Size-Dependent Fault-Driven Relaxation and Faceting in Zincblende CdSe Colloidal Quantum Dots

Surface chemistry and core defects are known to play a prominent role in governing the photophysical properties of nanocrystalline semiconductors. Nevertheless, investigating them in small nanocrystals remains a complex task. Here, by combining X-ray scattering techniques in the wide- and small-angle regions and using the Debye Scattering Equation (DSE) method of analysis, we unveil a high density of planar defects in oleate-terminated zincblende (ZB) CdSe colloidal quantum dots (QDs) and size-dependent faceting within a square-cuboid morphology. Atomistic models of faulted ZB nanocrystals, based on the probabilistic stacking of CdSe layers in cubic and hexagonal sequences, and data analysis point to the preferential location of faults near the center of nanocrystals. By finely modeling faulting and morphological effects on the X-ray scattering pattern, a relaxation of the Cd-Se bond distance parallel to the stacking direction, up to +3% (2.71 Å) with respect to the reference bulk value (2.63 Å) is detected, at the cubic/hexagonal transitions. The smallest nanocrystals show cubic 100 facets; 111 facets appear above 4 nm and progressively extend at larger sizes. These structural and morphological features likely vary depending on the synthesis conditions; nevertheless, since planar defects are nearly ubiquitous in CdSe QDs, the modeling approach here presented has a general validity. This work also points to the great potential of combining small- and wide-angle X-ray scattering and DSE-modeling techniques in gaining important knowledge on atomic-scale defects of semiconductor nanocrystals, underpinning the comprehension of the impact of structural defectiveness on the exciting properties of these QDs.