Organic Electronics 37 (2016) 61e73

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Organic Electronics
journal homepage: www.elsevier.com/locate/orgel

A comprehensive theoretical study of halide perovskites ABX3

Jingyu Qian, Bin Xu**, Wenjing Tian*
State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun, 130012, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Solar cells based on halide perovskites have recently been attractive due to their excellent power con-
Received 6 April 2016 version efficiency (PCE), lower cost and simple manufacture. Here, a series of halide perovskites (ABX3:
Received in revised form A ¼ CH3NH3, CH(NH2)2, Cs, Rb; B ¼ Pb, Sn, Ge; X ¼ I, Br, Cl, F) were investigated by Density Functional
18 May 2016
Theory (DFT) calculations, together with Shockley-Queisser Maximum Solar Cell Efficiency (S-Q) and
Accepted 31 May 2016
Spectroscopic Limited Maximum Efficiency (SLME) mathematical models. The results indicate that: the
electronic structure of germanium perovskites bears a close similarity to that of lead perovskites with a
small energy difference between the nonbonding orbital and antibonding orbitals, but with a large
Keywords:
Perovskites
energy difference comparing with that of tin perovskites (0.6e1.7 eV for CsGeI3 at Z point of the Brillouin
Theoretical study zone, 0.7e1.4 eV for CH3NH3PbI3 and 1.4e2.2 eV for CH3NH3SnI3 at R point of the Brillouin zone), which
Electrical is attributable to the atomic level, where the 4s orbital energy of Ge (11.5 eV) is close to the 6s orbital
Optical energy of Pb (11.6 eV), but the 5s orbital energy of Sn (10.1 eV) is significantly high. Therefore,
Lead free germanium perovskites possess as high absorption coefficient around solar spectrum as lead perovskites,
while tin perovskites only have low absorption coefficient, which makes the short-circuit current of
CsGeI3 and CH3NH3PbI3 (0.017 Acm2 and 0.016 Acm2, simulated by SLME with a 200 nm absorber
under AM1.5G) are higher than that of CH3NH3SnI3 (0.015 Acm2) even if the bandgap of CsGeI3 and
CH3NH3PbI3 (1.51 eV and 1.55 eV) are larger than that of CH3NH3SnI3 (1.21 eV). Meanwhile, the effective
mass of electrons and holes are approximate for germanium perovskites and lead perovskites (0.14:0.19
for CsGeI3 and 0.12:0.12 for CH3NH3PbI3), indicating a balanced electrons and holes transport, whereas
the electrons transport is much slower than the holes transport for tin perovskites due to the effective
mass of electron is much larger than that of hole (0.17:0.04 for CH3NH3SnI3). As a result, the PCE of CsGeI3
(27.9%) and CH3NH3PbI3 (26.7%) is higher than that of CH3NH3SnI3 (19.9%).
© 2016 Elsevier B.V. All rights reserved.

1. Introduction drastically at a high temperature [7] about 425 K or takes a slow

Since the first photovoltaic device based on organometal halide
perovskites (CH3NH3PbI3) with a power conversion efficiency (PCE)
of 3.8% was reported by Kojima et al. [1], CH3NH3PbI3 based pe-
rovskites has attracted more and more attention due to their rapid
increase in PCE, for example 9.7% in 2011 [2], 15.4% in 2013 [3], and
20.1% in 2015 [4], and 22.1% in 2016 [5], which approaches the PCE
of polycrystal silicon solar cells [6]. Although great achievements
for perovskites solar cells have been made in the last six years, there
are still some issues should be addressed when considering their
future commercial applications. On one hand, CH3NH3PbI3 is rela-
tively not stable because a decomposition reaction occurs
* Corresponding author.
** Corresponding author.
E-mail address: wjtian@jlu.edu.cn (W. Tian).
process at room temperature [8], where CH3NH3PbI3 decomposes
into a solid (PbI2) and two gases (CH3NH2 and HI). On the other
hand, environmental problems drag on the further development of
halide perovskites solar cells based on CH3NH3PbI3 for the practical
employment in daily life due to the heavy element, lead.
In order to overcome these two difficulties, much effort has been
made over the last years. For example, in 2014, Feng et al. reported a
first attempt by using CH3NH3SnI3 instead of CH3NH3PbI3 with an
efficiency of 5.7% [9]. Noel et al. fabricated another CH3NH3SnI3
perovskite lead-free solar cell with a PCE of 6.4% [10]. Kumar et al.
presented a photovoltaic device by using CsSnI3 as the active layer
and achieved an efficiency of 2%, but the entire device needed to be
fabricated and tested inside the glovebox due to the tendency for Sn
to get oxidized [11]. Sabba et al. reported a composite perovskite
CsSnI2$9Br0.1 and achieved a PCE of 1.76% [12]. Besides, Huang et al.
achieved an efficiency of 3.2% based on a CsGeI3 perovkite solar cell

http://dx.doi.org/10.1016/j.orgel.2016.05.046
1566-1199/© 2016 Elsevier B.V. All rights reserved.
62 J. Qian et al. / Organic Electronics 37 (2016) 61e73
[13].
For the theoretical investigations, most scientists focused on
CH3NH3PbI3 and paid more attention to exploring of its outstanding
performance, such as the optical properties [14] and electrical
properties [15]. There are some theoretical investigations about
other halide perovskites. For example, Stoumpos et al. prepared a
CsGeI3 crystal and investigated its band structure with DFT/LDA
method. In the meanwhile they found out the large second har-
monic generation response is attributed to the high density of
states in valence band due to sp-hybridization of the Ge and I or-
bitals [16]. Saparov et al. synthesized a lead-free layered perovskite
Cs3Sb2I9 and calculated its electronic structures with DFT/GGA
method. It showed that Cs3Sb2I9 possesses a nearly direct band gap
(less than 0.02 eV difference between the direct and indirect band
gaps) and a similar high-level of absorption compared to
CH3NH3PbI3 [17]. However, there is almost no report on the theo-
retical study of the comprehensive and systematic analysis of the
halide perovskites as the active materials for solar cells.
In this paper, we investigated a series of halide perovskites
ABX3, where A can be CH3NH3, CH(NH2)2, Cs, or Rb; B and X belong
to the same main group of lead and iodine in the periodic table of
the elements respectively (B ¼ Pb, Sn, Ge; X ¼ I, Br, Cl, F), by using
DFT calculations, accompanying with Shockley-Queisser Maximum
Solar Cell Efficiency (S-Q) and Spectroscopic Limited Maximum
Efficiency (SLME) mathematical models. A systematical investiga-
tion of the optical and electrical properties indicated that the
electronic structure of germanium perovskites bears a close simi-
larity to that of lead perovskites with a small energy difference
between the nonbonding orbital and antibonding orbital, but with
a large energy difference comparing with that of tin perovskites
(0.6e1.7 eV for CsGeI3 at Z point of the Brillouin zone, 0.7e1.4 eV for
CH3NH3PbI3 and 1.4e2.2 eV for CH3NH3SnI3 at R point of the Bril-
louin zone). The germanium perovskites possess as high absorption
coefficient around solar spectrum as lead perovskites, while tin
perovskites only have a low absorption coefficient, which makes
the short-circuit current of CsGeI3 and CH3NH3PbI3 (0.017 Acm2
and 0.016 Acm2, simulated by SLME with a 200 nm absorber under
AM1.5G) higher than that of CH3NH3SnI3 (0.015 Acm2) although
the bandgap of CsGeI3 and CH3NH3PbI3 (1.51 eV and 1.55 eV) are
larger than that of CH3NH3SnI3 (1.21 eV). The effective mass of
electrons and holes are approximate for germanium perovskites
and lead perovskites (0.14:0.19 for CsGeI3 and 0.12:0.12 for
CH3NH3PbI3), indicating a balanced electrons and holes transport,
whereas the electrons transport is much slower than the holes
transport because tin perovskites due to the effective mass of
electron is much larger than that of the holes (0.17:0.04 for
CH3NH3SnI3). As a result, the PCE of CsGeI3 (27.9%) and CH3NH3PbI3
(26.7%) is higher than that of CH3NH3SnI3 (19.9%).
2. Computational methods
2.1. First-principles calculations
The crystal structure optimization and electronic structure cal-
culations of halide perovskites ABX3 were performed by using the
Vienna Ab-initio Simulation Package (VASP) [18] and the Cam-
bridge Sequential Total Energy Package (CASTEP) [19].
In VASP, Electronion interactions were described by the
projector-augmented wave (PAW) potentials [20] and the gener-
alized gradient approximation (GGA) parametrized by Per-
dewBurkeErnzerhof (PBE) [21] was used for the electron
exchange-correction function. A cutoff energy of 500 eV was
used. The convergence threshold for self-consistent-field (SCF)
iteration was set at 106 eV, and the atomic positions were fully
optimized until all components of the residual forces were smaller
than 0.001 eV/Å. For the density of states (DOS) for each perovskite,
the width of the gaussian smearing was 0.1 eV, with 6  6  6 and
12  12  12 k-point meshes centered at the G point. For the band
structure of halide perovskites ABX3, 100 k-points between high
symmetric points were used. Spin-orbit coupling (SOC) was also
taken into account for both DOS and band structure, and all of the
parameters were in parallel to what has been mentioned above
except the choice of k-points, for which a 6  6  6 k-point mesh
and 20 k-points between high symmetric points were chosen,
respectively. To account for the underestimation of the band gap in
standard DFT calculations, the accurate electronic structures were
then calculated by using the HeydScuseria Ernzerhof (HSE06)
hybrid functional [22], in which the cutoff energy was improved to
800 eV and the exact HartreeFock (HF) exchange contribution for
the hybrid functional was tuned to 50% and 75% to match experi-
mental values, as discussed later. Limited by computing power, only
high symmetric points were calculated by HSE06.
In CASTEP, Electronion interactions were described by the ul-
trasoft pseudopotential [23]. Except for GGA/PBE, the local-density
approximation (LDA) was used for the electron exchange-
correction functional, too. The cutoff energy, k-point mesh, SCF
tolerance and the residual force for per atom were the default,
which was automatically set by package when the quality of
calculation was set as ‘ultra-fine’.
The charge distributions of Csþ, CH3NH3þ and CH(NH2)2þ were
calculated at the DFT level using B3LYP hybrid functional [24] and
SDD basis set, as implemented in the Gaussian 09 package [25],
which was also used to describe the molecular orbital of CH3NH3þ,
CH(NH2)2þ, PbI64 and Cs4PbI6.
2.2. Semiempirical calculations
The experimental optical band gap of halide perovskites ABX3
was taken into calculation for the absorption spectrum, with the
use of scissor operator [26]. We calculated the dielectric frequency
spectra firstly with the cutoff energy of 500 eV and a 12  12  12 k-
point mesh, and the imaginary part was determined by a summa-
tion over empty states in the following equation [27]:

