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Solar Energy 122 (2015) 678699
www.elsevier.com/locate/solener

Review

Perovskites: Solar cells & engineering applications materials

and device developments
Milos Petrovic a,b, Vijila Chellappan b,, Seeram Ramakrishna a,
a
Department of Mechanical Engineering, National University of Singapore, Singapore 117576, Singapore
b
Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 3 Research Link, Singapore 117602,
Singapore

Received 26 May 2015; received in revised form 11 September 2015; accepted 23 September 2015

Communicated by: Associate Editor Takhir Razykov

Abstract

Recent advancements in the area of perovskite photovoltaics have drawn wide attention of scientic community, mainly because of
exceptional light absorbing properties exhibited by these organometallic halides. One of the main advantages perovskites have is their
ability to be processed from solutions at relatively low temperatures. This paper briey describes main structural, optical and electrical
properties of perovskite materials, as well as the most popular solution processing techniques. We reect on current progress in fabri-
cation of solar cells containing organicinorganic perovskites, device inner workings and eect of cell architecture on eciency, along
with prospective ne tuning of device properties through alteration of organometallic halide structure. Over the span of only three years,
reported photoconversion eciencies of such devices went from 3.8% to over 19%, with further increase being expected in near future.
Finally, we describe other prospective applications for dierent perovskite materials. There is no doubt that perovskite photovoltaics
possess great potential to provide bright future for the eld of solar cells research, but whether they are going to live up to their expec-
tations, remains to be seen.
2015 Elsevier Ltd. All rights reserved.

Keywords: Perovskite materials; Solar cells; Solution processing

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 679
2. Solution processing techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
2.1. Spin-coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
2.2. Spray coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
2.3. Screen printing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
2.4. Dip-coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 681
2.5. Thermal evaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 681
3. Optical properties of perovskites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 681

Corresponding authors.
E-mail addresses: milos@nus.edu.sg (M. Petrovic), c-vijila@imre.a-star.edu.sg (V. Chellappan), seeram@nus.edu.sg (S. Ramakrishna).

http://dx.doi.org/10.1016/j.solener.2015.09.041
0038-092X/ 2015 Elsevier Ltd. All rights reserved.
 M. Petrovic et al. / Solar Energy 122 (2015) 678699 679

4. Electrical properties of perovskites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 683

5. Solar cell developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
6. The inner workings of perovskite solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 688
7. Challenges and prospects for solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 691
8. Engineering applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 691
9. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 694
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 694
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 694

1. Introduction where rA, rB and rC are radii of A, B and C ions, respec-

tively. Ideal cubic structure occurs when s 1, while
Term perovskite is used when referring to a large group s < 1 indicates that A is too small and s > 1 means A is
of compounds with a crystal structure resembling the min- too large to t in the cavity between BC6 octahedrons.
eral perovskite CaTiO3. General formula of perovskites is Structural diversity arises from the distortions of ideal
ABC3, where A and B represent cations, and C is an anion. cubic structure as a result of octahedral tilting (Glazer,
A-site cations are usually bigger and more electropositive 1972; Lufaso and Woodward, 2001; Howard and Stokes,
in comparison to ones located at B-site, while the C site 1998) or JahnTeller eect (Millis, 1998; Lufaso and
is commonly occupied by oxide ion O2
, or halide ions Woodward, 2004). Octahedral tilting occurs when cation
(Cl
, Br
, F
). The crystal structure of perovskite depicted at the A-site is too small to ll cavity between BC6 octahe-
in Fig. 1(a) is ideal cubic, where A cation is located between drons, resulting in lowering of system symmetry. In order
eight BC6 octahedral units, while in each of them B cation to maintain connectivity, each octahedron must rotate
is 6-fold coordinated by surrounding C ions. Even though whenever one of them changes its position around the axis
the basic structure of perovskites is fairly simple, there is normal to the layer. These rotations may result in out of
still a large number of possible structural variations among phase (when rotation direction is altering between dier-
them, because A and B sites are able to accommodate vir- ent layers) or in phase (same direction rotation) tilting.
tually any element from periodic table (Schlom et al., 2008) JahnTeller distortion occurs when electronic congura-
as illustrated in Fig. 1(b). Size of A and B ions greatly inu- tion of cation is orbitally degenerated, yielding unstable
ences the structure of perovskite crystal lattice, and their ground state. This eect happens as a result of linear
radii correlation is expressed through tolerance factor s: decrease in energy following displacement within the crys-
tal, while at the same time elastic energy of system
rA rC
s p increases. Distortional displacement can manifest either
2rB rC through elongation or shortening of the octahedral bonds,

Fig. 1. (a) Cubic perovskite structure ABC3, where grey sphere is A cation, blue and red spheres represent B and C ions, respectively; reproduced from
King and Woodward (2010) with permission from The Royal Society of Chemistry; (b) possible combination of elements which can occupy sites in
perovskite crystal lattice (Schlom et al. (2008), Copyright (2008), this material is reproduced with permission of John Wiley & Sons, Inc.). (For
interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)
680 M. Petrovic et al. / Solar Energy 122 (2015) 678699
causing a minimum in total energy (Wolfram and
Ellialtioglu, 2006). Hybrid perovskites are synthesized in
an attempt to combine positive properties of inorganic
(high electrical mobility) and organic (photosensitivity)
materials into a single component. General formula for
such perovskites is (RNH3)2BC4, where B site is occupied
with divalent cations (Cu2+, Ni2+, Co2+, Fe2+, Mn2+,
Cr2+, Pd2+, Cd2+, Ge2+, Sn2+, Pb2+, Eu2+) or in some
cases trivalent (Mitzi, 2000) (Bi3+,Sb3+) and C is a halogen.
Inorganic layers consist of octahedral BC6 structure inter-
posed between organic cations, thus forming 2D domains
(Mitzi et al., 2001). Besides utilizing single layer per-
ovskites, it is possible to synthesize hybrids with multiple
layer orientations (Mitzi et al., 1994) by controlling crystal-
lization process through alteration of inorganicorganic
material ratio, or by derivation of layers with various octa-
hedral units from three-dimensional ABC3 structure (Mitzi
et al., 1995). In such cases, organic material consists of
alkyl chain with either diamonium (+NH3RNH+ 3 ) or
monoammonium (R-NH+ 3 ) cations packed in monolayers
and bilayers, respectively. In the case of monoammonium,
hydrogen cations form ionic bond with halogen atoms
from inorganic component, while R chains establish Van
der Waals connection joining two organic layers together.
However, in case of diammonium cations, gap between
two adjacent perovskite sheets is completely covered with
a single layer, so there are no dipole interactions present
in the system (Mitzi et al., 2001).
2. Solution processing techniques
Solution processability is one of the most important
advantages when utilizing perovskites, because of their
good solubility (Mitzi, 2004) which in turn allows usage
of low-cost processing techniques such as spin-coating
(Suarez et al., 2014), screen printing (Bebelis et al., 2007)
or dip-coating (Liu and Kelly, 2014). Another way of pro-
cessing perovskites is through vapor deposition, mainly
thermal evaporation (Chung et al., 2012a).
2.1. Spin-coating
Spin-coating is a well-known, rapid technique used for
producing uniform, quality thin lms on a variety of sub-
strates. Being relatively simple, this coating method is
widely used in fabrication of organic electronics (Hoggan
et al., 2004) and optical device coatings (Liang et al.,
2013), among many others. Spin-coating process involves
deposition of perovskite solution onto a substrate, fol-
lowed by rotation at high speed and consequent drying,
resulting in a formation of thin perovskite lm. Thickness
of formed lm is controlled through several parameters,
such as viscosity of the solution, temperature and spinning
velocity. Post-processing usually includes annealing in
order to promote evaporation of residual solvent and
improve crystallinity (Yang et al., 2004). Advantages of
spin-coating method, to name a few, are low-cost, fast
processing, possibility of multilayer depositing
(Komikado et al., 2007) and small quantities of solution
needed for covering large substrate area (Jiang and
McFarland, 2004). On the other hand, disadvantages
include signicant losses of coating material (Han et al.,
2004) (over 90%), lack of compatibility with roll to roll pro-
cessing (Brabec and Durrant, 2008) and sensitivity to the
rate of evaporation which can result in numerous defects
in the nal product (Yang et al., 2015a; Melo et al., 1989).
2.2. Spray coating
Another technique suitable for fabrication of thin lm
perovskites is spray pyrolysis, providing easy control over
lm composition as well as simple experimental setup
(Perendisa et al., 2005; Fu et al., 2005; Princivalle et al.,
2004). This method is usually employed in synthesis of per-
ovskite oxides, where thin lm deposition is achieved by
spraying solution on the substrate, followed by chemical
reaction between constituents present in the system, form-
ing a layer of perovskite. Coating solution is designed in
the way that all unwanted products are volatile at working
temperature. Commonly used types of spray coating are
ultrasonic (Furusaki et al., 1995) (atomization is caused
by ultrasonic frequencies) and electrostatic (atomization
is achieved through exposure to electric eld). During
ultrasonic spray deposition, nozzle is utilized to deliver
solution in a form of a spray containing droplets of uni-
form diameter, with the help of various gases (Suh and
Suslick, 2005; Michel et al., 2006) acting as carriers and
focusing spray onto the substrate (Steirer et al., 2009). Dur-
ing electrostatic spray deposition method, positive high
voltage is used to create aerosol from perovskite solution
which is blown through the nozzle and subsequently depos-
ited on the grounded substrate. Potential dierence
between nozzle and substrate electrode is ensuring good
coverage with perovskite lm (Taniguchi and
Schoonman, 2002). Spray coating is a very eective tech-
nique for deposition of perovskite oxide thin lms, whose
properties are dependent on process parameters, mainly
temperature (Marrero-Lopez et al., 2014). Higher substrate
temperatures induce rough and porous lms, while low
temperatures may cause cracking of deposited layer. More-
over, temperature largely aects texture and crystallinity
(Taniguchi et al., 2003) of the sample. Properties and mor-
phology of deposited lms can also be altered through
usage of various additives (Dong et al., 2011; Tan et al.,
2010). One of important advantages of spray coating,
besides low cost and size selectivity of the droplets, is pos-
sibility to use highly diluted solutions.
2.3. Screen printing
This is a cheap and eective printing technique allowing
fabrication of printed layers with 2D patterns. The biggest
advantage of this technique in comparison to spin-coating
is very ecient utilization of material, resulting in virtually
 M. Petrovic et al. / Solar Energy 122 (2015) 678699
no loss of paste used for printing. Prerequisites for success-
ful screen-printing are highly viscous coating solution,
together with low volatility and large wet lm thickness.
Mechanism behind this type of printing is relatively simple;
screen made of steel mesh (or synthetic material) is
attached to a frame under tension, making it possible to
create printing pattern by lling a part of the screen with
an emulsion impermeable to the coating solution. After
bringing the working solution in contact with the substrate,
the screen is dragged across it, allowing solution leakage
through unprotected parts of the mash, reproducing
desired pattern. Volume between frame meshes and thick-
ness of emulsion is known as volume of the screen Vs,
which is given as a volume of printing solution used per
area of the open screen. This is an important parameter
required for estimation of dry lm thickness together with
viscosity of coating solution, speed of moving screen and
force applied to it. Partially deposited lm thickness can
be described using pick-out ratio e) and following
relationship:
C form coating over it. Because the process is conducted
dVse
q
where C and q are concentration of solid material in coat-
ing solution and density in deposited lm, respectively.
Despite its main drawback requirement for low volatility
of used materials as well as high viscosity, there are reports
of screen-printing method being employed in fabrication of
solar cells (Krebs et al., 2007; Mohammadi et al., 2012).
Most common way to utilize screen-printing when han-
dling perovskites is fabrication of thick lm gas sensors
(Cerda et al., 2002; Martinelli et al., 1999) and cathodes
for fuel cells (Herle et al., 2001; Bebelis et al., 2006).
2.4. Dip-coating
Another very simple, yet eective process (batch or con-
tinuous) used for lm formation through immersion of
substrate in coating solution. After exposure to the solu-
tion for a certain period of time, wetting of substrate sur-
face and subsequent lm formation takes place.
Following this deposition step is withdrawal of substrate
from the solution bath and evaporation of solvent, result-
ing in formation of lm with uniform thickness. Further
post-treatment step may be necessary in order to obtain
nal coating. Main forces governing dip-coating process
are gravitational force, viscous drag, surface tension and
force of inertia. Their eect on the nal thickness d of
deposited lm can be described using LandauLevich
(Jackson et al., 1981) equation:
2=3
gU
dk p ;
c1=6  qg
where k is a constant, U denotes speed of substrate with-
drawal, c is surface tension, q and g are liquid density
and viscosity, respectively. This method of perovskite
681
processing provides possibility to fabricate thin layers
which can be deposited over membranes (Gurauskis
et al., 2012; Othman and Kim, 2008), or interconnectors
during fabrication of intermediate-temperature solid oxide
fuel cells (Yoon et al., 2008).
2.5. Thermal evaporation
Even though it cant be classied as a solution process-
ing method, thermal evaporation deserves to be mentioned
because it plays important role in processing of per-
ovskites, especially in fabrication of photovoltaic devices.
Thermal evaporation is a method of material deposition
directly from the vapor phase, and is widely used in fabri-
cation of thin lms, magnetic and optical devices. During
deposition process, evaporant is heated to a temperature
high enough to induce vaporization, while the substrate is
kept at temperature below freezing point of evaporating
material. Atoms or molecules being thermally released
from evaporant surface travel to the substrate where they
under reduced pressure (less than 10
5 bar), vapor travels
between source and the substrate following straight line,
without any kind of interaction with residual gas atoms.
Essentially, there are two possible approaches to perovskite
lm formation: using single (Chondroudis et al., 2000) and
dual-source (Liu et al., 2013) evaporation system. Single
source deposition relies on fast heating and evaporation
of organicinorganic perovskite suspension, placed on a
metal sheet. After applying large current through the metal
sheet, sharp increase of temperature results in ablation of
material from metal holder and subsequent deposition
onto substrate. On the other hand, dual-source deposition
uses organic and inorganic salts which are simultaneously
evaporated from two separate sources. In the case of single
source ablation, high temperature ensures fast evaporation
of inorganic component, while avoiding thermal decompo-
sition of the organic part. Furthermore, there is no need for
post-processing, because organicinorganic perovskite self-
assembles on the substrate during deposition (Mitzi et al.,
1999), unlike in dual-source method, where annealing is
required in order to obtain fully crystallized perovskite
lm. Table 1 summarizes some of the advantages and
drawbacks of abovementioned perovskite processing
techniques.
3. Optical properties of perovskites
Optical properties of organometallic perovskites are
inuenced by both organic and inorganic components.
Perovskites having 2D geometry with general formula
(RNH3)2MX4, where metal cations are Sn(II), Pb(II) or
Ge(II) are equivalent to quantum well structures, with
inorganic layers (smaller band gaps) acting like wells, while
organic layers (larger band gaps) play the role of barriers.
Smaller dielectric constant of organic layers coupled with
packed thin quantum wells, leads to dielectric connement
682 M. Petrovic et al. / Solar Energy 122 (2015) 678699

