited
films and evaporated films to establish their upper limits. Over the next phase of development in this field,
one can look forward to an explosion of systematic transient spectroscopy studies of various
pristine/heterojunction configurations over the entire charge generation to charge extraction timescale, in
particular: (i) the dynamic interplay and interactions between the excitons and the free charge population
and their effects on the charge separation, recombination and transport; (ii) the interfacial charge
dynamics and the mechanism of the charge injection at the perovskite/mesoporous TiO
2
;
perovskite/semiconductor nanostructure; and perovskite/graphene interfaces; and (iii) the exact role of
higher lying states (if any) for charge separation. Time-resolved optical pump-terahertz probe
spectroscopy would be extremely useful to monitor the early time excitons and free-carrier dynamics and
populations in the pristine films and heterojunctions. These studies could be extended with transient
microwave photoconductance measurements over longer time scales for correlation with device
properties. Double excitation techniques like the pump-push probe spectroscopy can be used to study the
higher lying electronic states and their roles in the charge transfer. Field modulation techniques like field
assisted pump-probe spectroscopy could also lead to new insights on the interplay of the exciton
dissociation and the free carrier dynamics on the charge transfer under device conditions. With the
concerted efforts of various research groups, a complete picture and detailed model of the charge transfer
processes of perovskite solar cells will be unravelled. Understanding the structure-function relations in
perovskite solar cells through UOS holds the key to the development of optimal solar cells with
efficiencies that could surpass the 20% target.

CH
3
NH
3
PbI
3
vs CH
3
NH
3
PbI
3-x
Cl
x
: Highly efficient solar cells have been prepared from CH
3
NH
3
PbI
3
and
CH
3
NH
3
PbI
3-x
Cl
x
. The precursor solution of the latter compound consists of 3 parts of CH
3
NH
3
I for 1 part
of PbCl
2
. Although initial studies had termed the mixed composition as CH
3
NH
3
PbI
2
Cl, the
crystallographical and optical absorption properties are identical to that of CH
3
NH
3
PbI
3
.
33
Stranks et.al.
have shown,
77
the diffusion lengths measured in CH
3
NH
3
PbI
3-x
Cl
x
are significantly longer than that in
CH
3
NH
3
PbI
3
, although the device performance of both compositions are comparable. In addition, while
the charge carrier mobilities in both CH
3
NH
3
PbI
3-x
Cl
x
and CH
3
NH
3
PbI
3
are similar, the bimolecular
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recombination rates in the mixed halide system are approximately one order lower, suggesting that
electronic structure modulation by Cl has a role in reducing the spatial overlap of the electron and holes.
78

Colella et. al. have also proposed that Cl within CH
3
NH
3
PbI
3
can act as a dopant, improving the transport
properties.
88
XPS measurements have revealed that the final composition of the CH
3
NH
3
PbI
3-x
Cl
x
contains
significantly low amount of Cl (Cl/Cl+I=2.2%) within them.
59
XRD analysis of evaporated CH
3
NH
3
PbI
3-
x
Cl
x
films
55
also revealed impurity peaks of PbI
2
, although the precursors were PbCl
2
and CH
3
NH
3
I. This
points to the Cl source (either PbCl
2
or CH
3
NH
3
Cl) playing a role in the film formation. The development
of a preferred orientation in CH
3
NH
3
PbI
3-x
Cl
x
films
33
in contrast to CH
3
NH
3
PbI
3
films
35
again indicates
that the Cl plays a role in film formation. Studies on CH
3
NH
3
PbI
3
and CH
3
NH
3
PbI
3-x
Cl
x
films with
similar film properties (morphological and crystallographical) are required, to reveal the electronic role of
Cl within the perovskite.

