Journal of Luminescence 131 (2011) 17531757

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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Electronic structure calculations and optical properties of a new

organicinorganic luminescent perovskite: (C9H19NH3)2PbI2Br2
H. Abid a,c,n, A. Samet a, T. Dammak a, A. Mlayah b, E.K. Hlil c, Y. Abid a
a

e, Faculte des sciences, Universite de Sfax, Tunisie

Laboratoire de Physique Applique
Centre dElaboration de Materiaux et dEtudes Structurales (CEMES), CNRSUniversite de Toulouse, 29 rue Jeanne Marvig, 31055 Toulouse, France
c
el, CNRSUniversite J. Fourier, BP 166, 38042 Grenoble, France
Institut Ne
b

a r t i c l e i n f o

abstract

Article history:
Received 16 June 2010
Received in revised form
5 March 2011
Accepted 8 March 2011
Available online 31 March 2011

(C9H19NH3)2PbI2Br2 compound is a new crystal belonging to the large hybrid organicinorganic

perovskites compounds family. Optical properties are investigated by optical absorption UVvisible
and photoluminescence (PL) techniques. Bands to band absorption peak at 2.44 eV as well as an
extremely strong yellowgreen photoluminescence emission at 2.17 eV is observed at room temperature. First principle calculations based on the DFT and FLAPW methods combined with LDA
approximation are performed as well. Density of state close to the gap is presented and discussed in
terms of optical absorption and photoluminescence experimental results. The perfect agreement
between experimental data and electronic structure calculations is highlighted.
& 2011 Elsevier B.V. All rights reserved.

Keywords:
Absorption
Photoluminescence
Exciton
Electronic structure calculations
DFT
FLAPW

1. Introduction
Recently, layered organicinorganic hybrid perovskite materials
have attracted substantial attention due to their unique electrical,
optical and magnetic properties as well as their excellent lm
process ability [19]. The perovskite compounds based on the
chemical formula (RNH3)2PbX4 and (NH3RNH3)2 MX4 (Rorganic
group; Xhalogen) naturally form a multi-quantum-well structure,
where the two-dimensional inorganic semiconductor layers of PbX4
correspond to the wells and the organic layers act as barriers (with
small dielectric constant and much larger band gap energy). For
example, the dielectric constants of the inorganic and organic layers
are ew 6.1 and eb 2.1, respectively, in PhEPbI4 [10]. The two
dimensionality of the layered structure combined with the dielectric
connement effect enables the formation of a stable exciton with a
large binding energy of several hundred meV in the inorganic
semiconductor layer of PbX4 [1114]. Several attractive optical
properties are induced by the exciton presence such as efcient
photoluminescence at room temperature [1519]. As a consequence,
their unusual semiconducting properties have been widely studied

Corresponding author at: Laboratoire de Physique Appliquee, Faculte des

sciences, Universite de Sfax, Tunisie.
Tel.: 216 21 121 192; fax: 216 73 27 34 37.
E-mail address: haithamlpa@yahoo.fr (H. Abid).
0022-2313/$ - see front matter & 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jlumin.2011.03.034

and used for photoluminescence materials, thin-lm eld-effect

transistors, electroluminescent devices, etc. [8,2022].
Hybrid organic/inorganic perovskite naturally forms a periodic
two-dimensional quantum well structure with alternating organic
(not displayed in Fig. 1) and inorganic layers. Each inorganic layer,
consisting of a sheet of PbI2Br4 octahedra of a single-atom scale
thickness, serves as a quantum well which has a large quantum size
connement of electrons and holes [23]. We consider such organic
inorganic layered compound, with two dimensionality and strong
electronhole correlation, to be an interesting system for exciton
studies in two dimensions.
In the present work, we report on the optical properties of new
self-organized organicinorganic (C9H19NH3)2PbI2Br2 compound.
Optical absorption UVvisible and photoluminescence (PL) measurements were performed. In addition, electronic structure of
the title compound is investigated and discussed using DFT
theory and then compared to experimental data.

2. Sample preparation and characterization

(C9H19NH3I) precipitates are rst formed by adding an aqueous
solution of HI (aqueous solution, 57%) to nonylamine (C9H19NH2).
Next, (C9H19NH3 I  )/PbBr2 in a molar ratio of 2:1 are dissolved
in N, N-dimethylformamide (DMF). The obtained solution is kept at
room temperature. Two weeks later, platelet crystals are formed.

