Eutectic Combinations as a Pathway to the Formation of Substrate-Based Au-Ge Heterodimers and Hollowed Au Nanocrescents with Tunable Optical Properties
A Sundar and P Farzinpour and KD Gilroy and T Tan and RA Hughes and S Neretina, SMALL, 10, 3379-3388 (2014).
Pairs of immiscible elements with deep eutectics are used to synthesize periodic arrays of heterodimers and hollowed metal nanocrescents. In the devised route, substrate-immobilized Au or Ag nanostructures act as heterogeneous nucleation sites for Ge adatoms. At elevated temperatures the adatoms collect in sufficient quantities to transform each site into a AuGe liquid alloy which, upon cooling, phase separates into elemental components sharing a common interface. The so-formed Au-Ge and Ag-Ge heterodimers exhibit a complex morphology characterized by a noble metal nanocrescent which partially encapsulates one end of the Ge domain. Through the use of a selective etch the Ge component is removed, leaving behind a periodic array of hollow noble metal nanocrescents on the surface of the substrate. Optical characterization of both the heterodimers and nanocrescents indicates that the presence of Ge gives rise to a relative blue-shift in the localized surface plasmon peak, a result that is in stark contrast to the red-shifts typically observed when plasmonic nanostructures are in contact with a dielectric medium. Simulations are used to both rationalize the observed shift and show the potential for deriving unexpected behaviors when semishell-like noble metal structures are in contact with high permittivity dielectric mediums.
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