Hole Transporting Layers: The hole transporting material of choice for perovskite solar cells is spiro-
oMeTAD, which has been well studied due to its popularity in solid-state DSCs. However, the high
commercial prices of spiro-oMeTAD (due to synthesis complexity) as well as its tendency to be
uncontrollably doped by O
2
, necessitate the development of other alternatives. The wide variety of hole
transporting organic layers originally developed for organic thin film transistors as well as light emitting
devices could possibly be applied in conjuction with the perovskite system. An early study on alternatives
to Spiro-oMeTAD for perovskite solar cells, had indicated that thiophene based systems may not be
suitable.
34
Arylamine based hole transporters such as poly-triarylamine,
34
N,N-di-p-methoxyphenylamine-
substituted pyrene derivatives
89
and swivel cruciform thiophene-based molecules
90
have shown
performances between 11-12%. An interesting development
91
has been the utilisation of inorganic CuI
hole transport layer with CH
3
NH
3
PbI
3
. Although they performed worse than spiro-oMeTAD solar cells
due to high recombination, the work does indicate the possibility of applying other inorganic hole
transporters such as CuSCN to the perovskite system. An equally intriguing avenue is the application of
nanocarbon (eg. Graphite, carbon nanotubes, graphene-polymer composites) based hole transporters. As
has been pointed out by Johansson and coworkers, the efficiencies can be primarily determined by
recombination at the perovskite-HTM interface.
76
The low thicknesses of HTM layers (~100 nm) in well
optimised solar cells as well as the utilisation of dopants, point to very low losses within the HTM itself,
indicating the crucial nature of the perovskite-HTM interaction.

Newer Perovskite Compositions: Much of the high efficiency solar cells have focussed on CH
3
NH
3
PbI
3
as
the light absorber. Although this composition currently yields the most efficient solar cells, newer
perovskite compositions which have tuneable bandgaps would be of interest to tandem solar cell
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configurations or in power applications that require high voltages. Seok and coworkers have elegantly
shown how partial substitution of I with Br can yield colourful solar cells with varying photocurrent onset.
A benefit of the partial substitution also seems to be improved stability.
37
Similarly, Hodes and Cohen
have demonstrated CH
3
NH
3
PbBr
3-x
Cl
x
solar cells with open circuit voltages as high as 1.5V.
92
Another
key effort required is the reduction of bandgap of the perovskite solar cells for increased spectral response
and therefore improved efficiencies. CH
3
NH
3
PbI
3
based solar cells do not efficiently harvest photons
close to its optical absorption onset (600-780 nm), resulting in photocurrents not approaching the
theoretical maximum. The development of formamidinium (HC(NH
2
)
2
+
) lead perovskites
93-96
with a
lower bandgap (1.48 eV) that allows for high photocurrents is thus a promising development. These high
photocurrents allowed Eperon et. al to demonstrate planar heterojunction solar cells with power
conversion efficiencies of upto 14.2%.
93
The most pressing demand for newer photoactive perovskites is
driven by the need to replace Pb. Hodes has estimated that a production capacity of 1000 GW per year
from CH
3
NH
3
PbI
3
solar cells requires less than 10,000 tons of lead much lower than the 4 million tons
per year of lead used for lead-acid batteries currently.
97
Thus, although the total amount of lead that is
required is low, the risk of leaching Pb into the environment needs to be managed. Sn
2+
may serve as a
replacement to Pb
2+
, but its tendency to be easily oxidised is drawback.
98
Computational predictions play
a critical role in Pb replacement efforts, due to the large variety of halide perovskites possible.

Towards Printability and Scalability: The rapid growth in the efficiencies of perovskite solar cells within
a short time period has been catalogued previously.
97, 99
A target of 20% PCE value has also been
identified as attainable in the perovskite solar cells. However, as important as the pursuit of efficiency is
the pursuit of development activities aimed at depositing the perovskite materials through scalable
manufacturing techniques such as screen printing. Carnie et.al have demonstrated that Al
2
O
3

nanoparticles can be mixed in directly with perovskite solution and spuncoated to form a composite
photoactive layer.
51
Further development of similar process recipes could yield compositions that could
be screen printed, blade coated or applied through slot die coating. A fully printable perovskite solar cells
albeit with an unconventional device configuration has been demonstrated by Han and coworkers.
100
The
device architecture consisted of a screen printed TiO
2
layer, ZrO
2
layer and a carbon black/ graphite
composite layer onto which CH
3
NH
3
PbI
3
was dropcasted. Such devices displayed an efficiency of 6.64%.
A critical barrier in the implementation of a printable perovskite solar cell is the deposition of the electron
selective compact layer (typically TiO
2
formed by spray pyrolysis at high temperature). Planar perovskite
solar cells employing organic electron and hole transport layers do not suffer from this limitation, but still
display lower efficiencies than mesoporous layer based solar cells.
45, 53, 58, 59, 62
Approaches to avoid the
high temperature process during the formation of the compact layer includes the utilization of
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electrodeposited ZnO
41
or a spuncoated ZnO nanoparticle layer
57
. A similar nanoparticle based approach
has been demonstrated by the utilization of a spuncoated graphene flake-TiO
2
nanoparticle layer as the
compact layer yielding efficiencies of 15.6%.
101
Very recently, a new low temperature compact layer
TiO
2
deposition recipe has yielded impressive efficiencies of up to 15.9% for a solar cell fabricated at
temperatures less than 150
o
C.
102