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H. Abid et al. / Journal of Luminescence 131 (2011) 17531757

potential method. The core electrons were described by atomic

wave functions, which can be solved relativistically.

5. Results and discussion

5.1. Optical study

Fig. 1. Schematic picture of the (C9H19NH3)2PbI2Br2 crystal structure. NH3 heads

(not shown) are located at the cavities of octahedra, and alkyl tails (not shown)
extend toward both sides of inorganic layers.

The X-ray powder diffraction (XRPD) was examined on a Enraf

operNonius diffractometer using Mo Ka radiation (l 0.71073 A)
ated in the y2y Bragg geometry. The diffractogram of
(C9H19NH3)2PbI2Br2 compound is indexed on monoclinic space
b8.8441 A,
c23.0031 A and
group P21/m with a25.2331 A,
b 104.01401. The structure on single crystal was not very well
resolved because of the quality of the crystal; however, for DFT
calculations, we have used atomic positions of metal halide sublattice from the structure of homologue compound [24]. A schematic
unit-cell is given in Fig. 1 (organic part not displayed).

The UVvisible optical absorption and photoluminescence

spectra of the (C9H19NH3)2PbI2Br2 lm, measured at room temperature, are presented in Fig. 2. As shown a strong absorption
band centered at 2.44 eV and a yellowgreen luminescence at
2.17 eV are observed.
The exhibited yellow luminescence at 2.17 eV, when excited at
488 nm, is strong and can be observed even at room temperature
with naked eye. The exciton luminescence originates from the
electronic transitions within the inorganic perovskite layer, rather
than the organic layer, since the simple organic molecules being
employed are optical by inert (transparent in the visible spectral
region) [27]. The Stokes shift (270 meV) of UVvisible absorption
and PL emission spectra is due to the exciton binding energy.
In the layered (C9H19NH3)2PbI2Br2 material, the lowest exciton
state arises from the excitations between the valence band (VB)
consisting of a mixture of Pb (6s) and I (5p) orbitals states, and the
conduction band (CB) derived mainly from the Pb (6p) orbital. The
energy of Br (4p) orbital is lower than that of the I (5p). That is
why; excitonic transitions of PbBr type are expected at higher
energy than those of PbI type. Therefore, excitonic transitions of
PbI-type are observed experimentally for the pure compound.
Thus, the only one peak, attributed to the PbI type exciton
observed in photoluminescence emission, is certainly due to the
fast relaxation of the PbBr type excitons towards the lower
energy.
A simple model illustrating the formation and recombination
process of the PbI2 type exciton is shown in Fig. 3. Under the
excitation of (488 nm) irradiation, an electron (e) is excited from
the valence band (VB) to the conduction band (CB), leaving a hole

3. Experimental measurements
Thin lm of microcrystalline (C9H19NH3)2PbI2Br2 was synthesized on glass (SiO2) substrate by a spin-coater (WS-400B-6NPPLITE_I) at 400 rpm and for 45 s duration [25]. Optical absorption
spectrum of this thin lm was measured using a conventional
UVvisible spectrometer (Hitachi, U1100 spectrophotometer).
Incident light beam was kept perpendicular to the substrate
surface. Photoluminescence (PL) was measured on single crystals
using a monochromatic argon laser (488 nm). Laser spot was
focused on the sample using an  100 microscope objective and
all measurements were carried out at room temperature.

Fig. 2. Photoluminescence (PL) spectrum of single crystals (C9H19NH3)2PbI2Br2,

optical absorption (Abs) spectrum of spin-coated (C9H19NH3)2PbI2Br2 lm.

4. Electronic structure calculations

We used the full potential linearized augmented plane wave
(FLAPW) method [26]which performing DFT calculations on the
basis of the local density approximation (LDA). The KohnSham
equation and energy functional were evaluated self-consistently. For
these calculations, the space was divided into the interstitial and the
non-overlapping mufn tin spheres centered on the atomic site. The
basis function inside each atomic sphere was a linear expansion
of the radial solution of a spherical potential multiplied by spherical
harmonics. In the interstitial region, the wave function was
expanded into plane waves and no shape approximation for the
potential was introduced in this region consistent with the full

Fig. 3. Simple model for the formation and recombination of the exciton in
(C9H19NH3)2PbI2Br2.

