Self-assembly
of nanocrystals is a promising route for creating
macroscale materials that derive function from the properties of their
nanoscale building blocks. While much progress has been made assembling
nanocrystals into different superlattices, controlling the relative
orientations of nanocrystals in those lattices remains a challenge.
Here, we combine experiments with computer simulations to study the
self-assembly of patchy heterostructural nanocrystals (HNCs),
consisting of near-spherical quantum dots decorated with regular arrangements
of small gold satellites, into close-packed superlattices with pronounced
orientational alignment of HNCs. Our simulations indicate that the
orientational alignment is caused by van der Waals interactions between
gold patches and is sensitive to the interparticle distance in the
superlattice. We demonstrate experimentally that the degree and type
of orientational alignment can be controlled by changing ligand populations
on HNCs. This study provides guidance for the design and fabrication
of nanocrystal superlattices with enhanced structural control.
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