2
4pe
ε2 ðuÞ ¼ j〈vjpjc〉j2 rcv ðZuÞ½f ðEv Þ  f ðEc Þ
me u
Where v represents valence bands and c represents conduction
bands. The real part could be obtained by the Kramers-Kronig
relation:
Z∞
2 u0 ε2 ðu0 Þ
ε1 ðuÞ ¼ P du
p u0 2  u2
0
In which P denotes the principal value. The frequency depen-
dent absorption coefficient was then given by:
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u
uε ðuÞ þ ε2 ðuÞ þ ε2 ðuÞ
t 1 1 2
aðuÞ ¼ u
2
2.3. Shockley-Queisser Maximum Solar Cell Efficiency (S-Q) [28].
The standard AM1.5G and AM0 solar spectrum were used to
calculate the efficiency. The IeV curve under illumination was
described as I ¼ Ish þ I0 ½1  expðqV=kTc Þ, where Ish is the short
circuit current, I0 is the reverse saturation current, V is the voltage
between electrodes, Tc is the temperature of the solar cell, k is
 J. Qian et al. / Organic Electronics 37 (2016) 61e73
Boltzmann constant, and q is electronic charge. Ish was calculated
R∞
by Ish ¼ q Eg Isun ðEÞdE, where Eg is the bandgap of material, and
Isun(E) the sunlight photon flux at energy E. I0 was calculated by
R∞
I0 ¼ q Eg Ibb ðE; Tc ÞdE, where Ibb(E,Tc) is the black-body spectrum at
temperature Tc.
2.4. Spectroscopic Limited Maximum Efficiency (SLME) [29].
Developed from S-Q, the SLME method takes the photon ab-
sorptivity aabs ðEÞ into account. In this case,
R∞ R∞
Ish ¼ q 0 aabs ðEÞIsun ðEÞdE and I0 ¼ q 0 aabs ðEÞIbb ðE; Tc ÞdE.
3. Results and discussions
3.1. Crystal structures
The perovskite ABX3 is composed of three elements. There are
two requirements for the formation of ABX3 perovskite. On one
hand, the valence of anions must be balanced with that of cations,
i.e., 3N(X)þN(B)þN(A) ¼ 0, where N(x) represents the valence of
ion x. On the other hand, the ionic radia of A, B and X need to meet
the condition of the tolerance factor t [30]: 0.75 < t < 1, where
t ¼ pffiffiRffi A þRB , and Rx is the ionic radius. So we selected B (þ2) and X
2ðRB þRX Þ
(1) from the same main group of lead (þ2) and iodine (1) in the
periodic table of the element (Ge (2þ) and Sn (2þ) for B; F (1), Cl
(1), Br (1) and I (1) for X), respectively, and A was selected from
the first main group (Na (þ1), K (þ1), Rb (þ1) and Cs (þ1)). Then we
calculated the tolerance factor t of a series of perovskites composed
of elements we selected (Fig. S1a). From Fig. S1a, theoretically, we
would expect the existence of all perovskite ABX3 based on the
elements we chose. However, only CsSnI3, CsGeI3, CsPbBr3, CsSnBr3,
CsGeBr3, CsPbCl3, CsSnCl3, CsGeCl3, CsPbF3, CsSnF3, CsGeF3, RbGeI3
and RbPbF3 exist in practice [12,31e38], and [39], because the
tolerance factor t might be more tight (0.806 < t < 1) for the system
of halide perovskites.
According to the requirements for the formation of ABX3
perovskite, some organic ions, such as CH3NH3 (þ1) and CH(NH2)2
(þ1), carrying one positive charge and possessing a similar size as
Cs (þ1) can also serve as A part of perovskites so as to form
CH3NH3PbI3, CH3NH3SnI3, CH3NH3PbBr3, CH3NH3PbCl3,
CH3NH3SnBr3, CH(NH2)2PbI3 and CH(NH2)2SnI3.
In fact, the implication of the tolerance factor equation is that
the ionic radius of A should not be too large or too small (when A is
too large or too small, B and X will self-assemble and unable to form
a 3D network) so that the frame made up of B and X should be
stable (Fig. 1m). For example, Csþ with an ionic size of 1.67 Å, is not
large enough to prop the frame built by Pb and I, so Pb and I in
CsPbI3 form a 1D structure by self-assembly as shown in Fig. 1a. We
estimated the equivalent ionic size of CH3NH3þ and CH(NH2)2þ at
2e2.2 Å and 2.2e2.4 Å respectively (Fig. S1b). The size of
CH(NH2)2þ is too big and reaches the critical point due to observing
both 3D structure (Fig. 1j) and D structure (Fig. 1k) at room tem-
perature. The size of CH3NH3þ falls in between Csþ and
CH(NH2)2þ, which makes CH3NH3PbI3 has a twisty 3D structure
(Fig. 1i) at room temperature (at 162.2e327.4 K, CH3NH3þ is unable
to support the frame built by Pb and I fully) and a neat 3D structure
(Fig. 1f) at high temperature (at >327.4 K, CH3NH3þ is able to
support the frame built by Pb and I). Compared with 3D perov-
skites, 1D perovskites have a larger bandgap and higher probability
of electron-hole recombination, which are not favorable to serve as
the active materials for solar cells [40]. So in this paper we only
chose 3D perovskites (CsSnI3, CsGeI3, CsPbBr3, CsSnBr3, CsGeBr3,
CsPbCl3, CsSnCl3, CsGeCl3, CsPbF3, CsSnF3, CsGeF3, RbGeI3, RbPbF3,
CH3NH3PbI3, CH3NH3SnI3, CH3NH3PbBr3, CH3NH3PbCl3,
63
CH3NH3SnBr3, CH(NH2)2PbI3 and CH(NH2)2SnI3) as the investigated
targets.
In order to get the initial structures, we collected the experi-
mental lattice constant of the existent halide perovskites at room
temperature or near room temperature as listed in Table S1. When
A part of perovskite (ABX3) is an inorganic atom, most of the pe-
rovskites like CsSnI3, CsSnBr3, CsSnCl3, CsPbBr3, CsPbCl3, RbPbF3,
RbGeI3 and CsPbF3 (Fig. 1b) possess the symmetry of m3m and the
smallest repeat unit is a 1  1  1 cell, while CsGeI3, CsGeBr3 and
CsGeCl3 (Fig. 1c) have the space group of R3m and the smallest
repeat unit is a 1  1  1 cell. When A part is organic ions
(CH(NH2)2 and CH3NH3), the crystal structures of perovskite (ABX3)
obtained from x-ray diffraction (XRD) only confirm the frame
formed by B and X, so CH3NH3PbCl3, CH3NH3PbBr3, CH3NH3SnBr3,
CH3NH3SnI3 and CH3NH3PbI3 at high temperature (Fig. 1f) have a
symmetry of m3m and the smallest repeat unit is a 1  1  1 cell
[41]. However, the organic ions (CH(NH2)2 and CH3NH3) arranged
disorderedly in the lattice of perovskite, which has to be relaxed to
the fixed orientations during calculations. For perovskites with
CH3NH3 (CH3NH3PbCl3, CH3NH3PbBr3, CH3NH3SnBr3, CH3NH3SnI3
and CH3NH3PbI3 at high temperature), CeN bond should be aligned
approximately with [111] direction (Fig. 1e) in order to reach the
lowest energy [42]. For CH3NH3PbI3 at room temperature, the
frame formed by lead and iodinep possesses
ffiffiffi pffiffiffi a space group of I4/mcm
and the smallest repeat unit is a 2  2  2 supercell, so the CeN
bond should be aligned approximately along [001] direction
(Fig. 1h) to reach the lowest energy [43]. For CH(NH2)2PbI3, the
frame formed by lead and iodine possesses
pffiffiffi paffiffiffispace
pffiffiffi group of P3m3
and the smallest repeat unit is a 2  2  3 supercell. For
CH(NH2)2SnI3, the frame formed by tin and iodine possesses pffiffiffi apspace
ffiffiffi
group of Imm2 and the smallest repeat unit is a 2 2  2 2  2
supercell (Fig. 1g). Different perovskites possess different repeat
units and crystal structures. Therefore, for the purposes of simpli-
fication and comparison, in the further calculations, an initial
structure as shown in Fig. 1e was applied for CH3NH3PbCl3,
CH3NH3PbBr3, CH3NH3SnBr3, CH3NH3SnI3 and CH3NH3PbI3, and the
smallest repeat unit is a 1  1  1 cell; an initial structure in Fig. 1d
for CH(NH2)2PbI3 and CH(NH2)2SnI3, and the smallest repeat unit is
a 1  1  1 cell; an initial structure in Fig. 1b for CsSnI3, CsPbBr3,
CsSnBr3, CsPbCl3, CsSnCl3, CsPbF3, CsSnF3, CsGeF3, RbGeI3 and
RbPbF3 and the smallest repeat unit is a 1  1  1 cell; and an initial
structure in Fig. 1c for CsGeI3, CsGeBr3, CsGeCl3 and the smallest
repeat unit is a 1  1  1 cell.
In order to calculate the electronic structures, the optical and
electrical properties of halide perovskites, we optimized the atomic
positions and lattice parameters by using GGA/PBE method with
Vasp program, GGA/PBE method and LDA method with Castep
program, respectively. The optimized lattice parameters together
with the experimental parameters are shown in Fig. 2. From Fig. 2,
we found that the lattice parameters of perovskites increase obvi-
ously when X part changes from F, Cl, Br to I, but increase slightly
when B part changes from Ge, Sn to Pb. All the theoretical lattice
parameters of perovskites calculated by GGA/PBE (Vasp) are almost
larger than the experimental lattice constant [44], except for the
perovskites (ABX3, B]Ge) because Ge perovskite possesses a twisty
3D structure, and the bond length of Ge-X is not corresponding to
