C H A P T E R

2
X-ray diffraction and Raman
spectroscopy for lead halide
perovskites
Mohammad Ziaur Rahman and Tomas Edvinsson
Department of Engineering Sciences, Solid State Physics, Ångström Laboratory,
Uppsala University, Uppsala, Sweden

2.1 Introduction

The broad field of perovskites have been attractive for condensed matters physics and
material sciences for many years due to the breath of physical properties that can be
found in the system. Oxide and fluoride perovskites have been extensively studied over
the years since they exhibit a plethora of intriguing photonic and electronic properties,
ionic conductivity, multiferroicity, piezoelectricity, superconductivity, and metal-
insulator transitions, where their properties can be tuned by the octahedral tilting with
inclusion of different metals [1]. Hybrid perovskite solar cells (HPSCs), based on
organic-inorganic lead halide materials, have recently emerged as a promising class of
materials in photovoltaic technology [2,3]. Following the report of solid state perovskite
solar cells with efficiencies up to 10% in 2012 [4], a great surge in world-wide research
efforts into perovskite solar cells research can be noticed- evident by more than 4000
publications on HPSCs in 2018. These efforts and the previous experience in the other
hybrid organic-inorganic solar cell systems (e.g. the dye-sensitized solar cell) lead to a
certified record efficiency surpassing 23% in lab scale devices in 2018 [5]. Other possible
application for the hybrid metal halide perovskite materials are hybrid light emitting
diodes (HLEDs) or utilization as X-ray scintillators [6].
Perovskites are materials with a crystal structure analogous with CaTiO3, having a gen-
eral chemical formula ABX3, where A is a large cation, B a smaller sized cation, and X is
an anion (Fig. 2.1). In the lead halide perovskites that are investigated for photovoltaics, B
is normally Pb21, X is a halide (i.e. I-, Br-, Cl-), while A is a small organic dipolar cation,

Characterization Techniques for Perovskite Solar Cell Materials

DOI: https://doi.org/10.1016/B978-0-12-814727-6.00002-5 23 Copyright © 2020 Elsevier Inc. All rights reserved.
24 2. X-ray diffraction and Raman spectroscopy for lead halide perovskites

FIGURE 2.1 (A) Perovskite crystal structure ABX3 for a cubic symmetry and (B) the cubic structure of the
MAPbI3 hybrid perovskite [7]. Reproduced with permission from reference T.J. Jacobsson, M. Pazoki, A. Hagfeldt,
T. Edvinsson, Goldschmidt’s rules and strontium replacement in lead halogen perovskite solar cells: theory and preliminary
experiments on CH3NH3SrI3, J. Phys. Chem. C 119 (2015) 25673
25683. Copyright 2015, American Chemical Society.

such as methylammonium (MA, CH3NH31), formamidinium (FA, HC(NH2)21), or a

relatively large inorganic cation such as Cs1 then forming a fully inorganic perovskite.
The structure, bandgap and further optoelectronic properties depends on the halide and
the cation composition.
The iodide compounds, APbI3, have a bandgap of 1.45, 1.60 and 1.73 eV for A 5 FA, MA
and Cs, respectively. Utilizing MA as an A-cation and varying the halide, the MAPbX3
materials have bandgaps of 1.6, 2.2 and 3.0 eV for X 5 I, Br and Cl, respectively [6]. Here, an
intermediate tunability allows bandgap optimization for tandem solar cells or HLED
application with tunable wavelength. For example, the band gap of MAPb(I1-xBrx)3 can be
linearly tuned between 1.60 eV and 2.33 eV by increasing the Br content (Fig. 2.2) [8,9].
Recently, a new record efficiency of 23.7% for a perovskite solar cell was reported on
the NREL chart for certified cell efficiencies [5]. This value surpasses the record efficiencies
reported for many established photovoltaic technologies based on polycrystalline materi-
als, such as CdTe (22.1%), CIGS (22.9%), and multicrystalline Si (22.3%) [5]. All of the com-
peting technologies, however, still have problem in competing with single crystalline Si
(26.1%) or Si heterostructured solar cells (26.6%) that have shown a dramatic price drop in
the last few years. Notably, the efficiency of the reported HPSC devices were measured
for small area lab devices (,1 cm2), while the ability to reach stable high efficiencies with
large area cells ( . 1 cm2) remains a grand challenge. For example, MAPbI3 is sensitive to
water exposure and high temperatures [10]. Recently, it has been reported that HPSC
could sustain good stability up to 1000 h under continuous illumination with a light source
equivalent to one sun (i.e. 1000 W m22 at AM1.5 G). However, such high stability was
achieved by tailoring the contact materials rather than the perovskite material [11,12].
Presumably, a higher efficiency can also be attained with multi-cation cascades.
Nonetheless, it is likely that the perovskites have to go to tandem approaches for being
truly competitive with single crystal silicon. Tandem devices made from metal halide per-
ovskites represent a highly tunable system that potentially can be made with very cost-
effective methods and short energy pay-back time compared to epitaxially grown III-V

Characterization Techniques for Perovskite Solar Cell Materials

 2.1 Introduction 25

FIGURE 2.2 (Top) Optical photographs, (A) PL of films, and (B) band gap change with linear bandgap
tuning by I-to-Br halogen exchange. (C) Incident-photon-to-current-efficiency (IPCE) for solar cell devices with
Br fraction up to 10%. [9]. Adapted with permission from reference B.-w. Park, B. Philippe, S.M. Jain, X. Zhang,
T. Edvinsson, H. Rensmo, et al., Chemical engineering of methylammonium lead iodide/bromide perovskites: tuning of
opto-electronic properties and photovoltaic performance, J. Mater. Chem. A 3 (2015) 21760
21771. Copyright 2015, Royal
Society of Chemistry.

Characterization Techniques for Perovskite Solar Cell Materials

26 2. X-ray diffraction and Raman spectroscopy for lead halide perovskites

semiconductor tandem systems. Toward the design of highly efficient tandem HPSCs, or
fully inorganic PSCs, it is crucial to quantify their crystalline structure and symmetries.
Because, such understanding is vital to control the structure as well as the fundamental
optoelectronic properties for a resilient device structure with a durable performance.
In this context, X-ray diffraction and Raman spectroscopy provide useful information of
the material properties, such as the crystal structure, symmetries, displacements, defects,
micro-crystallinity, orientations, vibrations, phonon lifetimes, and their interdependence
on material alterations. These techniques contribute with crucial information that is neces-
sary to find structure-to-property relationships from materials to function.

2.1.1 XRD and Raman spectroscopy

Structural and chemical characterization with X-ray and Raman techniques, respectively
have proven successful in uncovering a broad range of microstructural, morphological
and chemical features from sub-Ångström molecular chemistry to device-scale alignment.
These techniques become more popular with advancement in instrumentation, X-ray and
light source brightness, and detector technologies. These techniques now allow one to
have high quality data and quantitative information to obtaining precise description of the
molecular structure and microstructure of the materials of interest. This wealth of informa-
tion combined with electrical characterization and modeling is nowadays commonly been
practiced in everything from fundamental investigations to the facilitation of design rules
for a rational design of materials and complete devices.
The discovery of the possibility to diffract X-rays from crystal and the constructive
reflection maximum condition by Max von Laue with the incoming (k) and outgoing

wavevectors (k0 ) satisfying R (k- k0 ) 5 2πm where R is the Bravais lattice vector of
the crystal and m the Miller index triplet, was monumental for the later development
and use of X-ray diffraction. The Laue condition can also be written in the equivalent
form ei(k-k )  R 5 1, where Δk 5 (k- k0 ) is referred to as the scattering vector. Utilizing
0

monochromatic X-rays that are elastically scattered, W.H Bragg and W.L Bragg
constructed a geometric analog satisfying the Laue condition, where the constructive dif-
fraction could be formulated into the Bragg equation
2dhkl sinθb 5 nλ (2.1)
Where dhkl is the distance between diffraction planes with Miller index (h k l ), λ is the
wavelength of the incoming X-ray, θB is the Bragg angle, and n is a positive integer
representing the diffraction order. The Laue constraint for the intensity I(R)- maximum
is now naturally fulfilled by the constructive interference for a fixed wavelength and
replacing the general angle θ with the angle for which the intensity is at maximum, θB.
The geometric situation is illustrated in Fig. 2.3A in a Bragg-Brentano setup where the

two extra path lengths of dhkl sinθ for the bottom lattice plane elastic scattering can be
seen and XRD diffractograms for cubic Pm-3m and tetragonal I4/mcm MAPbI3 (Fig. 2.3C).
Although the maximum intensity at angle θ is instructive to infer the set of distances in
the crystalline materials, and thus reflecting the internal structure and symmetry, also the
peak shape contains information from the number of crystalline planes to form or to cancel