Table II: Compilation of high efficiency perovskite solar cells reported thus far (1
st
Feb 2014)
Report Device structure
Device
parameters
Efficiency Active area
Sub-150 C processed meso-
superstructured perovskite solar
cells with enhanced efficiency
Energy & Environmental Science
2014, 7, 1142-1147.
FTO/TiO
2
/mesoporous
Al
2
O
3
/CH
3
NH
3
PbI
3-x
Cl
x
/Spiro-
OMeTAD/Ag
J
sc
= 21.5
mA/cm
2

V
oc
= 1.02 V
FF = 0.71
15.9% 0.0625 cm
2

Perovskite solar cells with a planar
heterojunction structure prepared
using room-temperature solution
processing techniques. Nat
Photonics 2014, 8,133-138
ITO/ZnO/CH
3
NH
3
PbI
3
/Spiro-
OMeTAD/Ag

J
sc
= 20.4
mA/cm
2

V
oc
= 1.03 V
FF = 0.749
15.7% 0.07065 cm
2

Low-Temperature Processed
Electron Collection Layers of
Graphene/TiO2 Nanocomposites in
Thin Film Perovskite Solar Cells
Nano Letters 2014, 14, 724-730
FTO/Graphene-
TiO
2
/mesoporous-
Al
2
O
3
/CH
3
NH
3
PbI
3-x
Cl
x
/Spiro-
OMeTAD/Au
J
sc
= 21.9 mA/cm
2

V
oc
= 1.04 V
FF = 0.73

15.6%

0.0625 cm
2

Efficient planar heterojunction
perovskite solar cells by vapour
deposition, Nature 2013, 501, 395-
398.
FTO/TiO
2
/CH
3
NH
3
PbI
3-
x
Cl
x
/Spiro-OMeTAD/Ag
J
sc
= 21.5
mA/cm
2

V
oc
= 1.07 V
FF = 0.67

15.4% 0.076 cm
2

Sequential deposition as a route to
high-performance perovskite-
sensitized solar cells, Nature 2013,
499, 316-319.

FTO/TiO
2
/
mesoporousTiO
2
/CH
3
NH
3
PbI
3

/Spiro-OMeTAD/Au
J
sc
= 20 mA/cm
2

V
oc
= 0.993 V
FF = 0.73

J
sc
= 21.3
mA/cm
2

V
oc
= 1.0 V
FF = 0.66
15.0%

14.1%
(certified)

0.285 cm
2

0.209 cm
2

Much of the high efficiency reports on perovskite solar cells have been demonstrated on cell areas much
less than 1 cm
2
(Table II). Malinkiewicz et. al. who reported an efficiency of 12.04% (cell area = 0.09cm
2
)
fabricated a ~1cm
2
solar cell using the same process which yielded an efficiency of 8.27%.
62
The primary
difference in the photovoltaic parameters was the FF which reduced from 0.67 to 0.52 when going to the
larger area solar cells. The reason for the reduction in the FF is unclear, but could arise from series
resistance in the electrode itself. The first perovskite based modules have also been reported (up to 16.8
cm
2
module area) by Matteocci et. al. who employed both P3HT and Spiro-OMeTAD as hole transporters
yielding efficiencies of 5.1%.
103
Such large scale demonstrations of perovskite solar cells are necessary
for perovskite solar cells to develop into a technology for widespread deployment.

