Modulation of Morphology and Optical Property of Multi-Metallic PdAuAg and PdAg Alloy Nanostructures.

In this work, the evolution of PdAg and PdAuAg alloy nanostructures is demonstrated on sapphire (0001) via the solid-state dewetting of multi-metallic thin films. Various surface configurations, size, and arrangements of bi- and tri-metallic alloy nanostructures are fabricated as a function of annealing temperature, annealing duration, film thickness, and deposition arrangements such as bi-layers (Pd/Ag), tri-layers (Pd/Au/Ag), and multi-layers (Pd/Au/Ag × 5). Specifically, the tri-layers film shows the gradual evolution of over-grown NPs, voids, wiggly nanostructures, and isolated PdAuAg alloy nanoparticles (NPs) along with the increased annealing temperature. In contrast, the multi-layers film with same thickness show the enhanced dewetting rate, which results in the formation of voids at relatively lower temperature, wider spacing, and structural regularity of alloy NPs at higher temperature. The dewetting enhancement is attributed to the increased number of interfaces and reduced individual layer thickness, which aid the inter-diffusion process at the initial stage. In addition, the time evolution of the Pd150 nm/Ag80 nm bi-layer films at constant temperature show the wiggly-connected and isolated PdAg alloy NPs. The overall evolution of alloy NPs is discussed based on the solid-state dewetting mechanism in conjunction with the diffusion, inter-diffusion, alloying, sublimation, Rayleigh instability, and surface energy minimization. Depending upon their surface morphologies, the bi- and tri-metallic alloy nanostructures exhibit the dynamic reflectance spectra, which show the formation of dipolar (above 700 nm) and quadrupolar resonance peaks (~ 380 nm) and wide dips in the visible region as correlated to the localized surface plasmon resonance (LSPR) effect. An absorption dip is readily shifted from ~ 510 to ~ 475 nm along with the decreased average size of alloy nanostructures.

Morphological and optical properties of PdxAg1-x alloy nanoparticles.

Alloy nanoparticles (NPs) can offer a wide range of opportunities for various applications due to their composition and structure dependent properties such as multifunctionality, electronic heterogeneity, site-specific response, and multiple plasmon resonance bands. In this work, the fabrication of self-assembled PdxAg1-x NPs alloy nanostructures with distinct size, density, shape, and composition is demonstrated via the solid-state dewetting of sputtered Pd/Ag thin films on c-plane sapphire. The initial stage of bilayer dewetting exhibits the nucleation of voids, followed by the expansion of voids and cluster breakdown and finally shape transformation along with the temperature control. Bilayer composition shows a substantial influence on the dewetting such that the overall dewetting is enhanced along with the increased Ag composition, i.e. Pd0.25Ag0.75 > Pd0.5Ag0.5 > Pd0.75Ag0.25. On the other hand, the size and density of NPs can be efficiently controlled by varying the initial thickness of bilayers. Reflectance peaks in UV and near-infrared (NIR) regions and a wide absorption band in the visible region arisen from the surface plasmon resonance are observed in reflectance spectra. The peak intensity depends on the composition of PdxAg1-x NPs and the NIR peaks gradually blue-shift with the size decrement.

Correction: Compositional effect on the fabrication of Ag x Pd1-x alloy nanoparticles on c-plane sapphire at distinctive stages of the solid-state-dewetting of bimetallic thin films.

[This corrects the article DOI: 10.1039/C7RA11058H.].

Investigation on the morphological and optical evolution of bimetallic Pd-Ag nanoparticles on sapphire (0001) by the systematic control of composition, annealing temperature and time.

Multi-metallic alloy nanoparticles (NPs) can offer additional opportunities for modifying the electronic, optical and catalytic properties by the control of composition, configuration and size of individual nanostructures that are consisted of more than single element. In this paper, the fabrication of bimetallic Pd-Ag NPs is systematically demonstrated via the solid state dewetting of bilayer thin films on c-plane sapphire by governing the temperature, time as well as composition. The composition of Pd-Ag bilayer remarkably affects the morphology of alloy nanostructures, in which the higher Ag composition, i.e. Pd0.25Ag0.75, leads to the enhanced dewetting of bilayers whereas the higher Pd composition (Pd0.75Ag0.25) hinders the dewetting. Depending on the annealing temperature, Pd-Ag alloy nanostructures evolve with a series of configurations, i.e. nucleation of voids, porous network, elongated nanoclusters and round alloy NPs. In addition, with the annealing time set, the gradual configuration transformation from the elongated to round alloy NPs as well as size reduction is demonstrated due to the enhanced diffusion and sublimation of Ag atoms. The evolution of various morphology of Pd-Ag nanostructures is described based on the surface diffusion and inter-diffusion of Pd and Ag adatoms along with the Ag sublimation, Rayleigh instability and energy minimization mechanism. The reflectance spectra of bimetallic Pd-Ag nanostructures exhibit various quadrupolar and dipolar resonance peaks, peak shifts and absorption dips owing to the surface plasmon resonance of nanostructures depending on the surface morphology. The intensity of reflectance spectra is gradually decreased along with the surface coverage and NP size evolution. The absorption dips are red-shifted towards the longer wavelength for the larger alloy NPs and vice-versa.