Dimensional and Optoelectronic Tuning of Lead-free Perovskite Cs3 Bi2 I9-n Brn Single Crystals for Enhanced Hard X-ray Detection.

Inorganic Bi-based perovskites have shown great potential in X-ray detection for their large absorption to X-rays, diverse low-dimensional structures, and eco-friendliness without toxic metals. However, they suffer from poor carrier transport properties compared to Pb-based perovskites. Here, we propose a mixed-halogen strategy to tune the structural dimensions and optoelectronic properties of Cs3 Bi2 I9-n Brn (0≤n≤9). Ten centimeter-sized single crystals are successfully grown by the Bridgman technique. Upon doping bromine to zero-dimensional Cs3 Bi2 I9 , the crystal transforms into a two-dimensional structure as the bromine content reaches Cs3 Bi2 I8 Br. Correspondingly, the optoelectronic properties are adjusted. Among these crystals, Cs3 Bi2 I8 Br exhibits negligible ion migration, moderate resistivity, and the best carrier transport capability. The sensitivities in 100 keV hard X-ray detection are 1.33×104 and 1.74×104  µC Gyair -1 cm-2 at room temperature and 75 °C, respectively, which are the highest among all reported bismuth perovskites. Moreover, the lowest detection limit of 28.6 nGyair s-1 and ultralow dark current drift of 9.12×10-9  nA cm-1 s-1 V-1 are obtained owing to the high ionic activation energy. Our work demonstrates that Br incorporation is an effective strategy to enhance the X-ray detection performance by tuning the dimensional and optoelectronic properties.

Anisotropic Performance of High-Quality MAPbBr3 Single-Crystal Wafers.

It has been proved that bulk single crystals of a halide perovskite behave much better than its polycrystalline counterparts in multiple application scenarios. Thus, the growth of large-sized and high-quality single crystals is significant to guarantee their ultimate device performances. Here, based on our recently invented settled temperature and controlled antisolvent diffusion system, improvements achieved in this work include the following: (1) We modified the growth system to optimize the control over both mass and heat transport to alleviate defect formation. State-of-the-art-quality MAPbBr3 crystals were grown, and from the bulk crystals, differently oriented crystalline wafers were fabricated with the full width at half-maximum of X-ray rocking curves of 40-86 arcsec. (2) The optical band gaps revealed no anisotropy on differently oriented wafers, whereas the refractive index and extinction coefficient exhibited obvious anisotropy. (3) Angle-resolved polarized Raman spectra demonstrate distinct in-plane anisotropy on (100) and (110) wafers but not on the (111) wafer. The equilibrium MA+ orientations are deduced to adopt the <111> direction with the antiparallel MA+ orientation between adjacent domains. (4) Radiation detectors fabricated on differently oriented wafers proved photoresponse anisotropy to both visible and X-ray radiation, following a general order of (100) > (110) > (111). Because anisotropy is an inevitable issue for various applications employing crystalline materials, this study, based on the clarification of the debatable intrinsic dipole configuration in the pseudocubic crystal lattice, will provide quantitative information on physicochemical property anisotropy and subsequently facilitate optimization of device performance referring to crystal orientations of halide perovskite crystals.