Does Sb2Se3 Admit Nonstoichiometric Conditions? How Modifying the Overall Se Content Affects the Structural, Optical, and Optoelectronic Properties of Sb2Se3 Thin Films

Sb₂Se₃ is a quasi-one-dimensional (1D) semiconductor, which has shown great promise in photovoltaics. However, its performance is currently limited by a high V_oc deficit. Therefore, it is necessary to explore new strategies to minimize the formation of intrinsic defects and thus unlock the absorber’s whole potential. It has been reported that tuning the Se/Sb relative content could enable a selective control of the defects. Furthermore, recent experimental evidence has shown that moderate Se excess enhances the photovoltaic performance; however, it is not yet clear whether this excess has been incorporated into the structure. In this work, a series of Sb₂Se₃ thin films have been prepared imposing different nominal compositions (from Sb-rich to Se-rich) and then have been thoroughly characterized using compositional, structural, and optical analysis techniques. Hence, it is shown that Sb₂Se₃ does not allow an extended range of nonstoichiometric conditions. Instead, any Sb or Se excesses are compensated in the form of secondary phases. Also, a correlation has been found between operating under Se-rich conditions and an improvement in the crystalline orientation, which is likely related to the formation of a MoSe₂ phase in the back interface. Finally, this study shows new utilities of Raman, X-ray diffraction, and photothermal deflection spectroscopy combination techniques to examine the structural properties of Sb₂Se₃, especially how well-oriented the material is.