Extensive attention has focused on the structure optimization of perovskites, whereas rare research has mapped the structure heterogeneity within mixed hybrid perovskite films. Overlooked aspects include material and structure variations as a function of depth. These depth-dependent local structure heterogeneities dictate their long-term stabilities and efficiencies. Here, we use a nano-focused wide-angle X-ray scattering method for the mapping of film heterogeneities over several micrometers across lateral and vertical directions. The relative variations of characteristic perovskite peak positions show that the top film region bears the tensile strain. Through a texture orientation map of the perovskite (100) peak, we find that the perovskite grains deposited by sequential spray-coating grow along the vertical direction. Moreover, we investigate the moisture-induced degradation products in the perovskite film, and the underlying mechanism for its structure-dependent degradation. The moisture degradation along the lateral direction primarily initiates at the perovskite-air interface and grain boundaries. The tensile strain on the top surface has a profound influence on the moisture degradation.

PbS quantum dot (QD) solar cells demonstrate great potential in solar energy conversion with a broad and flexible spectral response. Even though long-term storage stabilities of QD solar cells were reported in literature, the operation stability from a more practical aspect, to date, has been not yet investigated. Herein, we observe the structure degradation process of a PbS QD-ink based solar cell during the device operation. Simultaneously to probing the solar cell parameters, the overall structure evolutions of the QDs in both, active layer and hole transport layer of the solar cell are studied with grazing-incidence small- and wide-angle X-ray scattering (GISAXS/GIWAXS). We find a spontaneous decrease of the QD inter-dot distance with an increase in the spatial disorder in the active layer (PbX₂–PbS QDs, X = I, and Br) during the operation induced degradation. Consequently, the structure disorder-induced broadening of the energy state distribution is responsible for the decrease in open-circuit voltage V_oc leading to the device degradation. These findings elucidate the origin of light-soaking as well as the structure degradation of QD ink-based solar cells and indicate that the stability of the device can be realized by the positional stabilization of the QDs in the QD solid.

Colloidal PbS quantum dots (QDs) are attractive for solution-processed thin-film optoelectronic applications. In particular, directly achieving QD thin-films by printing is a very promising method for low-cost and large-scale fabrication. The kinetics of QD particles during the deposition process play an important role in the QD film quality and their respective optoelectronic performance. In this work, the particle self-organization behavior of small-sized QDs with an average diameter of 2.88 ± 0.36 nm is investigated for the first time in situ during printing by grazing-incidence small-angle X-ray scattering (GISAXS). The time-dependent changes in peak intensities suggest that the structure formation and phase transition of QD films happen within 30 seconds. The stacking of QDs is initialized by a templating effect, and a face-centered cubic (FCC) film forms in which a superlattice distortion is also found. A body-centered cubic nested FCC stacking is the final QD assembly layout. The small size of the inorganic QDs and the ligand collapse during the solvent evaporation can well explain this stacking behavior. These results provide important fundamental understanding of structure formation of small-sized QD based films prepared via large-scale deposition with printing with a slot die coater.