the lattice parameter.
By comparing the lattice parameters calculated by GGA/PBE
(Vasp), GGA/PBE (Castep) and LDA (Castep) and the experimental
parameters, the relative errors between theory and experiment
were obtained as listed in Table S1. The relative errors between the
lattice parameters optimized by GGA/PBE (Castep) and the exper-
imental parameters are 0.9%e5.0% for CsGeI3, CsPbBr3, CsSnBr3,
CsPbCl3, CsSnCl3, CsGeCl3, CsPbF3, CsSnF3, CsGeF3, RbGeI3, RbPbF3,
CH3NH3PbCl3, CH3NH3PbBr3, CH3NH3SnBr3, CH3NH3SnI3,
64 J. Qian et al. / Organic Electronics 37 (2016) 61e73
Fig. 1. Ball-and-stick representations (a) CsPbI3 (space group: Pbnm), (b) CsSnI3 (space group: Pm3m), (c) CsGeI3 (space group: R3m), (d) CH(NH2)2PbI3 (space group: P1), (e)
CH3NH3PbI3 (space group: P1), (f) CH3NH3PbI3 (space group: Pm3m), (g) CH(NH2)2SnI3 (space group: Imm2), (h) CH3NH3PbI3 (space group: P1), (i) CH3NH3PbI3 (space group: I4/
mcm), (j) CH(NH2)2PbI3 (space group: P3m1) and (k) CH(NH2)2PbI3 (space group: P3). The sectional views of (l) CH(NH2)2PbI3 and (n) CH3NH3PbI3. The relationship of A, B and X in
perovskites (ABX3) (m).
Fig. 2. Relationship between the experimental lattice constant and theoretical lattice
constant. The theoretical lattice constants of perovskites were calculated by using Vasp
with GGA/PBE (green points), Castep with GGA/PBE (red points) and Castep with LDA
(blue points). (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
CH3NH3PbI3, CH(NH2)2PbI3 and CH(NH2)2SnI3, and 11.3% for CsSnI3,
-2.0% for CsGeCl3 and -1.2% for CsGeBr3. However, the relative er-
rors between the optimized results obtained by LDA (Castep) and
experiment values are 0.1% ~ 3.4% for CsSnI3, CsGeI3, CsPbBr3,
CsSnBr3, CsPbCl3, CsSnCl3, CsPbF3, CsSnF3, CsGeF3, RbGeI3, RbPbF3,
CH3NH3PbCl3, CH3NH3PbBr3, CH3NH3SnBr3, CH3NH3SnI3,
CH3NH3PbI3, CH(NH2)2PbI3 and CH(NH2)2SnI3, and -6.4% for
CsGeCl3 and -5.6% for CsGeBr3. The relative errors of the theoretical
lattice parameters calculated by GGA/PBE (Vasp) are 1.7%e4.3%
for CsSnI3, CsGeI3, CsPbBr3, CsSnBr3, CsGeBr3, CsPbCl3, CsSnCl3,
CsGeCl3, CsPbF3, CsSnF3, CsGeF3, RbGeI3, RbPbF3, CH3NH3PbCl3,
CH3NH3PbBr3, CH3NH3SnBr3, CH3NH3SnI3, CH3NH3PbI3,
CH(NH2)2PbI3 and CH(NH2)2SnI3, which are tolerated for further
calculations. So the electronic structures, the optical and electrical
properties are calculated by GGA/PBE (Vasp) in this study.
3.2. Electronic structures
3.2.1. Density of states (DOS) and band structures
Based on the relaxed structures, we calculated the electronic
structures of the above halide perovskites ABX3, which are
commonly described by the density of states (DOS) and band
structures.
The typical DOS of CsPbF3, CsPbCl3, CsPbBr3, CH3NH3PbBr3,
CH3NH3PbI3, CH3NH3SnI3, CH(NH2) 2SnI3, CsGeI3, including the
similarities and differences, as shown in Fig. 3.
From the view point of similarities, the formation and the order
of bands are analogous because of the similar framework structures
formed by B and X and chemical constitutions of these halide pe-
rovskites. The valence band maximum (VBM) is derived from the p
orbitals of X and s orbitals of B, and their overlapping indicates the
significant hybridization with each other. The p orbitals of B and a
bit of p orbitals of X constitute the conduction band minimum
(CBM). Below VBM, a mass of states derived from the p orbitals of B
and d orbitals of X, which are situated in the same energy level.
Within these p orbitals of B, most of them are nonbonding orbitals
(VBM-1) and the rest form the conventional coordinate bonds
(X/B) in terms of the classical valence bond theory, but ionic-
covalent bonds and coordinate bonds are not distinguishable
here. For example, there are six Br atoms around one Pb atom with
the same distance between Pb and Br (2.937 Å), which indicates
homogeneous bonds rather than two ionic-covalent bonds
together with four coordinate bonds.
From the perspective of differences, the PDOS of part A (Cs,
CH3NH3, and CH(NH2)2) and the energy differences among bands
(for example: △ECBM, VBM, △EVBM, VBM-1) are various. Firstly, for
part A of perovskite (ABX3), different compositions have different
PDOS. The energy of the p orbitals of Cs is far below its VBM
(Fig. 3g). When it comes to the PDOS of CH3NH3 (Fig. 3e), we can see
that sharp peaks belong to the s orbitals of hydrogen and p orbitals
of carbon and nitrogen, which is the localized covalent bond (CeH
 J. Qian et al. / Organic Electronics 37 (2016) 61e73
Fig. 3. Density of states (DOS) and partial densities of states (PDOS) (a) CsPbF3, (b) CsPbCl3 (c) CsPbBr3 (d) CH3NH3PbI3 (e) CH3NH3SnI3 (f) CH(NH2) 2SnI3 (g) CsGeI3 (h) RbGeI3
calculated using PBE functions. The energy of valence band maximum is set to zero.
and NeH). CH(NH2)2 is also different from CH3NH3, whose LUMO,
HOMO and HOMO-1 are derived from the p orbitals of carbon and
nitrogen (Fig. 3f). However, from PDOS and DOS, part A does not
seem to play a direct role in determining the basic electronic
structures of frameworks formed by B and X and the important role
of A is donating an electron to the B-X frame and supporting the
perovskite structure. So, we ignore the effect of different part A
when we discussed DOS. Secondly, the energy difference between
ECBM and EVBM (△ECBM, VBM) and the energy difference between
EVBM and EVBM-1 (△EVBM, VBM-1) are various. After comparing the
bandgap of CsPbF3 (2.55 eV), CsPbCl3 (2.10 eV), CsPbBr3 (1.66 eV)
and CH3NH3PbI3 (1.53 eV) (Fig. 3) with the same Pb as the part B of
perovskite (ABX3), the band gap becomes smaller when X part
changes from F, Cl, Br to I, and the energy difference between VBM
and VBM-1 becomes smaller (~2.1 eV for CsPbF3, ~1.0 eV for
CsPbCl3, ~0.8 eV for CsPbBr3, ~0.5 eV for CH3NH3PbI3). However,
when we choose the same I as part X (CsGeI3, CH3NH3PbI3 and
CH3NH3SnI3), we find the band gap for CsGeI3, CH3NH3PbI3 and
CH3NH3SnI3 is 1.07 eV, 1.36 eV and 0.46 eV, respectively, and the
energy difference between VBM and VBM-1 (~0.5 eV for CsGeI3,
~0.5 eV for CH3NH3PbI3, ~0.8 eV for CH3NH3SnI3) shows the rela-
tionship: △E(Pb)VBM, VBM-1 z△E(Ge)VBM, VBM-1 < △E(Sn)VBM, VBM-
1. In the periodic table of elements, the atomic number decreases
from I, Br, Cl to F in VIIA and the energy difference of CsPbF3,
CsPbCl3, CsPbBr3 and CH3NH3PbI3 between bands becomes smaller;
while when the atomic number decreases from Pb, Sn to Ge in IVA,
65
the relationship of energy difference between bands is △E(Pb)VBM,
VBM-1 z△E(Ge)VBM, VBM-1 < △E(Sn)VBM, VBM-1. Therefore, the
electronic structure of Ge perovskites is found to be abnormal.
In order to get the detailed information about the electronic
structures, we calculated the band structure of halide perovskites
ABX3. Different high symmetrical points of the Brillouin zone (BZ)
and paths between the high symmetrical points are chosen ac-
cording to the symmetry provided by XRD data. For the crystal with
the space groups of Pm3m, we described the band structure along
the path X (0.5 0 0) / R (0.5 0.5 0.5) / M (0.5 0.5 0) / G (0
0 0) / R (0.5 0.5 0.5), such as CsPbBr3 (Fig. 4c). For the crystal with
a small organic molecule (possess Pm3m space group approxi-
mately), we described the band structure along the path X (0.5
0 0) / R (0.5 0.5 0.5) / M (0.5 0.5 0) / G (0 0 0) / R (0.5 0.5 0.5),
such as CH3NH3PbBr3. In addition, we chose the path G (0 0 0) / Z
(0.5 0.5 0.5) / F (0.5 0.5 0) / G (0 0 0) to describe the band
structure of the crystal with R3m space groups, like CeGeI3 (Fig. 4f).
From the view of similarities, we find all of them are the direct-
band-gap materials, which are different from Si, a typical indirect
bandgap material whose the electronic transition from VBM to CBM
needs the help of phonon [45]. As for DOS discussed above, we find
the similarity of these halide perovskites in band structure and
steep VBM and CBM, which means good characteristics of the
electrons delocalization. In fact, a physical quantity related to the
electrons delocalization is the effective mass (m*) of electrons
(holes), which will be discussed later. Unlike VBM and CBM, the
66 J. Qian et al. / Organic Electronics 37 (2016) 61e73