H. Abid et al. / Journal of Luminescence 131 (2011) 17531757

( ) in the VB. The electron (  ) and the hole move freely in the CB
and VB, forming an exciton. The recombination of the electron
and the hole in the exciton yields a yellowgreen emission at
2.17 eV (570 nm). The prominent feature of the exciton state in
this system is the exceptionally large binding energy 270 meV
(2.442.17eV0.27 eV). According to the studies in Ref.
[8,1519], the enhancement is due to the unusual alternate
organicinorganic layered structure enabling the exciton state
to be very stable even at room temperature.
As already pointed out in many published works devoted to
the optical properties of organicinorganic perovskites, the rather
large exciton binding energy in these materials, in reference to
semiconductor materials, is due to a natural multi-quantum-well
structure combined with a dielectric connement effect.
The UVVis absorption peak mainly consists of one band with
maximum at 2.44 eV. The former is due to band gap absorption
and it is assigned to the excitation of free electron-hole pairs
within the [PbI4Br2]4  octahedral. This peak is due mainly to the
absorption between Pb (6p) and [Pb (6s)I (5p)] (band to band).
Now, we will be interested in the electronic structure calculations
to see how these experimental results will agree with theoretical
conclusions.

1755

Fig. 4. Total DOS of Cs2PbI2Br2 compound.

5.2. Electronic structure calculations

Electronic structure calculations have been performed for the
title compound using the very accurate full potential linearized
augmented plane wave (FLAPW) method. According to earlier
study using various methods to simulate the positive charge, our
positive charge carried by organic entities was simulated by
placing a cesium atom (Cs) on the ammonium site [28,29]. The
unit-cell parameters and atomic positions used for calculations
are listed in Table 1. DOS obtained from WIEN2k (inorganic
part cesium) will be compared with experimental results to
conrm and to justify the use of alkaline metal (Cs). Electronic
properties (gap and permitted excitonic levels) are roughly
imposed by the inorganic parts, while the cationic organic entities
do not contribute and can only inuence the geometry of the
inorganic structure. So, having found a way to properly describe
the charge of organic cations [29], DOS can be calculated keeping
only the inorganic component. The full potential WIEN2k code
[30], known as a Benchmark in DFT-based band structure calculations, has been used for this purpose. The RMTkMAX 7.0 condition
was used to dene the size of the basis set considering the

following mufn tin radii: RMT(Pb) 2.7 Aand

RMT(I) 2.5 A,
RMT(Cs)2.9 A.
The (10  11  2) k-point densities
RMT(Br)2.4 A,
were included as well.
Here, our aim is not only to simulate absorption from WIEN2k
code but also to understand transitions involved in optical
absorption and photoluminescence phenomena as well from
DOS analysis in zone close to the Fermi level [31]. In this respect,
total density of state (TDOS) calculated for (C9H19NH3)2PbI2Br2
crystal is presented in Fig. 4. It mainly originates from the
projected DOS on Br and I atoms in the valence band, as seen in
Fig. 5, whereas the projected DOS on Cs prevails in unoccupied
states. Analysis details of the projected DOS on atoms reported in
Table 1
Atomics positions (C9H19NH3)2PbI2Br2 compound used for DFT calculations.
Atom

Pb
I
Br
Cs

0.000000
0.681612
0.064939
0.409310

0.000000
0.194493
0.073822
0.131023

0.000000
0.984155
0.081932
0.595534

Fig. 5. Projected DOS on Pb atom in Cs2PbI2Br2 compound and the corresponding

l-decomposed DOS of like-states s, p, d and f.

Fig. 6. Projected DOS on I atom in Cs2PbI2Br2 compound and the corresponding

l-decomposed DOS of like-states s, p, d and f.

Figs. 68 give evidence that the valence band of TDOS originates

mainly from like-states Br (4p) and I (5p) whereas the conduction
band contains almost uniquely like-states Cs (5p). Fermi level,
taken as reference, is localized at the valence band top and the
presence of gap, estimated at 2.17 eV, points to the semiconductor character of this compound. This gap corresponds to the
visible light absorption energy. Projected DOS examination points
to the fact that all atoms Br, Pb and I in (C9H19NH3)2PbI2Br2 are
expected to contribute to visible light absorption involving
transitions between valence bands (full bands) and conduction
bands (empty bands), verifying Dl 71 selections rules; where l
is the orbital quantum number. Gap from calculations agrees
nicely with observed peak at 2.17 eV in photoluminescence

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H. Abid et al. / Journal of Luminescence 131 (2011) 17531757

Fig. 7. Projected DOS on Br atom in Cs2PbI2Br2 compound and the corresponding

l-decomposed DOS of like-states s, p, d and f.

