Structural Dimensionality Dependence of the Band Gap in A_n+1B_nX_{3 n+1}Ruddlesden-Popper Perovskites: A Global Picture

Dimensionality engineering in An+1BnX3n+1 Ruddlesden-Popper (RP) perovskites has recently emerged as a promising tool for tuning the band gap to improve optoelectronic properties. However, the evolution of the band gap is dependent on the material; distinguishing the effects of different factors is urgently needed to guide the rational design of high-performance materials. Through first-principles calculations, we perform a systematic investigation of RP oxide, chalcogenide, and halide perovskites. The results reveal that in addition to the confinement effect and the change in octahedral rotation motions and/or amplitudes, interfacial rumpling and a change in the A-site cation coordination number also determine the evolution of the band gap. More importantly, we emphasize that the evolution of the band gap in RP perovskites is not dependent on the material family. Instead, the B-site frontier orbital type (s, p, and d) and bandwidth, A-site cation, interfacial rumpling, and structural distortions simultaneously determine the evolution of the band gap. These insights enable a complete and deeper understanding of various experimental observations.