Fig. 4. Band structure of (a) CsPbF3 (b) CsPbCl3 (c) CsPbBr3 (d) CH3NH3PbI3 (e) CH3NH3SnI3 (f) CsGeI3 (g) CH3NH3PbBr3 calculated using PBE functionals with and without SOC (grey
dot line) and the energy of valence band maximum is set to zero, where red line represents CBM, purple line represents VBM and blue line represents other band. Charge dis-
tribution (h) of CH(NH2)þ þ þ
2 (left) CH3NH3 (middle) Cs (right), where blue represents positive charge and red represents neutral. Schematic diagram of the dipole polarization of
organic molecules (i). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

bands below VBM seem to be flat and reflect the nonbonding

properties of halide perovskites. b j¼E j
H (1)
0 0
In terms of differences, the energy difference among bands is
various. From CsPbF3 (Fig. 4a), CsPbCl3 (Fig. 4b), CsPbBr3 (Fig. 4c) to And Schrodinger’s equation with SOC is expressed as follows
CH3NH3PbI3 (Fig. 4d), we can see that the energy differences be- [47]:
tween VBM and VBM-1 (including four orbitals) at R point are

_ _
different (3.7e4.2 eV for CsPbF3, 1.7e2.3 eV for CsPbCl3, 1.3e2.0 eV H0 þ H SO j ¼ ðE0  ms Bl Þj (2)
for CsPbBr3, 0.7e1.4 eV for CH3NH3PbI3). However, compared the
band structure of CsGeI3 and CH3NH3PbI3 to that of CH3NH3SnI3,
Where
CH3NH3SnI3 is rather different due to the larger energy difference R
E0  ms  Bl ¼ E0 þ 12  m80 Ze Z
2 2

between VBM and VBM-1 (0.6e1.7 eV for CsGeI3 at Z point of the pm2
 j* r13 jdt  ½jðj þ 1Þ  lðl þ 1Þ 
e

Brillouin zone, 0.7e1.4 eV for CH3NH3PbI3 and 1.4e2.2 eV for sðs þ 1Þ . The energy level (E0) defined by n and l splits into sub-
R
CH3NH3SnI3 at R point of the Brillouin zone). The relationship of the (E0  12  m80 Ze Z
2 2
levels pm2e
 j* r13 jdt  ðl þ 1Þ ¼ E0  DSOC and
energy difference between bands (F > Cl > Br > I, Pb z Ge < Sn)
m0 Ze2 Z2 R * 1
calculated by band structures is in accordance with that calculated E0 þ 2  8pm2  j r3 jdt  l) with different total moments, j ¼ lþ1/
1
e
according to the peaks of DOS. 2 and j ¼ l-1/2.

3.2.2. Spin-orbit coupling (SOC) Z4

SOC effects, which make both conduction and valence bands
near band edges more dispersive [46], need to be taken into
consideration when discussing the electronic structure of materials
containing element with a large atomic number.
Schrodinger’s equation without considering SOC is expressed as
follows:
For a hydrogenlike atom; DSOC ∝ (3)
n3
Where Z is the atomic number and n is the main quantum number.
In these halide perovskites, CBM is three-fold degeneration if
SOC is neglected, as shown in Fig. 4c. When the SOC effect is
considered, CBM splits into a two-fold low-lying p1/2 manifold and
 J. Qian et al. / Organic Electronics 37 (2016) 61e73 67

a four-fold high-lying p3/2 manifold if the spin degeneracy is
counted. This splitting can induce a down-shift of CBM (△soc).
According to the analyses of DOS, the CBM of perovskite (ABX3) is
derived from the p orbitals of part B mainly, and we find the Z4/n3
values of Ge (Z ¼ 32, n ¼ 4), Sn (Z ¼ 50, n ¼ 5) and Pb (Z ¼ 82, n ¼ 6)
are 16,384, 50,000 and 2,09,315. We divide the Z4/n3 values of Ge,
Sn and Pb by 209315, and the ratio value of Z4/n3 s becomes 0.078:
0.239: 1, which is in parallel the ratio of △soc for Ge perovskites
(0.04 eVe0.13 eV): △soc for Sn perovskites (0.29 eVe0.39 eV):
△soc for Pb perovskites (0.96 eVe1.62 eV) as listed in Table 1. It
might be a coincidence, but eq. (3) reflects the nature of SOC, i.e.,
the relativistic effect. When an atom has more protons, the
Coulomb force between atomic nucleus and electron, which is the
centripetal force when electrons revolve around the atomic nu-
cleus, becomes stronger, resulting in the fast moving of electrons.
When the speed of electrons is close to the speed of light, the
relativistic effect is more obvious, which is so called SOC.
Comparing Ge, Sn and Pb perovskites, the SOC effect for Ge pe-
rovskites is weak, and that for Pb perovskites is strong, while Sn
perovskites is just in the middle due to the difference of part B.
Perovskites containing organic ions (Fig. 4f and g) have different
band structure with SOC, compared with perovskites containing
inorganic ions (Fig. 4c). If the crystal has a center of inversion, each
band will preserve its spin degeneracy, like CsPbBr3. However,
when we replace Csþ with CH3NH3þ, there is no center of inversion
in CH3NH3PbBr3 and the p3/2 and p1/2 bands will additionally be
split by spin-orbit interaction, removing the spin degeneracy
(Fig. S2).
The SOC has also been found to be important in other com-
pounds containing heavy 6p cations [48], which makes both con-
duction and valence bands near band edges more dispersive and
the electrical conductivity better.
3.2.3. Exchange-correlation energy
As shown in Table 1, we calculated the band gap of halide pe-
rovskites by using PBE with and without SOC. The DFT approxi-
mated by GGA or LDA has a system error (underestimated
exchange-correlation energy: △XC) caused by the failure of
describing excited state [44], which leads to the famous problem of
underestimating bandgap of semiconductor, as shown in Fig. S3,
and people set the error into the part of exchange-correlation en-
ergy (Exc) of GGA-DFT and LDA-DFT. Comparing △XC with
△XC þ△SOC, we can see the band gap of perovskites with Pb as part
B calculated by PBE is in good agreement with experiments just
because the losing sight of SOC effect offsets the underestimated
exchange-correlation energy, △XC. Compared the bandgap value of
perovskites calculated by PBE and SOC, we can see that with the
same part B, the band gap of halide perovskites increases from I, Br,
Cl to F (0.37 eV for CH3NH3PbI3, 0.64 eV for CsPbBr3, 1.07 eV for
CsPbCl3 and 1.59 eV for CsPbF3). However, compared with the
experimental bandgap (1.52 eV for CH3NH3PbI3, 2.25 eV for CsPbBr3
and 3.00 eV for CsPbCl3), the sort of halogen has a deep influence on
the bandgap caused by the exchange-correlation energy. From
Table 1, we can see △XC of the halide perovskites grows from I, Br,
Cl to F (for example, 1.15 eV for CH3NH3PbI3, 1.61 eV for CsPbBr3,
1.93 eV for CsPbCl3 and 2.51 eV for CsPbF3).
The core of DFT is the Kohn-Sham method [44]:
E ¼ EðNÞ þ ET ðrÞ þ EV ðrÞ þ EJ ðrÞ þ EXC ðrÞ, where r is electric den-
sity, Exc(r) is the exchange-correlation energy which can be
decomposed into exchange energy [Ex(r)] and correlation energy
[Ec(r)]. To correct the system error of GGA-DFT and LDA-DFT, we
adopted HF/DFT method (HSE06), by adding a part of exact ex-
change energy of HF into Exc:
HSE ¼ aESR ðm; rÞ þ ð1  aÞE PBE;SR ðm; rÞ þ E PBE;LR ðm; rÞ þ E PBE ðrÞ,
Exc x x x c
where a is the pecentage of HF exact exchange and m is the range-
separation. The default pecentage of Ex in HSE06 is 25%, and we
adjusted it to 50% and 75% for different materials because perov-
skites with smaller halogen radius need higher pecentage of EX.
By using HSE06, we can estimate the band gap of halogen
perovskite (ABX3). As a reference, the band gap of CsGeI3 (1.55 eV)
is calculated by HSE06, which is rather close to its experimental
value (1.51 eV). The band gap of RbGeI3, whose absorption spec-
trum has never been reported and experimental band gap is still
unknown, was speculated to be 0.85 eV.

Table 1
Band gaps of halide perovskites calculated by using PBE functionals with and without SOC and HSE06 functionals without SOC.

PBE PBE þ SOC △soc △xc HSE06 (25%HF) HSE06 (50%HF) HSE06 (75%HF) EXP.

