In Situ Epitaxial Growth of Centimeter-Sized Lead-Free (BA)₂CsAgBiBr₇/Cs₂AgBiBr₆ Heterocrystals for Self-Driven X-ray...

Halide perovskite heterocrystals, composed of distinct perovskite single crystals, have generated great interest for both fundamental research and applied device designs. One of the key advantages of using such a heterocrystal is its built-in electric potential, which enhances charge transport and suppresses the noise in the solid-state devices. On the basis of this strategy, high-performance optoelectronic devices (e.g., X-ray detectors) have been successfully demonstrated. However, the toxicity of metal cations (Pb) in those reported heterocrystals hinders their wider applications. Thus, developing lead-free halide perovskite heterocrystals is significant but remains highly challenging. Here, we report a solution-processed in situ heteroepitaxial approach that enables us to create the first lead-free halide perovskite heterocrystal, (BA)₂CsAgBiBr₇/Cs₂AgBiBr₆(BA = n-butylammonium), with dimensions of up to 10 × 7 × 6 mm³. The as-grown heterocrystals have high crystalline quality and present near atomically sharp interfaces. More excitingly, the (BA)₂CsAgBiBr₇/Cs₂AgBiBr₆ heterogeneous integration allows the formation of a built-in electric potential in the junction, which triggers spontaneous charge separation/transport. Consequently, X-ray detectors using the heterocrystals can operate in a self-driven mode and exhibit an impressive sensitivity (206 μC Gy^-1 cm^-2) superior to that of the pristine Cs₂AgBiBr₆ crystal detectors, an ultralow dark current, and operational stability. Our findings provide the first demonstration of lead-free halide perovskite heterocrystals and may open up opportunities for a host of sustainable and miniaturized perovskite optoelectronic devices.