Layer Engineering of Quantum Organic–Inorganic Superlattices by Thermodynamic Design

Abstract Quantum organic–inorganic superlattices, constructed by vertically stacking two-dimensional inorganic crystals and organic molecular layers, offer a powerful platform for encoding emergent electronic states through an interfacial design. However, the precise layer engineering of such hybrid architectures, particularly the deterministic control over vertical stacking periodicities, has remained elusive because of the absence of a predictive thermodynamic framework governing the staging effect in hybrid systems. Here, we demonstrate that thermodynamic design, based on the quantitative competition between intercalant chemical potential and host elastic deformation energy, provides a principled route to programmable layer engineering of organic–inorganic superlattices. By precisely modulating the chemical potential of the intercalant, we achieve selective access to stage-1 intercalation (alternating 1-layer (1L) molecule/1L-SnSe2) and stage-2 intercalation (alternating 1L-molecule/2L-SnSe2) configurations with high structural fidelity. Atomic-resolution imaging reveals long-range periodic order across both staging phases, while angle-resolved photoemission spectroscopy reveals that the engineered layer sequence directly governs the interfacial charge transfer and electronic band structure evolution. The resulting superlattices exhibit stacking-dependent carrier densities and programmable superconducting transitions, establishing the layer sequence as a synthetic handle for quantum functionality. This work establishes thermodynamic design as a guiding principle for the rational layer engineering of quantum-hybrid solids.