CH3NH3SnI3 0.59 0.30 0.29 0.91 0.79 1.05 1.33 1.21a

CsSnI3 0.45 0.06 0.39 1.21 0.74 1.11 1.27b
RbGeI3 0.44 0.31 0.13 0.85
CH(NH2)2SnI3 0.65 0.33 0.32 1.08 1.00 1.40 1.41a
CH(NH2)2PbI3 1.72 0.10 1.62 1.38 2.15 1.48a
CsGeI3 1.07 0.99 0.08 0.52 1.55 1.51c
CH3NH3PbI3 1.49 0.37 1.12 1.15 1.83 1.52a
CsSnBr3 0.62 0.28 0.34 1.47 1.05 1.55 1.75b
CH3NH3SnBr3 0.77 0.47 0.30 1.68 1.11 1.52 1.98 2.15d
CH3NH3PbBr3 1.86 0.77 1.10 1.46 2.38 2.23e
CsPbBr3 1.75 0.64 1.11 1.61 2.35 2.25f
CsGeBr3 0.63 0.57 0.05 1.80 1.15 1.78 2.43 2.37g
CsSnCl3 0.98 0.64 0.33 2.26 1.50 2.09 2.73 2.90h
CsPbCl3 2.19 1.07 1.11 1.93 2.89 3.00i
CH3NH3PbCl3 2.30 1.19 1.11 1.92 2.93 3.63 3.11j
CsGeCl3 1.02 0.99 0.04 2.32 1.69 2.40 3.16 3.31g
RbPbF3 2.84 1.79 1.05 3.86
CsPbF3 2.55 1.59 0.96 3.54
a
Reported by Stoumpos et al. [33].
b
Reported by Sabba et al. [12].
c
Reported by Tang et al. [23].
d
Reported by Chiarella et al. [36].
e
Reported by Kulkarni et al. [49].
f
Reported by Stoumpos et al. [31].
g
Reported by Lin et al. [50].
h
Reported by Borriello et al. [51].
i
Reported by Yunakova et al. [32].
j
Reported by Baikie et al. [52].
68 J. Qian et al. / Organic Electronics 37 (2016) 61e73
3.2.4. Molecular orbital
In order to learn more about the electronic structures and
discuss the optical transition of perovskites, we took metal ionic
compounds like Cs4PbBr6 and PbBr64 as model compounds and
calculated their molecular orbitals as shown in Fig. 5. For PbBr64,
from the low energy to high energy, there are bonding orbitals
formed by the s orbitals of Pb and p orbitals of Br, nonbonding
orbitals formed by the p orbitals of Br (orbitals for coordinate bonds
are included.), antibonding orbitals formed by the s orbitals of Pb
and p orbitals of Br (Orbital1*), antibonding orbitals formed by the p
orbitals of Pb and p orbitals of Br (Orbital2*), and antibonding or-
bitals for coordinate bonds formed by the d orbitals of Pb and p
orbitals of Br. When we added four Cs atoms around PbBr64, the
assignment of the molecular orbitals changed due to the addition of
d orbitals of Cs insert between Orbital1* and Orbital2*.
According to the orbital energy of R point of BZ and PDOS, the
molecular orbital of CsPbBr3 was given in Fig. 6. The unit cell of
CsPbBr3 has the same structure as that of CsSnI3 (Fig. 1b), where a
Cs atom is located in the center of the unit cell, Br atoms on the edge
of the frame and Pb atoms at the corner. As a result, the main bonds
are the ionic bonds formed between Cs and Br and the covalent
bonds formed between Pb and Br, while no bond is formed between
Pb and Cs because of no direct contact with each other. The dis-
tribution of the orbital energy and orbital parity is rather important
for the absorption spectrum, and the situation is similar for
different perovskites. As an example, we only discuss CsPbBr3 here.
According to the schematic diagram of the molecular orbitals
formation of perovskites, different molecular orbital energies of
perovskites boil down to different atomic orbital energies. We
calculate the atomic orbital energy of F, Cl, Br, I, Ge, Sn and Pb as
shown in Fig. S4. The outmost p orbital energy of F, Cl, Br and I
increases from 11.1 eV, -8.4 eV, -7.7 eV to 6.8 eV. The outmost p
orbital energy of Ge, Sn and Pb increases from 3.7 eV, -3.3 eV to
3.1 eV, and the outmost s orbital energy of Ge, Sn and Pb changes
from 11.6 eV, -10.2 eV to 11.5 eV. The change of the atomic
orbital energies explains the changes of bandgaps (CsPbF3
(2.55 eV), CsPbCl3 (2.10 eV), CsPbBr3 (1.66 eV) and CH3NH3PbI3
(1.53 eV)) as well as the changes of energy differences between
VBM and VBM-1 (~0.5 eV for CsGeI3, ~0.5 eV for CH3NH3PbI3,
~0.8 eV for CH3NH3SnI3).
Fig. 5. Molecular orbitals of (a) PbBr64 and (b) Cs4PbBr6. Red line represents occupied
molecular orbital and blue line represents unoccupied molecular orbital. The energy of
HOMO is set to zero. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
Fig. 6. The formation of CsPbBr3 molecular orbitals. The energy of CsPbBr3 molecular
orbitals based on the average orbital energy at special k point of BZ. Red line represents
occupied molecular orbital and blue line represents unoccupied molecular orbital.
Detail methods are described in Fig. S13. (For interpretation of the references to colour
in this figure legend, the reader is referred to the web version of this article.)
3.3. Absorption spectrum
According to the transition matrix element and selection rules
[44], when hvn jpjcm i ¼ 0, transitions from the occupied state n (vn)
to the unoccupied state m (cm) are forbidden; and when
hvn jpjcm is0, transitions from vn to cm are allowed. In other words,
allowed transitions require the parity of wave functions (occupied
state and unoccupied state) to be opposite in a system with the
inversion symmetry. For example, if the wave function of the
occupied state is odd function, the transitions to the unoccupied
state with an even wave function are allowed, but the transitions
are forbidden to the unoccupied state with odd wave function.
Taking CsPbBr3 as an example, if we set Pb as the center of sym-
metry, the wave function of the Antibonding Orbital1* (Ob1*)
formed by the s orbitals of Pb and p orbitals of Br is an even function
and that of the Antibonding Orbital2* (Ob2*) formed by the p or-
bitals of Pb and p orbitals of Br is an odd function, so transitions
from Ob1* to Ob2* are allowed. There are so many Nonbonding
orbitals (Non-Ob) located between Ob1* and Bonding orbital2 (Ob2),
where we can find both symmetrical and antisymmetric orbital
distributions, which means that the transitions from Non-Ob to
Ob2* are possible. The possibility of transitions from Bonding
orbital1 (Ob1) to Ob2* is existent, because the symmetry of Ob1 is
the opposite of Ob2*. While the transition from Ob2 to Ob2* is
impossible, since the wave functions of both Ob2 and Ob2* are odd
function.
In the perovskites we chose, the transitions from Ob1* to Ob2*
and from Non-Ob to Ob2* have been taken into consideration. As
shown in Fig. 7, the energy of transition from Ob1* to Ob2* de-
termines the value of the optical band gap and the energy of
transition from Non-Ob to Ob2* determines the intensity of molar
absorption coefficient within the scope of solar spectrum. A small
energy difference between the transition from Ob1* to Ob2* and the
transition from Non-Ob to Ob2* means a better absorption
spectrum.
The simulate absorption spectra of several representative pe-
rovskites have been shown in Fig. 8. By comparing Pb perovskites,
from CsPbCl3, CsPbBr3 to CH3NH3PbI3, the edge of the absorption
peak gives red-shift due to the various halogens. Comparing iodic
perovskites, we can see CsGeI3 and CH3NH3PbI3 have relatively
higher absorption coefficient than CH3NH3SnI3 in the range of solar
spectrum. When comparing the DOS of CH3NH3SnI3 (Fig. 3a) with
those of CH3NH3PbI3 (Fig. 3d) and CsGeI3 (Fig. 3c), we find the
 J. Qian et al. / Organic Electronics 37 (2016) 61e73 69

Fig. 7. Orbital energies of ABX3 with a small energy difference between Antiboding orbital1* and Nonbonding orbital (a) resulting in a good absorption spectrum fitting with solar
spectrum (b). Orbital energies of ABX3 with a large energy difference between Antiboding orbital1* and Nonbonding orbital (c) resulting in a poor absorption spectrum fitting with
solar spectrum (d). Blue dot line represents solar spectrum, green line represents transition 1 with gaussian smearing, pink line represents transition 2 with gaussian smearing, red
line represents transition 3 with gaussian smearing and grey line represents total absorption spectrum. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)

3.4. Effective masses of electrons and holes

As the active material of solar cell, not only a good ability of

charge carrier transport is necessary but also a balanced electron
and hole transportation is rather important in order to avoid charge
accumulation [53]. In fact, benefitting from the 3D structure, the
carrier mobility of perovskites is relatively high. For example, the
experimental carrier mobility of both electrons and holes in poly-
crystalline CH3NH3PbI3 can reach to 10 cm2v1 s1 approximately
[54]. While CsSnI3 is p-type semiconductor with a hole carrier
mobility of 585 cm2v1 s1 [55]. In theory, the carrier mobility of
electrons (holes) is inversely proportional to the effective mass (m*)
of electrons (holes), which can be calculated by fitting the VCM
" #1
v2 εðkÞ
(CBM) to m* ¼ h2 v2 k
, where εðkÞ is the energy dispersion

