Organic Spacers Modulated Low Dose X‐Ray Detection in Hybrid Halide 2D Perovskites: Unveiling Exciton Dynamics

In this study, we investigate how modulating organic spacers in perovskites influences their X-ray detection performance and reveal the mechanism of low-dose detection with high sensitivity using femtosecond-transient absorption spectroscopy (fs-TAS). Particularly, we employ N,N,N',N'-tetramethyl-1,4-phenylenediammonium (TMPDA) and N,N-dimethylphenylene-p-diammonium (DPDA) as organic spacers to synthesize 2D perovskite single crystals (SCs). We find that DPDA-based SCs exhibit reduced interplanar spacing between inorganic layers, leading to increased lattice packing. Density functional theory (DFT) results indicate the reduced effective mass and lower lattice distortion in (DPDA)PbBr4 suppressing the formation of self-trapped exciton (STEs) and electron-phonon coupling and enhancing carrier delocalization in these SCs. Further, X-ray detection measurements reveal that (DPDA)PbBr4 demonstrates higher sensitivity than (TMPDA)PbBr4, attributed to its enhanced carrier delocalization, and higher mobility-lifetime product. The limit of detection (LoD) for (DPDA)PbBr4 is determined to be 13 nGy/s, significantly lower than both commercial detectors and state-of-the-art perovskite-based X-ray detectors. Furthermore, fs-TAS study reveals that (DPDA)PbBr4 crystals exhibit prolonged hot STE cooling and decay lifetimes, which directly correlate with their higher sensitivity. This study highlights the impact of organic spacers on X-ray detection performance, providing a framework for designing ultra-low LoD detectors essential for health and security applications.