Ion Beam Milling as a Symmetry-Breaking Control in the Synthesis of Periodic Arrays of Identically Aligned Bimetallic Janus Nanocrystals.

Bimetallic Janus nanostructures represent a highly functional class of nanomaterials due to important physicochemical properties stemming from the union of two chemically distinct metal segments where each maintains a partially exposed surface. Essential to their synthesis is the incorporation of a symmetry-breaking control that is able to induce the regioselective deposition of a secondary metal onto a preexisting nanostructure even though such depositions are, more often than not, in opposition to the innate tendencies of heterogeneous growth modes. Numerous symmetry-breaking controls have been forwarded but the ensuing Janus structure syntheses have not yet achieved anywhere near the same level of control over nanostructure size, shape, and composition as their core-shell and single-element counterparts. Herein, a collimated ion beam is demonstrated as a symmetry-breaking control that allows for the selective removal of a passivating oxide shell from one side of a metal nanostructure to create a configuration that is transformable into a substrate-bound Au-Ag Janus nanostructure. Two different modalities are demonstrated for achieving Janus structures where in one case the oxide dissolves in the growth solution while in the other it remains affixed to form a three-component system. The devised procedures distinguish themselves in their ability to realize complex Janus architectures arranged in periodic arrays where each structure has the same alignment relative to the underlying substrate. The work, hence, provides an avenue for forming precisely tailored Janus structures and, in a broader sense, advances the use of oxides as an effective means for directing nanometal syntheses.