Control over the Pd shell
morphology: switching between smooth
and rough Pd layers to alter the plasmonic properties. (a) Schematic
representation of the Pd overgrowth with increasing Na2PdCl4 concentration, leading to an increase in roughness
of the Pd shell. (b) HAADF-SEM images and corresponding EDX intensity
maps of Au@Pd@SiO2 NRs grown with 0.18 mM (XPd = 0.14) and 0.83 mM (XPd = 0.39). (c) Measured extinction spectra of the Au@Pd@SiO2 NRs in water, grown with 0–0.83 mM Na2PdCl4 and XPd = 0–0.39. (d,
e) Finite-difference time-domain (FDTD)-calculated extinction spectra
of Au@Pd@SiO2 NRs with a thin (d) and a thick (e) Pd shell
as a function of the Pd packing fraction p of the
shell, where p < 1 and p = 1
correspond to a discontinuous and continuous Pd shell, respectively
(see the Experimental Section for details).
The Au@Pd@SiO2 NRs with a thin and a thick Pd shell correspond
to experimental results with 0.083 mM Na2PdCl4 (Au core: 58.5 × 17.7 nm; Au@Pd NR: 60.5 × 19.7 nm) and
0.83 mM Na2PdCl4 (Au@Pd NR: 78.6 × 19.4
nm), respectively. (f, g) HRTEM image and EDX intensity map of Au@Pd@SiO2 NRs with a rough shell morphology before (f) and after (g)
thermal treatment for 1 h at 300 °C in H2. See Table S3 for the full set of experimental details.