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Materials Today: Proceedings 4 (2017) 5154–5160 www.materialstoday.com/proceedings

ISMAI 2016

Properties of Lead-Free Hybrid Organic-Inorganic Halide


Perovskite CH3NH3BX3 Using Density Functional Theory
N. Suhailia, M.F.M. Taiba,d, *, M.K. Yaakoba,d, O.H. Hassanb,d, M.Z.A. Yahyac,d
a
Faculty of Applied Sciences, Universiti Teknologi MARA 40450 Shah Alam, Malaysia
b
Department of Industrial Ceramics, Faculty of Art & Design, Universiti Teknologi MARA, 40450 Shah Alam, Malaysia
c
Faculty of Defence Science & Technology, Universiti Pertahanan Nasional Malaysia, 57000 Kuala Lumpur, Malaysia
d
Institute of Science, Universiti Teknologi MARA, 40450 Shah Alam, Malaysia

Abstract

First principles calculations on structural, electronic and optical properties of the orthorhombic phase (No. 62: Pnma space group)
lead-free Sn(II) hybrid halide perovskite CH3NH3SnI3 were systematically carried out. Work on Pb(II)-based CH3NH3PbI3 hybrid
halide perovskite of the same space group is also included for comparative purposes. All calculations were performed using the
local density approximation (LDA) and the generalized gradient approximation (GGA) schemes. The obtained lattice parameters
and cell volumes are consistent with the available experimental data and other theoretical works. According to the electronic
band structure, both of the semiconductor compounds have a direct band gap. A band gap of 0.935 eV yielded for CH3NH3SnI3
compound, which is smaller compared to CH3NH3PbI3 (1.721 eV). In addition, we found that the optical absorption spectrum of
the hybrid halide perovskite is red shifted with the reduction of the electronic band gap.
© 2017 Elsevier Ltd. All rights reserved.
Selection and Peer-review under responsibility of Conference Committee Members of International Symposium on Materials and
Asset Integrity (ISMAI 2016).

Keywords: Density Functional Theory; Electronic Properties; Optical Properties; Lead-Free

* Corresponding author. Tel.: +60355437833; Fax.: +60355444562


E-mail address: mfariz@salam.uitm.edu.my

2214-7853 © 2017 Elsevier Ltd. All rights reserved.


Selection and Peer-review under responsibility of Conference Committee Members of International Symposium on Materials and Asset Integrity
(ISMAI 2016).
N. Suhaili et al. / Materials Today: Proceedings 4 (2017) 5154–5160 5155

1. Introduction

The hybrid organic-inorganic halide perovskite, adopts the perovskite crystal structure. It has ABX3 general
chemical formula with organic cations occupied at the ‘A-site’, while ‘B-site’ commonly a large divalent metal
cations and the ‘X-site’ is the halide anions. Methylammonium lead iodide perovskite CH3NH3PbI3 is the first hybrid
halide perovskite that was fully identified several decades ago by Weber [1]. However, this compound only became
a considerable scientific attention in 2009 after its discovery as a potential visible light sensitizers for photovoltaics
by Miyasaka and coworkers [2]. The CH3NH3PbI3-based solar cells have made a splendid achievement in terms of
increased power-conversion efficiency (PCE) from 3.8% in 2009 to > 20% at the end of 2015 [3, 4]. This rapid
research progress, along with their unique properties such as high optical absorption coefficient, excellent charge
carrier mobility, tunable band gaps and low production cost have also made them a promising material to be
incorporated in other optoelectronic devices beyond photovoltaics viz. light-emitting diodes (LED), field-effect
transistor (FET), lasers and photodetectors [5–7]. However, one environmental challenge with this material is the
toxicity of lead in CH3NH3PbI3 hybrid halide perovskite compound. Therefore, the replacement of lead (Pb) in the
material is necessary to realize the commercialization and utilization of this class of materials in optoelectronic
industries. By moving up the group of 14 elements, the most possible substitutes for Pb(II) ions in hybrid halide
perovskite is the Sn(II) ions. Many studies have been done regarding to the Sn-based system from both theoretical
and experimental viewpoints [8–12]. Among the studies, there are only a few works that focused on the
orthorhombic phase of hybrid halide perovskite, as it is said to be less important in the practical applications.
However, from experimental perspectives, it has been reported that, orthorhombic phase at low temperature shows
no orientation disordered of the [CH3NH3]+ ions as compared to cubic and tetragonal phase [13, 14]. The organic
molecules in orthorhombic phase have fixed alignments which make it easier to be simulated in its true form, thus
enables us to have a relevant comparative study between the theoretical and experimental data. In this paper, we
present the first principles calculations based on Kohn-Sham approach on the ground state structural, electronic and
optical properties of CH3NH3BI3 (B= Pb, Sn) hybrid halide perovskite with orthorhombic structure (No. 62: Pnma
space group), where the conventional DFT calculations were performed at (T=0K). In order to replace Pb(II)
element in Pb-based hybrid halide perovskite, we perform the Sn-based material as an alternative and compare the
structural, electronic and optical properties with Pb-based material. This study would be helpful in providing a better
theoretical insight of the material properties.