Characterization Techniques for Perovskite Solar Cell Materials

 2.1 Introduction 27

FIGURE 2.3 (A) Schematic illustration of a Bragg-Brentano geometry XRD setup, (B) illustration of a XRD
setup with multiple angles for generation of 2D q-range and construction of pole figures [16]. (C) Synchrotron
XRD patterns of MAPbI3 for the cubic Pm-3m and the tetragonal I4/mcm structure, and R-symmetry point super-
lattice peaks [17]. (D) GIWAXS images and structure orientation information of polycrystalline and (E) near
single-crystalline (BA)2(MA)3Pb4I13 Ruddlesden
Popper phases [18]. (B) Adapted with permission from
reference K. Inaba, S. Kobayashi, K. Uehara, A. Okada, S.L. Reddy, T. Endo, High resolution X-ray diffraction analyses of
(La, Sr)MnO3/ZnO/Sapphire(0001) double heteroepitaxial films, Adv. Mater. Phys. Chem. 03 (2013) 72
89. Copyright
2013, Scientific Research. (C) Reproduced with permission from reference P.S. Whitfield, N. Herron, W.
E. Guise, K. Page, Y.Q. Cheng, I. Milas, et al., Structures, phase transitions and tricritical behavior of the hybrid perovskite
methyl ammonium lead iodide, Sci. Rep. 6 (2016) 35685. Copyright 2016 Nature Publishing Group. (D and E) Reproduced
with permission from reference H. Tsai, W. Nie, J.-C. Blancon, C.C. Stoumpos, R. Asadpour, B. Harutyunyan, et al., High-
efficiency two-dimensional Ruddlesden
Popper perovskite solar cells, Nature 536 (2016) 312. Copyright 2016 Nature
Publishing Group.

the non-constructive interference signal. Peak shape analysis can here be used to extract
local disorder, strain, and crystallite size. The ability to separate of distortion and particle
size broadening in X-ray patterns, however, as well as coupling effect from local disorder
and strain have to be taken into care when performing detailed peak shape analysis
[13,14]. When the sample is single crystalline or textured one can quantify the crystal sym-
metry or crystallite orientations by extending the diffraction analysis to other directions
compared to the Bragg angle, either by using a wide-angle detector, repositioning the
detector to angular ranges perpendicular to the Bragg angle, or rotate the sample
(Fig. 2.3B).
In the most general case, one can construct a pole figure to fully characterize the distri-
bution of diffractions from a textured sample with a variation in crystallite orientations by

Characterization Techniques for Perovskite Solar Cell Materials

28 2. X-ray diffraction and Raman spectroscopy for lead halide perovskites

rotating the sample axes while having the corresponding Bragg reflection of interest fixed,
successively change the Bragg angle, and add data from an additional perpendicular axis
rotations (rocking curve) of the sample. The two first parts of this are illustrated in
Fig. 2.3D and E where diffraction pattern from gracing incident wide angle X-ray scatter-
ing (GIWAXS) of polycrystalline and near single-crystalline perovskite derived
Ruddlesden
Popper (RP) phases are shown. The crystallographic unit cell of RP phases
can be seen as an elongation of the dimensions in the perovskite structure, keeping layers
of perovskite symmetries (ABX3) in between with the general RP phase composition for-
mula An11BnX3n11 [15]. For more complicated A-site cation compositions in RP phases,
they can also be represented as An-1A0 2BnX3n11, where A and A0 (A-prime) represent two
different cations and B refers to the Pb, Bi, or Sn metal cations usually incorporated in the
hybrid metal halides. The A cations are located in the perovskite layer with a 12-fold
cuboctahedral coordination to the anions while the A0 cations have a 9-fold coordination
and are located at the interface between the perovskite layer and the intermediate layer
before the next perovskite layer.
Apart from a general structure determination and peak shape analysis, more details can
be extracted from diffraction by analyzing the diffraction intensities or shifts in more
detail. First, one should note that X-rays are diffracted from the electron clouds around
the nuclei forming the lattice planes where any anisotropic polarization will give an error
in the determination of the derived nuclei positions. In these cases, neutron diffraction
characterization is advised for a high resolved structure determination. The amplitude of
the scattering (within the Fraunhofer condition) from electrons around a nuclei can be
described by a phase factor e2iΔk  r(i,j) containing the scattering vector Δk and the pair-
wise distance between all pairs of point charges r(i,j). It can be formulated into an integral
of the contribution from a charge distribution into an atomic form factor [19].
ð
fatom 5
atom

ρe ðrÞ e2Δk  r dr (2.2)

where ρe(r) is the electron density charge distribution around the atom, and can formally
be determined via the square of the electronic wave function. For a distribution of atoms,
one can combine the individual atomic form factors into a structure factor
PN
F5 fatom eiΔkrn where fatom is the integral in Eq. 2.2 and rn denotes the position of the
n51
n-th atom in the structure. Combining this with the Laue condition and the notation for
Miller indices, one could obtain
X
N
FðhklÞ 5 fatom e½i2πðhxn 1kyn 1lzn Þ (2.3)
n51

For the simple cubic systems, with N 5 1 and the atoms in the primitive unit cells at
(0,0,0), reflections can be seen for all miller index combinations. For the FCC lattice with
N 5 2 and cubic sub-symmetry with at the basis (0,0,0) and (1/2, 1/2, 1/2), the structure factor
becomes 4fatom when all hkl are even or odd and 0 otherwise. Of interest here is a general
form factor for the perovskite structure (ABX3), here exemplified for the cubic structure
with space group Pm3m with the A-site cation at (0,0,0), B cation at (1/2, 1/2, 1/2), and 3 X

Characterization Techniques for Perovskite Solar Cell Materials

 2.1 Introduction 29
halogens at (0, 1/2, 1/2), (1/2, 0 1/2), (1/2, 1/2, 0) and the possibility that the B-site cation have a
small off-center displacement (ΔB) or tilt of the X-B-X axis from two different positions of
the halide ion (denoted X and X2 with a shift of ΔX and ΔX2, respective) formulated from
Eq. 2.3 as
2 2 3 3
 
6
6 fB  exp4i2πl
1
2
1 ΔB 5 1 7
7
6 7
6 8 97
Fperovskite ðhklÞ 5 fA 1 eiπðh1kÞ 6
6 > exp ½i2πlΔ  1 3>
7 (2.4)
> 2 =7
>
X
6 <   7
6 fX
4  >
> exp 4i2πl
1
1 Δ X2

1 1 exp ½iπðh 2 kÞ

5 >
>
7
5
: 2 ;

Hybrid perovskites are considered approximately cubic at high temperature from

the thermally averaged structure from the motion of the organic A-site cation, while an
off-center shift of the B-site central metal will also introduce a pseudo-cubic structure. A
small elongation of the unit cell (e.g. 0.5%) along the c-axis compared to the a-axis will
result in a tetragonal structure with c/a 5 1.005, where already a ΔX of 5 picometer (pm)
will result in a detectable shift for the corresponding pseudo-cubic reflection of
about 0.2 using Cu Kα radiation and Eq. 2.1. A Glazer notation [20] for octahedral tilting
is often used to categorize symmetries from different tilt combinations using subscripts
of 0, 1 , and
with respect to tilts around the x, y, and z-axes of the underlying
cubic perovskite structure Pm3m where a, b, and c represents the magnitudes of the tilts.
As an example, a2b1b1 denotes a negative tilt around the x-axis and positive tilts
around the y- and z-axes, where the double notation of b1b1 denotes a similar magni-
tude in the tilts about the y- and z-axes. Glazer found 23 different perovskite structures
from the possible tilts [20,21], while more recent analysis of sub-symmetry dependent
groups have reduced this to 15 [22]. Taking symmetry breaking from off-center displace-
ments as for ΔB 6¼ 0 in Eq. 2.4, forty (40) additional symmetries are possible [23].
Recalling the temperature induced phase transitions from a tetragonal I4/mcm crystal
structure into cubic Pm-3m structure for higher temperatures in Fig. 2.3C, and that the
out-of-phase rotations are located at the R-symmetry point (1/2 1/2 1/2) at the Brillouin
zone (BZ) boundaries and the in-phase rotations are at the M-symmetry point (1/2 1/2 0),
the phase transition lead to new lattice vectors, with modified unit cells where the M- or
R-symmetry points fold over to the Γ point in the lower symmetry phase, corresponding
to an orthorhombic P4/mbm and tetragonal I4/mcm symmetry for the M-symmetry point
and R-symmetry point instability, respectively [17]. The corresponding Glazer notations
is then naturally the untilted a0a0a0 for the cubic structure, while the tilting and broken
symmetry along the c-axis can be represented by a0a0c2 for the tetragonal crystal
structure.
Analysis of symmetries and textures on different scales can be obtained by combining
GIWAXS and gracing incident small angle X-ray scattering (GISAXS) with a detector
placed at longer distances from the sample (Fig. 2.4). Localized spots occur for the diffrac-
tion of the textured films, with successive transformation to even semi-circle intensities for
films with fully randomly ordered crystallites.

