Tuning the intrinsic structural and stoichiometric properties by different means is used for increasing the green energy production efficiency of complex oxide materials. Here, we report on the formation of self-assembled nanodomains and their effects on the photoelectrochemical (PEC) properties of LaFeO (LFO) epitaxial thin films as a function of layer's thickness. The variation with the film's thickness of the structural parameters such as in-plane and out-of-plane crystalline coherence length and the coexistence of different epitaxial orientation-<100>SrTiO//<001> LFO, <100>SrTiO//<110> LFO and [110] LFO//[10] STO, as well as the appearance of self-assembled nanodomains for film's thicknesses higher than 14 nm, is presented.
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