Silver Nanorice Structures: Oriented Attachment-Dominated Growth, High Environmental Sensitivity, and Real-Space Visualization of Multipolar Resonances

We have synthesized and investigated the anisotropic growth of interesting silver nanorice. Its growth is kinetically controlled at 100 °C, and both oriented attachment and Ostwald ripening are involved, with the former growth mode dominating the anisotropic growth of the nanorice along the ⟨111⟩ direction. This one-directional growth is initiated by an indispensable seed-selection process, in which oxygen plays a critical role in oxidatively etching twinned silver crystals. The inhibition of this process by removing oxygen essentially blocks the nanorice growth. Although increasing reaction temperature to 120 °C accelerates the one-dimensional growth along the ⟨111⟩ direction, further temperature increase to 160 °C makes the oriented attachment dominated one-directional growth disappear; instead, the diffusion-controlled two-dimensional growth leads to the emergence of highly faceted truncated triangular and hexagonal plates mainly bound by low energy faces of {111}. Interestingly, we also found that the longitudinal surface plasmon resonance of the nanorice structures is highly sensitive to the refractive index of surrounding dielectric media, which predicts their promising applications as chemical or biological sensors. Moreover, the multipolar plasmonic resonances in these individual nanorice structures are visualized in real space, using high-resolution electron energy-loss spectroscopy.