Role of f Electrons in the Optical and Photoelectrochemical Behavior of Ca(La1–xCex)2S4 (0 ≤ x ≤ 1)

This study focuses on a solid solution series, Ca(La 1- x Ce x ) 2 S 4 (0 ≤ x ≤ 1), where the f electron density is absent in CaLa 2 S 4 and is progressively increased until it is maximized in CaCe 2 S 4 . Correspondingly, these samples, synthesized by a sealed ampule method, showed progressive variations in color ranging from gray for CaLa 2 S 4 o orange-red for CaCe 2 S 4 . The crystal structural nuances of both the end members and three solid solutions with x = 0.25, 0.50, and 0.75 were established with the complementary use of synchrotron X-ray diffraction and neutron scattering. Interestingly, these data were consistent with a two-phase composition centered around each nominal solid solution stoichiometry. Optical characterization via diffuse reflectance spectroscopy and Tauc analyses showed a shrinking of the energy band gap (from the UV to vis range) when Ce was progressively introduced into the host CaLa 2 S 4 structure. These data were in concert with electronic band structure calculations, using density functional theory, which showed the progressive formation of an intermediate f band when Ce was introduced intro the structure. Photoelectrochemical measurements in an aqueous redox electrolyte, as well as surface photovoltage and Kelvin probe measurements, revealed all samples to be n-type semiconductors. The valence and conduction band edge positions of the end members and the three solid solutions could be mapped, on both the redox and vacuum reference energy scales, by combining these measurements with the optical data.