First-Principle Study of the Structural, Electronic, and Optical Properties of Cubic Cesium Lead Halide Perovskites for Photovoltaic System


Muhammad Waqas


Lead halide perovskites have attracted considerable attention as optoelectronic materials because these materials have high photovoltaic conversion efficiency. The current study is based on Density Functional Theory (DFT). This theory was used to calculate the structural, optical, and electronic properties of the lead halide perovskites CsPbX3 (X = Chlorine (Cl), Bromine (Br), Iodine (I)) compounds . In order to calculate the above mentioned properties of cubic perovskites CsPbX3 (X = Cl, Br, I), Full Potential Linear Augmented Plane Wave (FP-LAPW) method was implemented in conjunction with DFT utilizing LDA, GGA-PBE and mBJ approximations. A good agreement was found between experimentally measured values and theoretically calculated lattice constants. These compounds have a direct and wide band gap located at the point of R-symmetry, while the band gap decreases from ‘Cl’ to ‘I’ down the group. The densities of electrons revealed a strong ionic bond between Cs and halides and a strong covalent bond between ‘Pb’ and (Cl, Br, and I). The dielectric functions (reflectivity, refractive indices, absorption coefficients), optical conductivities (real and imaginary part) and other optical properties indicated that these compounds have novel energy harvester applications. The modeling of these perovskite compounds shows that they have high absorption power and direct band gaps in visible ultraviolet range and it also shows that these compounds have potential applications in solar cells.


How to Cite
Waqas M. First-Principle Study of the Structural, Electronic, and Optical Properties of Cubic Cesium Lead Halide Perovskites for Photovoltaic System. SIR [Internet]. 2020Jun.8 [cited 2020Oct.30];4(2):1-16. Available from:


[1] Moreira RL, Dias A. Comment on prediction of lattice constant in cubic perovskites. J Phys Chem Solids. 2007; 68(8): 1617–1622.
[2] Trots DM, Myagkota SV. High-temperature structural evolution of caesium and rubidium triiodoplumbates. J Phys Chem Solids. 2008;69(10): 2520–2526.
[3] Nikl M, Nitsch K, Chval J. Optical and structural properties of ternary nanoaggregates in CsI-PbI2 co-evaporated thin films. J
Phys: Condens Matter. 2000;12(8): 1939. doi: 10.1088/0953-8984/12/8/335
[4] Verma AS, Kumar A, Bhardwaj SR. Correlation between ionic charge and the lattice constant of cubic perovskite solids. Phys Status Solidi B. 2008;245(8): 1520–1526.
[5] Dualeh A, mehi T, Tétreault N, et al. "Impedance spectroscopic analysis of lead iodide perovskite-sensitized solid-state solar cells. ACS Nano. 2013;8(1): 362–373.
[6] Burschka J, Pellet N, Moon S-J, et al. Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature. 2013;499(7458): 316–319. doi: 10.1038/nature12340
[7] Zheng, J, Deng X, Zhou X, et al. Efficient formamidinium–methylammonium lead halide perovskite solar cells using Mg and Er co-modified TiO 2 nanorods. J Mater Sci: Mater Electron. 2019;30(12): 11043–11053.
[8] Yun JS, Seidel J, Kim J, et al. Critical role of grain boundaries for ion migration in formamidinium and methylammonium lead halide perovskite solar cells. Adv Energy Mater. 2016;6(13): 1600330.
[9] Ahmad M, Rehman G, Ali L, et al. Structural, electronic and optical properties of CsPbX3 (X= Cl, Br, I) for energy storage and hybrid solar cell applications. J Alloys Compd. 2017;705: 828–839.
[10] Begum R, Chin XY, Damodaran B, et al. Cesium lead halide perovskite nanocrystals prepared by anion exchange for light-emitting diodes. ACS Appl Nano Mater. 2020;3(2): 1766–1774.
[11] Zubko P, Gariglio S, Gabay M, et al. Interface physics in complex oxide heterostructures. Annu Rev Condens Matter Phys. 2011;2(1): 141–165.
[12] Fan J, Shavel A, Zamani R, et al. Control of the doping concentration, morphology and optoelectronic properties of vertically aligned chlorine-doped ZnO nanowires. Acta Mater. 2011;59(17): 6790–6800.
[13] Queisser HJ, Werner JH. Principles and technology of photovoltaic energy conversion. Paper presented at: 4th International Conference on Solid-State and Integrated Circuit Technology; October 24–28, 1995; Beijing, China.
[14] Fadla MA, Bentria B, Benghia A, et al. First-principles investigation on the stability and material properties of all-inorganic cesium lead iodide perovskites CsPbI3 polymorphs. Phys B: Condens Matter. 2020; 585: 412118.
[15] Busipalli DL, Lin KY, Nachimuthu S, Jiang JC. Enhanced moisture stability of cesium lead iodide perovskite solar cells–a first-principles molecular dynamics study. Phys Chem Chem Phys. 2020;22(10): 5693–5701.
[16] Alay-e-Abbas, SM, Nazir S, Noor NA, Amin N, Shaukat A. Thermodynamic stability and vacancy defect formation energies in SrHfO3. J Phys Chem: C. 2014;118(34): 19625–19634.
[17] Sutton R, Eperon G, Miranda L, et al. Bandgap‐tunable cesium lead halide perovskites with high thermal stability for efficient solar cells. Adv Energy Mater. 2016;6(8): 1502458.
[18] Hong X, Ishihara T, Nurmikko AV. Dielectric confinement effect on excitons in PbI 4-based layered semiconductors. Phys Rev: B. 1992;45(12): 6961.
[19] Burgelman M, Nollet P, Degrave S. Modelling polycrystalline semiconductor solar cells. Thin Solid Films. 2000;361: 527–532.
[20] Andreev VM, Grilikhes VA, Rumi͡ant͡sev VD. Photovoltaic conversion of concentrated sunlight. London: Wiley; 1997.
[21] Bloss WH, Pfisterer F, Schubert M, Walter T. Thin‐film solar cells. Prog Photovolt: Res Appl. 1995;3(1): 3–24.
[22] Sievers RK, Hunt TK, Butkiewicz D, et al. Prototype AMTEC cell development. Paper presented at: International Energy Conversion Engineering Conference; August 07-12, 1994; Monterey, CA, US.
[23] Ita J, Stixrude L. Density and elasticity of model upper mantle compositions and their implications for whole mantle structure. In: E. Takahashi, R. Jeanloz and D. Rubie, eds. Evolution of the Earth and Planets. New York: American Geophysical Union; 1993: 111–130. doi:10.1029/GM074p0111
[24] Boinapally VR. Computational study of structural and electrical properties of methylammonium lead iodide perovskite [master’s thesis]. Ohio: University of Toledo, College of Engineering; 2015.
[25] Lee MM, Teuscher J, Miyasaka T, Murakami TM, Snaith H. Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites. Science. 2012;338(6107): 643–647.
[26] Lebedev AI. Ab initio calculations of phonon spectra in ATiO3 perovskite crystals (A= Ca, Sr, Ba, Ra, Cd, Zn, Mg, Ge, Sn, Pb). Phys Solid State. 2009;51(2): 362–372.
[27] Miura K, Azuma M, Funakubo H. Electronic and structural properties of ABO3: role of the BO coulomb repulsions for ferroelectricity. Materials. 2011;4(1): 260–273.
[28] Ashcroft NW, Mermin ND. Solid state physics. New York: Holt, Rinehart and Winston; 1976.
[29] Cahill DG, Pohl R. Lattice vibrations and heat transport in crystals and glasses. Annu Rev Phys Chem. 1988;39(1): 93–121.
[30] Levy GC, Hunt TK, Sievers RK. AMTEC: current status and vision. Paper presented at: 32nd Intersociety Energy Conversion Engineering Conference, IECEC-97. IEEE; 1997.
[31] Cole T. Thermoelectric energy conversion with solid electrolytes. Science. 1983;221(4614): 915–920.
[32] Tsymbal EY, Kohlstedt H. Tunneling across a ferroelectric. Science. 2006;313(5784): 181–183. doi: 10.1126/science.1126230
[33] Huang, Y-H, Dass RI, Xing Z-L, Goodenough JB. Double perovskites as anode materials for solid-oxide fuel cells. Science. 2006;312(5771): 254–257. doi: 10.1126/science.1125877
[34] Yamada H, Ogawa Y, Ishii Y, et al. Engineered interface of magnetic oxides. Science. 2004;305(5684): 646–648. doi: 10.1126/science.1098867
[35] Shannon RD. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst Section A. 1976;32(5): 751–767.