Characterization Techniques for Perovskite Solar Cell Materials

30 2. X-ray diffraction and Raman spectroscopy for lead halide perovskites

FIGURE 2.4 (A) Illustration of how GIWAXRD and GISAXS can be used for texture analysis in thin films
depending on the required dimensions where (B) represents randomly oriented arrangements of crystallites with
circular diffraction rings, except for the slightly oriented (200) reflection. (C) corresponds to a textured and
preferentially oriented films with diffraction patterns as arcs of different intensities and (D) corresponds to a
highly oriented films produce more localized diffraction spots/ellipses [24]. Reproduced with permission from
reference J. Rivnay, S.C.B. Mannsfeld, C.E. Miller, A. Salleo, M.F. Toney, Quantitative determination of organic semicon-
ductor microstructure from the molecular to device scale, Chem. Rev. 112 (2012) 5488
5519. Copyright 2012, American
Chemical Society.

Thermal, light- and chemical induced phase transformations are also important to
characterize and relates to mechanical stability during day-night operation, and long-
time stability. Certainly, the promises of lead halide perovskites (LHPs) as a solar cell
material is undeniable but it is very important that the crystal structure integrity and
chemical composition can be retained during extended use. LHP undergoes degradation
in contact with water, humidity, light, and temperature [25,26]. The hybrid lead halogen
perovskites are water soluble salts where uncapsulated perovskites take on water very

Characterization Techniques for Perovskite Solar Cell Materials

 2.1 Introduction 31
easily [27], while light exposure can break the bonds into halogen vacancy-halogen
interstitial pairs that enable halogens to migrate [28], or convert any oxygen that might
be present into highly reactive superoxide [29]. Particularly, blue and ultraviolet light
generate electrons in antibonding N2p-H1 s orbitals with degradation of the MA1 organic
cation [30,31]. Moreover, when exposed to heat and light, perovskites react with almost
all metals. Because, heat volatilizes halide species and light enhances halogen mobility
[26]. Additionally, due to remarkably low fracture energy (below 1 J m22) and high their
thermal expansion coefficient, approximately 10 times higher than that of glass substrates
or transparent conducting oxide electrodes [32], perovskites build up stress during
temperature changes that may lead to delamination or accelerated decomposition
[32
34]. Therefore, design of structurally stable perovskites remains a grand challenge to
make solar panels with metal halide perovskite that will last for .25 years. With XRD
measurements, it is possible to devise design strategies toward a structurally
stable perovskites as well as approached to cap the 3D perovskites with 2D perovskites
as a chemical effusion blocking layer. We here below discuss few of the recent XRD stud-
ies on LHP.
Methylammonium lead iodide (MAPbI3), a common LHP, showed reversible phase
transition between tetragonal and cubic symmetry at solar cell operating temperatures
[35]. For example, MAPbI3 crystallize at room temperature to a wide bandgap hexagonal
symmetry (P63mc) and a trigonal (P3m1) black phase at a higher temperature [36]. This
structural phase transition adversely influences photovoltaic properties [35]. Therefore, the
development of temperature immune perovskites is highly essential. Cation exchange is
one of the possible schemes to overcome the phase transition with MAPbI3 [37
40]. This
can be done by employing formamidinium lead iodide (FAPbI3) as a mixture with
MAPbI3 [40]. In this mixture of MAPbI3 and FAPbI3, the exchange of the organic cation
from methylammonium (MA) to formamidinium (FA) results in a material with either a
trigonal structure (black color, α phase) or a hexagonal structure (yellow color, δ phase)
depending on the synthesis temperature [36,40]. Notably, no significant δ phase transition
happened within the solar cell operating temperature. Because, a phase transition from the
δ phase to α phase takes place at B125  C, which is way higher than the solar cell operat-
ing temperature [37].
Incorporation of a smaller cation (MA) with a high dipole moment stabilizes the trigo-
nal phase of FAPbI3 without any lattice shrinkage or changes in the optical properties due
to enhanced I
H hydrogen bonds between the cation and the inorganic cage or to an
increase in the Madelung energy of the structure [38
41]. As a result, the δ phase transi-
tion can be completely suppressed as is shown in temperature-dependent X-ray diffrac-
tion. Fig. 2.5A illustrates the differences between the crystal structure of MAPbI3 and
FAPbI3. When using a mixture of MA and FA, the incorporation of MA formed a 3D net-
work of layered octahedra by reducing the number of shared iodide ions from three to
one. At room temperature, the octahedra are not perfectly aligned but results in a close to
identical twist of every second octahedral layer in the c direction. The unit cell expands
with increasing temperature to help aligning the octahedra perfectly along the c axis, yet
maintaining the tetragonal structure. To be precise, the tetragonal symmetry collapses and
the trigonal structure of α
FAPbI3 is formed if the perovskite structure consists of .80%

Characterization Techniques for Perovskite Solar Cell Materials

32 2. X-ray diffraction and Raman spectroscopy for lead halide perovskites

FIGURE 2.5 (A) Illustration of the crystal structure of PbI2 and MAPbI3 at different temperatures together
with the α
FAPbI3 and δ
FAPbI3 phase and (B and C) comparison between the experimental and theoretical
XRD patterns [36]. Reproduced with permission from reference A. Binek, F.C. Hanusch, P. Docampo, T. Bein, Stabilization
of the trigonal high-temperature phase of formamidinium lead iodide, J. Phys. Chem. Lett. 6 (2015) 1249
1253. Copyright
2015, American Chemical Society.

of FA [36]. This can be observed in X-ray diffraction measurements by a shift of the dif-
fraction pattern to lower angles. The XRD patterns of the synthesized yellow FAPbI3 and
stabilized black FAPbI3 and their theoretical patterns are illustrated in Fig. 2.5B and C.
Temperature-dependent XRD measurements is widely practiced to investigate the
phase transformation between the between different phases of LHP. In XRD patterns, a
few peaks disappear when the tetragonal phase transforms into the cubic structure whilst
some double peaks merge into single peaks. A peak shift in the XRD with the temperature
not only gives information about the phase transformation, but also about thermal expan-
sion coefficients. With this information, one can evaluate how the materials behaves under
thermal stress. A contour plot of individual groups of peaks in XRD measurements as a
function of the temperature between 35 and 95  C is given in in Fig. 2.6, in which the
phase transformation between the tetragonal and cubic phases is clearly seen. At room
temperature, the data perfectly agree with a tetragonal structure. However, some peaks
disappear and some double peaks merge into single peaks at higher temperatures that
matches the cubic structure, as is seen in Fig. 2.6. Noticeably, the phase transformation

Characterization Techniques for Perovskite Solar Cell Materials

FIGURE 2.6 (A) Temperature dependent X-ray diffractograms of some selected diffraction peaks for analysis of the cubic-to-tetragonal phase
transition and lattice expansion coefficient. (B) Refined lattice parameters during orthorhombic-to-cubic phase transitions using synchrotron X-ray
powder diffraction. The 3D figure show the (200) cubic Bragg peak and the (220)/(004) tetragonal Bragg peaks as a function of temperature.
Reproduced with permission from (A) reference T.J. Jacobsson, L.J. Schwan, M. Ottosson, A. Hagfeldt, T. Edvinsson, Determination of thermal expansion coeffi-
cients and locating the temperature-induced phase transition in methylammonium lead perovskites using X-ray diffraction, Inorg. Chem. 54 (2015) 10678
10685.
Copyright 2015, American Chemical Society. (B) Reference P.S. Whitfield, N. Herron, W.E. Guise, K. Page, Y.Q. Cheng, I. Milas, et al., Structures, phase transi-
tions and tricritical behavior of the hybrid perovskite methyl ammonium lead iodide, Sci. Rep. 6 (2016) 35685. Copyright 2016, Nature Publishing Group.
34 2. X-ray diffraction and Raman spectroscopy for lead halide perovskites

was pinpointed to 54  C within 1  C of uncertainty [32]. This fully reversible process

occurs at the temperature swings of an operational solar cell.
The phase transition has also been studied with time-of-flight neutron powder
diffraction and high resolution synchrotron X-ray powder diffraction [17]. The X-ray
data for d6
MAPbI3 (Fig. 2.6B) showed very clearly that the cubic and tetragonal phases
coexisted over a wide temperature range (nearly 30 K)- referring that this phase transi-
tion was first-order. The orthorhombic-to-tetragonal phase transition was also first-order
from Pnma to I4/mcm symmetry with co-existing phases (Fig. 2.6B). The Pnma is not a
subgroup of I4/mcm- meaning that a continuous second-order phase transition is not pos-
sible. It is because the Pnma to I4/mcm transformation requires modes with two different
irreducible representations to condense, and thus has two primary order parameters.
These requirements violate one of the Landau conditions for a second-order phase transi-
tion to occur [42].
Raman spectroscopy is a useful tool to investigate the lattice vibrations symmetry, the
temperature and pressure phase diagrams, the degree of crystallinity, the structural
changes in mixed halide perovskites, and the stability of halide perovskites during their
operation in solar cells [43
47]. These possibilities also lead to study the vibrational
properties, electron
phonon interactions, dielectric screening, heat transport, and elastic
properties of MAPbI3 and its related compounds [48
50].
In the Raman Effect, a small portion of light is idealistically scattered close to the
incoming monochromatic light, if the polarizability α of the electron cloud is changing
during the vibration. The polarizability is formally a tensor but can for polarized light and
an isotropic material in a fixed geometry be treated as scalar and defined as the ability to
create a dipole µ 5 αE in a given electrical field E. A fundamental evaluation of the polar-
izability requires a quantum mechanical picture but we will here just briefly show the
inelastic scattering process without further details on the intensity of the inelastically scat-
tered light. The polarizability
  for a small nuclei displacement, z0, in a bond can be Taylor
expanded as α 5 α0 1 @α @z 0 z 1 . . . where α0 is the polarizability that does not depend on
the externally varying field and ð@α=@zÞo is the change in polarizability during a displace-
ment in z-direction. Fixing the coordination system and only consider a plane polarized
light, the scalar electric field E 5 E0cos(2πν 0t), with ν 0 as the frequency of the light and con-
sidering only the time-dependent part of the electric field at a fixed location, denoting the
material vibration frequency as ν M and recalling that μ 5 αE, one formulate the dipole con-
tributions as
   