2. Computational Details

The properties of orthorhombic (No. 62: Pnma space group) CH3NH3BI3 (B= Pb, Sn) hybrid halide perovskite
were investigated using density functional theory (DFT) [15] performed by applying the plane-wave pseudopotential
approach in Cambridge Serial Total Energy Package (CASTEP) computer code [16]. Periodic DFT calculations
were treated within the Kohn-Sham schemes of the local density approximation (LDA) by Ceperley and Alder [17]
as parameterized by Perdew and Zunger [18] (LDA-CAPZ) and semi-local generalized gradient approximation
(GGA) exchange-correlation functional. Typical functionals parameterized by Perdew-Burke-Ernzerhof (PBE) [19]
and Perdew-Burke-Ernzerhof revised for solid (PBEsol) [20] were adopted for semi-local GGA method. The
simulation cell made up of four repeated CH3NH3BI3 units which include 48 atoms for all calculations. Electron
orbital taken to be valence are 5d, 6s, 6p states of Pb atom and 5s, 5p states of Sn atom. The lattice constants and
atomic positions were fully optimized with the criterion that the calculated residual force, stress and displacement of
each atom are smaller than 0.01 eV/Å, 0.02 GPa and 5×10-4 Å, respectively. The total energy change was set to
5×10-6 eV/atom to relax the structural parameters and to ensure good convergence. Ultrasoft pseudopotential with an
energy cut-off of 310 eV was used to perform all calculations except for the evaluation of the optical properties, for
which a norm-conserving pseudopotential with an energy cut-off of 850 eV was selected. The reciprocal space
integration was sampled using a 2×2×2 Monkhorst-Pack grid [21]. Our convergence tests showed that, further
increase in plane-wave cut-off energy and grid parameter reveals little difference in the results, thus indicating those
values are good enough to be used.
5156 N. Suhaili et al. / Materials Today: Proceedings 4 (2017) 5154–5160

3. Results and Discussion

3.1. Structural Parameters

The unit cells of the low temperature orthorhombic phase (No. 62: Pnma space group) of CH3NH3BI3 (B= Pb,
Sn) hybrid halide perovskite are visualized in Fig. 1. This structure consists of a network of corner sharing [BI6]
octahedral of the B-site cations with the iodide anions and the organic cations [CH3NH3]+ locates in between the
octahedral corners. The lattice parameters optimized with different functionals are compared (Table 1) with the
available experimental values and other theoretical works. In general, the results of Pb-based CH3NH3PbI3
compound calculated using the LDA functional underestimates all the lattice parameters, while the GGA functional
overestimates them. Among the tested functionals, GGA-PBEsol shows the best agreement with the crystallographic
parameters with the percentage difference is less than 1.82%. The calculated structural parameters are acceptable as
we are comparing the calculated results with the experimental data obtained at 100 K. As mentioned before, the
ground state calculations using the DFT approach were performed at 0 K. Thus, the differences between our results
with the experimental data are as predicted. In addition, at low temperature, the lattice parameters of the
orthorhombic crystal vary only a little [14] which explained why the percentage difference is quite small. Our
results also agree with other theoretical values using different computer codes. In this paper, we also report the
structural parameters of Sn-based CH3NH3SnI3 perovskite. The lattice parameters and cell volumes of hybrid halide
perovskite are directly proportional to the radius of its metal site. As the atomic size decreases from Pb to Sn atom,
the lattice of the structure is also decreases in order to maintain the equilibrium of the structure. For the following
calculations of the electronic and optical properties, the validated functional DFT-GGA-PBEsol has been employed.