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Stability studies: The 3-D methylammonium trihalogenoplumbates (II) crystals (i.e., CH
3
NH
3
PbCl
3

CH
3
NH
3
PbBr
3
and CH
3
NH
3
PbI
3
) are known to undergo 1
st
order phase transitions.
104, 105
In particular,
CH
3
NH
3
PbI
3
undergoes a tetragonal I to cubic phase transition at ~327K (or ~54
O
C), which is close to
the device operating temperatures under direct sunlight. This cubic-tetragonal transition results in the
methylammonium ions exhibiting a disordered character while the PbX
6
octahedron exhibiting a
displacive character.
105, 106
Systematic studies on such effects on the carrier dynamics and on the device
properties under operation are warranted. Since the phase transitions involve a volume change, it is
pertinent to investigate whether infiltrating the perovskite within mesoporous layers, can improve
temperature stability. Reports on long term device performance tests are few, with 500h stabilities under
constant illumination being reported by Grtzel and coworkers.
35
Snaith and coworkers have reported
performance data for 1000h in MSSCs and have pointed towards UV induced changes in TiO
2
based solar
cells due to desorption of surface-adsorbed oxygen.
107
Systematic studies on the degradation mechanisms
(including the hole transport layers) are required to manage the lifetimes of these solar cells. Newer
perovskite compositions which do not undergo phase transitions at device operational temperatures
should be pursued as well.

In summary, the field of perovskite solar cells has rapidly grown to become the most efficient
solution processed photovoltaics, leapfrogging other 3
rd
generation photovoltaic technologies. As this
field matures, rapid improvements in the power conversion efficiencies will become harder to come by.
Thus, a deeper understanding of the fundamental working mechanisms become increasingly important-
especially if efficiencies exceeding 20% need to be achieved. Concurrently, technological developments
in the area of scalable manufacturing techniques, toxicity and stability need to be effectively addressed.

Acknowledgements
We would like to acknowledge Subodh Mhaisalkar and Pablo P. Boix for technical discussions and Tom
Baikie and Swee Sien Lim for the figures. T.C.S. acknowledges the financial support from NTU start-up
grant M4080514, SPMS collaborative Research Award M4080536, Ministry of Education AcRF Tier 2
grant MOE2013-T2-1-081. N.M. acknowledges the financial support from NTU start-up grant M4081293
and from Singapore National Research Foundation (NRF) through the Competitive Research Program
(NRF-CRP4-2008-03). T.C.S. and N.M. also gratefully acknowledge the Singapore NRF for the funding
through the Singapore-Berkeley Research Initiative for Sustainable Energy (SinBeRISE) CREATE
Programme.

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Biographies

Dr. Tze-Chien Sum is an Assistant Professor at the Division of Physics and Applied Physics, School of Physical and
Mathematical Sciences, Nanyang Technological University (NTU) where he leads the Femtosecond Dynamics
Laboratory. He received his Ph.D in 2005 from the National University of Singapore, where he worked on the
development of a new direct-write lithographic technique (proton beam writing) for photonic applications. Upon
joining NTU in 2005 as a Lecturer, he switched to the exciting field of ultrafast optical spectroscopy or
Femtosecond time-resolved spectroscopy and established the xC-Lab research group a lab for the investigation of
exCited-state phenomena. His research focuses on investigating light matter interactions; energy and charge transfer
mechanisms; and probing carrier and quasi-particle dynamics in a broad range of emergent nanoscale and light
harvesting systems using Femtosecond time-resolved spectroscopy.

Dr. Nripan Mathews is an Assistant Professor at the School of Materials Engineering in Nanyang Technological
University. He pursued his PhD at a joint Commissariat l'nergie atomique (CEA) - Centre national de la
recherche scientifique (CNRS) - Universite de Pierre et Marie Curie (Paris VI University) laboratory in the area of
molecular crystals, studying the signatures of optical excitations within them (2008). He was also a visiting scientist
at Prof. Michael Grtzels laboratory at cole Polytechnique Fdrale de Lausanne (EPFL), working on a pan-
european project on photoelectrochemical hydrogen production. His research focuses on a wide variety of novel
materials (metal oxides, organic semiconductors, graphene, carbon nanotubes, sulfides, selenides) and novel
morphologies (One dimensional structures such as nanowires and nanotubes, thin films as well as two dimensional
nanosheets) produced through a range of fabrication procedures. He has focussed primarily on the electronic and
optical properties of these materials and how they can be adapted for practical applications.

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TOC Graphical Abstract:

This article reviews the fundamental photophysics and working mechanisms of perovskite solar
cells and highlights the current state-of-the-art and open questions in this maturing field.

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