Interfaced metal heterodimers in the quantum size regime

Synthesis of nanoparticle dimers made of asymmetric compositions is very challenging because of the difficulty in manipulating the nanoparticles’ surface chemistries in order to control the assembly and/or growth of different nanoparticles. In this Letter, we report a seed-mediated, surface-confined epitaxial overgrowth strategy that enables the synthesis of high-quality interfaced Au–Ag heterodimers in the quantum size regime (diameters <10 nm). Au and Ag share a common face-centered cubic lattice and have nearly identical lattice constants, which facilitates epitaxial overgrowth and allows direct contact between the Au and Ag domains. Quantum size effects, formation of the Au/Ag interfaces, and chemical interactions with surfactant molecules strongly influence the optical properties of the dimers and lead to the observation of unique surface plasmon resonances. In particular, we find an unusual enhancement of the characteristic Au surface plasmon resonance and the emergence of a charge transfer plasmon across the Au/Ag domains, which together lead to broad-band absorption spanning visible to near-infrared wavelengths. A model that captures the changes in optical behavior due to chemical interactions and quantum size effects is used to calculate the absorption spectra of the interfaced heterodimers, resulting in good agreement with experimental measurements.