1 @α 1 @α
μ 5 α0 E0 cosð2πυ0 Þ 1 z0 E0 cos½2πðυ0 1 υM Þt 1 z0 E0 cos½2πðυ0 2 υM Þt (2.5)
2 @z 0 2 @z 0
The re-radiated field ER at position r can then be formulated from the acceleration
of the dipole, via the second time derivative of the dipole using conventional classical
electrodynamics and a fixed coordinate system extracting the contribution in z-direction
with [51]
 
q @2 μ=@t2 sinΦz
ER 5 (2.6)
4πε0 c2 r

Characterization Techniques for Perovskite Solar Cell Materials

 2.1 Introduction 35
where q is the charge, ε0 the permittivity of vacuum, c the speed of light. Combining
Eqs. 2.5 and 2.6, the first term in Eq. 2.5 will contributes to the elastic (Rayleigh) scattering,
the second to the anti-Stokes inelastic scattering and the third to the Stokes inelastic scat-
tering. As the intensity of the scattered light is proportional to the square of the field, this
relation and that the light frequencies are extracted as inner derivatives of μ in Eq. 2.5,
give the well known λ24 dependence on both the elastic and inelastic scattering intensity.
The transitions between energy levels are the extracted as Δν 5 1/λincident-1/λscattered and
most commonly reported as a Raman shift in cm21 from the incoming laser frequency
(defined as zero).
The lattice vibrations of MAPbI3 can categorically be classified into three distinct
groups: internal vibrations of the organic MA cations that span the frequencies between
300 and 3200 cm21; libration and spinning modes of MA cations between 60 and
180 cm21; and internal vibrations of the inorganic PbI3 network below 120 cm21 [52]. See
Fig. 2.7A and B.
The normal modes of MAPbI3 are thus resulting from both vibrations of the PbI3 net-
work and vibrations of the MA cations and their couplings. Study the symmetry of the
normal modes using a group analysis in each case show that there are 48 normal modes
as vibrations of the PbI3 network (3 acoustic and 45 optical modes), consistent with the
number of Pb and I atoms in the unit cell. Whereas for the MA cations, there are 4 spin-
ning modes, 20 normal modes that are combinations of 12 translations and 8 librations
modes, and 72 internal vibrations [52,53]. The symmetry representations of vibrations
of the PbI3 network is Γ 5 7B1 u 1 6B2 u 1 7B3 u 1 5Ag 1 4B1 g 1 5B2 g 1 4B3 g 1 7Au where
the g type (gerade, even) contains inversion symmetry of the phase and the u type (unger-
ade, odd) a phase change of the corresponding orbitals. The internal vibrations of an iso-
lated MA cation has a symmetry representations of A2 1 5A1 1 6E, with the E modes being
doubly degenerate [52]. The modes of the MA cations appear grouped in quadruples of
nearly degenerate frequencies—suggesting that the inter-cation coupling is small. The
modes of the MA cations can be described as symmetric or asymmetric CH3- and NH3-
deformation modes, symmetric C
N stretching modes, symmetric or asymmetric C
H
and N
H stretching modes, and asymmetric CH3
NH3 rocking modes.
For PbI3 network, Ag, B1 g, B2 g, and B3 g symmetries are predicted to be Raman-active
(Fig. 2.7C), whereas B1 u, B2 u, and B3 u symmetries are predicted to be IR-active. None of
the modes is at the same time Raman- and IR-active revealing a center-of-inversion sym-
metry. The Au modes are expected to be silent [54]. For MA cations, the molecular intra-
molecular vibrations can be assigned while their Raman and IR activity shifts from their
inclusion and symmetry adoption in the hybrid lead halide perovskites are still under
investigation [55].
IR spectroscopic vibrational investigation in the 700
3500 cm21 region on inorganic
and hybrid (layered) perovskites provide useful guidelines for the LHPs Raman spectral
assignment [49,56]. Hybrid perovskites are intrinsically complex materials where assign-
ment of the Raman spectrum of MAPbI3 are helped by first-principles DFT calculations,
explaining of the general role of various types of interactions and local structural disorder
for the materials properties. Recently, a combined experimental and theoretical Raman
vibrational analysis of MAPbI3 in the low-frequency region was employed to figure out
the bands associated to the vibrations of the interacting inorganic/organic constituents

Characterization Techniques for Perovskite Solar Cell Materials

36 2. X-ray diffraction and Raman spectroscopy for lead halide perovskites

FIGURE 2.7 (A) Comparison between the measured (a) and calculated (b) Raman spectra of MAPbI3 in the
orthorhombic structure. (B) Schematic representation of the most important Raman-active modes of the PbI3
network in MAPbI3. The symmetry and calculated frequency of each normal mode are indicated at the top of the
each panel, and the solid black lines indicate the unit cell [52]. Reproduced with permission from reference M.A. Pérez-
Osorio, Q. Lin, R.T. Phillips, R.L. Milot, L.M. Herz, M.B. Johnston, et al., Raman spectrum of the organic
inorganic halide
perovskite CH3NH3PbI3 from first principles and high-resolution low-temperature raman measurements, J. Phys. Chem.
C 122 (2018) 21703
21717. Copyright 2018, American Chemical Society.

Characterization Techniques for Perovskite Solar Cell Materials

 2.2 Resonance Raman spectroscopy of halide substituted hybrid perovskites 37
[52]. The proposed assignment of the low frequency Raman spectrum of orthorhombic
MAPbI3 is indicated in Fig. 2.7A and B by the dashed black lines. The measured peak at:
9 cm21 (labeled as “0”) is assigned to Pb
I
Pb rocking modes with Ag symmetry; the
peak at 26 cm21 corresponds to Pb
I
Pb bending modes with Ag symmetry (1); the small
peak at 32 cm21 originates from Pb
I
Pb bending modes with B2 g symmetry (2); the
peaks at 42 and 49 cm21 are assigned to Pb
I
Pb bending modes with Ag (3) and B2 g (4)
symmetries, respectively; the peak at 58 cm21 corresponds to librational modes of the MA
cations (5); the peak at 85 cm21 is assigned to librational modes of the MA cations as well
as to Pb
I stretching modes with B3 g symmetry (6); the peak at 97 cm21 stems from Pb
I
stretching modes of Ag symmetry (7), and the small peak at 142 cm21 (8) is assigned to
librational modes of the MA cations [52]. The Raman spectrum of the related organohalide
MAPbCl3 perovskite shows various bands between 40 and 321 cm21, associated to the
librations of the MA organic cations and a band at 483 cm21, assigned to the MA torsional
mode [50]. The frequency of the MA torsional modes in the crystal structures may be the
result of two opposite effects associated to the interactions between the cation and the
inorganic cage. The deformation of the MA molecule shifts the torsional mode toward
higher frequencies while the formation of hydrogen bonding interactions shifts this mode
toward lower frequencies [55
58], while the physics of the inorganic cage of the structure
is more well known [57,58]. The orientational disorder of the organic cations in MAPbI3
results in torsional frequency being spread over a large range of values [59].
Generally, the Raman peaks observed below 50 cm21 in the experiments are internal
vibrations of the inorganic PbI3 network, whereas the features at 58 and 142 cm21is inter-
nal vibrations of the inorganic network as well as combinations of MA libration and the
inorganic network vibrations at higher wavenumbers. Because the Raman peaks P1, P3, P4,
P5 (at 26, 42, 49, and 58 cm21) are intense and well separated, they could be used as mar-
kers for monitoring of the MAPbI3 structure and stoichiometry. Particularly, the ratios of
the intensities P1/P5, P3/P5, and P4/P5 could be used to monitor the PbI2/MAI ratio in the
system to measure deviations from the ideal stoichiometry or to monitor degradation [49].

