This study focused on investigating the optoelectronic properties of molybdenum trioxide (α-MoO₃) thin films using the atomic layer deposition (ALD) technique through different cycle numbers and theoretical investigation. Initial band gap calculations using standard DFT with GGA-PBE resulted in a value of 1.19 eV, which deviated significantly from experimental measurements. The GGA + U method with Hubbard U corrections was applied for the first time to improve the accuracy. This refinement led to a more precise band gap value of 3.09 eV, closely matching previously reported experimental data. The electronic parameters of the α-MoO₃ photodetector, such as ideality factor (n), barrier height (Φ₀), and series resistance (R_s), were analyzed using the thermionic emission theory and confirmed by Cheung and Nord's methods. The results demonstrated that the sample deposited with 100 pulses exhibited higher photodetector performance under UV illumination, despite having a lower R_s.

Ultrathin MoO₃ semiconductor nanostructures have garnered significant interest as a promising nanomaterial for transparent nano- and optoelectronics, owing to their exceptional reactivity. Due to the shortage of knowledge about the electronic and optoelectronic properties of MoO₃/n-Si via an ALD system of few nanometers, we utilized the preparation of an ultrathin MoO₃ film at temperatures of 100, 150, 200, and 250 °C. The effect of the depositing temperatures on using bis(tbutylimido)bis(dimethylamino)molybdenum (VI) as a molybdenum source for highly stable UV photodetectors were reported. The ON–OFF and the photodetector dynamic behaviors of these samples under different applied voltages of 0, 0.5, 1, 2, 3, 4, and 5 V were collected. This study shows that the ultrasmooth and homogenous films of less than a 0.30 nm roughness deposited at 200 °C were used efficiently for high-performance UV photodetector behaviors with a high sheet carrier concentration of 7.6 × 10¹⁰ cm⁻² and external quantum efficiency of 1.72 × 10¹¹. The electronic parameters were analyzed based on thermionic emission theory, where Cheung and Nord’s methods were utilized to determine the photodetector electronic parameters, such as the ideality factor (n), barrier height (Φ₀), and series resistance (R_s). The n-factor values were higher in the low voltage region of the I–V diagram, potentially due to series resistance causing a voltage drop across the interfacial thin film and charge accumulation at the interface states between the MoO₃ and Si surfaces.