Table 1
Advantages and disadvantages of dierent perovskite processing techniques.
Processing technique Advantages Disadvantages
Spin-coating Low cost, fast, easy adjustment of lm thickness, Non uniform lm thickness, loss of coating material,
multilayer depositing no patterning
Screen-printing Low-cost, adjustable layer thickness Screen blocking, can be slow
Spray coating Low-cost, use of highly diluted solutions, uniform layer thickness Dicult to control process parameters
Dip-coating Low-cost, simple Can be slow, non-uniform lm surface, no patterning
Vapor deposition Uniform layer thickness, easy monitoring of deposition Complex equipment, dicult synthesis of multicomponent
rate, patterning materials, can be slow

eect, resulting in a formation of excitons with strong bind-
ing energy. Materials with larger dielectric constant have
noticeably smaller exciton binding energy (Ishihara et al.,
1992). Substitution of halide or metal ions enables adjust-
ment of spectral position of respective optical transitions
due to the fact that binding energy of exciton is dependent
on the band gap of inorganic layer (Papavassiliou and
Koutselas, 1995). Some of the important optical properties
exhibited by perovskites are: photoluminescence (Dammak
et al., 2009), nonlinear optical eect (Ishi et al., 1997) and
highly ecient electroluminescence (Hattori et al., 1996).
Papavassiliou et al. (1999) showed that optical absorption
spectra of organicinorganic hybrid perovskites having for-
mula (C5H4CH2NH3)2PbX4 exhibits both Weiner lines
(originating from inorganic layers) and Frankel exciton
bands (arising from organic molecules). Dierent halogens
may be used in order to observe changes in photolumines-
cence and absorption of perovskites. Fig. 2(a) illustrates
shift in the light emission for dierent substituents, ranging
from green (I), over blue (Br) to ultraviolet (Cl). Sharp and
narrow peaks together with small Stokes shift between
absorption and emission spectra reect properties of exci-
ton conned within organic layer. These electronhole
pairs have very large binding energy, roughly 100 times
bigger than exciton states in respective bulk materials
(Cheng and Lin, 2010). Reason for this type of behaviour
lies in the quantum connement eect and sandwich like
structure of hybrid perovskites (Hong et al., 1992). Organic
molecules with lower dielectric constant are more inert
towards charge carriers, thus enhancing binding electric
interactions between electrons and holes creating excitons,
while the recombination of charge carriers yields strong
photoluminescence even at room temperature. Interactions
between Frenkel and Weiner excitons when their bands are
close to each others, result in quenching of inorganic exci-
ton luminescence and strengthened light emission from
organic component (Agranovichy et al., 1998). Another
way of aecting optical properties of organicinorganic
perovskites is through substitution of metal ions as shown
by Mitzi (1996), who observed red shift in the photolumi-
nescence peak as a function of dierent metals (Ge, Sn,
Pb) within perovskite. He came to the conclusion that
stereoactivity of the metal(II) lone pair belonging to IV B
group elements is important only in the case of Ge(II),
and is less signicant for Pb(II) and Sn(II) because for
these two elements lone pair electrons are included into
conduction band. Optoelectrical activity of hybrid per-
ovskites can be improved by replacing alkyl chains with
high crystalline fullerene derivatives (Kawabata et al.,
2009). In this case, highly organized structure within
organic layer improves generation of photocurrent. When
tailoring organic layer structure it is important to keep in
mind the size of RNH3+ groups, which should be large
enough to prevent falling into inorganic layers and thus,
altering structure from 2D to 3D (Zhang et al., 2010). Con-
versely to 2D structured perovskites, 3D organicinorganic

