Large‐Scale,Long‐Range‐Ordered Patterning of Nanocrystals via Capillary‐Bridge Manipulation

Deterministic assembly of nanoparticles with programmable patterns is a core opportunity for property‐by‐design fabrication and large‐scale integration of functional materials and devices. The wet‐chemical‐synthesized colloidal nanocrystals are compatible with solution assembly techniques, thus possessing advantages of high efficiency, low cost, and large scale. However, conventional solution process suffers from tradeoffs between spatial precision and long‐range order of nanocrystal assembly arising from the uncontrollable dewetting dynamics and fluid flow. Here, a capillary‐bridge manipulation method is demonstrated for directing the dewetting of nanocrystal inks and deterministically patterning long‐range‐ordered superlattice structures. This is achieved by employing micropillars with programmable size, arrangement, and shape, which permits deterministic manipulation of geometry, position, and dewetting dynamics of capillary bridges. Various superlattice structures, including one‐dimensional (1D), circle, square, pentagon, hexagon, pentagram, cross arrays, are fabricated. Compared to the glassy thin films, long‐range‐ordered superlattice arrays exhibit improved ferroelectric polarization. Coassembly of nanocrystal superlattice and organic functional molecule is further demonstrated. Through introducing azobenzene into superlattice arrays, a switchable ferroelectric polarization is realized, which is triggered by order–disorder transition of nanocrystal stacking in reversible isomerization process of azobenzene. This method offers a platform for patterning nanocrystal superlattices and fabricating microdevices with functionalities for multiferroics, electronics, and photonics.