Fig. 9. Details, with appropriate scale close to the Fermi level, of l-decomposed
DOS of like-states s, p and d of Br atom in Cs2PbI2Br2.

Fig. 8. Projected DOS of Pb, I and Br in Cs2PbI2Br2 compound for comparison.

Fig. 10. Details, with appropriate scale close to Fermi level, of l-decomposed DOS
of like-states s, p and d of I atom in Cs2PbI2Br2.

measurements and not to 2.44 eV as expected from absorption

experiment.
Taking into account that excitation energy is 2.54 eV, all rst
transitions, with Dl 71, on one hand from the Fermi level to
level at 2.44 eV, and, on the other, from level energies lower than
the Fermi level to levels at 2.44 eV, are permitted since, in both
cases, the energy transition is equal to 2.54 eV. First electrons at
2.17 eV are expected to immediately transit back to the Fermi
level; hence they contribute to recorded photoluminescence peak
at 2.17 eV. The remaining electrons having energy greater than
2.17 eV start rstly to undergo continuous loss energy due to
their collisions with vibrating atoms and progressively come to
the conduction band onset at 2.17 eV before their transition to
Fermi level. As a consequence, levels at 2.17 are full and no
additional transitions from levels lower than Fermi level to
2.17 eV are permitted. Only transitions from Fermi level to levels
higher and closer to 2.44 eV are still not forbidden. Lifetime of
electrons implied in rst transition from Fermi the level is very
short to be observed and only additional transitions from levels
lower than the Fermi level to level at 2.44 eV should be detected.
From the point of view of this picture, measured gap should be
equal to 2.44 and not to 2.17 eV as calculated by the FLAPW
method.
Here we have to pay attention that both approaches, experiment and calculations, agree perfectly and conclude that observed
exciton involves transitions from conduction band onset at
2.17 eV to the Fermi level in photoluminescence process.
Now, we will analyze from which atoms transitions inducing
the exciton, are originating. For this purpose, small projected DOS
of I and Br are displayed in Figs. 9 and 10, respectively, with
appropriate scale to estimate their contributions. It is worth

noticing that transitions for exciton take place from p in conduction band to s in valence band according to Dl 71 selection
rules. Analysis of Fig. 9 gives evidence that transitions between s
and p of Br do not contribute to the observed exciton since their
corresponding energy is higher than the exciton energy . As seen
in Figs. 6 and 10, both p band conduction and s band valence of Pb
and I atoms are separated by a gap of 2.17 eV and transitions
inducing the observed exciton are expected to be accomplished
between these bands (from p to s). This conclusion is only from
the point of view of selection rules. If we consider the magnitude
of the transition, related, as known theoretically, to squared
modulus of probability transition, it is more probable that the
observed exciton is induced by transition from p states to s states
of Br atom since these states are more magnicent than I ones as
we can see in Figs. 6 and 10. In addition, detailed TDOS analysis
enables a rough estimate of the energy binding of the feature
ascribed to the exciton. large value of 270 eV can be reasonably
deduced and it is worth underlining that this calculated value
agrees with that estimated previously from our measurements.

6. Conclusion
In this study, a new two-dimensional nano-hybrid material
with the general formula (C9H19NH3)2PbI2Br2 has been synthesized as thin lms by spin coated and single crystal methods.
Their optical properties have been investigated. Both absorption
peaks and a strong yellowgreen luminescence, with substantially large exciton binding energy at room temperature, are
observed. Electronic structure calculations based on DFT principle
are performed using the FLAPW method as well. They explain that

H. Abid et al. / Journal of Luminescence 131 (2011) 17531757

the observed peak at 2.44 eV is assigned to the light absorption

involving transitions from valence band to conduction band for at
least all heavy atoms. The exciton observed at 2.17 eV in photoluminescence process, as well as its large binding energy, is
asserted by calculations. In addition, transitions from Br (4p)
like-states in conduction band to Br (4s) like-states in valence
band are highlighted as the main transitions implied in exciton
phenomena.
Based on these concluding remarks, our new yellow single
crystals are considered as potential candidates for future optical
device applications with the organicinorganic hybrid perovskite
materials.

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