Pb/Sn
I
N
C
H

(A-site)

(a) (b) (c)

Fig. 1. The crystal structure of CH3NH3BI3 (B= Pb, Sn) with orthorhombic (No. 62: Pnma space group) phase (a) without or; (b) with the
[BI6] octahedral and; (c) the organic cation part [CH3NH3]+
N. Suhaili et al. / Materials Today: Proceedings 4 (2017) 5154–5160 5157

Table 1. Calculated lattice parameters and cell volumes of orthorhombic (No. 62: Pnma space group) phase of CH3NH3BI3 (B= Pb, Sn) hybrid
halide perovskite using local functional LDA-CAPZ and semi-local functional GGA-PBE and GGA-PBEsol in comparison with the experimental
values and other theoretical work. Values in the parentheses represent the percentage difference from available experimental data in references.

Material Method Lattice Parameter (Å) Volume (Å3)


a b c
CH3NH3PbI3 LDA-CAPZ 8.641 12.428 8.371 898.943
(-2.54%)a (-1.59%)a (-2.40%)a (-6.39%)a
(-2.21%)b (-1.21%)b (-2.15%)b (-5.47%)b
GGA-PBE 9.236 13.058 8.670 1045.614
(+4.17%)a (+3.40%)a (+1.08%)a (+8.88%)a
(+4.53%)b (+3.80%)b (+1.34%)b (+9.95%)b
GGA-PBEsol 8.997 12.742 8.528 977.644
(+1.48%)a (+0.89%)a (-0.57%)a (+1.80%)a
(+1.82%)b (+1.29%)b (-0.32%)b (+2.80%)b
Exp. (T=100K) a 8.866 12.629 8.577 960.338
Exp. (T=100K) b 8.836 12.580 8.555 951.010
Theory c 9.226 12.876 8.619 1023.880

CH3NH3SnI3 LDA 8.549 12.280 8.254 866.501


GGA-PBE 9.033 12.938 8.562 1000.632
GGA-PBEsol 8.869 12.580 8.506 949.142
d
Theory 8.556 12.428 8.326 885.400
a
Neutron powder diffraction (Ref.[13])
b
X-ray powder diffraction (Ref.[14])
c
Vienna ab initio simulation package (VASP) DFT-GGA-PBE (Ref.[22])
d
CASTEP semi-empirical pairwise corrections DFT-GGA-PBE+D2 (Ref.[8])

