Strategic Doping for Precise Structural Control and Intense Photocurrents Under Visible Light in Ba₂M_0.4Bi_1.6O₆ (M =...

Developing functional perovskites is important for advancing solar energy conversion technologies. This study investigates the effects of dopants on the structural, optical, electronic, and solar conversion performances of Ba₂M_0.4Bi_1.6O₆ double perovskites. X-ray diffraction (XRD) and Rietveld refinement confirm crystallization in the I2/m space group (M = La, Ce, Pr, Pb), and Fm3¯m and I2/m space groups (M = Y). The B1-O-B2 structure modulates to highly ordered (M = La, Y), partially ordered (M = Pr), or disordered (M = Ce, Pb). UV-vis spectra show strong light absorption, with Tauc plots estimating ~1.57 eV (M = La) and ~1.73 eV (M = Pr) optical band gaps. Under AM 1.5G illumination, the M = La photoelectrode generates photocurrents of 1 mA cm^-2 at 0.3 V_RHE, surpassing M = Ce and Pb (1 μm, 4-times spin-coating). Increasing its thickness to 7.7 μm (4-times dip-coating) further enhances the photocurrents to 2.3 mA cm^-2 at 0.2 V_RHE, outperforming all counterparts due to improved stability. Fine-tuning crystal and electronic structures via strategic B-site doping provides a new route for engineering Ba₂Bi₂O₆-based double perovskites for broad solar energy conversion applications.