2.2 Resonance Raman spectroscopy of halide substituted hybrid perovskites

Halide substitution in metal halide perovskites (MHPs) with the nominal composition
CH3NH3PbI2X, where X is I, Br, or Cl, influences the morphology, charge quantum yield,
and local interaction with the organic MA cation. Raman spectroscopies combined with
theoretical vibration calculations supported the early findings that iodide-chloride
perovskites phase separate and have also revealed that halide substitution with halides
forming a shorter bond length to Pb can delocalizes the charge to the MA cation;
therefore, liberate the vibrational movement of the MA cation that lead to a more adap-
tive organic phase [60].
Raman spectroscopy with 532 nm laser excitation are performed within the absorption
profile of MHP materials and are thus under resonance (electronically exciting) conditions,
providing information on vibrations in excited state and can also give clues for the charge
separation/transfer mechanisms. Fundamental vibrations in the isolated clusters and the
trends in the splitting of the degenerate states when different halogens are included

Characterization Techniques for Perovskite Solar Cell Materials

38 2. X-ray diffraction and Raman spectroscopy for lead halide perovskites

were investigated with low-frequency Raman measurements (down to 10 cm21) and non-
periodic DFT calculations with an emphasis on the ordering of the peaks to determine
Raman properties of MHPs [60].
The experimental Raman spectrum for MAPbI3 shows vibration peaks at 40, (54), (63),
71, 94, 108, 135, and 145 cm21, whereas MAPbI2Cl shows corresponding peaks at 40, NA,
NA, 71, 97, 110, and a broad peak at 166 cm21 as seen in Fig. 2.8. The NA (not applicable)
notation, emphasize that the peaks cannot be resolved and the spectra instead show a
shoulder in that area. Besides the strongest Raman peaks at 69
73, 94
97, and
108
110 cm21, peaks also at 40 and 54 cm21 depends on halide composition during
synthesis.
Periodic DFT calculations provides a suitable model system for single-crystalline
materials where the different orientation of the cations must be considered to be
periodic. For non-periodic or non-crystalline materials, cluster calculations can instead
be informative for the study of local effects in the inorganic octahedron and the behavior
of the organic cation. In the present example, an inorganic octahedron unit cluster PbX6
with Oh symmetry is used with two MA-dipole canceling cations. A PbI6 octahedron has
15 internal degrees of freedom (3 N
3, where N is the number of iodine atoms).
According to group theoretical representation [61], it can be written as
A1 g 1 Eg 1 2T1 u 1 T2 g 1 T2 u, where A1 g, Eg, and T2 g are Raman active, the two T1 u
modes are IR active, and T2 u is a silent mode (neither Raman or IR active). PbI6 as a
molecular unit within the lattice belongs to the Oh symmetry group. Deviation from this
symmetry would result in splitting of the degenerate states, and eventually complete
removal of symmetry and 15 different bands.
Calculated Raman spectra for PbX6 and (MA)2PbX6 clusters are shown in Fig. 2.8A
G,
and experimental data for MAPbI3 and MAPbI2Cl are shown in Fig. 2.8H and I. The
calculations reveal three different groups of vibrational modes, a triply degenerate
asymmetric X-Y, X-Z, and Y-Z vibrations (mode A), a double-degenerate asymmetric
“breathing” (mode B), and non-degenerated symmetric “breathing” (mode C), as well as
the MA vibrations (rotation, wagging, MA
MA stretch) shown in Fig. 2.8J. A shift in the
Raman peaks in (MA)2PbX6 clusters to higher wavenumbers (energy) compared to those
in the PbX6 clusters were observed, caused by the organic cations that extend the motion
of X from the Pb21 atom. The calculated Raman spectrum of (MA)2PbCl6 (see Fig. 2.8C)
differs somewhat from the other clusters while mode A shifts to lower wavenumbers
and mode B appears as two peaks. Notably, all (MA)2PbX6 structures showed Raman
activity of the MA groups between 140 and 180 cm21 and Pb-I vibrations at lower
wavenumbers.
DFT calculations on mixed halide clusters, such as (MA)2PbI5Cl and (MA)2PbI4Cl2 has
previously shown that a single Cl substitution does not result in large differences in calcu-
lated Raman vibrational spectra compared to the (MA)2PbI6 cluster, while larger changes
are found for two introduced Cl atoms. These results carries valuable information for the
possibility to identify doped phases. Fig. 2.8F and G show “Raman activities compared to
the (MA)2PbI6 cluster, which is assigned to asymmetric vibrations of Pb
I between 40 and
95 cm21. Moreover, there are two small appearances of additional vibration modes, for
instance N10 (green color, N
Cl stretch via H at 240 cm21) and D2 (green color, Pb
Cl
stretch at 190 cm21) in Fig. 2.8F. The case of (MA)2PbI4Cl2 with double Cl substitution

Characterization Techniques for Perovskite Solar Cell Materials

FIGURE 2.8 (A) Experimental Raman spectra, (B) the three main vibrational modes of the ideal and perturbed inorganic Oh octahedra, and bi-
methylammonium-installed octahedra DFT-calculated Raman spectra for (C) PbI6 with 2 MAPbI6, (D) PbBr6 with 2 MAPbBr6, and (E) PbCl6 with 2
MAPbCl6, and comparison of 2 MAPbI6 with (F) 2 MAPbI5Br, (G) 2 MAPbI4Br2 (H) 2 MAPbI5Cl, and (I) 2 MAPbI4Cl2. (J, K) Normalized experimental
Raman spectra recorded at very low laser intensity (,0.01 mW) [60]. Reproduced with permission from reference B.-w. Park, S.M. Jain, X. Zhang,
A. Hagfeldt, G. Boschloo, T. Edvinsson, Resonance Raman and excitation energy dependent charge transfer mechanism in halide-substituted hybrid perovskite solar
cells, ACS Nano 9 (2015) 2088
2101. Copyright 2015, American Chemical Society.
40 2. X-ray diffraction and Raman spectroscopy for lead halide perovskites

in the octahedral unit in Fig. 2.8G has rather different vibration modes, viz., mode D4
(violet color, asymmetric Pb
Cl stretch, 75
82 cm21) and highly increased intensity of
mode D20 (violet color, asymmetric Pb
Cl stretch at 185 cm21) compared with mode D2
(green colored solid line in Fig. 2.8F). Moreover, in Fig. 2.8G the Raman activity of mode
M4 (violet color, at 138
143 cm21) is shown to shift to lower wavenumber compared to
mode M3 (green color, Fig. 2.8F), but mode N20 (violet color, at 247 cm21) is shifted to
higher wavenumber for mode M20 (green color, Fig. 2.8F)” [60].
Observing the new vibration signatures with relative intensity shifts in the Raman
activities of (MA)2PbI4Cl2 compared to the undoped analog, it is thus possible to identify
local halide substitution or different phases. For example, both the single- and double-Cl-
substituted OMHPs have shown commonly a decreased Raman intensity of modes C3 and
C4 (green and violet colors) compared to mode C0 (black color).
The DFT-calculated Raman spectra for three vibrational modes and the experimental
Raman signal of MAPbI3 (Fig. 2.8A, H, and I) showed three shoulders or peaks in the
70
120 cm21 associated to modes A, B, and C. Additional four peaks (m, d, e, and f)
appear between 140 and 400 cm21 are assigned to MA rotation, MA wagging, and sym-
metric MA
MA stretch [60,62]. Because of the limitation of cluster models to emulate the
full symmetry of the crystal, cluster analysis should only be taken as representative of the
local modes of the crystalline system, but can as such be used to analyze the details of
chloride effects during crystallization [63] or effects from local charge delocalization and
transfer [60]. If one analyze the Raman spectrum of MAPbI2Cl in more detail, it can be
seen that the mode B as peak “b0 ” shows peak shift to lower intensity. This is correlated
with disordered inorganic frameworks where higher Raman activities have been observed
previously from the due to increased electron
phonon interaction between the central cat-
ionic metal and anionic oxygen [64]. This same effect holds for MAPbI3 and the
sub
MAPbI3 crystal in MAPbI2Cl on modes A and C. In the range of 136
150 cm21, that
MAPbI3 sample shows 1.3 times higher Raman intensity at 143 cm21 than that of
MAPbI2Cl at B145 cm21 as is seen in Fig. 2.8.
During resonance excitation at 532, absence of the feature at 143 cm21 nm implies the
disappearance of initial and final state polarization for the corresponding Raman
rotation/wagging in the MA cation. The difference at 143
145 cm21 between MAPbI3
and MAPbI2Cl samples seems well correlated with the local charge transfer yield [60]
and could be part of the origin of the improvements in the mixed halogen systems
[65,66]. DFT calculations for OMHPs display the transitions of charges from the HOMO
to LUMO (with LUMO 1 1 and LUMO 1 2). For example, the HOMO of 2MAPbI6
showed an I 5p π-bonding orbital while its LUMO, LUMO 1 1, and LUMO 1 2 were
decomposed to “Pb(6 s)
I(5p)” σ-antibonding, “Pb(6p)
I(5p)” σ-antibonding, and “Pb
(6 s)
I(5p)” σ-antibonding orbitals, respectively [60]. The observed 7 times lower inten-
sity for the 143 cm21 mode in the MAPbI2Cl sample corresponds to a loss of polarization
on mode M of internal MAPbI3. A photoexcited state that cannot change polarizability of
an MA cation radical or neutral MA molecule can then play an important role as an
organic cation charge stabilizer or a neutral dipolar molecule in the cage of the inorganic
framework [67]. The understanding of these phenomena lies deep within the origin of
the relative intensities in Raman measurements that comes from the losses of the electro-
magnetic energy in the incident light to an excited vibration level and the change in

Characterization Techniques for Perovskite Solar Cell Materials

 2.3 Raman spectroscopy probing bleaching and recrystallization process of CH3NH3PbI3 film 41
polarizability of the electron cloud during the vibration, and thus also the local electron
density properties during the light-matter interaction, and subsequent vibrations and
delocalization.

