Methylammonium Tin Iodide Perovskite: Structural, Electronic and

Thermodynamic Properties by a DFT Study with Different Exchange

Correlation Functionals
Catherine Paschala,c, Alexander Pogrebnoia, Tatiana Pogrebnayaa, Nicola Serianib
a
Department of Materials, Energy Science and Engineering, The Nelson Mandela African Institution of Science and
Technology, Arusha, United Republic of Tanzania
b
The Abdus Salam International Centre for Theoretical Physics, Strada Costiera 11, 34151 Trieste, Italy
c
Department of Science, Mwenge Catholic University, Moshi, United2.0.
Republic of Tanzania
Electronic Properties
Introduction
• The orthorhombic crystal has a direct bandgap at Γ symmetry
• The rate of population growth and increase in points with different calculated bandgap energies from the LDA,
industrialization are reflected in the energy demand for day- PBE, and PBEsol DFT functionals.
to-day activities. • The bandgap energies for the optimized CH3NH3SnI3 structure,
• Due to the number of years required to replenish the fossil
to the best accuracy of the XC functionals, are obtained: 1.12 eV
fuels and the effects they pose to the environment, the
(PBE) and 0.98 eV (PBEsol), which are comparable to the
search for viable renewable energy resources is of very
experimental data 1.2 -1.35 eV [1].
importance. • The LDA functional brings to the value of 0.46 eV which is much
• Solar energy is one of the most promising sources due to its
lower than experimental.
availability. • The LDA XC functional from standard DFT has been found to
• Perovskite materials have recently gained popularity due to
underestimate the bandgap energies of solid-state
their higher power conversion efficiency (PCE) as compared
semiconductors and insulators by about 40% [2].
to silicon. • The 5p-states of the I atoms are the main contributors to the
Methodology valence band maxima with a slight overlapping with the 5s-
states of tin while the conduction band is populated by the 5p-
states of Sn atoms responsible for formation of the conduction
Convergence band minima.
tests using Structure
Scf calculation
Quantum relaxation
Espressso

Bands PDOS Thermodynamic

calculation calculation properties

Results and Discussions
1.0. Convergence Tests
The kinetic-energy cutoff
(ecutwfc) and charge
density cutoff (ecutrho) for
the system were obtained
through convergence tests
as 50 with 450 Ry, 60 with
600 Ry and 70 with 490 Ry,
for the LDA, PBE, and
PBEsol functionals,
respectively.
Fig. 1: The lattice parameters and ecutwfc
as obtained using the LDA XC functional
Fig. 2: The Band Structure and PDOS of the O-phase tin perovskite using PBE and
PBEsol XC functionals
3.0. The Thermodynamics
Following the decomposition of the CH3NH3SnI3 perovskite into
solid state products, CH3NH3I and SnI2, the enthalpy of the
reaction ΔrH°(0 K) = 37 kJ mol–1 and enthalpy of formation
ΔfH°(CH3NH3SnI3, 0 K) = –390 kJ mol–1 were evaluated, indicating
stability of the O-phase CH3NH3SnI3 at low temperature.
Acknowledgement
The authors thank the African Development Bank (AfDB) for
funding this work.
Reference
[1] Stoumpos, Constantinos C, Malliakas, Christos D, & Kanatzidis, Mercouri G. (2013).
Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high
mobilities, and near-infrared photoluminescent properties. Inorganic chemistry, 52(15), 9019-
9038.
[2] Perdew, John P, & Zunger, Alex. (1981). Self-interaction correction to density-functional
approximations for many-electron systems. Physical Review B, 23(10), 5048.