relation function described by band structures, as shown in

Fig. 8. Simulate absorption spectrum of CsPbCl3 (green line), CsPbBr3 (red line),
CH3NH3PbI3 (brown line), CH3NH3SnI3 (grey line) and CsGeI3 (blue line). AM1.5G is
drawn with a purple line. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
energy difference between VBM and VBM-1 is ~0.5 eV for CsGeI3,
~0.5 eV for CH3NH3PbI3, and ~0.8 eV for CH3NH3SnI3, which means
the n-Ob of iodine in CsGeI3 and CH3NH3PbI3 is closer to CBM than
that in CH3NH3SnI3, so the intensity of the molar absorption co-
efficients of CsGeI3 and CH3NH3PbI3 is greater than that of
CH3NH3SnI3 within the scope of solar spectrum, fitting with the
mechanism described in Fig. 7. This is one of the reasons why
CH3NH3SnI3 and CH3NH3PbI3 have the similar bandgap but
different conversion efficiency.
Table S2. We found out that the effective masses for electrons and
holes of perovskites (ABX3) with the same part A and part B become
smaller from CsSnCl3 (0.28:0.09), CsSnBr3 (0.22:0.06) to CsSnI3
(0.17:0.04) and from CsPbF3 (0.45:0.26), CsPbCl3 (0.28:0.18) to
CsPbBr3 (0.22:0.14). The effective masses for holes of Sn perovskites
are smaller than those of Ge and Pb perovskites, resulting in the
higher hole mobility of Sn perovskites. Compared the effective
masses for electrons and holes of perovskites (ABX3) with the same
part B and part X, the difference of the effective masses for elec-
trons and holes reduces when a polar CH3NH3þ replaces Csþ, like
CsSnBr3 (0.22:0.06) and CH3NH3SnBr3 (0.23:0.07). While the
effective masses for electrons and holes are approximate for the
following halogen perovskites: CsGeI3 (0.14:0.19), CsPbBr3
(0.21:0.14), CH3NH3PbCl3 (0.19:0.19), CH3NH3PbBr3 (0.17:0.16),
CH3NH3PbI3 (0.12:0.12) and CH(NH2) 2PbI3 (0.19:0.19).
70 J. Qian et al. / Organic Electronics 37 (2016) 61e73
3.5. PCE simulated by S-Q and SLME mathematic models
Shockley-Queisser Maximum Solar Cell Efficiency (S-Q) and
Spectroscopic Limited Maximum Efficiency (SLME) mathematical
models have been introduced to make a good understanding of the
optical and electrical properties of halide perovskites. AM1.5G (the
solar spectrum around the surface of the earth where the solar
energy might be used for daily life power supply), AM0 (the solar
spectrum around the near-earth orbit where the solar energy might
be used for artificial satellite power supply) and bandgaps serve as
input parameters in S-Q, and AM1.5G, AM0 and absorption spectra
in SLME. Similar PCE of perovskites by using S-Q and SLME are
show in Fig. 9. From Fig. 9, we can see that perovskites with
different halogen gather together at the bottom, in the middle and
at the top of the curve of S-Q. From Cl, Br to I, the similar PCE travels
from the foot of the ’hill’ (~5.0% (AM0), ~3.0% (AM1.5G)) to the
mountainside (~17.5% (AM0), ~17.5% (AM1.5G)) to the ’mountain’
top (~27.5% (AM0), ~32.0% (AM1.5G)). The relative height of PCE
simulated by AM1.5G and AM0 are polytropic and dependent on
the bandgap of halide perovskites due to the difference of AM1.5G
and AM0 (at ultraviolet region, the light intensity of AM1.5G is
lower than that of AM0 due to the absorption of O3). For details, the
photons at the ultraviolet region possess high energy but produce
the same output work (hvEg, where vEg is the band gap of material)
as photons in lower energy region. So, at 1e2 eV, PCE simulated by
AM1.5G (from 30.1% to 32.5%e22.5%) is higher than PCE simulated
by AM0 (from 27.5% to 29.0%e22.5%), while, at 2e4 eV, PCE simu-
lated by AM1.5G (from 22.5% to 0%) is lower than PCE simulated by
AM0 (from 22.5% to 1.2%). Different from the PCE simulated by
AM1.5G and AM0, the short-circuit current density, open-circuit
voltage and fill factor changes straightforward with the bandgap.
No matter the value of bandgap is large or small (from 0.5 eV to
4 eV), the short-circuit current density simulated by AM0 (from
0.060 Acm2 to 0 Acm2) is larger than that simulated by AM1.5G
(from 0.045 Acm2 to 0 Acm2) as shown in Fig. S5, because the
light intensity (maximum 2.20 W m2 nm1 at 490 nm) around the
Fig. 9. Solar spectra (top) and simulated PCE for halide peroveskites by using S-Q and
SLME models (bottom). PCE for halide peroveskites simulated by using S-Q model with
AM0 are marked as blue points. PCE for halide peroveskites simulated by using S-Q
model with AM1.5G are marked as red points. PCE for halide peroveskites simulated by
using SLME model with AM0 are marked as blue triangles. PCE for halide peroveskites
simulated by using SLME model with AM1.5G are marked as red triangles. (For
interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)
near-earth orbit is stronger than that around the surface of the
earth (maximum 1.60 W m2 nm1 at 500 nm). According to S-Q
mathematic model, the short-circuit current is described as
R∞
Ish ¼ q Eg Isun ðEÞdE, which means that a photon produces a pair of
electron and hole and the short-circuit current is in proportion to
the light intensity. In addition, the open-circuit voltage depends on
the bandgap (from 0.5 eV to 4 eV) mainly and has little difference
between AM1.5G and AM0 (from 0.3 eV to 3.5 eV). For the fill factor,
the same situation is obtained due to a perfect semiconductor
behavior assumption. When the band gap changes from 0.5 eV to
4 eV, the fill factor varies from 72% to 95%.
In S-Q, the simulated PCE only depends on the band gap so that
the materials with the similar bandgap (for example, 1.51 eV,
1.55 eV and 1.21 eV for CsGeI3, CH3NH3PbI3 and CH3NH3SnI3) have a
near simulated PCE value (31.2%, 31.0% and 32.0% for CsGeI3,
CH3NH3PbI3 and CH3NH3SnI3 simulated by AM1.5G; 28.5%, 28.4%
and 29.0% for CsGeI3, CH3NH3PbI3 and CH3NH3SnI3 simulated by
AM0). In SLME, when the absorption spectra of materials are taken
into consideration, materials with similar bandgap have obviously
different PCE. Furthermore, the simulated PCE depends on the
thickness of the active layer. According to Beer’s Law, lg(T/
T0) ¼ Kabc, where T/T0 presents transmittance, Ka is the molar
absorption coefficient, b is the absorption depth and c is the con-
centration. The percentage of photons which are absorbed by the
absorber depends on Ka and b, while c is a solid constant. A thicker
absorber means a better absorbing ability. However, for a solar cell,
the thickness of an absorber is constrained by the carrier diffusion
length. Once the thickness of the absorber goes beyond the carrier
diffusion length, most of the carriers generated by photons may
recombine and enormously reduce the conversion efficiency.
Therefore there is an appropriate value of the thickness between
the absorption depth and the carrier diffusion length of the selected
materials, which we set to 200 nm, a typical value in the experi-
ment. By considering the absorption coefficient and thickness, the
PCE was calculated by using SLME (27.9%, 26.7% and 19.9% for
CsGeI3, CH3NH3PbI3 and CH3NH3SnI3 simulated by AM1.5G; 26.2%,
25.3% and 19.1% for CsGeI3, CH3NH3PbI3 and CH3NH3SnI3 simulated
by AM0). As shown in Fig. 9, the PCE simulated by SLME is lower
than that simulated by S-Q because there is no consideration of the
absorption in S-Q. For the short-circuit current density, open-circuit
voltage and fill factor of these materials (Table S3), CsGeI3
(0.017 Acm2 for JSC, 1.23 V for VOp and 89.9% for FF simulated by
AM1.5G; 0.022 Acm2 for JSC, 1.24 V for VOp and 90.0% for FF
simulated by AM0) and CH3NH3PbI3 (0.016 Acm2 for JSC, 1.27 V for
VOp and 90.1% for FF simulated by AM1.5G; 0.021 Acm2 for JSC,
1.28 V for VOp and 90.2% for FF simulated by AM0) possess higher
values than CH3NH3SnI3 (0.016 Acm2 for JSC, 1.02 V for VOp and
88.3% for FF simulated by AM1.5G; 0.020 Acm2 for JSC, 1.03 V for
VOp and 88.4% for FF simulated by AM0).
Putting all the theory calculations and simulations results and
experiments data together enables us to draw a clear overall picture
for the properties of the halide peroveskites. Based on the PCE of
halide peroveskites simulated by S-Q model, the results indicate
the PCE of perovskites (ABX3) increase from Cl to Br to I, because the
bandgap becomes narrower when X changes from Cl to Br to I. We
summarize the structure, optical properties, electrical properties,
as well as the PCE from the theoretical simulations and experi-
ments of iodic peroveskites in Table 2. From the results of Table 2,
we know that the structure of all iodic perovskites, including
FAPbI3, MAPbI3, MASnI3, CsSnI3, FASnI3 and CsGeI3, possess 3D
framework, which benefits the charge carrier transport of these
perovskites.
In addition, except for CsSnI3, other iodic perovskites show the
polarity in their band structures which results in the internal
junction to aid electron-hole separation [59]. This is one of the
 J. Qian et al. / Organic Electronics 37 (2016) 61e73 71

Table 2
A summarization the bandgap, transition behavior, absorption spectrum, effective mass, polarity of crystal and SOC of iodic perovskites.

