Tracking the Breakdown of Quantum Confinement during Structural Degradation of FAPbI₃

Bulk formamidinium lead triiodide (FAPbI₃) films host spontaneously formed quantum-confined (QC) domains, but their structural origin remains unclear. Using controlled material degradation in humid air as a dynamic lattice perturbation, we track the evolution of QC features in thin-film absorption of FAPbI₃. With aging, above-bandgap QC features redshift and diminish, indicating weakened electronic confinement. Concurrently, X-ray diffraction reveals that breakdown of α-phase connectivity coincides with the loss of short-range higher-order hexagonal (nH, n > 2) polytypes as the material converts to the 2H δ-phase. Such polytypic nanodomains may generate peaked absorption features by forming higher-energy barriers confining charge carriers within α-FAPbI₃ or by introducing distinct electronic states associated with mixed octahedral connectivity. Progressive degradation dismantles this framework, causing the disappearance of the QC features. Our results identify the structural motifs underpinning QC effects and propose that controlling higher-order (n > 2) hexagonal polytypes offers a route to tuning quantum confinement in FAPbI₃ films.