Makoto KOBAYASHI, Issei Oyabu, Hikaru Sugimoto, Eisuke Yamamoto, Minoru Osada
, as a model platform, we demonstrate that the combination of cation substitution and nitrogen doping enables systematic modulation of both composition and electronic band structure in 2D perovskites. DJ-type perovskite oxynitrides with substantial nitrogen incorporation can be obtained via an unexpected transformation from pseudo-Ruddlesden-Popper-type phases, induced by alkali metal salt-assisted nitridation followed by simple aqueous treatment, without altering the anion composition. These oxynitrides are subsequently exfoliated into single-layer nanosheets that preserve the perovskite framework and the designed cation stoichiometry. Direct determination of both valence and conduction band edges by combined ultraviolet and inverse photoelectron spectroscopy reveals composition-dependent, nonmonotonic band alignment behavior that cannot be resolved by indirect optical or electrochemical approaches. This work establishes an integrated materials and characterization framework for the rational electronic-structure design in 2D oxynitride nanosheets.