Twisted Tin‐Chloride Perovskite Single‐Crystal Heterostructures

Abstract Self‐assembly affords simpler synthetic routes to heterostructures compared with manual layer‐by‐layer stacking, yet controlling interlayer twist angles in a bulk solid remains an outstanding challenge. We report two new single‐crystal heterostructures: (Sn 2 Cl 2 )(CYS) 2 SnCl 4 (CYS = + NH 3 (CH 2 ) 2 S – ; Sn_CYS ) and (Sn 2 Cl 2 )(SeCYS) 2 SnCl 4 (SeCYS = + NH 3 (CH 2 ) 2 Se – ; Sn_SeCYS ) synthesized in solution, with alternating perovskite and intergrowth layers. Notably, compared to the recently reported lead analog, (Pb 2 Cl 2 )(CYS) 2 PbCl 4 ( Pb_CYS ), the tin heterostructures feature a twist between the perovskite and intergrowth layers. We trace this twist to local distortions at the Sn centers, which change the interfacial lattice‐matching requirements compared to those of the Pb analog. Electronic band structure calculations show that the striking differences in the relative energies of perovskite‐ and intergrowth‐derived bands in Sn_CYS and Pb_CYS arise from structural and not compositional differences. The structural anisotropy of Sn_CYS is also reflected in a large in‐plane photoluminescence linear anisotropy ratio. Interfacial strain further affords differential incorporation of Pb into the perovskite and intergrowth layers of the Sn heterostructures, resulting in redshifted optical absorption onsets. Thus, we posit that local structural distortions may be exploited to manipulate the twist angle and interfacial strain in bulk heterostructures, providing a new handle for tuning the band alignments of bulk quantum‐well electronic structures.