2.3 Raman spectroscopy probing bleaching and recrystallization

process of CH3NH3PbI3 film

Recently, Raman spectroscopy was employed to understand the pyridine-induced

bleaching and recrystallization process of CH3NH3PbI3 films, see Fig. 2.9A. The as-
prepared CH3NH3PbI3 film showed the typical features of the CH3NH3PbI3, with Pb
I
bending at 71 cm21, Pb
I stretching at 94 cm21 and the CH3NH31 libration mode at
111 cm21 [68,69], whereas the bleached film showed a substantial decrease in intensity of
the inorganic cage features at 50, 71 cm21 and 94 cm21. The results were compliable with
a full pyridine induced dissolution of the PbI6 framework and the CH3NH3PbI3 crystal-
line structure [70]. The disappearance of pyridine peak and stronger peaks for
CH3NH3PbI3 with time implies the recrystallization process as well as a reversible inter-
calation of pyridine in the perovskite framework. The simultaneous appearance of the
CH3NH31 libration mode and adsorbed pyridine mode are indicative of the association
of pyridine that helps in alignment and recrystallization of CH3NH31 groups into a more
ordered phase. Significantly, the relative enhanced intensity of the Raman spectrum of
recovered CH3NH3PbI3 film at band at 71 cm21 (Pb
I bending), 94 cm21 (Pb
I stretch-
ing) associated 111 cm21 (CH3NH31 libration mode) and the appearance of new band at
145 cm21 associated with ordering of CH3NH31 groups indicates enhanced crystallinity
following the recrystallization process [70]. Raman spectra of the intermediate phase (the
marked yellow region in Fig. 2.9B) at 34 and 49 cm21, during the pyridine-bleaching and
recrystallization process, can be attributed to plumbates (PbI32 and PbI642) [71].
Analyzing the Raman spectra of pyridine in the bleached phase, the bonding informa-
tion of pyridine can be retrieved while interacting with CH3NH3PbI3 (Fig. 2.9B). A shift of
11 cm21 is found for the symmetric ring breathing mode involving nitrogen. The pure pyr-
idine shows fingerprint vibrations at 991 and 1029 cm21. The 991 cm21 corresponds to the
ν(N
C) breathing mode and the 1029 cm21 is due to the hydrogen wagging on the ring.
Interaction with CH3NH3PbI3 shifts the ν(N
C) breathing mode of pyridine from 991 to
1002 cm21 but the band at 1029 cm21 remains unperturbed.
It means that pyridine likely bonds with CH3NH3PbI3 via the nitrogen group on the
pyridine ring. Among the possibilities are bondings within the halogen elimination
reaction of pyridine, pyridine bonding to Pb21, or to other positive species such as the
A-site cation. DFT calculations was further utilized to investigate the different possible
bonding situations, showing that the nitrogen is not fully bonded to a Lewis acid but steric
hindered where iodide interaction competed with a pure Lewis pair interaction [70].
Therefore, only partially bonding is prevailed due to a frustrated Lewis pair effect [72,73].
In a frustrated bonding situation, pyridine would bond to iodine via hydrogen from either
isolated protons or protons attached to the hydrogen in the CH3NH31 (MA1) ion or to
Pb21 exposed surfaces and pyridine
(PbIn)(22n) plumbate complexes [74].

Characterization Techniques for Perovskite Solar Cell Materials

42 2. X-ray diffraction and Raman spectroscopy for lead halide perovskites

FIGURE 2.9 (A) Room temperature optical bleaching of CH3NH3PbI3 perovskite by pyridine vapor. (B)
Sequential resonance Raman spectroscopy of the recovery of CH3NH3PbI3 film in ambient air after bleaching
with pyridine. The marked yellow region show vibrations characteristic of isolated plumbates in the intermediate
phase. (C) The ν(N
C) breathing mode of the pyridine ring unperturbed and bonded and the calculated shift
when interacting with possible species in the intermediate bleached phase: (pyr)
IH and (pyr)PbI2. Experimental
and theoretical assignments of the symmetric ring breathing and H-wagging modes of pyridine (top) and experi-
mental Raman shifts for pyridine in liquid capillary and when interacting with the perovskite during bleaching.
Reproduced with permission from reference S.M. Jain, Z. Qiu, L. Häggman, M. Mirmohades, M.
B. Johansson, T. Edvinsson, et al., Frustrated Lewis pair-mediated recrystallization of CH3NH3PbI3 for improved optoelec-
tronic quality and high voltage planar perovskite solar cells, Energy Environ. Sci. 9 (2016) 3770
3782. Copyright Royal
Society of Chemistry 2016.

Characterization Techniques for Perovskite Solar Cell Materials

 2.4 Conclusions 43
For a practical application, one should also note that care have to be taken with the
intensities used in confocal Raman spectroscopy as always, due to the high concentration
of light in the measured spot. For metal halide perovskites, a longer measurements or
higher intensity first lead to an improved crystallinity for a poor starting material,
followed by a possible temperature phase transition, and finally decomposition into the
precursor salts, e.g. PbI2 and MAI in the case of MAPbI3. Another concern is the change in
Raman activity and symmetry changes as a perfect cubic Pm-3 m metal halide perovskite
is Raman inactive as reported quite early for MAPbCl3 [50] and exemplified more recently
while monitoring formation of Bi-based double perovskites (MA)3Bi2I9 [75]. Apart from
the normal cancellation of the change in polarizability change from group theory analysis,
a recent study also report this from the aspect of center line broadening from local polar
fluctuations [76].

2.4 Conclusions

X-ray diffraction and Raman spectroscopy provide key structural and vibrational
information of LHP materials, containing information on the crystal structure, symme-
tries, displacements, defects, micro-crystallinity, orientations, thermal expansion, phase
transitions, vibrations, effects from doping, and local charge transfer effects and their
interdependence on material alterations. XRD techniques are more or less necessary to
elucidate the structural peripteries in modern material science where Raman spectros-
copy can be used as an important complement that provide vibrations characterization
under non-resonant and resonant conditions and aid in determination of structure-to-
property relationships from materials to function. The techniques can provide crystalline
and chemical features from sub-Ångström variations in the structure useful for both
understanding the molecular chemistry during creation and the structure and properties
of the resulting LHP crystalline materials. The chapter briefly introduces different com-
monly used XRD approaches as well as some recent results from their applications.
Raman spectroscopy is here a complementing technique that do not only provides infor-
mation about the chemical composition and phases in crystalline materials, but can also
be used for characterization of vibration in amorphous structures, molecular materials,
solvents, and gases. With this knowledge, one can extract chemical identities and pro-
cesses during syntheses as well as details in the crystalline materials via the observed
local or extended lattice vibrations, bonding interactions, orientations, symmetries, and
phonon modes to complement the structural characterization from XRD. A more detailed
analysis of relative intensities in resonance Raman measurements, related to the losses of
the electromagnetic energy in the incident light to an excited vibration level and the
change in polarizability of the electron cloud during the vibration, additionally allows
investigations of the primary light-matter interaction and subsequent charge
delocalization.

Acknowledgment
We acknowledge financial support from the Swedish Research Council (2015
03814), the Swedish Research
Council for sustainable development (2016-00908), and the Swedish Energy Agency (P44648-1).