Fig. 2. (a) Optical absorbance (ac) and photoluminescence (a0 c0 ) of perovskites containing lead iodide (a, a0 ), lead bromide (b, b0 ) and lead chloride (c, c0 );
(Papavassiliou et al., 1999, Copyright Wiley-VCH Verlag GmbH & Co. KGaA, reproduced with permission); (b) (RNH3)2MI4 (M = Ge(a) Sn(b), Pb(c))
photoluminescence spectra at room temperature; reproduced with permission from Mitzi (1996). Copyright (1996) American Chemical Society.
 M. Petrovic et al. / Solar Energy 122 (2015) 678699
lead halides exhibit strong energy splitting eect above con-
duction levels dominated by spinorbit coupling, causing
nearly isotropic absorbing behaviour. Additionally, they
express reverse band ordering in comparison to quantum
well and bulk structures encountered in standard semicon-
ducting materials (Pedesseau et al., 2014). Although these
organometallic lead halides essentially have the same elec-
tronic conguration, somewhat larger band gap character-
istic for Br substituted perovskites reduces dielectric
coecient and consequently leads to constriction of Bohr
radius, higher binding energy as well as strengthening of
low energy excitons. As a result of such properties, CH3-
NH3PbBr3 displays high stability and photoluminescence
when prepared in the form of nanoparticles. Spherical
shape promotes slow non-radiative recombination process,
resulting in long photoluminescence lifetime and relatively
small (<20%) emission loss under UV exposure (Gonzalez-
Carrero et al., 2015). Another interesting property of
methylamonium halides is correlation between photolumi-
nescence and type of material in contact with perovskite.
Namely, once grown into polymer lms, exciton transport
towards perovskite induces formation of secondary inacti-
vation route of locally excited states within polymer/per-
ovskite blend. It has been demonstrated, in fact, that
photoluminescence varies in at or mesoporous device
architectures and quenching in such case is not unequivo-
cally related to charge extraction, instead its proven to
be linked to crystallite size and properties of adjacent sub-
strate (Masi et al., 2015). Furthermore, solution processed
3D organometallic hybrids yield crystals devoid of high
concentration of defects, allowing them to exhibit amplied
spontaneous emission at room temperature as demon-
strated by Xing et al. (2014). Origin of this fairly low super-
luminescence threshold is based on the slow rates of non-
geminate and Auger recombination, as well as remarkable
absorption coecients. However, current density required
to induce lasing eect is 5.5 kA cm
2, which is relatively
high bearing in mind sensitivity towards temperature and
air exposure these organicinorganic hybrids have. More-
over, external quantum eciency of perovskite light emit-
ters is still trailing behind organic and quantum dot
LEDs, thanks to the imbalanced charge mobilities between
neighbouring layers. Recently, Tachikawa et al. (2015)
demonstrated connection between photoluminescence
quenching and charge traps present at the surface of
organometallic lead bromides, with the aid of high resolu-
tion transmission electron microscopy and single-particle
spectroscopic measurements. Origin of these trap energy
levels is ascribed to excess of lead cations, which promote
recombination process and can be controlled through pas-
sivation with donors such as thiophene or pyridine. Con-
trol over optical properties of organicinorganic
perovskites is possible to some extent thanks to the variety
of dierent metal cations, halides, as well as multitude of
organic molecules available for their synthesis. For
instance, it is possible to cover region between UV and
IR by changing either metal or halogen ions. Moreover,
683
various organic groups possess dierent energy gaps pro-
viding plethora of possibilities for tuning the optical prop-
erties of such perovskites. Incorporation of luminescent
molecules into organic layer brings signicant changes to
optical properties, which can be employed in fabrication
of highly stable light emitting diodes (Saka et al., 2005).
It is interesting to note that mixture of two types of halo-
gens within organicinorganic perovskite doesnt produce
two distinct absorption peaks, but only one. Position of
such peak can vary depending on the ratio between halo-
gens in the mixture (Kitazawa, 1997). Layered hybrid per-
ovskites exhibit useful optical properties, and as such are
employed in fabrication of LEDs (Gebauer and Schmidt,
1999), optical microcavities (Lanty et al., 2008), thermal
energy storage (Busico et al., 1979) and nonlinear optical
devices (Kondo et al., 1998). Perovskite titanite oxides with
3D structure are also known to exhibit considerable photo-
luminescence eect when doped with certain rare earth ele-
ments (Er, Yb, Eu). Furthermore, light emitting properties
can be additionally enhanced utilizing various synthesis
methods or through exposure to increased temperature
and external stress, as disturbance within interlattice order-
ing is shown to improve photoluminescence properties.
Additionally, stress induced by voltage poling induces rem-
nant polarization in some perovskite oxides, which results
in modication of crystal symmetry due to octahedral tilt-
ing and plane shifting stabilization. These structural transi-
tions are strongly correlated to photoluminescence of 3D
perovskite oxides as deviation from perfect crystal struc-
ture is necessary to induce luminescence eect (Bhargavi
and Khare, 2015).
4. Electrical properties of perovskites
Takahashi et al. (2007) showed that conductivity of
organicinorganic perovskites can be adjusted through
selection of suitable organic component. The role of
organic groups is to buckle inorganic sheets through inter-
molecular interactions, creating distortion within per-
ovskite structure, which in turn changes orbital overlap
used for carrier transport, thus aecting conductivity. It
should be noted that these organic groups are not acting
as dopants to inorganic layers, nor do they have direct con-
tribution to conductivity of the system. Furthermore, same
paper describes how oxidation of metal cation (Sn2+ to
Sn4+) caused by hole doping can signicantly alter conduc-
tivity of hybrid perovskite. Another way to adjust the con-
ductivity of organicinorganic hybrids explained by Mitzi
et al. (2001), consist of simultaneous growth of double
and triple perovskite layers, making use of various organic
cations. Essentially, small ions are incorporated into per-
ovskite crystal lattice, while large ones remain outside,
inducing deformation to sandwich-like structure. Conduc-
tivity increases as organometallic perovskite resembles 3D
structure closer, improving mobility of charge carriers.
Generally, electronic properties of organicinorganic
perovskites depend on inorganic component, because
684 M. Petrovic et al. / Solar Energy 122 (2015) 678699
p-conjugated organic compounds exhibit edge-to-face
interactions, thus no signicant electronic overlap occurs.
Perovskites with zero dimensional structure have noticeable
lower conductivity in comparison to 1D, 2D and 3D
hybrids, due to the fact that they lack extended inorganic
network. In one-dimensional perovskites, structure is
reduced causing increase in the density of states at some
energy levels, resulting in improved conductivity (Bianconi
et al., 1996). Even though the availability of carriers is
increased, actual conductivity is hindered by narrow con-
duction bands limiting their mobility. On the other hand,
structure of two and three-dimensional perovskites provides
wider bands, thus improving conductivity. Umebayashi
et al. (2003) conducted a research on the eect of
reduced dimension in (CH3NH3)PbI3 and (C4H9NH3)2PbI4
perovskites on their electronic structure, and after observing
spectral data discovered that 3D valence state possess
signicantly broader band gap in comparison to 2D state.
Moreover, density of states for 2D crystals exhibit sharp,
localized peaks in contrast to wider peaks characteristic
for 3D network. Fig. 3 illustrates the way in which reduced
dimension alters density of states on certain energy levels.
Another consequence of dimension alteration is increased
band gap, formed as a result of narrowed valence bands.
It should be noted that electron localizations in 2D
organicinorganic perovskites originate from conned
density of states in the axis perpendicular to the plane on
which layers are stacked. Increasing the number of
inorganic layers within the perovskite structure promotes
semiconductormetal transition, such is the case with
(RNH3)n
1SnnI3n+1 organicinorganic perovskite with
h1 0 0i layer orientation (Mitzi et al., 1995). Increased
thickness of perovskite sheets causes bandwidths of Sn 5s
and Sn 5p to broaden while stabilizing 5p antibonding
orbitals, resulting in a reduced band gap which in turn pro-
motes metallic behaviour of such organometallic hybrid.
Fig. 3. Ultraviolet, photoelectron spectroscopy spectra for (a) 3D RNH3PbI3 and (b) 2D (RNH3)2PbI4; (c) crystal structures of 2D and 3D lead iodide
perovskite. Reproduced with permission from: Umebayashi et al. (2003). Copyright 2003 by American Physical Society.
Stoumpos et al. (2013) investigated tin and lead iodide
perovskites with 3D structure, having CH3NH3+ or
formamidinium ions in the place of organic molecules. They
presented number of possibilities to tune the electrical prop-
erties of such pervoskites either by altering synthesis process
or through exposure to elevated temperatures. Obtained
results indicated that fabrication method is the major factor
aecting optoelectric properties of these materials. With
band gaps spanning from 1.1 to 1.7 eV as well as good con-
ductivity, strong photoluminescence at room temperature
and availability of solution processing, these perovskites
appear to be a good choice for semiconductors fabrication.
Chung et al. (2012b) and co-workers examined electrical
conductivity of tin halides having formula CsSnI3 and
observed eect of Sn vacancies within crystal structure.
Namely, intrinsic defects within structure of this perovskite,
allow generation of holes with high mobility, especially at
higher temperatures, making perovskite act as a p-type
metal, thus greatly improving electrical conductivity. When
discussing electrical properties of perovskites, special atten-
tion should be paid to their oxides. They have general for-
mula of ABO3 and are known to exhibit conductivity
similar to metals and higher thermal stability than oxides
of transitional metals (Jiang et al., 2014). For this reason,
some oxides such as LaCrO3, have extensively used in
fabrication of solid oxide fuel cells (Hilpert et al., 2003).
Common way of improving electrical conductivity in
perovskite oxides is through doping of A site cation. For
instance, in ZrO2Ln2O3, electrcal conductivity of zirco-
nium oxide is conditioned upon concentration and type of
dopant (Arachi et al., 1999), while Conductivity rises with
increased amount of dopant (oxygen vacancies), while acti-
vation energy for charge transport is determined by the size
of doping ions. Even though importance of A site element is
signicant for electrical properties of perovskite oxides, it
was found that presence of Cu at B site of the crystal is of
 M. Petrovic et al. / Solar Energy 122 (2015) 678699
tremendous importance for their superconductivity proper-
ties (Li and Zheng, 2013). Critical transition temperature
for superconductivity is closely connected with the number
of CuO layers within the perovskite structure, and increases
with every newly added layer. However, chemical stability
of such CuO sheets is small, which limits their stacking
capabilities. Doping at A and B sites results in formation
of complex perovskites with general formula AA0 BB0 O3,
where fractions of substituents can induce formation of
relaxor ferroelectric making them attractive for fabrication
of capacitors (Kerfah et al., 2011; Anoop et al., 2015).
Example of such perovskites is Eu and Zr doped BaTiO3
(Boutal et al., 2014), which acts as normal ferroelectric
material at high temperatures, but after being cooled below
certain point forms nanoscale polar regions. This change in
phase structure does not aect average crystal symmetry,
however behaviour of such ferroelectric material is
signicantly altered because dielectric constant exhibits
peak shift towards higher values when applied frequency
is increased. Table 2 lists some of the well-known perovskite
oxides and their properties.
5. Solar cell developments
Organicinorganic lead halides with general formula
RNH3PbX3 made an appearance in solar cell research dur-
ing 2009 (Kojima et al., 2009) as sensitizers for dye-
sensitized solar cells, having eciency of 3.81%. Although
reported devices were unstable, this pioneering work paved
the way for the success of organicinorganic hybrids in the
coming years. At the time of writing this paper, eciencies
as high as 20.1% have been reported, making hybrid per-
ovskites very attractive material for photovoltaic applica-
tions. Another important advantage is a possibility of
solution processing at low temperatures, while yielding
highly crystalline product. Perovskites can play several
roles in solar cell architecture; when used as sensitizers
(Manseki et al., 2014; Kim et al., 2013) they absorb inci-
dent light and supply transport materials with excited car-
riers. They can also act as electron (Lee et al., 2012) or hole
(Laban and Etgar, 2013) transporters depending on the
device structure, or even transport both charge carriers
(Stranks et al., 2013) through bulk perovskite layer, ensur-
ing collection at respective electrodes. Since their major
importance from the standpoint of solar devices is light
harvesting ability, it is important to pay close attention
to energy levels of each material used in photovoltaic
device in such a way that both electrons and holes are
Table 2
Selected perovskite oxides and their properties.
Property Perovskite oxide
Ferroelectric BaTiO3, La0.5Ba0.5CoO3, BiFeO3
Ionic conductivity La(Ca)AIO3, CaTiO3, SrZrO3, LaGaO3
Electrical conductivity LaCoO3, SrFeO3, LaCrO3, LaNiO3
Superconductivity YBa2Cu3O7, Ba0.6K0.4BiO3, La0.9Sr0.1CuO3
685
Fig. 4. Energy levels for various perovskite materials, hole transporters
(right) and electron transporters (left). Reproduced from Boix et al.
(2014). Copyright 2014, with permission from Elsevier.
extracted eciently. Fig. 4 depicts band gaps of commonly
used perovskite materials and various commercially avail-
able transport materials. Important catalyst for progress
in this area was given by Kim et al. (2012a,b) with intro-
duction of highly ecient (9.7%) all solid-state solar cells
utilizing solid state hole transporting material 2,20 ,7,70 -Tet
rakis[N,N-di(4-methoxyphenyl)amino]-9,90 -spirobiuorene
(spiro-OMeTAD). Another push towards highly ecient
perovskite solar cells was made by Burschka et al. (2013),
who pinpointed the importance of high quality perovskite
lms for device performance. They popularized two-step
deposition technique involving spin-coating of methylam-
monium iodide and subsequent submerging into lead
halide solution. Juarez-Perez et al. (2014) and co-workers
demonstrated importance of electron (compact TiO2) and
hole (spiro-OMeTAD) transporters, by comparing e-
ciency of CH3NH3PbI3 perovskite device in cases where
one or both of these layers are omitted. In a device without
electron transporting layer, ll factor decreased from 66%
to 44.4%, while eciency was almost halved to 5% from
9.1% obtained from the device having both transporter
materials. Even greater degradation in quality was
observed when hole transporter was removed from the cell,
causing decline in eciency and ll factor to 1.8% and
35.5% respectively. Essential role of charge transporting
layer was even more obvious when CH3NH3PbI3 layer
was used as absorber and carrier transporter, yielding e-
ciency of only 0.1%. However, high eciency (15%) with-
out hole transporting material is achievable with the proper
UV ozone treatment of the transparent electrode (Ke et al.,
2015) or addition of 5-ammoniumvaleric acid (Mei et al.,
2014). Ultraviolet treatment in the presence of O3 mole-
cules helps minimizing interface recombination, so in the
case of lead chloride perovskite further passivation is pro-
vided by process of Cl segregation, which in turn extends
carrier lifetime and improves photoconversion eciency.
On the other hand, addition of 5-ammoniumvaleric acid
induces partial substitution of methylammonium cations,
reducing number of defects within the crystal structure
and improving coverage of underlying scaold. This results
686 M. Petrovic et al. / Solar Energy 122 (2015) 678699
in extended charge decay time and improved quantum
yield. Despite the obvious benets of having separate layers
used as charge carriers, there is a problem of charge loss at
the interface of perovskite and transporting layers, related
to dissociation of excitons (Sun et al., 2014). In order to
circumvent these issues Roldan-Carmona et al. (2014)
fabricated exible thin lm device having 7% eciency,
