Effects of alkali-metals (X = Li, Na, K) doping on the electronic, optoelectronic, thermodynamic, and X-ray spectroscopic properties of X-SnI3 halide perovskites

The effect of alkali metals (Li, Na, K) doping at X sites in tin-based X-SnI3 halide perovskite on structural, electronic, phonon, thermodynamic, and X-ray core-level spectroscopic properties was investigated and correlated with optoelectronic efficiency in the development of a stable and environmentally friendly solar technology to replace toxic lead-based perovskite solar cells (PSCs). These calculations were carried out based on the density functional theory approach using the Quantum Espresso software with the generalized gradient approximation (GGA) exchange correlation Perdew Burke Ernzerhorf functional. In addition, the phonon frequency, thermodynamics, and X-ray spectroscopy calculations were completed in Materials Studio using the CASTEP code. Our results reveal that there is a clear correlation between the alkali metal's ionic radius, changes in the lattice structural parameters, and the electronic band gap, such that the lattice constants are 5.940, 5.868, and 5.897 angstrom and the band gaps are 1.20, 1.14, and 1.10 eV for LiSnI3, NaSnI3, and KSnI3, respectively. The highest lattice constant obtained for LiSnI3, indicates that Li atoms occupied interstitial positions in the perovskite crystal, whereas the direct band gap decreases as cationic size increases, with KSnI3 exhibiting the least band gap. Phonon calculations show that KSnI3 has the lowest negative vibration region in its phonon dispersion plot, indicating dynamic stability. Interestingly, all the structures are found to portray high optical absorption, high extinction coefficient, high polarizability. Additionally, the free energy computation of the perovskites shows a reduction with rising temperature, but enthalpy increases significantly with increasing temperature. Yet, due to phonon lattice vibrations, the heat capacity increased as the temperature rose. Although the XSnI3 (X = Li, Na, and K) perovskites under investigation will perform efficiently as semiconductors and can be used for optoelectronic applications, the KSnl3 perovskite material has the most desirable properties for the fabrication of solar cell devices.