Orbital−energy splitting in Ruddlesden−Popper layered halide perovskites for tunable optoelectronic properties

Abstract

The electronic orbital characteristics at the band edges play an important role in determining the electrical, optical and defect properties of perovskite photovoltaic materials. It is highly desirable to establish the relationship between the underlying atomic orbitals and the optoelectronic properties as a guide to maximize the photovoltaic performance. Here, using first-principles calculations and taking Ruddlesden-Popper (RP) phase layered perovskites Cs n +1 Ge n I n +1 Cl 2n as examples, we demonstrate how to rationally optimize the optoelectronic properties (e.g., band gap, transition dipole matrix elements, carrier effective masses, bandwidth) through a simple band structure parameter. Our results show that reducing the splitting energy |Δ c | between the in-plane p x , y and out-of-plane p z orbitals at the conduction band minimum (CBM) can effectively reduce the band gap and carrier effective masses while greatly improving the optical absorption in the visible region. Thereby, the orbital-property relationship with Δ c is well established through biaxial compressive strain. Finally, it is shown that this approach can be reasonably extended to several other non-cubic halide perovskites with similar p orbitals characteristics at the conduction band edge. Therefore, we believe that our proposed orbital engineering approach will provide atomic-level guidance for understanding the performance limits of layered perovskite solar cells. • Orbital−energy splitting in Ruddlesden−Popper layered halide perovskites. • Optimizing the optoelectronic properties through a simple band structure parameter. • Reducing the splitting energy .|Δ c | can effectively tune the optoelectronic properties.