Abstract: The physical properties and photoelectrochemical characterization of aluminium doped hematite α-Fe₂O₃, synthesized by spray pyrolysis, have been investigated in regard to solar energy conversion. Stable Al-doped iron (III) oxide thin films synthesized by a spray pyrolysis technique reveals an oxygen deficiency, and the oxide exhibits n-type conductivity confirmed by anodic photocurrent generation. The preparative parameters have been optimized to obtain good quality thin films which are uniform and well adherent to the substrate. The deposited iron oxide thin films show the single hematite phase with polycrystalline rhombohedral crystal structure with crystallite size 20–40 nm. Optical analysis enabled to point out the increase in direct band-gap energy from 2.2 to 2.25 eV with doping concentration which is attributed to a blue shift. The dielectric constant and dielectric loss are studied as a function of frequency. To understand the conduction mechanism in the films, AC conductivity is measured. The conduction occurs by small polaron hopping through mixed valences Fe^2+/3+ with an electron mobility 300 K of 1.08 cm²/(V.s). The α-Fe₂O₃ exhibits long term chemical stability in neutral solution and has been characterized photoelectrochemically to assess its activity as a photoanode for various electrolytes using white light to obtain I–V characteristics. The Al-doped hematite exhibited a higher photocurrent response when compared with undoped films achieving a power conversion efficiency of 2.37% at 10 at% Al:Fe₂O₃ thin films along with fill factor 0.38 in NaOH electrolyte. The flat band potential V_fb(-0.87 V_SCE) is determined by extrapolating the linear part to C^-2 = 0 and the slope of the Mott-Schottky plot.

Key words: photoelectrochemical, hematite, spray, photoanode