Formation and assembly-disassembly processes of ZnO hexagonal pyramids driven by dipolar and excluded volume...

ZnO hexagonal pyramids were obtained in hydrophilic media without any traditional stabilizers (capping agents). The absence of a thick organic shell reducing the anisotropy of nanoparticle (NP) interactions, oxide nature of the materials, and new geometry of the nanocrystals makes possible the observation of new self-organization phenomena. Several new features not present in the previous cases of NP self-organization were identified and discussed. The formation of ZnO pyramids involved recrystallization of larger amorphous NPs followed by the multistage disassembly of intermediate aggregates into individual virtually perfectly shaped nanocrystals. The evolution of NPs begins with crystallization of clustered plates within the original amorphous spherical colloids, and then agglomerated truncated pyramids are formed. These agglomerates further transform into chained pyramids, which eventually separate from each other. The crystallization and disassembly processes can be associated with the decrease of potential and anisotropy of the attractive force field around the crystallites represented in part by dipole moments. The reassembly of the pyramids can still be attained via engaging excluded volume interaction after adding similarly charged polymer. Overall, in this system, we see the first examples of (1) coupled crystallization and disassembly process; (2) induced assembly of nanoscale particles using excluded volume interactions, which were previously used only for aggregation of microscale colloids; and (3) nanoparticle assemblies with variable and experimentally verifiable relative orientation of dipoles including head-to-tail, tail-to-tail pairs, and antiparallel chains. Described assemblies of ZnO pyramids with collective behavior of individual building blocks as well as distinct and experimentally controlled stages of assembly and disassembly present a fundamentally interesting nanoparticle system with rich dynamic behavior.