We fabricated Au-Cu₂O core-shell octahedra, cuboctahedra, and nanocubes having sizes of 90-220 nm using 50 nm octahedral cores. The smaller particle sizes minimize the strong light scattering features from the Cu₂O shells and enable the surface plasmon resonance (SPR) absorption band of the gold cores to be clearly identified. Beyond a lower shell thickness limit, the SPR band positions of the gold cores are independent of the shell thickness, but are strongly dependent on the exposed particle surfaces. The plasmonic band red-shifts from Au-Cu₂O octahedra to cuboctahedra and nanocubes, and differs by as much as 26 nm between the octahedra and the nanocubes. The same facet-dependent optical effects were observed using larger octahedral gold cores and cubic gold cores. In contrast, simulation spectra show progressively red-shifted SPR band positions with increasing shell thickness. The Cu₂O shells are also found to exhibit facet-dependent optical behavior. These nanocrystals can respond to changes in the solvent environment such as solvents with different refractive indices, indicating that the plasmonic field of the gold cores can extend beyond the particle surfaces despite the presence of thick shells. Plane-selective spectral responses to low concentrations of surfactants were also recorded.
Other than the display of purely optical phenomenon, the recently-discovered facet-dependent optical properties of metal-Cu2O nanocrystals have become useful by illuminating Au-Cu2O nanocubes and octahedra having a surface plasmon resonance (SPR) absorption band in the near-infrared (NIR) region from octahedral Au cores with 808 nm light for heat generation. After 5 min of light irradiation, a solution of Au-Cu2O nanocubes can reach 65 °C with their Au SPR band matching the illuminating light wavelength. Photothermal efficiency has been found to be facet-dependent. In addition, short gold nanorods were employed to synthesize {100}-bound rectangular Au-Cu2O nanobars with a tunable longitudinal Au SPR absorption band covering a broad NIR range from ∼1050 to 1400 nm. Because the Au SPR bands can become fixed with relatively thin Cu2O shells of less than 15 nm, ultrasmall nanobars having a size of 61 nm directly red-shift the Au SPR band to 1047 nm. And 73 nm nanobars can give a Au SPR band at 1390 nm. Truncated nanobars exposing {100}, {110}, and {111} facets give a very blue-shifted Au SPR band. The nanobars also exhibit photothermal activity when illuminated by 1064 nm light. These small Au-Cu2O nanocrystals represent the simplest nanostructure design to absorb light covering the entire NIR wavelengths.
Au-Cu2 O core-shell nanocubes, octahedra, and rhombic dodecahedra display facet-dependent optical properties. Furthermore, different-sized Au-Cu2 O octahedra with 58, 65, 68, and 73 nm octahedral gold cores clearly show a transition from the shell thickness-independent gold surface plasmon resonance band for octahedra with smaller gold cores to progressive red-shifts of the band with increasing shell thickness in octahedra with larger gold cores.
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