Temperature and atmosphere tunability of the nanoplasmonic resonance of a volumetric eutectic-based Bi_2O_3-Ag metamaterial

Abstract

Nanoplasmonic materials are intensively studied due to the advantages they bring in various applied fields such as photonics, optoelectronics, photovoltaics and medicine. However, their large-scale fabrication and tunability are still a challenge. One of the promising ways of combining these two is to use the self-organization mechanism and after-growth engineering as annealing for tuning the properties. This paper reports the development of a bulk nanoplasmonic, Bi2O3-Ag eutectic-based metamaterial with a tunable plasmonic resonance between orange and green wavelengths. The material, obtained by a simple growth technique, exhibits a silver nanoparticle-related localized surface plasmon resonance (LSPR) in the visible wavelength range. We demonstrate the tunability of the LSPR (spectral position, width and intensity) as a function of the annealing temperature, time and the atmosphere. The critical role of the annealing atmosphere is underlined, annealing in vacuum being the most effective option for a broad control of the LSPR. The various potential mechanisms responsible for tuning the localized surface plasmon resonance upon annealing are discussed in relation to the nanostructures of the obtained materials.

Evolution of silver in a eutectic-based Bi2O3–Ag metamaterial

“…The best of the investigated annealing conditions, which led to the most intensive LSPR peak, was annealing at 600°C for 60 min in vacuum [22]. That is why such samples were investigated here further, as shown in Fig.…”

“…Detailed growth and preparation methods have been described elsewhere [21]. After growth, the samples were annealed in vacuum at 600°C for 60 min [22]. The obtained Bi 2 O 3 -Ag composites were characterized by the following methods: high-resolution transmission electron microscopy (HRTEM) connected with selected area electron diffraction and with scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy (EDX).…”

“…Recently, eutectic solidification [15,16] has been proposed as one of the most promising bottom-up methods for manufacturing of metamaterials [17][18][19][20], plasmonic materials [21,22] and photonic crystals [23,24]. Eutectic solidification enables crystallization of a two-phase solid, often with an interesting selforganized micro-/nanostructure (typical are rod-like and lamellar structures) from a miscible liquid phase at a certain temperature [25].…”

“…Eutectic composites have been investigated for various applications such as solar energy conversion [26][27][28], power generation gas turbines [29], scintillators [30,31] or second-harmonic generators [32]. The plasmonic effect was presented in a eutectic composite for the first time with a Bi 2 O 3 -Ag composite [21,22]. After annealing the Bi 2 O 3 -Ag eutectic material, metal nanoparticles (silver and bismuth) are formed, which are responsible for the occurrence of plasmonic resonance in the visible wavelength range, at *595 nm.…”

“…After annealing the Bi 2 O 3 -Ag eutectic material, metal nanoparticles (silver and bismuth) are formed, which are responsible for the occurrence of plasmonic resonance in the visible wavelength range, at *595 nm. Using different annealing conditions such as the atmosphere, time and temperature, it is possible to control the peak frequency of the LSPR [22]. However, the development of metallic silver in this material is not yet well understood.…”