Dynamic Behavior of Bound Interlayer Excitons in Interlayer-Doped Cs3Bi2Br9 Vacancy-Ordered Perovskite

Interlayer doping of the vacancy-ordered 2D perovskite Cs₃Bi₂Br₉ (CBB) enables the formation of bound interlayer excitons (BIEs), a unique charge-transfer excited state within the layered solid. BIEs previously reported with silver (Ag⁺) as an interlayer dopant exhibited bright broadband photoluminescence (PL) with prolonged lifetime at room temperature, offering potential applications in efficient white light emission, photocatalysis, and optoelectronics. However, the dynamic behavior of radiation and excited carriers remains poorly understood due to the limitations of ensemble spectroscopic measurements. Here, we investigate the temperature-dependent dynamics of Ag-doped Cs₃Bi₂Br₉ (Ag-CBB) using single-particle time-resolved PL spectroscopy and ultrafast transient absorption imaging. Single-particle PL measurements reveal three distinct emission regimes across temperature: (i) BIE-dominant emission at high temperatures, (ii) a mixture of radiation from BIEs and self-trapped excitons (STEs) at intermediate temperatures, and (iii) STE-dominant emission below 100 K. Rapid transient absorption mapping using Parallel Rapid Imaging with Spectroscopic Mapping (PRISM) reveals subpicosecond STE formation in pristine CBB and long-lived photoinduced absorption by BIEs, consistent with electron–hole separation and suppressed STE transfer. The spatial uniformity of these signals confirms homogeneous Ag doping across single crystals. These findings highlight the role of Ag interlayer dopants in governing the BIE dynamics.