Highly transparent thin films with the chemical formula BaSrMgWO₆ were deposited by spin coating using a solution of nitrates of Ba, Sr, and Mg and ammonium paratungstate in dimethylformamide with a Ba:Sr:Mg:W ratio = 1:1:1:1. XRD, SEM, EDX, and XPS investigations evidenced that annealing at 800 °C for 1 h results in an amorphous structure having a precipitate on its surface, and that supplementary annealing at 850 °C for 45 min forms a nanocrystalline structure and dissolves a portion of the precipitates. A textured double perovskite cubic structure (61.9%) was found, decorated with tetragonal and cubic impurity phases (12.7%), such as BaO₂, SrO₂, and MgO, and an under-stoichiometric phase (24.4%) with the chemical formula Ba_2−(x+y) Sr_xMg_yWO₅. From transmittance measurements, the values of the optical band gap were estimated for the amorphous (E_gdir = 5.21 eV, E_gind = 3.85 eV) and nanocrystalline (E_gdir = 4.69 eV, E_gind = 3.77 eV) phases. The presence of a lattice disorder was indicated by the high Urbach energy values and weak absorption tail energies. A decrease in their values was observed and attributed to the crystallization process, lattice strain diminution, and cation redistribution.

This study presents a systematic approach to engineering the electron transport layer (ETL) in perovskite solar cells using a spray deposition technique to fabricate sequentially compact and mesoporous titanium dioxide (c-TiO₂, m-TiO₂) films. The spray coating method leads to the development of a distinct reticulated morphology characterized by well-defined wavy-like surface features and significantly increased roughness—at least twice that of spin-coated mesoporous films. The increased interfacial area between the mesoporous TiO₂ and the perovskite layer facilitates more efficient charge transfer, contributing to higher device performance. By optimizing the deposition parameters, particularly the number of spray cycles for the m-TiO₂ layer, we achieve a significant enhancement in device performance, with improvements in power conversion efficiency (PCE), reduced series resistance, and minimized hysteresis. Our results demonstrate that an optimal film thickness promotes better perovskite anchoring, while excessive deposition impedes light transmission and increases sheet resistance. These findings advance the practical fabrication of high-performance perovskite solar cells using simple solution-processing techniques and highlights the potential of scalable spray deposition methods for industrial-scale fabrication.