Controlled anion mixing in halide perovskites has been shown to be an effective route to precisely tune optoelectronic properties in order to achieve efficient photovoltaic, light emission, and radiation detection devices. However, an atomistic understanding behind the precise mechanism impacting the performances of mixed halide perovskite devices, particularly as a radiation detector, is still missing. Combining high-level computational methods and multiple experiments, here we systematically investigate the effect of chlorine (Cl) incorporation on the optical and electronic properties, structural stability, ion migration, and the γ-ray radiation detection ability of MAPbBr3–x Cl x . We observe that precise halide mixing suppresses bromide ion migration and consequently reduces the dark current by close to a factor of two, which significantly increases the resistance of the mixed anion devices. Furthermore, reduced carrier effective masses and mostly unchanged exciton binding energies indicate enhanced charge carrier transport for these perovskite alloys. At the atomistic level, modifications to ion migration and charge carrier transport properties improve electronic properties and predominantly contribute to the better response and resolution in high-energy γ-ray detection with MAPbBr3–x Cl x as compared to MAPbBr3. This study provides a systematic approach to enhance the high-energy radiation detection ability of MAPbBr3–x Cl x -based devices by understanding the atomistic properties underpinning performance.

Understanding the type, formation energy and capture cross section of defects is one of the challenges in the field of organometallic halide perovskite (OMHP) devices. Currently, such understanding is limited, restricting the power conversion efficiencies of OMHPs solar cells from reaching their Shockley-Queisser limit. In more matured semiconductors like Si, the knowledge of defects was one of the major factor in successful technological implementation. This knowledge and its control can make a paradigm in development of OMHP devices. Here, we report on deep level (DL) defects and their effect on free charge transport properties of single crystalline methylammonium lead bromide perovskite (MAPbBr3). In order to determine DL activation energy and capture cross section we used photo-Hall effect spectroscopy (PHES) with enhanced illumination in both steady-state and dynamic regimes. This method has shown to be convenient due to the direct DL visualization by sub-bandgap photo-excitation of trapped carriers. DLs with activation energies of EV + 1.05 eV, EV + 1.5 eV, and EV + 1.9 eV (or EC -1.9 eV) were detected. The hole capture cross section of h = 4 × 10 -17 cm 2 is found using photoconductivity relaxation after sub-bandgap photo-excitation. Here, we found the DL defects responsible for non-radiative recombination and its impact on band alignment for the first time. Additionally, the transport properties of single crystal MAPbBr3 is measured by Time of Flight