DFT Study of the Effect of A-Site and Halide Substitution on the Structural and Elastic Behavior of APbX₃ Perovskites

Authors

Keywords:

GGA-PBE, Lead halide perovskites, Elastic constants, Mechanical stability, Structural properties

Abstract

In this work, density functional theory within the generalized gradient approximation (GGA-PBE) was employed to examine the mechanical and structural characteristics of cubic APbX₃ (A = Li, Na, K, Rb, Cs; X = F, I) perovskites. Comparing the larger ionic size of iodides to fluorides, the optimized lattice parameters increase with the A-site ionic radius. The Born-Huang stability criteria are satisfied by all computed elastic constants, indicating mechanical stability in the cubic phase. Cubic APbI₃ perovskite compounds tend to have lower bulk moduli and are easily compressible, especially when the heavier A-site cations are present, while APbF₃ compounds show increased stiffness as bulk and Young's moduli increase from Li to Cs. Poisson ratios suggest predominantly ionic bonding across all compositions. Overall, fluoride perovskites are mechanically more robust than their iodide counterparts, highlighting the strong influence of both A-site and halide substitution on structure–mechanical property relationships.

Dimensions

Abdulla, H. T., & Sami, S. A. (2023). First-principles study of structural, electronic, elastic and optical properties of alkali lead iodides MPbI3 (M= Li, Na, K). Ukr. J. Phys. Opt, 24(1), 1.

Alaei, A., Circelli, A., Yuan, Y., Yang, Y., & Lee, S. S. (2021). Polymorphism in metal halide perovskites. Materials Advances, 2(1), 47-63.

Boote, B. W., Andaraarachchi, H. P., Rosales, B. A., Blome‐Fernández, R., Zhu, F., Reichert, M. D., Vela, J. (2019). Unveiling the Photo‐and Thermal‐Stability of Cesium Lead Halide Perovskite Nanocrystals. ChemPhysChem, 20(20), 2647-2656.

Born, M., Huang, K., & Lax, M. (1955). Dynamical theory of crystal lattices. American Journal of Physics, 23(7), 474-474.

Giannozzi, P., Stefano, B., Bonini, N., Matteo, C., Roberto, C., Carlo, C., Cococcioni, M. (2009). QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. JOURNAL OF PHYSICS: CONDENSED MATTER, 395502.

Hayatullah, Murtaza, G., Khenata, R., Naeem, S., Khalid, M., & Mohammad, S. (2013). First principle calculations of the ground and excited state properties of RbPbF3. Chinese Physics Letters, 30(9), 097101.

Hoffman, A. E., Saha, R. A., Borgmans, S., Puech, P., Braeckevelt, T., Roeffaers, M. B., Van Speybroeck, V. (2023). Understanding the phase transition mechanism in the lead halide perovskite CsPbBr3 via theoretical and experimental GIWAXS and Raman spectroscopy. Apl Materials, 11(4).

Huang, H., Bodnarchuk, M. I., Kershaw, S. V., Kovalenko, M. V., & Rogach, A. L. (2017). Lead halide perovskite nanocrystals in the research spotlight: stability and defect tolerance. ACS energy letters, 2(9), 2071-2083.

Jin, H., Zeng, Y.-J., Steele, J. A., Roeffaers, M. B., Hofkens, J., & Debroye, E. (2024). Phase stabilization of cesium lead iodide perovskites for use in efficient optoelectronic devices. NPG Asia Materials, 16(1), 24.

Jishi, R. A., Ta, O. B., & Sharif, A. A. (2014). Modeling of lead halide perovskites for photovoltaic applications. The Journal of Physical Chemistry C, 118(49), 28344-28349.

Jong, U.-G., Yu, C.-J., Kim, Y.-S., Kye, Y.-H., & Kim, C.-H. (2018). First-principles study on the electronic and optical properties of inorganic perovskite Rb1-xCsxPbI3 for solar cell applications. arXiv preprint arXiv:1805.03341.

Kovalenko, M. V., Protesescu, L., & Bodnarchuk, M. I. (2017). Properties and potential optoelectronic applications of lead halide perovskite nanocrystals. Science, 358(6364), 745-750.

Laboratory, N. (2023). National renewable energy laboratory, best research-cell efficiency chart.

Pakravesh, F., & Izadyar, M. (2024). Theoretical insights into the electronic and optical properties of lithium-based perovskite for solar cell applications. Journal of Photochemistry and Photobiology A: Chemistry, 453, 115602.

Perdew, J. P., & Zunger, A. (1981). Self-interaction correction to density-functional approximations for many-electron systems. PHYSICAL REVIEW B, VOLUME 23, NUMBER 10.

Protesescu, L., Yakunin, S., Bodnarchuk, M. I., Krieg, F., Caputo, R., Hendon, C. H., Kovalenko, M. V. (2015). Nanocrystals of cesium lead halide perovskites (CsPbX3, X= Cl, Br, and I): novel optoelectronic materials showing bright emission with wide color gamut. Nano letters, 15(6), 3692-3696.

Quantum ESPRESSO Project. Pseudopotentials library. (2016), from https://pseudopotentials.quantum-espresso.org

Racine, J. (2006). gnuplot 4.0: a portable interactive plotting utility: Wiley Online Library.

Tan, X., Wang, S., Zhang, Q., Liu, H., Li, W., Zhu, L., & Chen, H. (2023). Stabilizing CsPbI3 perovskite for photovoltaic applications. Matter, 6(3), 691-727.

Wang, S., & Ye, H. (2003). First‐principles study on elastic properties and phase stability of III–V compounds. physica status solidi (b), 240(1), 45-54.

Yang, D., Cao, M., Zhong, Q., Li, P., Zhang, X., & Zhang, Q. (2019). All-inorganic cesium lead halide perovskite nanocrystals: synthesis, surface engineering and applications. Journal of Materials Chemistry C, 7(4), 757-789.

Yi, J., Ge, X., Liu, E., Cai, T., Zhao, C., Wen, S., Gao, J. (2020). The correlation between phase transition and photoluminescence properties of CsPbX 3 (X= Cl, Br, I) perovskite nanocrystals. Nanoscale advances, 2(10), 4390-4394.

Cubillos, M. V. (2015). The relationship between UV-irradiance, photoprotective compounds and DNA damage in two intertidal invertebrates with contrasting mobility characteristics. Journal of Photochememistry and Photobiology B: Biology, 149, 280-296. https://doi.org/10.1016/j.jphotobiol 2015.06.001

Published

2026-05-12

How to Cite

Mustapha, L. O., Tikarewa, G. A., & Amusa, R. A. (2026). DFT Study of the Effect of A-Site and Halide Substitution on the Structural and Elastic Behavior of APbX₃ Perovskites. Nigerian Journal of Physics, 35(2), 191-196. https://doi.org/10.62292/njp.v35i2.2026.525

Issue

Vol. 35 No. 2 (2026): Nigerian Journal of Physics - Vol. 35 No. 2

Section

Articles
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Copyright (c) 2026 Lateef O. Mustapha, Ganiu A. Tikarewa, Razak. A. Amusa

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This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.

How to Cite

Mustapha, L. O., Tikarewa, G. A., & Amusa, R. A. (2026). DFT Study of the Effect of A-Site and Halide Substitution on the Structural and Elastic Behavior of APbX₃ Perovskites. Nigerian Journal of Physics, 35(2), 191-196. https://doi.org/10.62292/njp.v35i2.2026.525