using thermally evaporated lead iodide perovskite
(CH3NH3PbI3) layer conned between two thin electron
(polyTPD) and hole (PCBM) blocking layers. Flexibility
is one of the major advantages of organometallic
perovskite solar cells, but quest for exible structure is
accompanied with degradation in performance as demon-
strated by Liu and Kelly (2014), who reported eciency
of 15.7% for device where ZnO and perovskite sensitizer
were deposited onto rigid ITO. However, once substrate
was replaced with more exible ITO/PET, eciency
dropped to 10%. Troughton et al. (2015) managed to fab-
ricate exible devices using inexpensive substrates as elec-
trodes, namely titanium foil for cathode and Ni mashed
PET for anode, while yielding respectable 10.3% eciency.
After being subjected to 200-cycles bending test, these cells
exhibited minimal drop in eciency, mainly as a conse-
quence of reduced ll factor caused by delamination
between hole transporter and transparent electrode. These
results may be considered as a proof of concept for
prospective roll-to-roll production of perovskite cells as
the large scale devices are less prone to degradation from
deformations. In an attempt to circumvent issues accompa-
nying thin lm devices, Im et al. (2011) demonstrated a way
to employ nanoscale particles as light absorbers relying on
size variations in order to adjust their energy levels. As a
result, ecient (6.5%) quantum dot sensitized devices were
fabricated, emulating multiband behaviour and exhibiting
high external quantum eciency, albeit with stability
issues. Nonetheless, high radiative eciency of quantum
dots coupled with good charge transfer properties of
perovskites, ensures superior optoelectronic behaviour
Fig. 5. Perovskite band gap adjustment with dierent cations at A site; (a) structure of ABX3 perovskite; (b) various A site cations; (c) UVVis spectra for
organometallic perovskites with Cs, methylammonium and formamidinium substituents; Reproduced from Eperon et al. (2014c) with permission from
The Royal Society of Chemistry.
(Ning et al., 2015). Namely, almost 80% of photogenerated
charge can be successfully converted to excitons within sys-
tem containing quantum dot nanocrystals seeded over per-
ovskite mash. First solution processed perovskite solar cell
without mesoporous structure having eciency over 10%
was reported by Eperon et al. (2014a). They observed
how change in perovskite coverage aects the eciency
of CH3NH3PbI3
xClx planar heterojunction solar devices
by varying thickness of TiO2 layer. Thicker layer increased
coverage, but above certain threshold (90%) eciency was
actually reduced. Reason for this phenomenon lies in
increased resistance of compact TiO2 layer due to its
thickness, resulting in reduced extraction of electrons
(Peng et al., 2004). However, by nding optimal ratio
between perovskite coverage and TiO2 thickness, eciency
of 12.22% was achieved (Xiao et al., 2015). Perovskite load-
ing can be further improved with addition of aluminium
oxide template which can be selectively removed with
KOH and HgCl2 solutions (Babu et al., 2014). Another
way of improving perovskite solar cells eciency is
through size manipulation of cations occupying A site in
a crystal lattice (Yang et al., 2004; Eperon et al., 2014c)
(Fig. 5). Commonly used lead halides have methylammo-
nium in this position, and such single junction cell has lim-
ited absorption caused be band gap size of approximately
1,55 eV. By replacing methylammonium with somewhat
bulkier formamidinium, band gap of RPbIxBr3
x
perovskite is reduced to 1.48 eV. As a result of reduced
band gap, solar cells fabricated with FAPbIBr2 provide
generation of high currents densities, thus enabling
eciency to reach 14.2%. Besides tuning the absorbing
layer, another way to improve eciency is by enabling fas-
ter charge delivery to electrodes. This can be achieved
through 1D nanowire arrays (Law et al., 2005), which pro-
vide direct transport path for electrons, while packing hole
transporting material between thechannels formed by
nanowire structure, resulting in better hole mobility
(Cardoso et al., 2012). Qiu et al. (2013) utilized this idea
 M. Petrovic et al. / Solar Energy 122 (2015) 678699
to fabricate solar cell using organometallic halide
CH3NH3PbI2Br as a sensitizer, TiO2 nanowires as an elec-
tron transporting material and spiro-MeOTAD as a hole
transporter. Even though achieved eciency (5%) is not
among the highest reported, this type of device architecture
is important because it allows formation of 1.5 lm thick
nanowire lms, noticeably thicker than ones found in
conventional submicron mesoporous layers, whose thick-
ness is limited by charge transport through nanocrystalline
system. However, thicker lms also promote overlapping
of nanobers, reducing the size of formed channels and
lowering loading capacity (Dharani et al., 2014).
Tathavadekar et al. (2015) demonstrated another approach
regarding electron transporter architecture by introducing
TiO2 nanobeads having several hundred nanometers in
diameter deposited over electron injecting base. Grain size
of formed perovskite crystals in this way is increased,
reducing the density at the interface between crystallites
as well as scattering of incident light, resulting in improved
performance of such devices. Other ways of increasing
crystal size include room temperature solventsolvent
extraction (Zhou et al., 2015) and spin-coating of per-
ovskite precursor on preheated substrate as demonstrated
by Nie et al. (2015), ensuring formation of millimetre-
scale grains, which in turn signicantly increases power
conversion eciency. Although these techniques utilize
dierent approach to lm growth, they all provide good
quality of deposited layers and improved substrate cover-
age. Solventsolvent extraction circumvents necessity for
annealing step, thus preventing formation of pinholes on
lm due to the fast evaporation of solvents commonly used
in preparation of perovskite solutions. On the other hand,
hot-casting relies on fast crystallization process caused by
heating of the substrate to 170190 C, modifying interfa-
cial area in a way which allows uninterrupted propagation
of excited charge carriers through deposited organometallic
lm. Very popular approach to this matter was introduced
by Jeon et al. (2014b), showing how dynamic dispersion of
toluene during spin-casting can be utilized to freeze
perovskite coating, enabling formation of very smooth
pinhole-free lm. Study of dierent hole transporting
polymers and their eect on solar device eciency was
conducted by Heo et al. (2013) while using CH3NH3PbI3
as light absorber, TiO2 as electron transporter and
various electron blockers: poly-triarylamine(PTAA), poly-
[2,1,3-benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl)-4H-
cyclopenta[2,1-b:3,4-b0 ]dithiophene-2,6-diyl]] (PCPDTBT),
poly-3-hexylthiophene (P3HT) and (poly-[[9-(1-octylnonyl)-
9H-carbazole-2,7-diyl]-2,5-thiophenediyl-2,1,3-benzothiadia-
zole-4,7-diyl-2,5-thiophenediyl]) (PCDTBT). Eciency
achieved with PTAA as a hole acceptor was 9%, signi-
cantly higher in comparison to devices fabricated using
organic layers assembled by tyophene derivatives.
Performance of these devices followed the trend matching
with increase of their highest occupied molecular orbital
energy levels (Morana et al., 2008; Shen et al., 2008):
P3HT (g = 6.7%) > PCPDTBT (g = 5.3%) > PCDTBT
687
(g = 4.2%). Furthermore, devices containing PTAA layer
exhibited higher open circuit voltage and ll factor than
equivalent cells fabricated using spiro-MeOTAD as a hole
transporter. In addition to carefully selected charge carrier
transporters, eciency of perovskite absorbers with methy-
lammonium ions can be improved by replacing a fraction
of them with suitable dopants, for example Cs (Choi
et al., 2014). Amount of Cs added, governs both optical
and electrical properties of newly formed CsxMA1
xPbI3
lead iodide, in such a fashion that increase in Cs fraction
promotes absorption in near ultraviolet range and
decreases it within the visible region. When doped with
30% of Cs, optical properties of perovskite start resembling
the ones of CsPbI3. Highest eciency (7.68%) for
CsxMA1
xPbI3 devices was observed when x = 0.1, which
is a noticeable improvement in comparison to nonmodied
MAPbI3 devices (5.51%). Generally, role of additives is to
improve coverage and consistency of perovskite lm. As
such, alkyl iodides may be used to improve crystallization
and lm morphology when present in small amounts as
shown by Chueh et al. (2015). These halogenated hydrocar-
bons act as provisional chelating agents for lead ions fol-
lowed by iodide discharge during heat treatment, while
additional morphology alterations can be achieved with
variations in length of alkyl chain and positioning of halo-
gen groups. Incorporation of small amounts (1.5 wt%) of
polystyrene into PCBM layer improves device open circuit
voltage due to the formation of very smooth lm over light
harvester, ensuring good hole blocking properties and con-
sequently reducing leakage current as demonstrated by Bai
et al. (2015). Higher percentage of dopant (6 wt%) had
negative eect on cell performance as insulating eect of
polymer became more prominent causing increase in series
resistance of PCBM lm and signicantly hampering elec-
tron transport. Hence, careful balancing between positive
and adverse eects of additives is necessary to achieve opti-
mal device performance. For thin lm devices, size of the
crystallites is of utmost importance as large crystallites pro-
vide uninterrupted extraction path between transporting
layers for a portion of excited charge carriers. Besides addi-
tives, another way to accomplish this goal is utilization of
solvent vapor during annealing process (Lian et al., 2015;
Huang et al., 2014). In this case solvent atmosphere
improves formation of high quality lm and scales down
grain boundary population, which in turn provides high
specimen crystallinity and photoconversion eciencies
exceeding 17%. In order to make perovskite solar cells
competitable to conventional silicone photovoltaics, one
of the issues that needs to be addressed is the cell size.
Impact of device area on eciency was reported by
Malinkiewicz et al. (2014), who observed decrease in e-
ciency from 12% to 8.27% that followed increase in size
from 0.09 to 0.98 cm2, respectively. Drop in eciency of
devices with larger area appeared as a result of reduced ll
factor. This phenomenon may be attributed to the process
of charge accumulation within the solar cell, which in
turn generates additional electric eld osetting a part of
688 M. Petrovic et al. / Solar Energy 122 (2015) 678699
built-in potential, resulting in inecient extraction of
charge carriers (Qi and Wang, 2013). Further improvement
of charge extraction can be achieved with the addition of
single wall carbon nanotubes to respective HTM, as shown
by Habisreutinger et al. (2014) who managed to improve
charge extraction through p-type layer by wrapping carbon
nanotubes with P3HT polymer. Another way of enhancing
device performance is through incorporation of Cl ions
into lead iodide structure (Jiang et al., 2015), causing local
changes in the energy oset within band structure at the
grain boundaries, thus improving collection of free carriers.
Recently, very interesting concept for solar cell fabrication
was demonstrated by Zhang et al. (2015a), who managed
to fabricate perovskite devices with wide range of tunable
colours. Their approach is based on fabrication of scaold
for perovskite light harvester consisting of overlapping lay-
ers of SiO2 and TiO2. Resulting colour of the device
depends on sum of partially reected and transmitted light
at the interfaces within cell structure. Photoconversion e-
ciency depends on crystal lattice parameter of the scaold
and it decreases as the lattice constant increases, resulting
in highest eciency for devices having blue hue (8.8%)
and lowest for ones with red tint (4.5%). As these devices
require much thinner active layers in order to achieve par-
tial absorption responsible for dierent colouring, power
conversion eciency is usually aected. Nonetheless,Deng
et al. (2015) introduced facile way to create highly ecient
(12.2%) colourful solar cells with simple doctor-blading
technique utilizing RayleighBernard eect. This approach
relies on temperature dierence along spread precursor
solution over heated substrate due to its thickness. Fast
evaporation of solvent creates multiple nucleation spots,
each acting as an independent heat convection cell. Each
of the formed polygonal photonic structures is accompa-
nied by coee-ring eect, where spacing between rings
and domain size can be simply adjusted by variation of
substrate temperature (100160 C) and concentration of
perovskite precursor solution. Table 3 lists some of the
published data on solar device performance, processing
techniques, role and type of organicinorganic perovskites
used in their fabrication.
6. The inner workings of perovskite solar cells
Even though the exact working principles of perovskite
photovoltaics are still long way from being fully under-
stood and determined, some light is shed on crucial ques-
tions such as stability crystallization, polarization kinetics
and hysteretic behaviour. Despite obvious advantages of
hybrid perovskite photovoltaics in comparison to OPVs
and DSSC, such as superior photoconversion eciency
and working parameters (open circuit voltage, short circuit
current, ll factor), such devices are accompanied with var-
ious issues, most important being lack of stability. Namely,
presence of amine salts in organometallic perovskites
causes degradation of solar cell after exposure to humid
environment (Liu and Zhang, 2014), due to rapid moisture
absorption characteristical for NH bonds. Furthermore,
exposure to UV light additionally decreases performance
of perovskite devices when mesoporous electron transport-
ing layer is a part of cell structure (Leijtens et al., 2013),
which is attributed to interactions between holes generated
within such layer and oxygen adsorbed on its surface.
Although eect of moisture on perovskite stability is nega-
tive, mildly humid environment appears to be benecial
during synthesis process as shown by You et al. (2014).
They managed to improve both eciency and ll factor
in devices where perovskite layer was annealed in ambient
air while humidity level was kept below 60%. Reasons for
improved performance of such devices may be assigned
to increment of grain size within perovskite structure as a
result of grain merging caused by accumulated moisture
as well as enhanced ion diusion in aqueous environment.
Yang et al. (2015b) conducted systematic study on lead-
iodide perovskite stability by means of in situ X-ray dirac-
tion and absorption spectroscopy, identifying formation of
lead-iodide octahedra as initial step in the process of device
degradation. Furthermore, in conventional device structure
hole transporting layer shields perovskite lm from atmo-
spheric conditions, so nature of this layer plays extremely
important role in stability of perovskite photovoltaics.
Hydrophilic hole transporters tend to retain moisture
longer, thus preventing penetration to organometallic lm.
Another issue that needs to be addressed is presence of
crystalline defects in perovskite structure which act as
dopants (Yin et al., 2014) and signicantly aect device
performance since they can act as recombination centers
in cases when their transition energy is within perovskite
band gap. Appearance of such defects may be induced
through deposition and variation of lm growth condi-
tions. Generally, organic component present in
organometallic perovskite is added in excess in order to
secure good substrate coverage and formation of uniform
layer, while anions are responsible for crystal growth kinet-
ics, thus inuencing device performance and lm morphol-
ogy. By using lead acetate instead of halides it is possible to
improve crystal growth due to higher volatility of acetate
salt, resulting in formation of very smooth layer (Zhang
et al., 2015b). Further control over crystallization process
in order to improve morphology of perovskite lm can
be achieved with addition of 1-chloronaphthalene into
deposition solution (Song et al., 2015). Films deposited in
such way prevent formation of large perovskite crystals
due to presence of big aromatic ring in the structure of
additive, while during evaporation sequence remaining
small crystals of perovskite can reorganize and form more
uniform structure, resulting in reduced number of defects
and trap states. Duan et al. (2015) indicated that defect
states may be important factor in hysteretic behaviour of
hybrid perovskite absorber which is recognized as a major
issue in determining actual performance of such devices.
Namely, external bias applied during currentvoltage mea-
surement causes perovskite solar cells to respond in the
form of hysteresis as a result of polarization which is
 M. Petrovic et al. / Solar Energy 122 (2015) 678699 689