3.2. Electronic Properties

Since the hybrid halide perovskite material has the potential application as a light harvesting medium, their
electronic structures are of crucial factors that need to be further explored. The calculated band structures of
orthorhombic CH3NH3PbI3 and CH3NH3SnI3 crystals along the high-symmetry lines in the first Brillouin zone are
presented in Fig. 2a, b (left panel). It can be seen that, both of the compounds exhibit a direct band gap at the G
symmetry point with the calculated electronic band gap of 1.721 eV and 0.935 eV, respectively. The exchange-
correlation functional from standard DFT usually underestimates the band gap energies of solid-state
semiconductors. However, for CH3NH3PbI3 compound in this study, the band gap is overestimated and is in good
agreement with experiment (1.68 eV) [23]. This result is purely coincidental due to the error cancellation taking
place between electron correlation and spin-orbit coupling (SOC) effects [24]. This trend has also been observed in
other work on CH3NH3PbI3 [25, 26]. On the other hand, the same error cancellation was observed not to be
transferable to CH3NH3SnI3 compound, for which the calculated band gap is smaller than the experimental value
(1.30 eV) from Ref. [12]. The accuracy of band gap calculations can be improved with the use of hybrid functional,
post-DFT methods, quasiparticle GW methods and by evaluating the SOC, but due to computational limitations, the
proper treatment on the band gap calculations remain difficult on our side. Despite the technical part, the obtained
results clearly indicating that the band gap energies of the hybrid halide perovskite are greatly affected by the
inorganic metal cations, showing good agreement with the previous studies [22, 27–28].
The partial density of state (PDOS) of CH3NH3PbI3 and CH3NH3SnI3 structures has been analyzed to further
understand the bonding mechanisms between the atoms. As illustrated in Fig. 2a (right panel), around the
fundamental band gap, only lead and iodine orbitals contribute to the DOS. The valence band maxima (VBM) which
lies at the Fermi level is dominated by the 5p states of I atom and partly contributed by 6s states of Pb atom, whereas
the conduction band minima (CBM) is originated from the 6p states of Pb atom. This result suggests that the band
gap energy of CH3NH3PbI3 is greatly related to the Pb-I bond and obviously, any changes in bond length or
compound composition will affect the size of the band gap. Thus, explaining the reason for the decrease of band gap
5158 N. Suhaili et al. / Materials Today: Proceedings 4 (2017) 5154–5160

from CH3NH3PbI3 (1.721 eV) to CH3NH3SnI3 (0.935 eV). For CH3NH3SnI3, the main contribution of VBM is from
the 5p states of I atom with an overlapping of Sn 5s states, while in the CBM, the main component is the 5p states of
Sn atom as shown in Figure 2b (right panel). Our results also show that, the organic [CH3NH3]+ cation only made a
small contribution to the formation of the VBM and the CBM around the Fermi energy level.

(a) CH3NH3PbI3, Eg=1.721 eV


 
 
 

5 6

4 5 Total
3
4 Pb - s
3
Pb - p
2 I- s
2
Energy (eV)

Energy (eV)
1 I- p
Eg
1 CH3NH3
0
0
-1
-1
-2 -2

-3 -3

-4 -4
G Z T Y S X U R 0 10 20 30 40 50

 
High Symmetry of Brillouin Zone Density of States (eV-1)
 

(b) CH3NH3SnI3, Eg=0.935 eV


5 6

4 5 Total
3 4 Sn - s
Sn - p
3
2 I- s
2
Energy (eV)

Energy (eV)

1
I- p
Eg 1 CH3NH3
0
0
-1
-1
-2 -2
-3 -3

-4 -4
G Z T Y S X U R 0 10 20 30 40 50

 
High Symmetry of Brillouin Zone Density of States (eV-1)

Fig. 2. Calculated energy band structures (left panel), total and partial density of states (right panel) of (a) CH3NH3PbI3 and; (b) CH3NH3SnI3
hybrid halide perovskite along the high-symmetry lines in the first Brillouin zone computed with DFT-GGA-PBEsol functional. The dashed lines
represent Fermi level at 0 eV

3.3. Optical Properties

The hybrid halide perovskite material, in particular the CH3NH3PbI3 compound has a superior optical absorption,
which makes the material suitable as an excellent light harvesting medium in solar cells. First principles calculations
have been used to calculate the optical absorption of CH3NH3PbI3 and CH3NH3SnI3 hybrid halide perovskite as
presented in Figure 3. In general, the optical properties can be computed from the complex dielectric function,

𝜀(𝜔) = 𝜀1 (𝜔) + 𝑖𝜀2 (𝜔) (1)


N. Suhaili et al. / Materials Today: Proceedings 4 (2017) 5154–5160 5159

which is mainly connected with the interaction of photons with electrons. The dielectric function 𝜀(𝜔) can be used
to describe the linear response of the system to an electromagnetic radiation. Its imaginary part 𝜀2 (𝜔) is related to
the electronic absorption of the material and can be calculated from the electronic structure based on the DOS and
the matrix elements between occupied and the unoccupied wave functions within the selection rules. The real part
𝜀1 (𝜔) of the dielectric function can be derived from the imaginary part subsequently by employing the Kramers-
Kronig transformation.