FAPbI3c MAPbI3c MASnI3 CsSnI3 FASnI3 CsGeI3

Structure Framework 3D 3D 3D 3D 3D 3D
Polarity Yes Yes Yes No Yes Yes
Optical properties Bandgap Well Well Well Well Well Well
Transition Direct Direct Direct Direct Direct Direct
Absorption Well Well Poor Middle Middle Well
Electrical properties Effective mass of carriers Equal Equal Unequal Unequal Unequal Equal
Other properties SOC Strong Strong Middle Middle Middle Weak
PCEa Theoryb 26.4% 26.7% 19.9% 25.6% 26.9% 27.9%
Experiment 16.4% [56] 22.1% [5] 5.2% [9] 0.1e2% [11] 0.1% [58]
20.2% [57] 6.4% [10] 3.2% [13]
a
Simulated under AM1.5G.
b
Simulated by SLME model.
c
FA ¼ CH(NH2)2 and MA ¼ CH3NH3.

reasons that the stimulation of PCE shows the similar result for
CsSnI3 perovskites (25.6%) and MASnI3 perovskites (19.9%), but only
0.1% (2% doping by F) of the PCE for CsSnI3 perovskites was achieved
from the experiment, which is much lower than that of MASnI3
perovskites (6.4%).
The bandgap of all the iodic perovskites is within 1e1.6 eV,
which is the most suitable value for the absorber of solar cells based
on both S-Q and SLME models. All the iodic perovskites are the
direct-band-gap materials, whose electronic transition from VBM
to CBM does not need the help of phonon.
The absorption coefficient of the iodic perovskites containing Pb
and Ge near the solar spectrum is similar. But the absorption co-
efficient of Sn perovskites is lower than that of Pb and Ge perov-
skites, and CH3NH3SnI3 shows very poor absorption coefficient,
especially.
In addition, CH3NH3PbI3 and CsGeI3 perform a balanced
electron-hole-transport (0.14:0.19 for CsGeI3 and 0.12:0.12 for
CH3NH3PbI3) due to the approximate effective mass of electrons
and holes, while the effective mass for the holes of Sn perovskites is
rather smaller than the electronic effective mass (0.17:0.04 for
CH3NH3SnI3), which may cause the unbalanced electron-hole-
transport.
The differences of the optical and electrical properties of Pb, Sn
and Ge perovskites could be originated from the different electronic
structure of perovskites. Among the halide perovskites, the elec-
tronic structure of Ge perovskites is almost the same as that of Pb
perovskites with a small energy difference between the
nonbonding orbital and antibonding orbital, but is different from
that of Sn perovskites because of the different outer-shell orbital
energy levels of Ge, Pb and Sn.
The effect of SOC for Pb, Sn and Ge perovskites is strong, middle
and weak, respectively owing to the difference of the nuclear
charge number of Pb, Sn and Ge. Although Ge perovskites exhibit
the weak effect of SOC, which may reduce its conductivity, the in-
fluence of SOC on the photovoltaic performance is unclear.
As a result, the experimental PCE of Pb perovskites is close to the
theoretical value, i.e., the PCE of CH3NH3PbI3 is 19.7% in experiment
and 26.7% in theory, and that of CH(NH2)2PbI3 is 20.2% in experi-
ment and 26.4% in theory, respectively. While Sn perovskites pre-
sent a lower experimental PCE compared with the theoretical
values, due to the poor absorption, unbalanced electron-hole-
transport and more defects (oxidation easily). It is worthy to note
that CsGeI3 possesses the similar optical and electrical properties as
Pb perovskites. However, up to date, the best experimental PCE of
CsGeI3 is 3.2%, which still exhibits a huge gap from the theoretical
value of 27.9% and needs to be optimized the design and fabrication
of the related devices.
4. Conclusions
We investigate the comprehensive properties of halide perov-
skites ABX3 (A ¼ CH3NH3, CH(NH2)2, Cs, Rb; B ¼ Pb, Sn, Ge; X ¼ I, Br,
Cl, F) by DFT calculations. The electronic structure, SOC, absorption
spectrum, effective masses of charge of halide perovskites ABX3 are
calculated to provide in-depth understanding of the relationship
between the structure of halide perovskites and their photovoltaic
properties. From the optical and electrical property point of view,
Ge perovskites possess a similar absorption spectrum and carrier
transport properties with Pb perovskites, however, Sn perovskites
present a low absorption coefficient near the solar spectrum and an
unbalanced electron and hole transport properties, which preju-
dices the photovoltaic properties.
The theoretical values of PCE of halide perovskites are simulated
by introducing S-Q and SLME model and compared with the
experimental values of halide perovskites. The enhanced exchange-
correlation energy in halogen with small atomic number, from Cl to
Br to I, decreases the bandgap and thus significantly increases the
PCE of perovskites. The introduction of I interstitials as the halide
into perovskites will lead to the best performance of solar cells in
both theoretical and experimental data. Notably, among the pe-
rovskites with I interstitials, the theoretical PCE of Ge perovskites is
close to that of Pb perovskites, and a little higher than Sn perov-
skites. The investigation and understanding in the present work
will provide the theoretical foundation for exploring and devel-
oping the lead free halide perovskites as high performance solar
cells materials.
Acknowledgements
This work was supported by 973 Program (2014CB643506), the
Natural Science Foundation of China (No. 21221063), Program for
Chang Jiang Scholars and Innovative Research Team in University
(No. IRT101713018) and Program for Changbaishan Scholars of Jilin
Province. We thank the China Scientific Computing Grid (ScGrid)
for computing services.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.orgel.2016.05.046.
References
[1] A. Kojima, K. Teshima, Y. Shirai, T. Miyasaka, Organometal halide perovskites
as visible-light sensitizers for photovoltaic cells, J. Am. Chem. Soc. 131 (2009)
6050e6055.
[2] N. Cai, S.J. Moon, L. Cevey-Ha, T. Moehl, R. Humphry-Baker, P. Wang,
72 J. Qian et al. / Organic Electronics 37 (2016) 61e73
S.M. Zakeeruddin, M. Gratzel, An organic d-pi-a dye for record efficiency solid-
state sensitized heterojunction solar cells, Nano Lett. 11 (2011) 1452e1456.
[3] M.Z. Liu, M.B. Johnston, H.J. Snaith, Efficient planar heterojunction perovskite
solar cells by vapour deposition, Nature 501 (2013) 395e398.
[4] N.J. Jeon, J.H. Noh, W.S. Yang, Y.C. Kim, S. Ryu, J. Seo, Compositional engi-
neering of perovskite materials for high-performance solar cells, Nature 517
(2015) 476e480.
[5] Best Research-Cell Efficiencies, www.nrel.gov/ncpv/images/efficiency_chart.
jpg (accessed: April 2016).
[6] H.S. Jia, L. Luo, B.L. Li, Z.H. Xu, X.K. Ren, Y.S. Jiang, L. Cheng, C.Y. Zhang, Per-
formance of polycrystal silicon color solar cells, Acta Phys. Sin. 62 (2013),
168802e168802.
[7] S.D. Stranks, G.E. Eperon, G. Grancini, C. Menelaou, M.J.P. Alcocer, T. Leijtens,
L.M. Herz, A. Petrozza, H.J. Snaith, Electron-hole diffusion lengths exceeding 1
micrometer in an organometal trihalide perovskite absorber, Science 342
(2013) 341e344.
[8] I. Deretzis, A. Alberti, G. Pellegrino, E. Smecca, F. Giannazzo, N. Sakai,
T. Miyasaka, A. La Magna, Atomistic origins of CH3NH3PbI3 degradation to
PbI2 in vacuum, Appl. Phys. Lett. 106 (2015) 6050e6055.
[9] F. Hao, C.C. Stoumpos, D.H. Cao, R.P.H. Chang, M.G. Kanatzidis, Lead-free solid-
state organic-inorganic halide perovskite solar cells, Nat. Phot. 8 (2014)
489e494.
[10] N.K. Noel, S.D. Stranks, A. Abate, C. Wehrenfennig, S. Guarnera, A. Haghighirad,
A. Sadhanala, G.E. Eperon, S.K. Pathak, M.B. Johnston, Lead-free organ-
iceinorganic tin halide perovskites for photovoltaic applications, Energy En-
viron. Sci. 9 (2014) 3061e3068.
[11] M.H. Kumar, S. Dharani, W.L. Leong, P.P. Boix, R.R. Prabhakar, T. Baikie, C. Shi,
H. Ding, R. Ramesh, M. Asta, M. Graetzel, S.G. Mhaisalkar, N. Mathews, Lead-
free halide perovskite solar cells with high photocurrents realized through
vacancy modulation, Adv. Mater. 26 (2014) 7122.
[12] D. Sabba, H.K. Mulmudi, R.R. Prabhakar, T. Krishnamoorthy, T. Baikie, P.P. Boix,
S. Mhaisalkar, N. Mathews, Impact of anionic BreSubstitution on open circuit
voltage in lead free perovskite (CsSnI3-xBrx) solar cells, J. Phys. Chem. C 119
(2015) 1763e1767.
[13] P.P. Boix, S. Agarwala, T.M. Koh, N. Mathews, S.G. Mhaisalkar, Perovskite solar
cells: beyond methylammonium lead iodide, J. Phys. Chem. Lett. 6 (2015)
898e907.
[14] X. Zhu, H.B. Su, R.A. Marcus, M.E. Michel-Beyerle, Computed and experimental
absorption spectra of the perovskite CH3NH3PbI3, J. Phys. Chem. Lett. 5
(2014) 3061e3065.
[15] M.H. Du, Efficient carrier transport in halide perovskites: theoretical per-
spectives, J. Mater. Chem. A 2 (2014) 9091e9098.
[16] C.C. Stoumpos, L. Frazer, D.J. Clark, Y.S. Kim, S.H. Rhim, A.J. Freeman,