[36] Makino K, Tomita K, Suwa K. Effect of chlorine on the crystal structure of a chlorine-rich hastingsite. Mineral Mag. 1993;57(389): 677–686.
[37] Li T-I, Stucky GD, McPherson G. The crystal structure of CsMnCI3 and a summary of the structures of RMX3 compounds. Acta Cryst Section B. 1973;29: 1330.
[38] Groat LA, John LJ, Bonnie CP. The crystal structure of argentojarosite, AgFe3 (SO4) 2 (OH) 6. Can Mineral. 2003;41(4): 921–928.
[39] Howie RA, Moser W, Trevena IC. The crystal structure of tin (II) iodide. Acta Cryst Section B. 1972;28(10): 2965–2971.
[40] Tomioka Y, Okimoto Y, Jung JH, Kumai R, Tokura Y. Phase diagrams of perovskite-type manganese oxides. J Phys Chem Solids. 2006;679(9): 2214–2221.
[41] Reaney IM, Iddles D. Microwave dielectric ceramics for resonators and filters in mobile phone networks. J Am Ceram Soc. 2006;89(7): 2063–2072.
[42] Hirata T, Ishioka K, Kitajima M. Vibrational spectroscopy and X-ray diffraction of perovskite compounds Sr 1− x M x TiO 3 (M= Ca, Mg; 0≤ x≤ 1). J Solid State Chem. 1996;124(2): 353–359.
[43] Kazim S, Nazeeruddin, Gratzel M, Ahmad S. Perovskite as light harvester: a game changer in photovoltaics. Angew Chem. 2014;53(11): 2812–2824.
[44] Alger DL. Some corrosion failure mechanisms of AMTEC cells. Paper presented at: 32nd Intersociety Energy Conversion Engineering Conference, IECEC-97. IEEE; 1997.
[45] Bankston CP, Shirbacheh M. AMTEC: high efficiency static conversion for space power (Working group papers, V. 2, Sect. 5). Marshall Space Flight Center Manned Mars Mission; 1986: 715–732.

[46] Ryan M, Kisor A, Williams R, Jeffries B-N, O’Connor D. Lifetimes of thin film AMTEC electrodes. Paper presented at: International Energy Conversion Engineering Conference; August 07-12, 1994; Monterey, CA, US.
[47] Perdew JP, CHevary JA, Vosko SH, et al. Atoms, molecules, solids, and surfaces: applications of the generalized gradient approximation for exchange and correlation. Phys Rev B. 1992;46(11): 6671.
[48] Kohn W, Sham LJ. Self-consistent equations including exchange and correlation effects. Phys Rev. 1965;140(4A): A1133.
[49] Payne MC, Teter MP, Allan DC, Arias TA, Joannopoulos JD. Iterative minimization techniques for ab initio total-energy calculations: molecular dynamics and conjugate gradients. Rev Mod Phys. 1992;64(4): 1045.