2 ∞ 𝜀2 (𝜔′ )𝜔′
𝜀1 (𝜔) = 1 + � 𝑑𝜔′ (2)
𝜋 0 𝜔 ′2 − 𝜔 2

2𝑒 2 𝜋
𝜀2 (𝜔) = � |⟨𝜓𝑘𝑐 |𝑢�𝑟|𝜓𝑘𝑣 ⟩|2 𝛿(𝐸𝑘𝑐 − 𝐸𝑘𝑣 − 𝐸) (3)
Ω𝑒0
𝑘,𝑣,𝑐

The electron charge is denoted by e, 𝑢� is the incident electric field, 𝜓𝑐 and 𝜓 𝑣 represent the CB and VB wave
functions at k-point, respectively. The relation of extinction coefficient 𝑘(𝜔) and absorption coefficient 𝛼(𝜔), with
the dielectric function can be defined by the following mathematical formula:
1�
|𝜀(𝜔)| − 𝜀1 (𝜔) 2
𝑘(𝜔) = � � (4)
2

2𝑘𝜔
𝛼(𝜔) = (5)
𝑐
The optical absorption spectrum tails start to rise at ~ 0.75 eV and ~ 1.75 eV, corresponding to the calculated
band gap energies of CH3NH3SnI3 and CH3NH3PbI3, respectively. Apart from that, it is seen that, the absorption
spectrum of the hybrid halide perovskite is red shifted with the reduction of the fundamental band gap. This result
suggests that the optical absorption is closely related to its electronic structure. From Fig. 3, the CH3NH3PbI3
compound clearly shows stronger optical absorption than the CH3NH3SnI3 compound in the region from 300nm to
400nm, but in the visible light region from 400nm to 750nm, the CH3NH3SnI3 reveals an encouraging absorption
coefficient compared to the benchmark Pb-based. Both the hybrid halide perovskite absorb light at ultraviolet (UV)
and visible light region, which shows that this class of material has superiority in utilizing solar energy.

140000 140000
20000
(a) (b)
120000 15000 120000

100000 10000 100000


CH3NH3PbI3
Absorption (cm )

Absorption (cm )
-1

-1

80000 5000 80000 CH3NH3SnI3

0
60000 0.0 0.5 1.0 1.5 2.0 60000

CH3NH3PbI3
40000 40000
CH3NH3SnI3
20000 20000

0 0
0 2 4 6 8 10 12 14 16 18 20 22 24 300 400 500 600 700 800 900 1000
Energy (eV) Wavelength (nm)

Fig. 3. Calculated absorption coefficients curve of CH3NH3PbI3 and CH3NH3SnI3 hybrid halide perovskite computed with DFT-GGA-PBEsol
functional. Top right inset graph is the enlargement of the absorption spectrum at x-axis: 0 → 2 eV
5160 N. Suhaili et al. / Materials Today: Proceedings 4 (2017) 5154–5160

4. Conclusions

In summary, we have performed first principles DFT calculations on structural, electronic and optical properties
of CH3NH3BI3 (B= Pb, Sn) hybrid halide perovskite with orthorhombic phase using CASTEP computer code. The
analysis of the electronic properties supports the conclusion that the hybrid halide perovskite studied in this paper
are a direct band gap crystal with the minimum band gap at the G symmetry point. Furthermore, the PDOS plot
reveals that the size of the band gap energy is related to the bonding between the divalent metal (Pb, Sn) cations
with the halide anions. Therefore, it can be predicted that, any changes made at both sites will eventually alter the
band gap values. This paper could pave the way for further theoretical studies such as substituting the iodide with
other halide group (Br or Cl) or partial substitution of the metal cations (CH3NH3PbxSn1-xI3). In the viewpoint of
optical absorption, CH3NH3SnI3 could be a promising nontoxic material for solar cell absorber.

Acknowledgements

The authors would like to thank Universiti Teknologi MARA (UiTM) for the facilities and support provided and
Ministry of Education Malaysia (MOE) for RAGS funding this research.

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