Oxygen-Vacancy-Induced Electronic Structure Modulation in ZnTiO3 Perovskite: A Combined DFT and SCAPS-1D Study Toward Photovoltaic Applications

Zinc titanate (ZnTiO3) is a chemically stable and non-toxic oxide perovskite whose photovoltaic potential remains largely unexplored due to its wide indirect bandgap. This study evaluates whether oxygen-vacancy (F-center) engineering can tailor its electronic structure and improve its suitability as a photovoltaic absorber. Density Functional Theory (DFT) calculations using VASP (PAW − GGA/PBE + U) were performed to evaluate structural stability, electronic properties, and electron affinity, while optical absorption was modeled through a combined Tauc–Gaussian approach. Device performance was assessed via SCAPS-1D simulations in an FTO/ZnO/ZnTiO3/Spiro-OMeTAD architecture. Oxygen vacancies induce bandgap narrowing from ~2.96 eV to ~1.47 eV and generate Ti-3d-dominated donor-like and deep intragap states. The calculated electron affinity is ~3.77 eV. Simulated single-layer devices reach Voc ≈ 1.11 V, Jsc ≈ 8.27 mA·cm−2, FF ≈ 83%, and a maximum efficiency of ~7.65%, primarily limited by moderate absorption strength and defect-assisted recombination. Multilayer configurations indicate that geometric optimization can significantly enhance projected efficiency, approaching 19.25% under idealized conditions. Although vacancy engineering extends visible-light absorption, the intrinsic indirect band-gap character constrains the ultimate photovoltaic performance of ZnTiO3.