Table 3
Various structure of organicinorganic perovskite solar cells, processing approach, additional treatment deposition technique and reported eciencies;
(SC: spin-coating; DSVD: dual source vapor deposition; SD: sequential deposition; VASP: vapor assisted solution processing; DC: drop-casting).
Device structure Additives/treatment Processing PCE Processing Reference
method (%) temperature
FTO/bl-TiO2/MAPbBr3/PIF8-TAA/Au HBr SC 10.4 100 C Heo et al. (2014)
FTO/c-TiO2/MAI3
XClX/spiro-OMeTAD/Ag DSVD 15.40 120325 C Liu et al. (2013)
FTO/bl-TiO2/MAPbI3/spiro-OMeTAD/Au Gass-assisted crystallization SC 17.1 35100 C Huang et al. (2014)
FTO/bl-TiO2/MAPbI3/spiro-OMeTAD/Au Electrospun nanobers SD 9.82 70 C Dharani et al. (2014)
FTO/bl-TiO2/TiO2:MAPbI3/Au No hole transporter SD 12.22 450 C Xiao et al. (2015)
ITO/PEDOT:PSS/MAPbI3/PC61BM/Al N-cyclohexyl-2-pyrrolidone SC 10.0 100 C Jeon et al. (2014a)
FTO/bTiO2/mpTiO2:(5AVA)x(MA)1
xPbI3/ZrO2: 5-ammonium valeric acid SC 12.8 50 C Mei et al. (2014)
(5AVA)x(MA)1
xPbI3/Graphite
FTO/TiO2/CsSnI3
xFx/N719/H2PtCl6/FTO Lead-free absorber DC 9.28 400 C Chung et al. (2012a)
FTO/c-TiO2/Al2O3:MAPbI3/spiro-OMeTAD/Ag Al2O3 scaold SC 10.90 100 C Lee et al. (2012)
ITO/PEDOT:PSS/MAPbI3
xClx/PC61BM/Bis-C60/Ag 1,4-Diiodobutane SC 13.09 90 C Chueh et al. (2015)
FTO/c-TiO2/MAPbI3/spiro-OMeTAD/Ag Non-halide lead source SC 14.0 150 C Zhang et al. (2015b)
FTO/bl-TiO2/MAPbI3
xClx/spiro-OMeTAD/Ag Vapor-assisted crystallization VASP 12.1 110150 C Chen et al. (2014)
FTO/c-TiO2/TiO2:MAPbI3/spiro-OMeTAD/Au Mesoscopic composite SD 12.60 70 C Burschka et al. (2013)
FTO/NiO/MAPbI3
xClx/PC60BM/Ag DSVD 7.26 120325 C Subbiah et al. (2014)
FTO/c-TiO2/Al2O3:MAPbI3/SWNT:P3HT/Ag Carbon nanotube/PMMA SC 15.4 100 C Habisreutinger et al.
(2014)
ITO/PEDOT:PSS/PolyTPD/MAPbI3/PCBM/Au PolyTPD DSVD 12.04 70250 C Malinkiewicz et al.
(2014)
FTO/TiO2/MAPbI3
xClx/spiro-OMeTAD/Au SC 11.40 90170 C Eperon et al. (2014a)
PET/AZO/PEDOT:PSS/MAPbI3/PCBM/Au Silver DSVD 7 70200 C Roldan-Carmona
et al. (2014)
FTO/c-TiO2/MA3PbI3/spiro-OMeTAD/Ag Solventsolvent extraction SD 15.2 Room Zhou et al. (2015)
temp.
FTO/TiO2/MAPbI3/spiro-OMeTAD/Au TiO2 nanobeads SC 7.7 70 C Tathavadekar et al.
(2015)
FTO/bl-TiO2/MAPbI3/Spiro-OMeTAD/Au Fast-crystallization SC 13.8 100 C Xiao et al. (2014)
deposition
ITO/PEDOT:PSS/MAPbI3/PC61BM/Al Poly(2-ethyl-2-oxazoline) SC 6.35 100 C Xue et al. (2015)
FTO/TiO2/MAPbI3
xClx/spiro-OMeTAD/Au PEG SC 13.20 100 C Chang et al. (2015)
FTO/TiO2/MAPb(I,Cl)3/spiro-OMeTAD/Au Mixed halide source SD 10.49 100 C Jiang et al. (2015)
ITO/PEDOT:PSS/CsxMA1
xPbI3/PCBM/Al Caesium SC 7.68 110 C Choi et al. (2014)
ITO/PEDOT:PSS/MAPbI3/PC61BM/Bis-C60/Ag 1,8-Diiodooctane SC 11.8 90 C Liang et al. (2014)
ITO/PEDOT:PSS/MAPbI3/PCBM/C60/BCP/Al Gass-assisted crystallization SC 13.60 70 C Lian et al. (2015)
ITO/PEDOT:PSS/MAPbI3
xClx/PCBM/Al 1-Chloro-naphthalene SC 9.46 100 C Song et al. (2015)
FTO/mp-TiO2/MAPbI3/electrolyte/Pt/FTO SC 3.81 4070 C Kojima et al. (2009)
ITO/PEDOT:PSS/MAI3
xClx/PC61BM/TPPI/Al Tetraphenyl phosphonium SC 13.0 100 C Sun et al. (2015)
iodide
FTO/c-TiO2/mp-TiO2:MAPbI3/spiro-OMeTAD/Au High humidity SC 15.76 50100 C Ko et al. (2015)
ITO/PEIE/Y:TiO2/MAPbI3
xClx/spiro-OMeTAD/Au Ethoxylated poly- SC 19.3 100 C Zhou et al. (2014)
ethyleneimine, yttrium
FTO/PEDOT:PSS/MAPbI3/PCBM/Al Hot-casting crystallization SC 18 170190 C Nie et al. (2015)
FTO/TiO2/MAPbI3/electrolyte/Pt/FTO Quantum-dot sensitized DC 6.5 40160 C Im et al. (2011)
FTO/TiO2:SiO2/MAPbI3
xClx/spiro-OMeTAD/Au SiO2 scaold SC 8.8 100 C Zhang et al. (2015a)
FTO/NiO NCs/MAPbI3
xClx/PC61BM:PS/Al Polystyrene SC 10.68 100 C Bai et al. (2015)

assumed to originate from rearrangements of organic
dipoles within organometallic structure (Brivio et al.,
2013) and ionic diusion (Yamada et al., 1995). Since
organic polymers such as PCBM have passivating eect
at trap sites (Xu et al., 2015), hysteretic eect is less promi-
nent in devices mimicking architecture of organic solar
cells, i.e. PEDOT:PSS/perovskite/PCBM. Alternatively,
bilayer of compact and thin mesoporous TiO2 scaold
can be used to reduce hysteresis, through improved carrier
extraction and increased contact area with loaded
perovskite (Jeon et al., 2014b). Exact origin of the hystere-
sis in organicinorganic hybrid perovskites is not fully
understood, but it is believed to be a mixture of eects
caused by carrier trapping/detrapping process, polarization
of ferroelectric domains and translocation of ions.
Ferroelectricity causes formation of domains within per-
ovskite structure as a response to structural reorganization
of crystal lattice at dierent temperatures. At room temper-
ature, methylammonium lead halides retain tetragonal ori-
entation which is accompanied by polarization eect. As
perovskite absorbs incident light, excited states provide
more rotational space for polar organic ion, which in turn
causes prominent hysteretic behaviour. Kutes et al. (2014)
proved existence of switchable ferroelectric domains within
690 M. Petrovic et al. / Solar Energy 122 (2015) 678699
MAPbI3 structure using large voltage bias. It should be
stressed that experimental conditions assume much higher
voltages than realistically achievable during solar cell oper-
ation, raising a question to which extent ferroelectric
response really aects hysteretic behaviour. More promi-
nent eect is expected to come from lling and emptying
of trap states present within these organometallic per-
ovskites. Namely, impurities/defects are responsible for
formation of allowed subgap energy levels within band
gap and depopulation of these trap energy states takes
place on a slow timeframes. This discharging process
results in reduced conductance and vice versa, which is
the chief reason for better device performance under
reverse scanning conditions (Sum et al., 2015). Moreover,
ion migration of halide and organic ions throughout absor-
ber and charge transporting layers leads to accumulation at
the interfaces and indirectly aects power conversion e-
ciency of the device (Tress et al., 2015). Another important
question regarding operating mechanism of perovskite
solar cells is the type of primary photoexcited species,
which is necessary to determine corresponding cell struc-
ture. Namely, in the case of excitons (energy transport)
additional interface is required to separate the charge,
unlike the option where free carriers (charge transport)
are primary species. Time-resolved and transient THz spec-
troscopy revealed that charge separation occurs shortly
(2 ps) after excitation, suggesting non-geminate recombina-
tion as a main route at higher charge densities. However, at
the ordinary working conditions carrier concentration can
be signicantly reduced, making it necessary to account for
monomolecular recombination pathway as well. Further-
more, recombination in organicinorganic hybrid
perovskites is mainly radiative, resulting in high photolu-
minescence quantum eciencies at lower temperatures.
High percentage of radiative recombination supports
researcher aspirations to reach ShockleyQueisser limit,
which rests at 30% for planar architecture with perfectly
reecting underlying layer (Sha et al., 2015). Even though
the cause of hysteretic behaviour remains to be fully
revealed, it has been proposed that discrepancies between
actual and measured photoconversion eciencies is also
aected by the mismatch between scanning parameters
and time frame needed for perovskite to reach electronic
steady state. This problem can be circumvented by using
slow scans which should ensure reaching of steady state
at every point during the measurements, as proposed by
Unger et al. (2014). In order to prevent overestimation of
device eciencies it is important to adopt certain measure-
ment standard for perovskite based photovoltaics.
Christians et al. (2015) suggested eight step approach in
order to secure accurate reporting of power conversion
eciency. In short, by measuring number of extracted
charge carriers at certain wavelength using incident photon
to current eciency (IPCE) technique and integrating
results over AM1.5G spectra, one should be able to yield
accurate short circuit current values under steady state con-
ditions. In order to minimize deviation during repeated
measurements it is suggested to use mask over reference
and measured device in order to secure same exposure area.
White light bias may also be included in order to prevent
deviations due to dierence in intensity between wave-
lengths used during IPCE measurements and one sun irra-
diation. Finally, solar cells with very small active areas
should be avoided, as theycan lead to overestimation of ll
factor. In order to conrm reliability of recorded eciency,
results should be compared with steady state current
acquired from measurement where voltage is kept constant
at maximum power point value. Some insight into excited
states behaviour of lead iodide is given by Stamplecoskie
et al. (2015) through spectroscopic studies response and
kinetic proling of tri/tetra iodoplumate complexes. They
discovered that perovskites having formula CH3NH3PbI2
are dened with two dierent states: charge separation
and transfer of free carriers, together forming dual excited
state through coupling. Eect of various organic and metal
ions on dielectric constant and polarization properties of
organometallic halides is described by Wu et al. (2015),
who used electroabsorption spectroscopy to investigate
dipoles response towards dierent frequencies. Magnitude
and changes in dipole moments indicate that both cations
indeed inuence dielectrical properties of hybrid per-
ovskites, however via dierent mechanisms occurring on
disparate timescales causing frequency dependent response.
Important details about kinetic properties of hybrid per-
ovskite photovoltaics has been published recently by
Bertoluzzi et al. (2015). They encountered that photovolt-
age decay occurs on two dierent timescales; fast one is
attributed to discharge/recombination of charge carriers
while long decay is dependent on stable polarization states
within perovskite sample. Such behaviour indicates
interdependent polarization/depolarization kinetics in the
presence of ferroic domains within the material. Recently,
interesting insight into interactions between perovskite
and organic layer at the interface was given by Lo et al.
(2015), who studied mechanism of photocharge generation
at perovskite/PCBM junction. Intriguingly, it appears that
interface acts as NN junction and as such it doesnt play a
role in exciton dissociation, indicating that free charge car-
riers are formed within perovskite layer. Even though most
of semiconductors fabricated via solution processing tend
to be plagued by numerous defects and large electric disor-
dering, lead halide perovskites exhibit high diusion
lengths, long recombination lifetime and fast charge extrac-
tion. Remarkable diusion lengths found in such polycrys-
talline perovskite thin lm solar cells (>2 lm) is determined
by concentration of charge carriers as well as their intrinsic
mobility. Innate charge mobility is closely dependent on
the quality of polycrystalline layer and lattice structure,
which is one of the reasons why devices employing physical
vapor deposition tend to provide longer diusion
pathways. Moreover, some reports give certain indications
that substitution of positive ions within perovskite leads to
unbalanced transport between electrons and holes (Eperon
et al., 2014c). Charge decay process in organicinorganic
 M. Petrovic et al. / Solar Energy 122 (2015) 678699
lead halides is correlated to charge density present in the
system; in the case of low carrier concentrations, geminate
recombination is dominant, while increase in carrier popu-
lation shifts the mechanism towards bimolecular recombi-
nation. Evidently, diusion length is signicantly reduced
at large charge densities as more carriers is generated,
which in turn increases probability of recombination. It
should be mentioned that dierent measuring techniques
can result in charge mobility values diverging by several
order of magnitude as a result of measurement mechanism.
Namely, techniques such as charge extraction by linearly
increasing voltage (CELIV) or transient absorption spec-
troscopy are performed on samples including absorber
and transporting layers, which undoubtedly has a negative
eect on charge extraction (Huang et al., 2015), whereas
THz spectroscopy can be applied on individual perovskite
lm for direct measurement of local drift mobility (Sum
et al., 2015). Dong et al. (2015) reported diusion lengths
exceeding 175 lm in large CH3NH3PbI3 (3 mm thick)
single crystals, as a result of long recombination lifetimes
and reduced number of trap states. However, as pointed
out by Stranks and Snaith (2015) these measurements
may overvalue actual carrier lifetime in the presence of
charge accumulation at the crystal surface. Interestingly,
Sanchez et al. (2014) indicated that recombination process
in planar perovskite solar devices might not be exclusively
tied to charge carrier decay time, by demonstrating how
devices with large disparity in photovoltage decay times
displayed similar photoconversion eciency.
7. Challenges and prospects for solar cells
Potential exhibited by organometallic perovskites in the
eld of photovoltaics is undeniable, however there are sev-
eral key aspects that need to be addressed and improved
before they can be considered as sustainable energy solu-
tion, with cost to generated electricity price ratio compara-
ble to hydrocarbon fuels. High eciencies exhibited by
these devices are accompanied with insucient stability
and reproducibility issues, but bearing in mind vast num-
ber of possible material combinations in synthesis of per-
ovskites, development of highly stable absorbers is to be
expected in years to come. One of the major goals is reduc-
ing of processing temperature, which is not only cost-
benecial (Graetzel et al., 2012), but also allows the use
of dierent substrates and incorporation into tandem solar
devices (Beiley and McGehee, 2012). Lead halides are
almost exclusively used as absorbers in perovskite solar
cells, raising the question of negative environmental
impact, since lead is a toxic material and its use in elec-
tronic devices may be more or less restricted, depending
on dierent countries and their respective national laws.
Hence, we can expect lead to be substituted with less toxic
elements, and rst steps in this direction have already been
taken by employing tin-iodide absorbers (Hao et al., 2014).
Finally, we shouldnt forget that organometallic per-
ovskites absorbing properties can be utilized outside of
691
the classical solar cell framework, and possibly be used in
building-integrated photovoltaics, due to their high e-
ciency and semitransparency (Eperon et al., 2014b). Judg-
ing by the amount of interest perovskite solar cells have
raised in the scientic community and results achieved
within a time frame of only three years, we can expect to
witness rapid advancement in processing and fabrication
techniques, tuning of interfaces between charge collectors
and perovskite sensitizer, as well as further improvements
in photoconversion eciency and cost reduction.
8. Engineering applications
Perovskites have been around for decades (Chandler
et al., 1993), and thanks to their diverse properties such
as superconductivity, ferromagnetism, luminescence, ionic
conductivity and electrochromism (Granqvist et al.,
1998), have displayed potential to be employed in wide
range of applications. Before sudden surge in interest
thanks to highly ecient ptohovoltaics, perovskites had
important role in fabrication of solid oxide fuel cells. High
usability they have in this area is reected by the role they
perform in such systems, appearing as constituents in the
electrolyte and building material for electrodes. Perovskite
oxides with oxygen deciency are important type of elec-
trolyte materials due to their substantial oxygen nonstoi-
chiometry and vast number of substituents which can
occupy A and/or B sites in the crystal (Hayashia et al.,
1999). Temperatures above 925 C lead to formation of
irregular cubic structure which results in conductivity cre-
ated by oxide ions. Signicant improvement step in usage
of perovskites as an integral part of the electrolyte was
made by Feng and Goodenough (1994) who introduced
double substituted strontium-magnesium doped lan-
thanum gallate. For fabrication of intermediate solid oxide
fuel cells, perovskites with general formula ABO3 where B
is a transition metal can be used as cathode materials. Most
important among them is lanthanum strontium manganite
known for its good thermal stability (in 700900 C range),
high electrical conductivity and compatibility with widely
used yttria stabilized zirconia electrolyte. For lower tem-
perature applications, A site substituted lanthanum ferrite
perovskites are considered to be a good choice because
their thermal expansion is tunable to a certain extent
(Ullmann et al., 2000). Perovskites containing cobalt (Bae
and Steele, 1998) are another option, as they possess good
electronic/ionic conductivity and oxygen reduction activ-
ity. However, at temperatures below 700 C, they tend to
form insulating phase with yttria stabilized zirconia and
as such require additional blocking layer in order to be suc-
cessfully incorporated into fuel cells. Special type of cath-
ode materials are ordered double perovskites having
combination of rare earth elements at A position resulting
in structure aligning, favourable for fast transport of oxy-
gen ions. Their general formula is A0 A00 B2O5+X, where B
site is usually occupied by Co and exhibit high oxygen
uptake together with the low specic area resistance
692 M. Petrovic et al. / Solar Energy 122 (2015) 678699
(Taskin et al., 2005). Even though there is a large number
of possible double perovskite structures thanks to the
plethora of available cation combinations, only several
types are actively studied (Zhou et al., 2009). When it
comes to anode materials, commonly used materials are
oxides containing Ti and Cr ions at B site of the perovskite
crystal. They have good chemical and dimensional stability
providing steady supply of O2
ions to the surface of elec-
trode. Furthermore, they are usually doped with Ga in
order to promote conductivity and hydrogen oxidation
activity (Escudero et al., 2009). Bearing in mind all possible
variations of perovskites structure coupled with low cost
and good thermal stability, one may assume that their role
as catalysts has a great potential. However, chemical stabil-
ity and low surface area are main reasons why stand-alone
perovskites havent attracted any noticeable attention in
this eld, unless they are used as coatings over suitable sup-
port (Biniwale et al., 2003; Han et al., 2013). On the other
hand, diversity and reactivity make them suitable for wide
range of sensing applications. Design of such sensing
devices depends on the particular purpose and it covers
various types of sensors. For instance, sensors (Wang
et al., 2013) based on LaTiO3Ag perovskite can be used
for highly accurate measurement of glucose levels in the
blood, having improved performance in comparison to
enzyme-based biosensors. Some other applications include:
hydrogen sensing (Bukhari and Giorgi, 2013), high temper-
ature CO2 detectors (Kannan et al., 2013), highly selective
mixed potential gas sensors (Sekhara et al., 2013), amino
acid sensors with low detection limits (Wang et al., 2012)
and La-based perovskite oxide devices for NOX detection
(Ueda et al., 2010). Generally, design of gas sensors based
on perovskites relies on SrTiO3 in the case of oxygen sens-
ing, while other gas detectors usually employ ferrites and
Co perovskite oxides (Fergus, 2007). As we already men-
tioned in the section discussing electrical properties of per-
ovskites, oxides containing copper are known for their
superconductive properties. It is interesting to note that
simple cuprate oxides are actually insulators, but when
doped with atoms having higher valence numbers they
become superconductors. Thanks to the increase in number
of charge carriers at Fermi level, these cuprate perovskites
act as a very ecient superconductors at high tempera-
tures, despite the fact that concentration of charge carriers
they have is about ten times lower than one found in their
conventional counterparts. Reason for this phenomenon
lies in the fact that only a small number of electrons in con-
ventional superconductors take part in coupling, whereas
for CuO based perovskites this number is signicantly
higher. Superconductivity in perovskite oxides containing
Cu happen in copper oxide layers which are separated by
atoms (Y, La, Ba, Bi) providing charge transport between
them (Volkova et al., 2000). Another type of oxides pos-
sessing good conductive properties is sodium doped tung-
sten oxide Na0.5WO3, known as the rst high
temperature superconductor not having copper in its struc-
ture (Zheng et al., 2011). When Na ions are replaced with
hydrogen, critical transition temperature rises up to
135 K, on par with the best superconducting materials
(Reich et al., 2009). Good example of non-oxide supercon-
ductive perovskites is MgCNi3, having simple cubic struc-
ture and single superconducting gap (Kinoda et al.,
2001). Critical transition temperature for this type of per-
ovskite depends on content of all three constituents, where
optimal C value is approximately 1.5 (MgC1.5Ni3) while
increase in Ni and Mg concentrations cause transition tem-
perature to rapidly decline (Das and Kremer, 2003). It
should be noted that polarizability of superconducting per-
ovskites is proportional to valence and volume of ions, and
these parameters may be used to predict low permittivity in
various crystal compositions, which is aected by availabil-
ity of cavities within crystal structure (Fratello and
Brandle, 1994). Feroelectric materials have very unique
properties, one of which is the ability to spontaneously
form reversible electric dipole moment within certain tem-
perature range under the inuence of applied electric bias.
Origin of this phenomenon is rooted in the structural sym-
metry as centers of negative and positive charge within fer-
roelectric material require inuence of external eld to
induce their overlapping. For this reason, ferroelectric per-
ovskites have raised interest as prospective materials for
non-volatile data storage. One of the most popular per-
ovskite oxides studied for such applications is BiFeO3,
which behaves as a single-phase multiferroic material at
room temperature. It is often considered for usage in
devices with exchange coupling conguration due to the
synergy between magnetic and ferroelectric ordering and
exchange merger with contact layer, enabling manipulation
over magnetization via external electric eld (Heron et al.,
2014). Such approach is very useful in design of spintronics
as it eliminates large energy loses caused by ohmic heating.
However, epitaxial growth of BiFeO3 lms over Si sub-
strate poses a formidable challenge for integration within
conventional semiconductor devices. This issue can be cir-
cumvented by templating silicone with suitable buer mate-
rial such as SrTiO3, which provides good lattice matching
with most of perovskites. Furthermore, doping of BiFeO3
with lanthanum has been proved to enhance capability of
perovskite oxide to defy eect of external magnetic eld,
while improving both coercivity and residual magnetism
(Yao et al., 2015). Various physical characteristics of per-
ovskite oxides arise as a consequence of phase-transitions
which are closely correlated to crystal defects/impurities,
concentration, processing conditions and temperature. In
order to fabricate highly functional devices from these
materials, one needs to establish control over these proper-
ties. Transition between dierent crystal congurations can
be controlled to a certain extent through size of crystallite;
in the case of ferroelectrics, nanocrystals suppress mutual
interactions and assume pseudocubic form. Fig. 6
illustrates correlation between magnetic and electric
properties of selected perovskite oxides. Light emitting
properties of perovskites can be utilized for fabrication of
light emitting diodes (LEDs) (Gebauer and Schmidt,
 M. Petrovic et al. / Solar Energy 122 (2015) 678699 693

