Fostering the Dense Packing of Halide Perovskite Quantum Dots through Binary-Disperse Mixing

[Image: see text] Due to their versatile applications, perovskite quantum dot (PQD)-based optoelectrical devices have garnered significant research attention. However, the fundamental packing behavior of PQDs in thin films and its impact on the device performance remain relatively unexplored. Drawing inspiration from theoretical models concerning packing density with size mixtures, this study presents an effective strategy, namely, binary-disperse mixing, aimed at enhancing the packing density of PQD films. Comprehensive grazing-incidence small-angle X-ray characterization suggested that the PQD film consists of three phases: two monosize phases and one binary mixing phase. The volume fraction and population of the binary-size phase can be tuned by mixing an appropriate amount of large and small PQDs. Furthermore, we performed multi-length-scale all-atom and coarse-grained molecular dynamics simulations to elucidate the distribution and conformation of organic surface ligands, highlighting their influence on PQD packing. Notably, the mixing of two PQDs of different sizes promotes closer face-to-face contact. The densely packed binary-disperse film exhibited largely suppressed trap-assisted recombination, much longer carrier lifetime, and thereby improved power conversion efficiency. Hence, this study provides fundamental understanding of the packing mechanism of perovskite quantum dots and highlights the significance of packing density for PQD-based solar cells.