Characterization Techniques for Perovskite Solar Cell Materials

44 2. X-ray diffraction and Raman spectroscopy for lead halide perovskites

References
[1] T.R.J.D. Perovskites, Structure-Property Relationships, John Wiley & Sons, Singapore, 2016.
[2] M.A. Green, A. Ho-Baillie, Perovskite solar cells: the birth of a new era in photovoltaics, ACS Energy Lett. 2
(2017) 822
830.
[3] M.A. Green, A. Ho-Baillie, H.J. Snaith, The emergence of perovskite solar cells, Nat. Photonics 8 (2014) 506.
[4] M.M. Lee, J. Teuscher, T. Miyasaka, T.N. Murakami, H.J. Snaith, Efficient hybrid solar cells based on meso-
superstructured organometal halide perovskites, Science 338 (2012) 643
647.
[5] https://www.nrel.gov/pv/assets/images/efficiency-chart.png.
[6] Y. Zhao, K. Zhu, Organic
inorganic hybrid lead halide perovskites for optoelectronic and electronic applica-
tions, Chem. Soc. Rev. 45 (2016) 655
689.
[7] T.J. Jacobsson, M. Pazoki, A. Hagfeldt, T. Edvinsson, Goldschmidt’s rules and strontium replacement in lead
halogen perovskite solar cells: theory and preliminary experiments on CH3NH3SrI3, J. Phys. Chem. C 119
(2015) 25673
25683.
[8] J.H. Noh, S.H. Im, J.H. Heo, T.N. Mandal, S.I. Seok, Chemical management for colorful, efficient, and
stable inorganic-organic hybrid nanostructured solar cells, Nano Lett. 13 (2013) 1764
1769.
[9] B.-w. Park, B. Philippe, S.M. Jain, X. Zhang, T. Edvinsson, H. Rensmo, et al., Chemical engineering of
methylammonium lead iodide/bromide perovskites: tuning of opto-electronic properties and photovoltaic
performance, J. Mater. Chem. A 3 (2015) 21760
21771.
[10] T.A. Berhe, W.-N. Su, C.-H. Chen, C.-J. Pan, J.-H. Cheng, H.-M. Chen, et al., Organometal halide perovskite
solar cells: degradation and stability, Energy Environ. Sci. 9 (2016) 323
356.
[11] A. Mei, X. Li, L. Liu, Z. Ku, T. Liu, Y. Rong, et al., A hole-conductor
free, fully printable mesoscopic perov-
skite solar cell with high stability, Science 345 (2014) 295
298.
[12] W. Chen, Y. Wu, Y. Yue, J. Liu, W. Zhang, X. Yang, et al., Efficient and stable large-area perovskite solar cells
with inorganic charge extraction layers, Science 350 (2015) 944
948.
[13] B.E. Warren, B.L. Averbach, The separation of cold-work distortion and particle size broadening in X-Ray
patterns, J. Appl. Phys. 23 (1952). 497-497.
[14] J. Rivnay, R. Noriega, R.J. Kline, A. Salleo, M.F. Toney, Quantitative analysis of lattice disorder and crystallite
size in organic semiconductor thin films, Phys. Rev. B 84 (2011) 045203.
[15] S.N. Ruddlesden, P. Popper, The compound Sr3Ti2O7 and its structure, Acta Crystallogr. 11 (1958) 54
55.
[16] K. Inaba, S. Kobayashi, K. Uehara, A. Okada, S.L. Reddy, T. Endo, High resolution X-ray diffraction analyses
of (La, Sr)MnO3/ZnO/Sapphire(0001) double heteroepitaxial films, Adv. Mater. Phys. Chem. 03 (2013)
72
89.
[17] P.S. Whitfield, N. Herron, W.E. Guise, K. Page, Y.Q. Cheng, I. Milas, et al., Structures, phase transitions and
tricritical behavior of the hybrid perovskite methyl ammonium lead iodide, Sci. Rep. 6 (2016) 35685.
[18] H. Tsai, W. Nie, J.-C. Blancon, C.C. Stoumpos, R. Asadpour, B. Harutyunyan, et al., High-efficiency two-
dimensional Ruddlesden
Popper perovskite solar cells, Nature 536 (2016) 312.
[19] R.W. James, The Optical Principles of the Diffraction of X-rays, Cornell University Press, New York, 1965.
[20] A.M. Glazer, The classification of tilted octahedra in perovskites, Acta Crystallogr. Sect. B 28 (1972) 3384
3392.
[21] A. Glazer, Simple ways of determining perovskite structures, Acta Crystallogr. Sect. A 31 (1975) 756
762.
[22] C.J. Howard, H.T. Stokes, Group-theoretical analysis of octahedral tilting in perovskites, Acta Crystallogr.
Sect. B 54 (1998) 782
789.
[23] C.J. Howard, H.T. Stokes, Structures and phase transitions in perovskites - a group-theoretical approach.
This article is dedicated to Helen D. Megaw (1907-2002), in appreciation of her many contributions to the
crystallography of inorganic and mineral compounds, including her seminal studies of perovskites. Some of
the material was presented by CJH in the Megaw memorial session at the 21st European Crystallography
Meeting, Durban, South Africa, August 2003, Acta Crystallogr. Sect. A 61 (2005) 93
111.
[24] J. Rivnay, S.C.B. Mannsfeld, C.E. Miller, A. Salleo, M.F. Toney, Quantitative determination of organic semi-
conductor microstructure from the molecular to device scale, Chem. Rev. 112 (2012) 5488
5519.
[25] C.C. Boyd, R. Cheacharoen, T. Leijtens, M.D. McGehee, Understanding degradation mechanisms and
improving stability of perovskite photovoltaics, Chem. Rev. 119 (2019) 3418
3451.
[26] C.C. Boyd, R. Cheacharoen, K.A. Bush, R. Prasanna, T. Leijtens, M.D. McGehee, Barrier design to prevent
metal-induced degradation and improve thermal stability in perovskite solar cells, ACS Energy Lett. 3 (2018)
1772
1778.

Characterization Techniques for Perovskite Solar Cell Materials

 References 45
[27] A.M.A. Leguy, Y. Hu, M. Campoy-Quiles, M.I. Alonso, O.J. Weber, P. Azarhoosh, et al., Reversible hydration
of CH3NH3PbI3 in films, single crystals, and solar cells, Chem. Mater. 27 (2015) 3397
3407.
[28] G.Y. Kim, A. Senocrate, T.-Y. Yang, G. Gregori, M. Grätzel, J. Maier, Large tunable photoeffect on ion con-
duction in halide perovskites and implications for photodecomposition, Nat. Mater. 17 (2018) 445
449.
[29] N. Aristidou, C. Eames, I. Sanchez-Molina, X. Bu, J. Kosco, M.S. Islam, et al., Fast oxygen diffusion and
iodide defects mediate oxygen-induced degradation of perovskite solar cells, Nat. Commun. 8 (2017) 15218.
[30] N.H. Nickel, F. Lang, V.V. Brus, O. Shargaieva, J. Rappich, Unraveling the light-induced degradation
mechanisms of CH3NH3PbI3 perovskite films, Adv. Electron. Mater. 3 (2017) 1700158.
[31] F. Lang, O. Shargaieva, V.V. Brus, H.C. Neitzert, J. Rappich, N.H. Nickel, Influence of radiation on the prop-
erties and the stability of hybrid perovskites, Adv. Mater. 30 (2018) 1702905.
[32] T.J. Jacobsson, L.J. Schwan, M. Ottosson, A. Hagfeldt, T. Edvinsson, Determination of thermal expansion
coefficients and locating the temperature-induced phase transition in methylammonium lead perovskites
using X-ray diffraction, Inorg. Chem. 54 (2015) 10678
10685.
[33] R. Cheacharoen, N. Rolston, D. Harwood, K.A. Bush, R.H. Dauskardt, M.D. McGehee, Design and under-
standing of encapsulated perovskite solar cells to withstand temperature cycling, Energy Environ. Sci. 11
(2018) 144
150.
[34] J. Zhao, Y. Deng, H. Wei, X. Zheng, Z. Yu, Y. Shao, et al., Strained hybrid perovskite thin films and their
impact on the intrinsic stability of perovskite solar cells, Sci. Adv. 3 (2017) eaao5616.
[35] T. Baikie, Y. Fang, J.M. Kadro, M. Schreyer, F. Wei, S.G. Mhaisalkar, et al., Synthesis and crystal chemistry of
the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications, J. Mater. Chem. A 1
(2013) 5628
5641.
[36] A. Binek, F.C. Hanusch, P. Docampo, T. Bein, Stabilization of the trigonal high-temperature phase of forma-
midinium lead iodide, J. Phys. Chem. Lett. 6 (2015) 1249
1253.
[37] C.C. Stoumpos, C.D. Malliakas, M.G. Kanatzidis, Semiconducting tin and lead iodide perovskites with
organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties, Inorg.
Chem. 52 (2013) 9019
9038.
[38] M.R. Filip, G.E. Eperon, H.J. Snaith, F. Giustino, Steric engineering of metal-halide perovskites with tunable
optical band gaps, Nat. Commun. 5 (2014) 5757.
[39] N. Pellet, P. Gao, G. Gregori, T.Y. Yang, M.K. Nazeeruddin, J. Maier, et al., Mixed-organic-cation perovskite
photovoltaics for enhanced solar-light harvesting, Angew. Chem. Int. Ed. Engl. 53 (2014) 3151
3157.
[40] N.J. Jeon, J.H. Noh, W.S. Yang, Y.C. Kim, S. Ryu, J. Seo, et al., Compositional engineering of perovskite mate-
rials for high-performance solar cells, Nature 517 (2015) 476
480.
[41] N.J. Jeon, J.H. Noh, Y.C. Kim, W.S. Yang, S. Ryu, S.I. Seok, Solvent engineering for high-performance inorga-
nic
organic hybrid perovskite solar cells, Nat. Mater. 13 (2014) 897.
[42] Landau Theory of Phase Transitions, in: Ultracold Quantum Fields, Springer, Netherlands, Dordrecht, 2009,
pp. 193
212.
[43] M.N. Iliev, M.V. Abrashev, J. Laverdière, S. Jandl, M.M. Gospodinov, Y.Q. Wang, et al., Distortion-
dependent Raman spectra and mode mixing in RMnO3 perovskites(R 5 La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho,
Y), Phys. Rev. B 73 (2006).
[44] M.N. Iliev, M.V. Abrashev, H.G. Lee, V.N. Popov, Y.Y. Sun, C. Thomsen, et al., Raman spectroscopy of ortho-
rhombic perovskitelike YMnO3 and LaMnO3, Phys. Rev. B 57 (1998) 2872
2877.
[45] J. Kim, J. Kwon, M. Kim, J. Do, D. Lee, H. Han, Low-dielectric-constant polyimide aerogel composite films
with low water uptake, Polym. J. 48 (2016) 829.
[46] Y. Guo, O. Yaffe, D.W. Paley, A.N. Beecher, T.D. Hull, G. Szpak, et al., Interplay between organic cations and
inorganic framework and incommensurability in hybrid lead-halide perovskite CH3NH3PbBr3, Phys. Rev.
Mater. 1 (2017).
[47] G. Abdelmageed, L. Jewell, K. Hellier, L. Seymour, B. Luo, F. Bridges, et al., Mechanisms for light induced
degradation in MAPbI3 perovskite thin films and solar cells, Appl. Phys. Lett. 109 (2016).
[48] A. Letoublon, S. Paofai, B. Ruffle, P. Bourges, B. Hehlen, T. Michel, et al., Elastic constants, optical phonons,
and molecular relaxations in the high temperature plastic phase of the CH3NH3PbBr3 hybrid perovskite, J.
Phys. Chem. Lett. 7 (2016) 3776
3784.
[49] M. Ledinsky, P. Loper, B. Niesen, J. Holovsky, S.J. Moon, J.H. Yum, et al., Raman spectroscopy of organic-
inorganic halide perovskites, J. Phys. Chem. Lett. 6 (2015) 401
406.