Fig. 6. Venn diagram depicting properties of selected perovskite oxides.

Table 4 Dohner et al. (2014). Remarkable colour rendering index

Dierent applications of perovskite materials and their advantages in and tunable chromaticity parameters are associated with
respect to conventional materials used for the same purpose. substantial emission in the red slice of visible light, which
Field of use Advantages in turns causes emission of warm (close to yellow part
Sensors Lower detection limit, higher sensitivity, wider linear of the spectrum) light in these devices. Recently, Hoye
range detection et al. (2015) reported uorine-free MAPbBr3 light emitters
Fuel cells High activity for oxidation and reduction reactions, by replacing widely used F8 electron injector with Mg
good conductivity doped zinc oxide. In this way, its possible to avoid multi-
Superconductors High working temperatures, transition temperature
dependable on carrier density
ple emission peaks caused by parasitic emission from F8
Light emitters Temperature tunable luminescence, adjustable and obtain green-light emitting device with clearly dened
emitting colour electroluminescence peak and improved brightness. Table 4
summarizes some of the areas (excluding photovoltaic
applications) where perovskite materials can be success-
fully utilized and advantages they have over conventional
1999), electroluminescent devices (ELDs) (Colle et al.,
materials used in respective research elds.
2001) and scintillators (Mares et al., 1998). One of the ear-
liest studies on perovskites luminescent properties was per-
formed on tungsten oxide double perovskite A0 A00 WXO6
(Oosterhout, 1977). For concentrations of X < 0.5 this per-
ovskite oxide emits light at room temperature, but with the
increase of X tungsten absorption starts dominating lumi-
nescence process, leading to light emission only at lower
temperatures. Exhibited temperature dependent lumines-
cence is important property that can be employed in vari-
ous measuring systems and medical imaging procedures.
Some of perovskite materials such as CaZrO3 (Shimizu
et al., 2009) display ability to have the colour of emitting
light adjusted using various doping atoms, namely addition
of Eu, TbMg or Tb cause red, blue and green lumines-
cence respectively, under UV excitation. Organicinorganic
lead bromides employed in solar cells are also suitable for
fabrication of LEDs when sandwiched between hole
blocking layer (PEDOT:PSS, TiO2) and electron injecting
layer poly(9,9-dioctyluorene) (F8). Such device congura-
tion ensures enclosure of charge within perovskite layer
and promotes radiative recombination resulting in visible
and infrared electroluminescence (Tan et al., 2014). Careful
balance between dierent halide ions within organometallic
hybrid allows emission of white light thanks to the rigid Fig. 7. Level of research activity for potential applications of perovskites
structure of N-MEDA-PbBr4
xClx as demonstrated by in various domains.
694 M. Petrovic et al. / Solar Energy 122 (2015) 678699
9. Conclusions
Perovskites are very interesting, diverse group of materi-
als, exhibiting wide range of useful properties dened by
their composition. Keeping in mind that majority of ele-
ments from periodic table can occupy place in their crystal
structure, it is no surprise that perovskites have been draw-
ing attention to themselves for several decades. From the
superconductors in 1970s to the recent solar cell absorbing
materials, various perovskites have been studied in an
attempt to utilize their unique characteristics. Recently,
organicinorganic perovskites came into spotlight because
of their useful light absorbing properties, and in that man-
ner we dedicated large portion of this paper to their role in
photovoltaic devices. However, we believe that other prop-
erties such as light emitting, sensing, conductivity, activity
for oxidation/reduction deserve to be mentioned as well,
since they have undeniable potential for suitable applica-
tions and have been around for years as illustrated in
Fig. 7. Future of perovskite solar cells looks very bright,
but regardless of prospective success in the area of photo-
voltaics, research activities for various application domains
of perovskite materials are bound to progress further,
granted by the sheer number of possible substituent combi-
nations within their structures.
Acknowledgements
Milos Petrovic wishes to thank A*STAR Singapore
International Graduate Award (SINGA), for providing
research scholarship.
References
Agranovichy, V.M., Baskoz, D.M., La Roccaz, G.C., Bassaniz, F., 1998.
Excitons and optical nonlinearities in hybrid organicinorganic
nanostructures. J. Phys. Condens. Matter. 10 (42), 93699400.
Anoop, G., Seo, J., Han, C.J., Lee, H.J., Kim, G.W., Lee, S.S., Park, E.Y.,
Jo, J.Y., 2015. Ultra-thin platinum interfacial layer assisted-photo-
voltaic response of transparent Pb(Zr, Ti)O3 thin lm capacitors. Sol.
Energy 111, 118124.
Arachi, Y., Sakai, H., Yamamoto, O., Takeda, Y., Imanishi, N., 1999.
Electrical conductivity of the ZrO2Ln2O3 (Ln=lanthanides) system.
Solid State Ionics 121 (14), 133139.
Babu, V.J., Vempati, S., Sundarrajan, S., Sireesha, M., Ramakrishna, S.,
2014. Eective nanostructured morphologies for ecient hybrid solar
cells. Sol. Energy 106, 122.
Bae, J.M., Steele, B.C.H., 1998. Properties of La0.6Sr0.4Co0.2Fe0.8O3
d
(LSCF) double layer cathodes on gadolinium-doped cerium oxide
(CGO) electrolytes: I. Role of SiO2. Solid State Ionics 106 (34), 247
253.
Bai, Y., Yu, H., Zhu, Z., Jiang, K., Zhang, T., Zhao, N., Yang, S., Yan,
H., 2015. High performance perovskite solar cells based on a PCBM:
polystyrene blend electron transport layer. J. Mater. Chem. A 3 (17),
90989102.
Bebelis, S., Kotsionopoulos, N., Mai, A., Rutenbeck, D., Tietz, F., 2006.
Electrochemical characterization of mixed conducting and composite
SOFC cathodes. Solid State Ionics 177 (1925), 18431848.
Bebelis, S., Kotsionopoulos, N., Mai, A., Tietz, F., 2007. Electrochemical
characterization of perovskite-based SOFC cathodes. J. Appl. Elec-
trochem. 37 (1), 1520.
Beiley, Z.M., McGehee, M.D., 2012. Modeling low cost hybrid tandem
photovoltaics with the potential for eciencies exceeding 20%. Energy
Environ. Sci. 5 (11), 91739179.
Bertoluzzi, L., Sanchez, R., Liu, L., Lee, J.W., Mas-Marza, E., Han, H.,
Park, N.G., Mora-Sero, I., Bisquert, J., 2015. Cooperative kinetics of
depolarization in CH3NH3PbI3 perovskite solar cells. Energy Environ.
Sci. 8 (3), 910915.
Bhargavi, G.N., Khare, A., 2015. Luminescence studies of perovskite
structured titanates: a review. Opt. Spectrosc. 118 (6), 902917.
Bianconi, A., Saini, N.L., Rossetti, T., Lanzara, A., Perali, M., Missori,
M., 1996. Stripe structure in the CuO2 plane of perovskite supercon-
ductors. Phys. Rev. B 54 (17), 1201812021.
Biniwale, R.B., Bawase, M.A., Labhsetwar, N.K., Kumar, R., 2003.
La(1
x)AxMn(1
y)ByO3 supported on honeycomb substrate charac-
terization and application for catalytic converter. Indian J. Chem. 42
(8), 18331839.
Boix, P.P., Nonomura, K., Mathews, N., Mhaisalkar, S.G., 2014.
Progress and future perspectives for organic/inorganic perovskite
solar cells. Mater. Today 17 (1), 1623.
Boutal, N., Rekhila, G., Tabi, K., Trari, M., 2014. Relaxor ferroelectric
and photo-electrochemical properties of lead-free Ba1
xEu2x/3(Ti0.75-
Zr0.25)O3 ceramics. Application to chromate reduction. Sol. Energy 99,
291298.
Brabec, C.J., Durrant, J.R., 2008. Solution-processed organic solar cells.
MRS Bull. 33 (7), 670675.
Brivio, F., Walker, A.B., Walsh, A., 2013. Structural and electronic
properties of hybrid perovskites for high-eciency thin-lm photo-
voltaics from rst-principles. APL Mater. 1 (4), 042111:1042111:5.
Bukhari, S.M., Giorgi, J.B., 2013. Ni doped Sm0.95Ce0.05FeO3
d per-
ovskite based sensors for hydrogen detection. Sens. Actuat. B Chem.
181, 153158.
Burschka, J., Pellet, N., Moon, S.J., Humphry-Baker, R., Gao, P.,
Nazeeruddin, M.K., Gratzel, M., 2013. Sequential deposition as a
route to high-performance perovskite-sensitized solar cells. Nature 499
(7458), 316319.
Busico, V., Carfagna, C., Salerno, V., Vacatello, M., Fittipaldi, F., 1979.
The layer perovskites as thermal energy storage systems. Sol. Energy
24 (6), 575579.
Cardoso, J.C., Grimes, C.A., Feng, X.J., Zhang, X.Y., Komarneni, S.,
Zanoni, M.V.B., Bao, N.Z., 2012. Fabrication of coaxial TiO2/Sb2S3
nanowire hybrids for ecient nanostructured organicinorganic thin
lm photovoltaics. Chem. Commun. 48 (22), 28182820.
Cerda, J., Arbiol, J., Dezanneau, G., Daz, R., Morante, J.R., 2002.
Perovskite-type BaSnO3 powders for high temperature gas sensor
applications. Sens. Actuat. B 84 (1), 2125.
Chandler, C.D., Roger, C., Hampden-Smith, M.J., 1993. Chemical aspects
of solution routes to perovskite-phase mixed-metal oxides from metal
organic precursors. Chem. Rev. 93 (3), 12051241.
Chang, C.Y., Chu, C.-Y., Huang, Y.C., Huang, C.W., Chang, S.Y., Chen,
C.A., Chao, C.Y., Su, W.F., 2015. Tuning perovskite morphology by
polymer additive for high eciency solar cell. ACS Appl. Mater.
Interf. 7 (8), 49554961.
Chen, Q., Zhou, H., Hong, Z., Luo, S., Duan, H.S., Wang, H.H., Liu, Y.,
Li, G., Yang, Y., 2014. Planar heterojunction perovskite solar cells via
vapor-assisted solution process. J. Am. Chem. Soc. 136 (2), 622625.
Cheng, Z., Lin, J., 2010. Layered organicinorganic hybrid perovskites:
structure, optical properties, lm preparation, patterning and templat-
ing engineering. CrystEngComm. 12 (10), 26462662.
Choi, H., Jeong, J., Kim, H.B., Kim, S., Walker, B., Kim, G.H., Kim, J.
Y., 2014. Cesium-doped methylammoniumlead iodide perovskite light
absorber for hybrid solar cells. Nano Energy 7, 8085.
Chondroudis, K., Mitzi, D.B., Brock, P., 2000. Eect of thermal annealing
on the optical and morphological properties of (AETH) PbX4 (X = Br,
I) perovskite lms prepared using single source thermal ablation.
Chem. Mater. 12 (1), 169175.
Christians, J., Manser, J., Kamat, P., 2015. Best practices in perovskite
solar cell eciency measurements. Avoiding the error of making bad
cells look good. J. Phys. Chem. Lett. 6 (5), 852857.
 M. Petrovic et al. / Solar Energy 122 (2015) 678699
Chueh, C.C., Liao, C.Y., Zuo, F., Williams, S.T., Liang, P.W., Jen, A.K.
Y., 2015. The roles of alkyl halide additives in enhancing perovskite
solar cell performance. J. Mater. Chem. A 3 (17), 90589062.
Chung, I., Lee, B., He, J., Chang, R.P.H., Kanatzidis, M.G., 2012a. All-
solid-state dye-sensitized solar cells with high eciency. Nature 485
(7399), 486489.
Chung, I., Song, J.H., Im, J., Androulakis, J., Malliakas, C.D., Li, H.,
Freeman, A.J., Kenney, J.T., Kanatzidis, M.G., 2012b. CsSnI3:
semiconductor or metal? High electrical conductivity and strong
near-infrared photoluminescence from a single material high hole
mobility and phase-transitions. J. Am. Chem. Soc. 134 (20), 8579
8587.
Colle, M., Brutting, W., Schwoerer, M., Yahiro, M., Tsutsui, T., 2001.
Electroluminescent devices using a layered organicinorganic per-
ovskite structure. Proc. SPIE 4105, 328337.
Dammak, T., Elleuch, S., Bougzhala, H., Mlayah, A., Chtourou, R.,
Abid, Y., 2009. Synthesis, vibrational and optical properties of a new
three-layered organic inorganic perovskite (C4H9NH3)4Pb3I4Br 6. J.
Lumin. 129 (9), 893897.
Das, A., Kremer, R.K., 2003. Suppression of superconductivity in Mn-
substituted MgCNi3. Phys. Rev. B 68 (6), 064503(1)064503(6).
Dharani, S., Mulmudi, H.K., Yantara, N., Trang, P.T.T., Park, N.G.,
Graetzel, M., Mhaisalkar, S., Mathews, N., Boix, P.P., 2014. High
eciency electrospun TiO2 nanober based hybrid organicinorganic
perovskite solar cell. Nanoscale 6 (3), 16751679.
Deng, Y., Wang, Q., Yuan, Y., Huang, J., 2015. Vividly colorful hybrid
perovskite solar cells by doctor-blade coating with perovskite photonic
nanostructures. Mater. Horiz. http://dx.doi.org/10.1039/C5MH00
126A.
Dohner, E.R., Hoke, E.T., Karunadasa, H.I., 2014. Self-assembly
of broadband white-light emitters. J. Am. Chem. Soc. 136 (5),
17181721.
Dong, Q., Fang, Y., Shao, Y., Mulligan, P., Qiu, J., Cao, L., Huang, J.,
2015. Electron-hole diusion lengths > 175 mm in solution-grown
CH3NH3PbI3 single crystals. Science 347 (6225), 967970.
Dong, F., Huang, Y., Zou, S., Liu, J., Lee, S.C., 2011. Ultrasonic spray
pyrolysis fabrication of solid and hollow PbWO4 spheres with
structure-directed photocatalytic activity. J. Phys. Chem. C 115 (1),
241247.
Duan, H.S., Zhou, H., Chen, Q., Sun, P., Luo, S., Song, T.B., Bob, B.,
Yang, Y., 2015. The identication and characterization of defect states
in hybrid organicinorganic perovskite photovoltaics. Phys. Chem.
Chem. Phys. 17 (1), 112116.
Eperon, G.E., Burlakov, V.M., Docampo, P., Goriely, A., Snaith, H.J.,
2014a. Morphological control for high performance, solution-pro-
cessed planar heterojunctionperovskite solar cells. Adv. Funct. Mater.
24 (1), 151157.
Eperon, G.E., Burlakov, V.M., Goriely, A., Snaith, H.J., 2014b. Neutral
color semitransparent microstructured perovskite solar cells. ACS
Nano 8 (1), 591598.
Eperon, G.E., Stranks, S.D., Menelaou, C., Johnston, M.B., Herz, L.M.,
Snaith, H.J., 2014c. Formamidinium lead trihalide: a broadly tunable
perovskite for ecient planar heterojunction solar cells. Energy
Environ. Sci. 7 (3), 982988.
Escudero, J., Irvine, J.T.S., Daza, L., 2009. Development of anode
material based on La-substituted SrTiO3 perovskites doped with
manganese and/or gallium for SOFC. J. Power Sources 192 (1), 4350.
Feng, M., Goodenough, J.B., 1994. A superior oxide-ion electrolyte. Eur.
J. Solid State Inorg. Chem. 31, 663672.
Fergus, J.W., 2007. Perovskite oxides for semiconductor-based gas
sensors. Sens. Actuat. B Chem. 123 (2), 11691179.
Fratello, V.J., Brandle, C.D., 1994. Calculation of dielectric polarizabil-
ities of perovskite substrate materials for high-temperature supercon-
ductors. J. Mater. Res. 9 (10), 25542560.
Fu, C.Y., Chang, C.L., Hsu, C.S., Hwang, B.H., 2005. Electrostatic spray
deposition of La0.8Sr0.2Co0.2Fe0.8O3 lms. Mater. Chem. Phys. 91 (1),
2835.
695
Furusaki, A., Konno, H., Furuichi, R., 1995. Perovskite-type lanthanum
chromium-based oxide lms prepared by ultrasonic spray pyrolysis. J.
Mater. Sci. 30 (11), 28292834.
Gebauer, T., Schmidt, G., 1999. Inorganicorganic hybrid structured
LEDs. Z. Anorg. Allg. Chem. 625 (7), 11241128.
Glazer, A.M., 1972. Classication of tilted octahedra in perovskites. Acta.
Crystallogr. Sect. B: Struct. Sci. 28 (11), 33843392.
Gonzalez-Carrero, S., Galian, R.E., Perez-Prieto, J., 2015. Maximizing the
emissive properties of CH3NH3PbBr3 perovskite nanoparticles. J.
Mater. Chem. 3 (17), 91879193.
Graetzel, M., Janssen, R.A.J., Mitzi, D.B., Sargent, E.H., 2012. Materials
interface engineering for solution-processed photovoltaics. Nature 488
(7411), 304312.
Granqvist, C.G., Azens, A., Hjelm, A., Kullman, L., Niklasson, G.A.,
Ronnow, D., Strmme Mattsson, M., Veszelei, M., Vaivars, G., 1998.
Recent advances in electrochromics for smart windows applications.
Sol. Energy 63 (4), 199216.
Gurauskis, J., Lohne, .F., Lein, H.L., Wiik, K., 2012. Processing of thin
lm ceramic membranes for oxygen separation. J. Eur. Ceram. Soc. 32
(3), 649655.