J.B. Ketterson, J.I. Jang, M.G. Kanatzidis, Hybrid germanium iodide perovskite
semiconductors: active lone pairs, structural distortions, direct and indirect
energy gaps, and strong nonlinear optical properties, J. Am. Chem. Soc. 137
(2015) 6804e6819.
[17] B. Saparov, F. Hong, J.P. Sun, H.S. Duan, W.W. Meng, S. Cameron, I.G. Hill,
Y.F. Yan, D.B. Mitzi, Thin-film preparation and characterization of Cs3Sb2I9: a
lead-free layered perovskite semiconductor,, Chem. Mater. 27 (2015)
5622e5632.
[18] G. Kresse, J. Furthmüller, Efficient iterative schemes for ab initio total-energy
calculations using a plane-wave basis set, Phys. Rev. B 54 (1996)
11169e11186.
[19] M.C. Payne, M.P. Teter, D.C. Allen, T.A. Arias, J.D. Joannopoulos, Iterative
minimization techniques for ab initio total-energy calculations: molecular
dynamics and conjugate gradients, Rev. Mod. Phys. 64 (4) (1992) 1045e1097.
[20] B. PE, Projector augmented-wave method, Phys. Rev. B 50 (1994)
17953e17979.
[21] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made
simple, Phys. Rev. Lett. 77 (1996) 3865e3868.
[22] J. Heyd, G.E. Scuseria, M. Ernzerhof, Hybrid functionals based on a screened
Coulomb potential, J. Chem. Phys. 118 (2003) 8207e8215.
[23] L.C. Tang, C.S. Chang, J.Y. Huang, Electronic structure and optical properties of
rhombohedral CsGeI3 crystal, J. Phys. Condens. Matter 12 (2000) 9129e9143.
[24] C.T. Lee, W.T. Yang, R.G. Parr, Development of the Colle-Salvetti correlation-
energy formula into a functional of the electron density, Phys. Rev. Lett. 37
(1988) 785e789.
[25] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb,
J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson,
H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino,
G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda,
J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven,
J.A. Montgomery Jr., J.E. Peralta, F. Ogliaro, M.J. Bearpark, J. Heyd, E.N. Brothers,
K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari,
A.P. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, N.J. Millam,
M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts,
R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski,
R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador,
J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. € Farkas, J.B. Foresman, J.V. Ortiz,
J. Cioslowski, D.J. Fox, Gaussian 09, Gaussian, Inc., Wallingford, CT, USA, 2009.
[26] W.J. Yin, T.T. Shi, Y.F. Yan, Unique properties of halide perovskites as possible
origins of the superior solar cell performance, Adv. Mater. 26 (2014)
4653e4658.
[27] P. Umari, E. Mosconi, F. De Angelis, Relativistic GW calculations on
CH3NH3PbI3 and CH3NH3SnI3 perovskites for solar cell applications, Sci. Rep.
4 (2014), 4467e4467.
[28] W. Shockley, H.J. Queisser, Detailed balance limit of efficiency of p-n junction
solar cells, J. Appl. Phys. 32 (1961) 510e519.
[29] L.P. Yu, A. Zunger, Identification of potential photovoltaic absorbers based on
first-principles spectroscopic screening of materials, Phys. Rev. Lett. 108
(2012) 1e5.
[30] S.C. Tidrow, Mapping comparison of Goldschmidt’s tolerance factor with
perovskite structural conditions, Ferroelectrics 470 (2014) 13e27.
[31] C.C. Stoumpos, C.D. Malliakas, J.A. Peters, Z. Liu, M. Sebastian, J. Im,
T.C. Chasapis, A.C. Wibowo, D.Y. Chung, A.J. Freeman, B.W. Wessels,
M.G. Kanatzidis, Crystal growth of the perovskite semiconductor CsPbBr3: a
new material for high-energy radiation detection, Cryst. Growth Des. 13
(2013) 2722e2727.
[32] O.N. Yunakova, V.K. Miloslavsky, E.N. Kovalenko, V.V. Kovalenko, Effect of
structural phase transitions on the exciton absorption spectrum of thin
CsPbCl3 films, Low. Temp. Phys. 40 (2014) 690e693.
[33] 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)
9019e9038.
[34] Y. Takahashi, R. Obara, Z.Z. Lin, Y. Takahashi, T. Naito, T. Inabe, S. Ishibashi,
K. Terakura, Charge-transport in tin-iodide perovskite CH3NH3SnI3: origin of
high conductivity, Dalton Trans. 40 (2011) 5563e5571.
[35] C. Bernal, K. Yang, First-principles hybrid functional study of the organ-
iceinorganic perovskites CH3NH3SnBr3and CH3NH3SnI3, J. Phys. Chem. C
118 (2014) 24383e24388.
[36] F. Chiarella, A. Zappettini, F. Licci, I. Borriello, G. Cantele, D. Ninno,
A. Cassinese, R. Vaglio, Combined experimental and theoretical investigation
of optical, structural, and electronic properties ofCH3NH3SnX3thin
films(X¼Cl,Br), Phys. Rev. B 77 (2008) 045129e045135.
[37] R. Mosca, P. Ferro, T. Besagni, D. Calestani, F. Chiarella, F. Licci, Effect of hu-
midity on the a.c. impedance of CH3NH3SnCl3 hybrid films, Appl. Phys. A 104
(2011) 1181e1187.
[38] G. Murtaza, I. Ahmad, M. Maqbool, H.A.R. Aliabad, A. Afaq, Structural and
optoelectronic properties of cubic CsPbF3for novel applications, Chin. Phys.
Lett. 28 (2011) 117803e117807.
[39] Y. Yamane, K. Yamada, K. Inoue, Mechanochemical synthesis and orderedis-
order phase transition in fluoride ion conductor RbPbF3, J. Phys. Chem. C
Nanomater. Interfaces Solid State Ionics 179 (2008) 605e610.
[40] W.J. Yin, T. Shi, Y. Yan, Unique properties of halide perovskites as possible
origins of the superior solar cell performance, Adv. Mater. 26 (2014)
4653e4661.
[41] T. Baikie, N.S. Barrow, Y.A. Fang, P.J. Keenan, P.R. Slater, R.O. Piltz, M. Gutmann,
S.G. Mhaisalkar, T.J. White, A combined single crystal neutron/X-ray diffrac-
tion and solid-state nuclear magnetic resonance study of the hybrid perov-
skites CH3NH3PbX3 (X ¼ I, Br and Cl), J. Mater. Chem. A 3 (2015) 9298e9307.
[42] C. Bernal, K.S. Yang, First-principles hybrid functional study of the organic-
inorganic perovskites CH3NH3SnBr3 and CH3NH3SnI3, J. Phys. Chem. C 118
(2014) 24383e24388.
[43] M.L. Agiorgousis, Y.Y. Sun, H. Zeng, S. Zhang, Strong covalency-induced
recombination centers in perovskite solar cell material CH3NH3PbI3, J. Am.
Chem. Soc. 136 (2014) 14570e14575.
[44] R.G.P.a.W. Yang, Density-functional Theory of Atoms and Molecules, OUP,
USA, 1995.
[45] W.J. Yin, J.H. Yang, J. Kang, Y. Yan, S.H. Wei, Halide perovskite materials for
solar cells: a theoretical review, J. Mater. Chem. A 3 (2014) 8926e8942.
[46] 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) 2999e3005.
[47] H.C. Siegmann, Magnetism, Springer, 2010.
[48] M.H. Du, D.J. Singh, Enhanced Born charge and proximity to ferroelectricity in
thallium halides, Phys. Rev. B 81 (2010).
[49] S.A. Kulkarni, T. Baikie, P.P. Boix, N. Yantara, N. Mathews, S. Mhaisalkar, Band-
gap tuning of lead halide perovskites using a sequential deposition process,
J. Mater. Chem. A 2 (2014) 9221e9225.
[50] Z.G. Lin, L.C. Tang, C.P. Chou, Characterization and properties of infrared NLO
crystals: AGeX3 (A¼Rb, Cs; X¼Cl, Br), J. Cryst. Growth 310 (2008) 3224e3229.
[51] I. Borriello, G. Cantele, D. Ninno, Ab initio investigation of hybrid organic-
inorganic perovskites based on tin halides, Phys. Rev. B 77 (2008),
235214e223523.
[52] T. Baikie, N.S. Barrow, Y. Fang, P.J. Keenan, P.R. Slater, R.O. Piltz, M. Gutmann,
S.G. Mhaisalkar, T.J. White, A combined single crystal neutron/x-ray diffrac-
tion and solid-state nuclear magnetic resonance study of the hybrid perov-
skites CH3NH3PbX3 (X ¼ I, Br and Cl), J. Mater. Chem. A 3 (2015) 9298e9307.
[53] M.A. Green, Third generation photovoltaics. Advanced solar energy conver-
sion, Phys. Today 57 (2004) 71e72.
[54] W. Christian, G.E. Eperon, M.B. Johnston, H.J. Snaith, L.M. Herz, High charge
carrier mobilities and lifetimes in organolead trihalide perovskites, Adv.
Mater. 26 (2014) 1584e1589.
[55] I. Chung, J.H. Song, J. Im, J. Androulakis, C.D. Malliakas, H. Li, A.J. Freeman,
J.T. Kenney, M.G. Kanatzidis, CsSnI3: semiconductor or metal? High electrical
conductivity and strong near-infrared photoluminescence from a single ma-
terial. High hole mobility and phase-transitions, J. Am. Chem. Soc. 134 (2012)
8579e8587.
 J. Qian et al. / Organic Electronics 37 (2016) 61e73 73

[56] S. Wozny, M.J. Yang, A.M. Nardes, C.C. Mercado, S. Ferrere, M.O. Reese,
W.L. Zhou, K. Zhu, Controlled humidity study on the formation of higher ef-
ficiency formamidinium lead triiodide-based solar cells, Chem. Mater. 27
(2015) 4814e4820.
[57] W.S. Yang, J.H. Noh, N.J. Jeon, Y.C. Kim, S. Ryu, J. Seo, I.S. Sang, High-perfor-
mance photovoltaic perovskite layers fabricated through intramolecular ex-
change, Science 348 (2015) 1234e1237.
[58] K. Thirumal, H. Ding, C. Yan, L.L. Wei, T. Baikie, L. Zhang, M. Sherburne, S. Li,
M. Asta, N. Mathews, Lead-free germanium iodide perovskite materials for
photovoltaic application, J. Mater. Chem. A 3 (2015) 23829e23832.
[59] 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) 2584e2590.