Anomalous Behavior in Dark-Bright Splitting Impacts the Biexciton Binding Energy in (BA)<sub>2</sub>(MA)<sub><i>n</i>-1</sub>Pb<sub><i>n</i></sub>Br<sub>3<i>n</i>+1</sub> (<i>n</i> = 1-3).

Cho, Jun Sang; So, Hyeon-Kyeong; Balvanz, Adam; Vasileiadou, Eugenia S; Fletcher, Jared; Kang, Hyeokju; Cho, Jeong Bin; Kim, Donggyu et al. · ACS Nano · 2024

basic_science · Level V

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Abstract

Two-dimensional Ruddlesden-Popper series are an excellent system for tuning physical properties of the perovskite by controlling the layer number (<i>n</i>). For instance, bandgap and exciton binding energies of the series gradually increase upon reducing <i>n</i> via enhanced quantum and dielectric confinements. Here, we present findings that challenge the anticipated trend in electron-hole exchange interaction within (BA)<sub>2</sub>MA<sub><i>n</i>-1</sub>Pb<sub><i>n</i></sub>Br<sub>3<i>n</i>+1</sub> (<i>n</i> = 1-3), which causes spin-dependent exciton level splitting into bright and dark states, where the latter is partially visible near the surface of the Br-based two-dimensional Ruddlesden-Popper series. Contrary to expectations, the smallest gap between bright and dark exciton levels is observed from <i>n</i> = 2 at 10 K. This anomaly results in the strongest biexciton binding between two dark excitons occurring at <i>n</i> = 2, rather than at <i>n</i> = 1 as initially hypothesized. The observed anomaly arises from a phase transition induced by octahedral tilting occurring only for <i>n</i> = 2 near 100 K as confirmed by temperature-dependent optical and X-ray diffraction measurements. Our results show that Coulomb interaction need not vary gradually with <i>n</i>, which can impact the optoelectronic properties of the Ruddlesden-Popper series.