Habisreutinger, S.N., Leijtens, T., Eperon, G.E., Stranks, S.D., Nicholas,
R.J., Snaith, H.J., 2014. Carbon nanotube/polymer composites as a
highly stable hole collection layer in perovskite solar cells. Nano Lett.
14 (10), 55615568.
Han, S., Derksen, J., Chun, J.H., 2004. Extrusion spin coating: an ecient
and deterministic photoresist coating method in microlithography.
IEEE Trans. Semicond. Manuf. 17 (1), 1221.
Han, A., Zhao, M., Ye, M., Liao, J., Zhang, Z., Li, N., 2013. Crystal
structure and optical properties of YMnO3 compound with high near-
infrared reectance. Sol. Energy 91, 3236.
Hao, F., Stoumpos, C.C., Cao, D.H., Chang, R.P.H., Kanatzidis, M.G.,
2014. Lead-free solid-state organicinorganic halide perovskite solar
cells. Nat. Photon. 8 (6), 489494.
Hattori, T., Taira, T., Era, M., Tsutsui, T., Saito, S., 1996. Highly ecient
electroluminescence from a heterostructure device combined with
emissive layered-perovskite and an electron-transporting organic
compound. Chem. Phys. Lett. 254 (12), 103108.
Hayashia, H., Inaba, H., Matsuyama, M., Lan, N.G., Dokiya, M.,
Tagawa, H., 1999. Structural consideration on the ionic conductivity
of perovskite-type oxides. Solid State Ionics 122 (14), 115.
Heo, J.H., Im, S.H., Noh, J.H., Mandal, T.N., Lim, C.S., Chang, J.A.,
Lee, Y.H., Kim, H.J., Sarkar, A., Nazeeruddin, M.K., Gratzel, M.,
Seok, S.I., 2013. Ecient inorganicorganic hybrid heterojunction
solar cells containing perovskite compound and polymeric hole
conductors. Nat. Photon. 7 (6), 486491.
Heo, J.H., Song, D.H., Im, S.H., 2014. Planar CH3NH3PbBr 3 hybrid
solar cells with 10.4% power conversion eciency, fabricated by
controlled crystallization in the spin-coating process. Adv. Mater. 26
(48), 81798183.
Herle, J.V., Ihringer, R., Cavieres, R.V., Constantin, L., Bucheli, O., 2001.
Anode supported solid oxide fuel cells with screen-printed cathodes. J.
Eur. Ceram. Soc. 21 (10-11), 18551859.
Heron, J.T., Schlom, D.G., Ramesh, R., 2014. Electric eld control of
magnetism using BiFeO3-based heterostructures. Appl. Phys. Rev. 1
(2), 021303:1021303:18.
Hilpert, K., Steinbrech, R.W., Boroomand, F., Wessel, E., Meschke, F.,
Zuev, A., Teller, O., Nickel, H., Singheiser, L., 2003. Defect formation
and mechanical stability of perovskites based on LaCrO3 for solid
oxide fuel cells (SOFC). J. Eur. Ceram. Soc 23 (16), 30093020.
Hoggan, E.N., Flowers, D., Wang, K., DeSimone, J.M., Carbonell, R.G.,
2004. Spin coating of photoresists using liquid carbon dioxide. Ind.
Eng. Chem. Res. 43 (9), 21132122.
Hong, X., Ishihara, T., Nurmikko, A.V., 1992. Dielectric connement
eect on excitons in PbI4-based layered semiconductors. Phys. Rev. B
45 (12), 69616964.
Howard, C.J., Stokes, H.T., 1998. Group theoretical analysis of octahe-
dral tilting in perovskites. Acta Crystallogr. Sect. B 54 (6), 782789.
696 M. Petrovic et al. / Solar Energy 122 (2015) 678699
Hoye, R.L.Z., Chua, M.R., Musselman, K.P., Li, G., Lai, M.L., Tan, Z.
K., Greenham, N.C., MacManus-Driscoll, J.L., Friend, R.H., Credg-
ington, D., 2015. Enhanced performance in uorene-free organometal
halide perovskite light-emitting diodes using tunable, low electron
anity oxide electron injectors. Adv. Mater. 27 (8), 14141419.
Huang, F., Dkhissi, Y., Huang, W., Xiao, M., Benesperi, I., Rubanov, S.,
Zhu, Y., Lin, X., Jiang, L., Zhou, Y., Gray-Weale, A., Etheridge, J.,
McNeill, C.R., Caruso, R.A., Bach, U., Spiccia, L., Cheng, Y.B., 2014.
Gas-assisted preparation of lead iodide perovskite lms consisting of a
monolayer of single crystalline grains for high eciency planar solar
cells. Nano Energy 10, 1018.
Huang, J., Shao, Y., Dong, Q., 2015. Organometal trihalide perovskite
single crystals: a next wave of materials for 25% eciency photo-
voltaics and applications beyond? J. Phys. Chem. Lett. 6 (16), 3218
3227.
Im, J.H., Lee, C.R., Lee, J.W., Park, S.W., Park, N.G., 2011. 6.5%
ecient perovskite quantum-dot-sensitized solar cell. Nanoscale 3 (10),
40884093.
Ishi, J., Mizuno, J., Kunugita, H., Ema, K., 1997. Third-order optical
nonlinearity due to excitons and biexcitons in a self-organized
quantum-well material (C6H13NH3)2PbI4. J. Nonlinear Opt. Phys.
Mater. 7 (1), 153159.
Ishihara, T., Hong, X., Ding, J., Nurmikko, A.V., 1992. Dielectric
connement eect for exciton and biexciton states in Pbl4-based two-
dimensional semiconductor structures. Surf. Sci. 267 (13), 323326.
Jackson, W.B., Amer, N.M., Boccara, A.C., Fournier, D., 1981.
Photothermal deection spectroscopy and detection. Appl. Opt. 20
(8), 13331344.
Jeon, Y.J., Lee, S., Kang, R., Kim, J.E., Yeo, J.S., Lee, S.H., Kim, S.S.,
Yun, J.M., Kim, D.Y., 2014a. Planar heterojunction perovskite solar
cells with superior reproducibility. Sci. Rep. 4, 6953:16953:7.
Jeon, N.J., Noh, J.H., Kim, Y.C., Yang, W.S., Ryu, S., Seok, S.I., 2014b.
Solvent engineering for high-performance inorganicorganic hybrid
perovskite solar cells. Nat. Mater. 13 (9), 897903.
Jiang, M., Wu, J., Lan, F., Tao, Q., Gao, D., Li, G., 2015. Enhancing the
performance of planar organo-lead halide perovskite solar cells by
using a mixed halide source. J. Mater. Chem. A 3, 963967.
Jiang, P., McFarland, M.J., 2004. Large-scale fabrication of wafer-size
colloidal crystals, macroporous polymers and nanocomposites by spin-
coating. J. Am. Chem. Soc. 126 (42), 1377813786.
Jiang, Q., Tong, J., Zhou, G., Jiang, Z., Li, Z., Li, C., 2014. Thermo-
chemical CO2 splitting reaction with supported LaxA1
xFeyB1
yO3
(A = Sr, Ce, B = Co, Mn; 0 6 x, y 6 1) perovskite oxides. Sol. Energy
103, 425437.
Juarez-Perez, E.J., Wubler, M., Fabregat-Santiago, F., Lakus-Wollny, K.,
Mankel, E., Mayer, T., Jaegermann, W., Mora-Sero, I., 2014. Role of
the selective contacts in the performance of lead halide perovskite solar
cells. J. Phys. Chem. Lett. 5 (4), 680685.
Kannan, R., Mulmi, S., Thangadurai, V., 2013. Synthesis and character-
ization of perovskite-type BaMg0.33Nb0.67
xFexO3
d for potential high
temperature CO2 sensors application. J. Mater. Chem. A 1 (23), 6874
6879.
Kawabata, Y., Yoshizawa-Fujita, M., Takeoka, Y., Rikukawa, M., 2009.
Relationship between structure and optoelectrical properties of
organicinorganic hybrid materials containing fullerene derivatives.
Synth. Meter. 159 (910), 776779.
Ke, W., Fang, G., Wan, J., Tao, H., Liu, Q., Xiong, L., Qin, P., Wang, J.,
Lei, H., Yang, G., Qin, M., Zhao, X., Yan, Y., 2015. Ecient hole-
blocking layer-free planar halide perovskite thin-lm solar cells. Nat.
Commun. 6, 6700:16700:7.
Kerfah, A., Tabi, K., Omeiri, S., Trari, M., 2011. Relaxor ferroelectric
and photocatalytic behaviour of Ba0.785Bi0.127Y0.017TiO3 composition.
Sol. Energy 85 (3), 443449.
Kim, B., Yeom, H.R., Yun, M.H., Kim, J.Y., Yang, C., 2012a. A
selenophene analogue of PCDTBT: selective ne-tuning of LUMO to
lower the bandgap for ecient polymer solar cells. Macromolecules 45
(21), 86588664.
Kim, H.S., Lee, C.R., Im, J.H., Lee, K.B., Moehl, T., Marchioro, A.,
Moon, S.J., Humphry-Baker, R., Yum, J.H., Moser, J.E., Gratzel, M.,
Park, N.G., 2012b. Lead iodide perovskite sensitized all-solid-state
submicron thin lm mesoscopic solar cell with eciency exceeding 9%.
Sci. Rep. 2, 591:1591:7.
Kim, H.S., Lee, J.W., Yantara, N., Boix, P.P., Kulkarni, S.A.,
Mhaisalkar, S., Gratzel, M., Park, N.G., 2013. High eciency solid-
state sensitized solar cell-based on submicrometer rutile TiO2 nanorod
and CH3NH3PbI3 perovskite sensitizer. Nano Lett. 13 (6), 24122417.
King, G., Woodward, P.M., 2010. Cation ordering in perovskites. J.
Mater. Chem. 20 (28), 57855796.
Kinoda, G., Nishiyama, M., Zhao, Y., Murakami, M., Koshizuka, N.,
Hasegawa, T., 2001. Tunneling spectroscopy of non-oxide perovskite
superconductor MgCNi3. Jpn. J. Appl. Phys. 40, L1365L1366.
Kitazawa, N., 1997. Excitons in two-dimensional layered perovskite
compounds: (C6H5C2H4NH3)2Pb(Br, I)4 and C6H5C2H4NH3)2Pb
(Cl, Br)4. Mat. Sci. Eng. B 49 (3), 233238.
Ko, H-S., Lee, J-W., Park, N-G., 2015. 15.76% eciency perovskite solar
cells prepared under high relative humidity: importance of PbI2
morphology in two-step deposition of CH3NH3PbI3. J. Mater. Chem.
A 3 (16), 88088815.
Kojima, A., Teshima, K., Shirai, Y., Miyasaka, T., 2009. Organometal
halide perovskites as visible-light sensitizers for photovoltaic cells. J.
Am. Chem. Soc. 131 (17), 60506051.
Komikado, T., Azusa, I., Koichi, M., Takashi, A., Shinsuke, U., 2007.
Multi-layered mirrors fabricated by spin-coating organic polymers.
Thin Solid Films 515 (78), 38873892.
Kondo, T., Iwamoto, S., Hayase, S., Tanaka, H., Ishi, J., Mizuno, M.,
Kazuhiro, E., Ryoichi, I., 1998. Resonant third-order optical nonlin-
earity in the layered perovskite-type material (C6H13NH3)2PbI4. Solid
State Commun. 105 (8), 503506.
Krebs, F.C., Spanggaard, H., Kjr, T., Biancardo, M., Alstrup, J., 2007.
Large area plastic solar cell modules. Mater. Sci. Eng. B 138 (2), 106
111.
Kutes, Y., Ye, L., Zhou, Y., Pang, S., Huey, B.D., Padture, N.P., 2014.
Direct observation of ferroelectric domains in solution-processed
CH3NH3PbI3 perovskite thin lms. J. Phys. Chem. Lett. 5 (19), 3335
3339.
Laban, W.A., Etgar, L., 2013. Depleted hole conductor-free lead halide
iodide heterojunction solar cells. Energy Environ. Sci. 6 (11), 3249
3253.
Lanty, G., Lauret, J.S., Deleporte, E., Bouchoule, S., Lafosse, X., 2008.
UV polaritonic emission from a perovskite-based microcavity. Appl.
Phys. Lett. 93 (8), 81101(1)81101(3).
Law, M., Greene, L.E., Johnson, J.C., Saykally, R., Yang, P.D., 2005.
Nanowire dye-sensitized solar cells. Nat. Mater. 4 (6), 455459.
Lee, M.M., Teuscher, J., Miyasaka, T., Murakami, T.N., Snaith, H.J.,
2012. Ecient hybrid solar cells based on meso-super structured
organometal halide perovskites. Science 338 (6107), 643647.
Leijtens, T., Eperon, G.E., Pathak, S., Abate, A., Lee, M.M., Snaith, H.J.,
2013. Overcoming ultraviolet light instability of sensitized TiO2 with
meso-superstructured organometal tri-halide perovskite solar cells.
Nat. Commun. 4 (2885), 18.
Li, C.Y., Zheng, X.M., 2013. Investigations on the g factors for the
Cu2+ sites in YBa1.9Na0.1Cu3O7
d and YBa2Cu3O7
d. Physica B 412,
2225.
Lian, J., Wang, Q., Yuan, Y., Shao, Y., Huang, J., 2015. Organic solvent
vapor sensitive methylammonium lead trihalide lm formation for
ecient hybrid perovskite solar cells. J. Mater. Chem. A 3 (17), 9146
9151.
Liang, J., Li, L., Niu, X., Yu, Z., Pei, Q., 2013. Fully solution-based
fabrication of exible light-emitting device at ambient conditions. J.
Phys. Chem. C 117 (32), 1663216639.
Liang, P.W., Liao, C.Y., Chueh, C.C., Zuo, F., Williams, S.T., Xin, X.K.,
Lin, J., Jen, A.K.Y., 2014. Additive enhanced crystallization of
solution-processed perovskite for highly ecient planar-heterojunction
solar cells. Adv. Mater. 26 (22), 37483754.
 M. Petrovic et al. / Solar Energy 122 (2015) 678699
Liu, D., Kelly, T.L., 2014. Perovskite solar cells with a planar
heterojunction structure prepared using room temperature solution
processing techniques. Nat. Photon. 8 (2), 133138.
Liu, M., Johnston, M.B., Snaith, H.J., 2013. Ecient planar heterojunc-
tion perovskite solar cells by vapour deposition. Nature 501 (7467),
395398.
Liu, W., Zhang, Y., 2014. Electrical characterization of TiO2/CH3NH3PbI3
heterojunction solar cells. J. Mater. Chem. A 2 (26), 1024410249.
Lo, M.F., Guan, Z.Q., Ng, T.W., Chan, C.Y., Lee, C.S., 2015. Electronic
structures and photoconversion mechanism in perovskite/fullerene
heterojunctions. Adv. Funct. Mater. 25 (8), 12131218.
Lufaso, M.W., Woodward, P.M., 2001. Prediction of the crystal structures
of perovskites using the software program SPuDS. Acta Cryst. B 57
(6), 725738.
Lufaso, M.W., Woodward, P.M., 2004. JahnTeller distortions, cation
ordering and octahedral tilting in perovskites. Acta Cryst. B 60 (1), 10
20.
Malinkiewicz, O., Yella, A., Lee, Y.H., Espallargas, G.M., Graetzel, M.,
Nazeeruddin, M.K., Bolink, H.J., 2014. Perovskite solar cells
employing organic charge-transport layers. Nat. Photon. 8 (2),
128132.
Manseki, K., Ikeya, T., Tamura, A., Ban, T., Sugiuraa, T., Yoshida, T.,
2014. Mg-doped TiO2 nanorods improving open-circuit voltages of
ammonium lead halide perovskite solar cells. RSC Adv. 4 (19), 9652
9655.
Mares, J.A., Cechova, N., Nikl, M., Kvapil, J., Kratky, R., Pospsil, J.,
1998. Cerium-doped RE3+AlO3 perovskite scintillators: spectroscopy
and radiation induced defects. J. Alloys Compd. 275, 200204.
Marrero-Lopez, D., Romero, R., Martn, F., Ramos-Barrado, J.R., 2014.
Eect of the deposition temperature on the electrochemical properties
of La0.6Sr0.4Co0.8Fe0.2O3
d cathode prepared by conventional spray
pyrolysis. J. Power Sources 255, 308317.
Martinelli, G., Carotta, M.C., Ferroni, M., Sadaoka, Y., Traversa, E.,
1999. Screen-printed perovskite-type thick lms as gas sensors for
environmental monitoring. Sens. Actuat. B 55 (23), 99110.
Masi, S., Colella, S., Listorti, A., Roiati, V., Liscio, A., Palermo, V.,
Rizzo, A., Gigli, G., 2015. Growing perovskite into polymers for easy-
processable optoelectronic devices. Sci. Rep. 5, 7725:17725:7.
Mei, A., Li, X., Liu, L., Ku, Z., Liu, T., Rong, Y., Xu, M., Hu, M., Chen,
J., Yang, Y., Gratzel, M., Han, H., 2014. A hole-conductor-free, fully
printable mesoscopic perovskite solar cell with high stability. Science
345 (6194), 295298.
Melo, F., Joanny, J.F., Fauve, S., 1989. Fingering instability of spinning
drops. Phys. Rev. Lett. 63 (18), 19581961.
Michel, C.R., Lopez, E.R., Zea, H.R., 2006. Synthesis of GdCo1
x
CuxO3
d (x = 0, 0.15, 0.30) perovskites by ultrasonic spray pyrolysis.
Mater. Res. Bull. 41 (1), 209216.
Millis, A.J., 1998. Lattice eects in magnetoresistive manganese per-
ovskites. Nature 392 (6672), 147150.
Mitzi, D.B., 1996. Synthesis, crystal structure, and optical and thermal
properties of (C4H9NH3)2MI4 (M = Ge, Sn, Pb). Chem. Mater. 8 (3),
791800.
Mitzi, D.B., 2000. Organicinorganic perovskites containing trivalent
metal halide layers: the templating inuence of the organic cation
layer. Inorg. Chem. 39 (26), 61076113.
Mitzi, D.B., 2004. Solution-processed inorganic semiconductors. J. Mater.
Chem. 14 (15), 23552365.
Mitzi, D.B., Chondroudis, K., Kagan, C.R., 2001. Organicinorganic
electronics. IBM J. Res. Dev. 45 (1), 2945.
Mitzi, D.B., Feild, C.A., Harrison, W.T.A., Guloy, A.M., 1994. Con-
ducting tin halides with a layered organic-based perovskite structure.
Nature 369 (6480), 467469.
Mitzi, D.B., Prikas, M.T., Chondroudis, K., 1999. Thin lm deposition of
organicinorganic hybrid materials using a single source thermal
ablation technique. Chem. Mater. 11 (3), 542544.
Mitzi, D.B., Wang, S., Feild, C.A., Chess, C.A., Guloy, A.M., 1995.
Conducting layered organicinorganic halides containing h1 1 0i ori-
ented perovskite sheets. Science 267 (5203), 14731476.
697
Mohammadi, M.R., Louca, R.R.M., Fray, D.J., Welland, M.E., 2012.
Dye-sensitized solar cells based on a single layer deposition of TiO2
from a new formulation paste and their photovoltaic performance. Sol.
Energy 86, 26542664.
Morana, M., Wegscheider, M., Bonanni, A., Kopidakis, N., Shaheen, S.,
Scharber, M., Zhu, Z., Waller, D., Gaudiana, R., Brabec, C., 2008.
Bipolar charge transport in PCPDTBT-PCBM bulk heterojunctions
for photovoltaic applications. Adv. Funct. Mater. 18 (12), 17571766.