Characterization Techniques for Perovskite Solar Cell Materials

46 2. X-ray diffraction and Raman spectroscopy for lead halide perovskites

[50] A. Maalej, Y. Abid, A. Kallel, A. Daoud, A. Lautié, F. Romain, Phase transitions and crystal dynamics in the
cubic perovskite CH3NH3PbCl3, Solid State Commun. 103 (1997) 279
284.
[51] J.D. Jackson, Classical Electrodynamics, 3rd ed., Wiley, New York, 1999.
[52] M.A. Pérez-Osorio, Q. Lin, R.T. Phillips, R.L. Milot, L.M. Herz, M.B. Johnston, et al., Raman spectrum of the
organic
inorganic halide perovskite CH3NH3PbI3 from first principles and high-resolution low-temperature
raman measurements, J. Phys. Chem. C 122 (2018) 21703
21717.
[53] D.L. Rousseau, R.P. Bauman, S.P.S. Porto, Normal mode determination in crystals, J. Raman Spectrosc. 10
(1981) 253
290.
[54] P.Y. Yu, M. Cardona, Vibrational properties of semiconductors, and electron-phonon interactions, in: P.Y.
Yu, M. Cardona (Eds.), Fundamentals of Semiconductors: Physics and Materials Properties, Springer Berlin
Heidelberg, Berlin, Heidelberg, 1996, pp. 99
147.
[55] R.G. Niemann, A.G. Kontos, D. Palles, E.I. Kamitsos, A. Kaltzoglou, F. Brivio, et al., Halogen effects on
ordering and bonding of CH3NH3 1 in CH3NH3PbX3 (X 5 Cl, Br, I) hybrid perovskites: a vibrational spec-
troscopic study, J. Phys. Chem. C 120 (2016) 2509
2519.
[56] J.-X. Cheng, X.S. Xie, Coherent anti-stokes raman scattering microscopy: instrumentation, theory, and appli-
cations, J. Phys. Chem. B 108 (2004) 827
840.
[57] J. Even, L. Pedesseau, J.-M. Jancu, C. Katan, Importance of spin
orbit coupling in hybrid organic/inorganic
perovskites for photovoltaic applications, J. Phys. Chem. Lett. 4 (2013) 2999
3005.
[58] D.B. Mitzi, Templating and structural engineering in organic
inorganic perovskites, J. Chem. Soc., Dalton
Trans. (2001) 1
12.
[59] A. Poglitsch, D. Weber, Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by milli-
meter-wave spectroscopy, J. Chem. Phys. 87 (1987) 6373
6378.
[60] B.-w. Park, S.M. Jain, X. Zhang, A. Hagfeldt, G. Boschloo, T. Edvinsson, Resonance Raman and excitation
energy dependent charge transfer mechanism in halide-substituted hybrid perovskite solar cells, ACS Nano
9 (2015) 2088
2101.
[61] G. Blasse, A.F. Corsmit, Electronic and vibrational spectra of ordered perovskites, J. Solid State Chem. 6
(1973) 513
518.
[62] C. Quarti, G. Grancini, E. Mosconi, P. Bruno, J.M. Ball, M.M. Lee, et al., The Raman spectrum of the
CH3NH3PbI3 hybrid perovskite: interplay of theory and experiment, J. Phys. Chem. Lett. 5 (2014) 279
284.
[63] G. Grancini, S. Marras, M. Prato, C. Giannini, C. Quarti, F. De Angelis, et al., The impact of the crystallization
processes on the structural and optical properties of hybrid perovskite films for photovoltaics, J. Phys. Chem.
Lett. 5 (2014) 3836
3842.
[64] G. Coslovich, B. Huber, W.S. Lee, Y.D. Chuang, Y. Zhu, T. Sasagawa, et al., Ultrafast charge localization in a
stripe-phase nickelate, Nat. Commun. 4 (2013) 2643.
[65] J.M. Frost, K.T. Butler, F. Brivio, C.H. Hendon, M. van Schilfgaarde, A. Walsh, Atomistic origins of high-
performance in hybrid halide perovskite solar cells, Nano Lett. 14 (2014) 2584
2590.
[66] T. Umebayashi, K. Asai, T. Kondo, A. Nakao, Electronic structures of lead iodide based low-dimensional
crystals, Phys. Rev. B 67 (2003).
[67] H.L. Bostrom, J.A. Hill, A.L. Goodwin, Columnar shifts as symmetry-breaking degrees of freedom in molecu-
lar perovskites, Phys. Chem. Chem. Phys. 18 (2016) 31881
31894.
[68] S.M. Jain, B. Philippe, E.M.J. Johansson, B.-w. Park, H. Rensmo, T. Edvinsson, et al., Vapor phase conversion
of PbI2 to CH3NH3PbI3: spectroscopic evidence for formation of an intermediate phase, J. Mater. Chem. A 4
(2016) 2630
2642.
[69] R. Gottesman, L. Gouda, B.S. Kalanoor, E. Haltzi, S. Tirosh, E. Rosh-Hodesh, et al., Photoinduced reversible
structural transformations in free-standing CH3NH3PbI3 perovskite films, J. Phys. Chem. Lett. 6 (2015)
2332
2338.
[70] S.M. Jain, Z. Qiu, L. Häggman, M. Mirmohades, M.B. Johansson, T. Edvinsson, et al., Frustrated Lewis pair-
mediated recrystallization of CH3NH3PbI3 for improved optoelectronic quality and high voltage planar
perovskite solar cells, Energy Environ. Sci. 9 (2016) 3770
3782.
[71] B.R. Vincent, K.N. Robertson, T.S. Cameron, O. Knop, Alkylammonium lead halides. Part 1. Isolated PbI64 2
ions in (CH3NH3)4PbI6•2H2O, Can. J. Chem. 65 (1987) 1042
1046.
[72] D.W. Stephan, G. Erker, Frustrated Lewis pair chemistry: development and perspectives, Angew. Chem. Int.
Ed. Engl. 54 (2015) 6400
6441.

Characterization Techniques for Perovskite Solar Cell Materials

 References 47
[73] D.W. Stephan, G. Erker, Frustrated Lewis pairs: metal-free hydrogen activation and more, Angew. Chem.
Int. Ed. Engl. 49 (2010) 46
76.
[74] H. Miyamae, H. Toriyama, T. Abe, G. Hihara, M. Nagata, The structure of PbI2-pyridine adducts. I. Lead(II)
iodide-pyridine (2/4), catena-di-[mu]-iodo-bis(pyridine)lead(II), [Pb2I4(C5H5N)4], Acta Crystallogr. Sect. C
40 (1984) 1559
1562.
[75] S.M. Jain, D. Phuyal, M.L. Davies, M. Li, B. Philippe, C. De Castro, et al., An effective approach of vapour
assisted morphological tailoring for reducing metal defect sites in lead-free, (CH3NH3)3Bi2I9 bismuth-based
perovskite solar cells for improved performance and long-term stability, Nano Energy 49 (2018) 614
624.
[76] O. Yaffe, Y. Guo, L.Z. Tan, D.A. Egger, T. Hull, C.C. Stoumpos, et al., Local polar fluctuations in lead halide
perovskite crystals, Phys. Rev. Lett. 118 (2017) 136001.

Characterization Techniques for Perovskite Solar Cell Materials