Quantum Confinement Effect in a Heteromorphic PbS/SnS(2) Superlattice Grown by Atomic Layer Deposition.

Quantum confinement in artificial superlattices enables the engineering of electronic and optical properties that exceed bulk limitations. Despite the unrivaled precision in thickness control and scalability of atomic layer deposition (ALD), the experimental demonstration of confinement effects in the superlattice geometry has remained elusive, especially for nonoxide systems. In this study, we report the experimental demonstration of distinct quantum confinement in the chalcogenide-based heteromorphic superlattices via an ALD supercycle approach. Polycrystalline PbS and amorphous SnS are alternately deposited with subnanometer thickness control, resulting in the formation of a well-defined heteromorphic superlattice structure with sharp, strain-relieved, and defect-passivated interfaces. Raman spectroscopy also revealed the activation of low-frequency vibrational modes, indicating strong interlayer coupling of strain-free layers within the superlattice. A systematic reduction in the PbS sublayer thickness below its excitonic Bohr radius enables a substantial and controllable widening of the bandgap, from 1.74 eV for PbS (14 nm)/SnS (5 nm) to 2.51 eV for PbS (3 nm)/SnS (5 nm), compared to 1.54 eV for individually grown PbS films. This marked bandgap modulation unambiguously demonstrates the strong quantum confinement of charge carriers within the strain-relaxed PbS layers. Density functional theory (DFT) calculations confirm the experimental observations, revealing the emergence of both lateral and vertical quantum confinement and elucidating the role of the superlattice architecture in shaping the electronic structure. Together, these results establish ALD as an effective platform for quantum superlattice engineering, enabling precise control of confinement effects in complex chalcogenide heterostructures and their integration into next-generation optoelectronics and quantum devices.