Nie, W., Tsai, H., Asadpour, R., Blancon, J.C., Neukirch, A.J., Gupta,
G., Crochet, J.J., Chhowalla, M., Tretiak, S., Alam, M.A., Wang, H.
L., Mohite, A.D., 2015. High-eciency solution-processed perovskite
solar cells with millimeter-scale grains. Science 347 (6221), 522525.
Ning, Z., Gong, X., Comin, R., Walters, G., Fan, F., Voznyy, O.,
Yassitepe, E., Buin, A., Hoogland, S., Sargent, E.H., 2015. Quantum-
dot-in-perovskite solids. Nature 523 (7560), 324328.
Oosterhout, A.B.Van, 1977. Tungstate luminescence in ordered per-
ovskites. Phys. Status Solidi A 41 (2), 607617.
Othman, M.R., Kim, J., 2008. Permeability and separability of oxygen
across perovskite-alumina membrane prepared from a solgel proce-
dure. Ind. Eng. Chem. Res. 47 (9), 30003007.
Papavassiliou, G.C., Koutselas, I.R., 1995. Structural, optical and related
properties of some natural three- and lower dimensional semiconduc-
tor systems. Synth. Metal 71 (13), 17131714.
Papavassiliou, G.C., Mousdis, G.A., Koutselas, I.B., 1999. Some new
organicinorganic hybrid semiconductors based on metal halide units:
structural, optical and related properties. Adv. Mater. Opt. Electron. 9
(6), 265271.
Pedesseau, L., Jancu, J.M., Rolland, A., Deleporte, E., Katan, C., Even,
J., 2014. Electronic properties of 2D and 3D hybrid organic/inorganic
perovskites for optoelectronic and photovoltaic applications. Opt.
Quant. Electron. 46 (10), 12251232.
Peng, B., Jungmann, G., Jager, C., Haarer, D., Schmidt, H.W., Thelakkat,
M., 2004. Systematic investigation of the role of compact TiO2 layer in
solid state dye-sensitized TiO2 solar cells. Coord. Chem. Rev. 248 (13
14), 14791489.
Perednisa, D., Wilhelmb, O., Pratsinisb, S.E., Gaucklera, L.J., 2005.
Morphology and deposition of thin yttria-stabilized zirconia lms
using spray pyrolysis. Thin Solid Films 474 (12), 8495.
Princivalle, A., Perednis, D., Neagu, R., Djurado, E., 2004. Microstruc-
tural Investigations of Nanostructured La1
xSrxCoO3
d thin layers on
porous supports by a polymeric solgel process. Chem. Mater. 16 (19),
37333739.
Qi, B., Wang, J., 2013. Fill factor in organic solar cells. Phys. Chem.
Chem. Phys. 15 (23), 89728982.
Qiu, J., Qiu, Y., Yan, K., Zhong, M., Mu, C., Yan, H., Yang, S., 2013.
All-solid-state hybrid solar cells based on a new organometal halide
perovskite sensitizer and one-dimensional TiO2 nanowire arrays.
Nanoscale 5 (8), 32453248.
Reich, S., Leitus, G., Popovitz-Biro, R., Goldbourt, A., Vega, S., 2009. A
possible 2D HXWO3 superconductor with a Tc of 120 K. J. Supercond.
Nov. Magn. 22 (4), 343346.
Roldan-Carmona, C., Malinkiewicz, O., Soriano, A., Mnguez Espal-
largas, G., Garcia, A., Reinecke, P., Kroyer, T., Dar, M.I., Nazeerud-
dine, M.K., Bolink, H.J., 2014. Flexible high eciency perovskite solar
cells. Energy Environ. Sci. 7 (3), 994997.
Saka, K.I., Sonoyama, T., Tsuzuki, T., Ichikawa, M., Taniguchi, Y., 2005.
Lead halide-based layered perovskites incorporated with a p-Ter-
phenyl laser dye. Chem. Lett. 34 (2), 212213.
Sanchez, R.S., Gonzalez-Pedro, V., Lee, J.W., Park, N.G., Kang, Y.S.,
Mora-Sero, I., Bisquert, J., 2014. Slow dynamic processes in lead
halide perovskite solar cells. Characteristic times and hysteresis. J.
Phys. Chem. Lett. 5 (13), 23572366.
Schlom, D.G., Chen, L.Q., Pan, X., Schmehl, A., Zurbuchen, M.A., 2008.
A thin lm approach to engineering functionality into oxide. J. Am.
Ceram. Soc. 91 (8), 24292454.
Sekhara, P.K., Mukundanb, R., Broshab, E., Garzon, F., 2013. Eect of
perovskite electrode composition on mixed potential sensor response.
Sens. Actuat. B Chem. 183, 2024.
698 M. Petrovic et al. / Solar Energy 122 (2015) 678699
Sha, W.E.I., Ren, X., Chen, L., Choy, W.C.H., 2015. The eciency limit
of CH3NH3PbI3 perovskite solar cells. Appl. Phys. Lett. 106 (22),
221104(1)221104(5).
Shen, L., Zhu, G., Guo, W., Tao, C., Zhang, X., Liu, C., Chen, W., Ruan,
S., Zhong, Z., 2008. Performance improvement of TiO2/P3HT solar
cells using CuPc as a sensitizer. Appl. Phys. Lett. 92 (7), 073307(1)
073307(3).
Shimizu, Y., Sakagami, S., Goto, K., Nakachi, Y., Ueda, K., 2009.
Tricolor luminescence in rare earth doped CaZrO3 perovskite oxides.
Mater. Sci. Eng. B 161 (13), 100103.
Song, X., Wang, W., Sun, P., Wanli, M., Chen, Z.K., 2015. Additive to
regulate the perovskite crystal lm growth in planar heterojunction
solar cells. Appl. Phys. Lett. 106 (3), 033901:1033901:5.
Stamplecoskie, K.G., Manser, J.S., Kamat, P.V., 2015. Dual nature of
excited state in organicinorganic lead halide perovskites. Energy
Environ. Sci. 8 (1), 208215.
Steirer, X., Reese, M.O., Rupert, B.L., Kopidakis, N., Olson, D.C.,
Collins, R.T., Ginley, D.S., 2009. Ultrasonic spray deposition for
production of organic solar cells. Sol. Energy Mater. Sol. Cells 93 (4),
447453.
Stoumpos, C.C., Malliakas, C.D., Kanatzidis, M.G., 2013. Semiconduct-
ing tin and lead iodide perovskites with organic cations: phase
transitions, high mobilities, and near-infrared photoluminescent
properties. Inorg. Chem. 52 (15), 90199038.
Stranks, S.D., Eperon, G.E., Grancini, G., Menelaou, C., Alcocer, M.J.P.,
Leijtens, T., Herz, L.M., Petrozza, A., Snaith, H.J., 2013. Electron
hole diusion lengths exceeding 1 micrometer in an organometal
trihalide perovskite absorber. Science 342 (6156), 341344.
Stranks, S.D., Snaith, H.J., 2015. Metal-halide perovskites for photo-
voltaic and light-emitting devices. Nat. Nanotechnol. 10 (5), 391402.
Suarez, B., Gonzalez-Pedro, V., Ripolles, T.S., Sanchez, R.S., Otero, L.,
Mora-Sero, I., 2014. Recombination study of combined halides (Cl,
Br, I) perovskite solar cells. J. Phys. Chem. Lett. 5 (10), 16281635.
Subbiah, A.S., Halder, A., Ghosh, S., Mahuli, N., Hodes, G., Sarkar, S.
K., 2014. Inorganic Hole Conducting Layers for Perovskite-Based
Solar Cells. J. Phys. Chem. Lett. 5 (10), 17481753.
Suh, W.H., Suslick, K.S., 2005. Magnetic and porous nanospheres from
ultrasonic spray pyrolysis. J. Am. Chem. Soc. 127 (34), 1200712010.
Sum, T.C., Chen, S., Xing, G., Liu, X., Wu, B., 2015. Energetics and
dynamics in organicinorganic halide perovskite photovoltaics and
light emitters. Nanotechnology 26 (34), 342001:1342001:31.
Sun, S., Salim, T., Mathews, N., Duchamp, M., Boothroyd, C., Xing, G.,
Sumbce, T.C., Lam, Y.M., 2014. The origin of high eciency in low-
temperature solution-processable bilayer organometal halide hybrid
solar cells. Energy Environ. Sci. 7 (1), 399407.
Sun, C., Xue, Q., Hu, Z., Chen, Z., Huang, F., Yip, H.L., Cao, Y., 2015.
Phosphonium halides as both processing additives and interfacial
modi ers for high performance planarheterojunction perovskite solar
Cells. Small 11 (27), 16136829.
Tachikawa, T., Karimata, I., Kobori, Y., 2015. Surface charge trapping in
organolead halide perovskites explored by single-particle photolumi-
nescence imaging. J. Phys. Chem. Lett. 6 (16), 31953201.
Takahashi, Y., Obara, R., Nakagawa, K., Nakano, M., Tokita, J., Inabe,
T.T., 2007. Tunable charge transport in soluble organicinorganic
hybrid semiconductors. Chem. Mater. 19 (25), 63126316.
Tan, Z.K., Moghaddam, R.S., Lai, M.L., Docampo, P., Higler, R.,
Deschler, F., Price, M., Sadhanala, A., Pazos, L.M., Credgington, D.,
Hanusch, F., Bein, T., Snaith, H.J.H., Friend, R.H., 2014. Bright light-
emitting diodes based on organometal halide perovskite. Nat.
Nanotechnol. 9 (9), 687692.
Tan, S., Yang, P., Li, C., Wang, W., Wang, J., Zhang, M., Jing, X., Lin,
J., 2010. Preparation, characterization and luminescent properties of
spherical CaTiO3:Pr3+ phosphors by spray pyrolysis. Solid State Sci.
12 (4), 624629.
Taniguchi, I., Schoonman, J., 2002. Electrostatic spray deposition of
perovskite-type oxides thin lms with porous microstructure. J. Mater.
Synth. Process. 10 (5), 267275.
Taniguchi, I., van Landschoot, R.C., Schoonman, J., 2003. Fabrication of
La1
xSrxCo1
yFeyO3 thin lms by electrostatic spray deposition. Solid
State Ionics 156 (12), 113.
Taskin, A.A., Lavrov, A.N., Ando, Y., 2005. Achieving fast oxygen
diusion in perovskites by cation ordering. Appl. Phys. Lett. 86 (9),
091910(1)091910(3).
Tathavadekar, M.C., Agarkar, S.A., Game, O.S., Bansode, U.P., Kulka-
rni, S.A., Mhaisalkar, S.G., Ogale, S.B., 2015. Enhancing eciency of
perovskite solar cell via surface microstructuring: superior grain
growth and light harvesting eect. Sol. Energy 112, 1219.
Tress, W., Marinova, N., Moehl, T., Zakeeruddin, S.M., Nazeeruddin, M.
K., Gratzel, M., 2015. Understanding the rate-dependent JV
hysteresis, slow time component, and aging in CH3NH3PbI3 per-
ovskite solar cells: the role of a compensated electric eld. Energy
Environ. Sci. 8 (3), 9951004.
Troughton, J., Bryant, D., Wojciechowski, K., Carnie, M.J., Snaith, H.D.
A., Watson, T.M., 2015. Highly ecient, exible, indium-free per-
ovskite solar cells employing metallic substrates. J. Mater. Chem. A 3
(17), 91419145.
Ueda, T., Nagano, T., Okawa, H., Takahashi, S., 2010. Amperometric-
type NOx sensor based on YSZ electrolyte and La-based perovskite-
type oxide sensing electrode. J. Ceram. Soc. Jpn. 118 (1375), 180183.
Ullmann, H., Tromenko, N., Tietz, F., Stover, D., Ahmad-Khanlou, A.,
2000. Correlation between thermal expansion and oxide ion transport
in mixed conducting perovskite-type oxides for SOFC cathodes. Solid
State Ionics 138 (12), 7990.
Umebayashi, T., Asai, K., Kondo, T., Nakao, A., 2003. Electronic
structures of lead iodide based low-dimensional crystals. Phys. Rev. B
67 (15), 155405(1)155405(6).
Unger, E.L., Hoke, E.T., Bailie, C.D., Nguyen, W.H., Bowring, A.R.,
Heumuller, T., Christoforo, M.G., McGehee, M.D., 2014. Hysteresis
and transient behavior in currentvoltage measurements of hybrid-
perovskite absorber solar cell. Energy Environ. Sci. 7 (11), 36903698.
Volkova, L.M., Polyshchuk, S.A., Herbeck, F.E., 2000. Correlation
between Tc and crystal chemical parameters of cation sublattice
An+1(Cu)n in perovskite layer of high-Tc cuprate superconductors. J.
Supercond. Nov. Magn. 13 (4), 583586.
Wang, Y., Luo, L., Ding, Y., Zhang, X., Xu, Y., Liu, X., 2012. Perovskite
nanoparticles LaNi0.5Ti0.5O3 modied carbon paste electrode as a
sensor for electrooxidation and detection of amino acids.
J. Electroanal. Chem. 667, 5458.
Wang, Y., Zhong, H., Li, X., Jia, F., Shi, Y., Zhang, W., Cheng, Z.,
Zhang, L., Wang, J., 2013. Perovskite LaTiO3Ag0.2 nanomaterials for
nonenzymatic glucose sensor with high performance. Biosens.
Bioelectron. 48, 5660.
Wolfram, T., Ellialtioglu, S., 2006. Electronic and Optical Properties of
d-band Perovskites. Cambridge University Press, Cambridge.
Wu, X., Yu, H., Li, L., Wang, F., Xu, H., Zhao, N., 2015. Composition-
dependent light-induced dipole moment change in in organometal
halide perovskites. J. Phys. Chem. C 19 (2), 12531259.
Xiao, Y., Han, G., Chang, Y., Zhang, Y., Li, Y., Li, M., 2015.
Investigation of perovskite-sensitized nanoporous titanium dioxide
photoanodes with dierent thicknesses in perovskite solar cells. J.
Power Sources 286, 118123.
Xiao, M., Huang, F., Huang, W., Dkhissi, Y., Etheridge, J., Gray-Weale,
A., Bach, U., Cheng, Y.B., Spiccia, L., 2014. A fast deposition-
crystallization procedure for highly ecient lead iodide perovskite
thin-lm solar cells. Angew. Chem., Int. Ed. 53 (37), 98989903.
Xing, G., Mathews, N., Lim, S.S., Yantara, N., Liu, X., Sabba, D.,
Gratzel, M., Mhaisalkar, S., Sum, T.C., 2014. Low-temperature
solution-processed wavelength-tunable perovskites for lasing. Nat.
Mater. 13 (5), 476480.
Xu, J., Buin, A., Ip, A.H., Li, W., Voznyy, O., Comin, R., Yuan, M.,
Jeon, S., Ning, Z., McDowell, J.J., Kanjanaboos, P., Sun, J.P., Lan,
X., Quan, L.N., Kim, D.H., Hill, I.G., Maksymovych, P., Sargent, H.,
2015. Perovskitefullerene hybrid materials suppress hysteresis in
planar diodes. Nat. Commun. 6, 7081:17081:8.
 M. Petrovic et al. / Solar Energy 122 (2015) 678699
Xue, Q., Hu, Z., Sun, C., Chen, Z., Huang, F., Yip, H.L., Cao, Y., 2015.
Metallohalide perovskitepolymer composite lm for hybrid planar
heterojunction solar cells. RSC Adv. 5 (1), 775783.
Yamada, K., Isobe, K., Tsuyama, E., Okuda, T., Furukawa, Y., 1995.
Chloride ion conductor CH3NH3GeCl3 studied by Ritveld analysis of
X-ray diraction and 35Cl NMR. Sold State Ionics 79, 152157.
Yang, X.N., Huang, B.B., Wang, H.B., Shang, S.X., Yao, W.F., Wei, J.
Y., 2004. Eect of La doping on structural and electrical properties of
Bi2Ti2O7 thin lms. J. Cryst. Growth 270 (12), 98101.
Yang, J., Clark, N., Long, M., Xiong, J., Jones, D.J., Yang, B., Zhou, C.,
2015a. Solution stability of active materials for organic photovoltaics.
Sol. Energy 113, 181188.
Yang, J., Siempelkamp, B., Liu, D., Kelly, T., 2015b. Investigation of
CH3NH3PbI3 degradation rates and mechanisms in controlled humid-
ity environments using in situ techniques. ACS Nano 9 (2), 19551963.
Yao, Q.R., Cai, J., Zhou, H.Y., Rao, G.H., Wang, Z.M., Deng, J.Q.,
2015. Inuence of La-doping on structure and magnetic behaviors in
BiFeO3 633, 170173.
Yin, W.J., Shi, T., Yan, Y., 2014. Unique properties of halide perovskites
as possible origins of the superior solar cell performance. Adv. Mater.
26 (27), 46534658.
Yoon, J.S., Lee, J., Hwang, H.J., Whanga, C.M., Moon, J.W., Kim, D.H.,
2008. Lanthanum oxide-coated stainless steel for bipolar plates in solid
oxide fuel cells. J. Power Sources 181 (2), 281286.
You, J., Yang, Y., Hong, Z., Song, T.B., Meng, L., Liu, Y., Jing, C.,
Zhou, H., Chang, W.H., Li, G., Yang, Y., 2014. Moisture assisted
perovskite lm growth for high performance solar cells. Appl. Phys.
Lett. 105 (18), 183902:1183902:5.
699
Zhang, W., Anaya, M., Lozano, G., Calvo, M., Johnston, M., Mguez, H.,
Snaith, H., 2015a. Highly ecient perovskite solar cells with tunable
structural color. Nano Lett. 15 (3), 16981700.
Zhang, S., Audebert, P., Wei, Y., Al Choueiry, A., Lanty, G., Brehier, A.,
Galmiche, L., Clavier, G., Boissiere, C., Lauret, J.S., Deleporte, E.,
2010. Preparations and characterizations of luminescent two dimen-
sional organicinorganic perovskite semiconductors. Materials 3 (5),
33853406.
Zhang, W., Saliba, M., Moore, D., Pathak, S., Horantner, M., Ster-
giopoulos, T., Stranks, S., Eperon, G., Alexander-Webber, J., Abate,
A., Sadhanala, A., Yao, S., Chen, Y., Friend, R., Estro, L., Wiesner,
U., Snaith, H., 2015b. Ultrasmooth organicinorganic perovskite thin-
lm formation and crystallization for ecient planar heterojunction
solar cells. Nat. Commun. 6 (6142), 110.
Zheng, H., Ou, J.Z., Strano, M.S., Kaner, R.B., Mitchell, A., Kalantar-
zadeh, K., 2011. Nanostructured tungsten oxide properties, synthe-
sis, and applications. Adv. Funct. Mater. 21 (12), 21752196.
Zhou, H., Chen, Q., Li, G., Luo, S., Song, T.B., Duan, H.S., Hong, Z.,
You, J., Liu, Y., Yang, Y., 2014. Interface engineering of highly
ecient perovskite solar cells. Science 345 (6196), 542546.
Zhou, Q., He, T., He, Q., Ji, Y., 2009. Electrochemical performances of
LaBaCuFeO5+X and LaBaCuCoO5+X as potential cathode materials
for intermediate-temperature solid oxide fuel cells. Electroch. Com-
mun. 11 (1), 8083.
Zhou, Y., Yang, M., Wu, W., Vasiliev, A.L., Zhu, K., Padture, N.P.,
2015. Room-temperature crystallization of hybrid-perovskite thin lms
viasolventsolvent extraction for high-performance solar cells. J.
Mater. Chem. A 3 (15), 81788184.