Density Functional Theory Investigation of Defect-Induced Electronic Behavior in Iodine-Deficient Mapbi₃ Perovskites for Solar Cells
DOI:
https://doi.org/10.65150/EP-gjetr/V2E9/2026-15Keywords:
Density Functional Theory, MAPbI, iodine vacancy, perovskite solar cells, VASP, defect formation energyAbstract
This work Demonstrated a Density Functional Theory (DFT) investigation of the electronic properties and iodine vacancy defects in methylammonium lead iodide (MAPbI₃) using the Vienna Ab initio Simulation Package (VASP). We analyzed the structural and electronic properties of both pristine and defective MAPbI₃ systems. Density of state (DOS) and band structure calculations confirmed that pristine MAPbI₃ is a direct-bandgap semiconductor. Our defect analysis revealed that iodine vacancies alter the electronic structure by introducing new states near the band edges. Formation energy calculations showed that the positively charged iodine vacancy (+1) possesses the lowest formation energy (0.20 eV), indicating its thermodynamic stability. The values of Charge transition levels for ε (+1/0), and ε (0/−1) were obtained as 1.12 eV and 1.52 eV respectively within the bandgap. The defect concentration analysis showed that the +1-charge state is the most stable and predominant at both 298 K and 333 K. This indicates that iodine vacancies play an important role in determining the charge transport and recombination behavior of MAPbI₃. Understanding these defect effects provides useful insight for optimizing the material properties and enhancing the efficiency and overall performance of perovskite solar cells.
References
1) Kojima, A., Teshima, K., Shirai, Y., & Miyasaka, T. (2009). Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. Journal of the American Chemical Society, 131(17), 6050-6051.
2) National Renewable Energy Laboratory (NREL). (2024). Best research-cell efficiency chart. https://www.nrel.gov/pv/cell-efficiency.html
3) International Energy Agency (IEA). (2023). World Energy Outlook 2023. Paris: IEA Publications.
4) Green, M. A., Ho-Baillie, A., & Snaith, H. J. (2014). The emergence of perovskite solar cells. Nature Photonics, 8, 506-514.
5) Eperon, G. E., Stranks, S. D., Menelaou, C., Johnston, M. B., Herz, L. M., & Snaith, H. J. (2014). Formamidinium lead trihalide: A broadly tunable perovskite for efficient planar heterojunction solar cells. Energy & Environmental Science, 7(3), 982-988.
6) Stranks, S. D., Eperon, G. E., Grancini, G., Menelaou, C., Alcocer, M. J. P., Leijtens, T., ... & Snaith, H. J. (2013). Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science, 342(6156), 341-344.
7) Yang, Y., Yang, M., Li, Z., Crisp, R., Zhu, K., & Beard, M. C. (2015). Comparison of recombination dynamics in CH₃NH₃PbI₃ and CH₃NH₃PbBr₃ perovskite films: Influence of exciton binding energy. Journal of Physical Chemistry Letters, 6(23), 4688-4692.
8) Yin, W. J., Shi, T., & Yan, Y. (2014). Unusual defect physics in CH₃NH₃PbI₃ perovskite solar cell absorber. Applied Physics Letters, 104(6), 063903.
9) Snaith, H. J. (2013). Perovskites: The emergence of a new era for low-cost, high-efficiency solar cells. Journal of Physical Chemistry Letters, 4(21), 3623-3630.
10) Park, N. G., Zhu, K., & Miyasaka, T. (2020). Perovskite solar cells: From the laboratory to the assembly line. Chemical Reviews, 120(15), 7867-7918.
11) Correa-Baena, J. P., Saliba, M., Buonassisi, T., Grätzel, M., Abate, A., Tress, W., & Hagfeldt, A. (2017). Promises and challenges of perovskite solar cells. Science, 358(6364), 739-744.
12) Abbas, G., Xu, W., Rauf, M., & Kyaw, A. K. K. (2024). A comprehensive review on defects-induced voltage losses and strategies toward highly efficient and stable perovskite solar cells. Photonics, 11(1), 87.
13) Guo, Y., Yuan, Y., Wang, Z., Zhang, J., & Zhou, Y. (2024). Understanding defects in perovskite solar cells through computation: Current knowledge and future challenges. Advanced Science, 11(16), 2305799.
14) Eames, C., Frost, J. M., Barnes, P. R. F., O'Regan, B. C., Walsh, A., & Islam, M. S. (2015). Ionic transport in hybrid lead iodide perovskite solar cells. Nature Communications, 6, 7497.
15) Azpiroz, J. M., Mosconi, E., Bisquert, J., & De Angelis, F. (2015). Defect migration in methylammonium lead iodide and its role in perovskite solar cell operation. Energy & Environmental Science, 8(7), 2118-2127.
16) Zhao, Y., et al. (2018). Interface engineering in perovskite solar cells: A theoretical approach. Advanced Energy Materials, 8(16), 1800732.
17) Snaith, H. J. (2018). Present status and future prospects of perovskite photovoltaics. Nature Materials, 17(5), 372-376.
18) Kymakis, E., Stratakis, E., & Kalyvas, N. (2018). Interfacial engineering of perovskite solar cells for improved performance and stability. Advanced Materials Interfaces, 5(22), 1801595.
19) Walsh, A., et al. (2018). Computational investigation of perovskite solar cells. Journal of Materials Chemistry C, 6(2), 321-330.
20) Yin, J., et al. (2020). Multi-scale modelling of charge transport in perovskite solar cells. Energy & Environmental Science, 13(6), 1627-1638.
21) Mosconi, E., et al. (2016). First-principles modelling of perovskite solar cells: Understanding the role of defects. Physical Review Applied, 6(4), 044012.
22) Kim, J., et al. (2019). Interface engineering for high-efficiency perovskite solar cells. Journal of Materials Chemistry A, 7(23), 14245-14253.
23) Bach, U., et al. (2019). Defects and interfaces in perovskite solar cells: A theoretical perspective. Nature Energy, 4(9), 738-746.
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Copyright (c) 2026 Sani Kado, Muhammad Y. Onimisi, Dahiru M. Sanni (Author)
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