Al-Mg co-doped TiO2 thin film as a promising ETL for perovskite solar cells: An experimental and DFT investigation

Solar cells offer a potential solution to the energy crisis, and perovskite solar cells are the latest frontrunner. However, low electrical conductivity of TiO₂ ETL serves as a bottleneck to its efficiency. In this study, Al-Mg co-doped anatase thin films are prepared by one-step spin coating method and then characterized to tackle this problem. XRD results show that doping leads to smaller crystallite size and decreased interplanar spacing, but increases the lattice strain and dislocation density. AFM images reveal that Al-Mg co-doping increases surface roughness. Surface morphology of the co-doped film is good, covering the whole substrate uniformly without any pinholes. XPS results ensure that the desired composition is achieved. UV–vis spectroscopy data show that optical bandgap increases with Al-Mg co-doping, leading to the highest bandgap for Ti_0.87Mg_0.1Al_0.03O_2, which also has the highest transmittance peak, reaching 90 % in the visible region. Urbach energies are also calculated to get a better estimate of the effective bandgaps. Band edge positions are calculated using Mulliken’s electronegativity, demonstrating improved band alignment due to Al-Mg co-doping. The bandgap trend is further corroborated with DFT + U simulations, which show that calculated bandgaps match the experimentally obtained optical bandgaps. Additionally, density of states reveal that Ti 3d orbital dominates the conduction band and O 2p orbital dominates the valence band, with hybridization taking place between different orbitals. Four-point probe test demonstrates that Al-Mg co-doping leads to a consistent decrease in sheet resistance of the thin film. Better band alignment and higher visible light transmittance combined with enhanced conductivity indicate that Al-Mg co-doped anatase thin film has high potential as an ETL for perovskite solar cells.