The effect of the oxidation of gallium nanoparticles (Ga NPs) on their plasmonic properties is investigated. Discrete dipole approximation has been used to study the wavelength of the out-of-plane localized surface plasmon resonance in hemispherical Ga NPs, deposited on silicon substrates, with oxide shell (Ga 2 O 3 ) of different thickness. Thermal oxidation treatments, varying temperature and time, were carried out in order to increase experimentally the Ga 2 O 3 shell thickness in the NPs. The optical, structural and chemical properties of the oxidized NPs have been studied by spectroscopic ellipsometry, scanning electron microscopy, grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy. A clear redshift of the peak wavelength is observed, barely affecting the intensity of the plasmon resonance. A controllable increase of the Ga 2 O 3 thickness as a consequence of the thermal annealing is achieved. In addition, simulations together with ellipsometry results have been used to determine the oxidation rate, whose kinetics is governed by a logarithmic dependence. These results support the tunable properties of the plasmon resonance wavelength in Ga NPs by thermal oxidation at low temperatures without significant reduction of the plasmon resonance intensity.
2D monolayer molybdenum disulphide (MoS2) has been the focus of intense research due to its direct bandgap compared with the indirect bandgap of its bulk counterpart; however its photoluminescence (PL) intensity is limited due to its low absorption efficiency.
Plasmonic gallium (Ga) nanoparticles (NPs) are well known to exhibit good performance in numerous applications such as surface enhanced fluorescence and Raman spectroscopy or biosensing. However, to reach the optimal optical performance, the strength of the localized surface plasmon resonances (LSPRs) must be enhanced particularly by suitable narrowing the NP size distribution among other factors. With this purpose, our last work demonstrated the production of hexagonal ordered arrays of Ga NPs by using templates of aluminium (Al) shallow pit arrays, whose LSPRs were observed in the VIS region. The quantitative analysis of the optical properties by spectroscopic ellipsometry confirmed an outstanding improvement of the LSPR intensity and full width at half maximum (FWHM) due to the imposed ordering. Here, by engineering the template dimensions, and therefore by tuning Ga NPs size, we expand the LSPRs of the Ga NPs to cover a wider range of the electromagnetic spectrum from the UV to the IR regions. More interestingly, the factors that cause this optical performance improvement are studied with the universal plasmon ruler equation, supported with discrete dipole approximation simulations. The results allow us to conclude that the plasmonic coupling between NPs originated in the ordered systems is the main cause for the optimized optical response.
New methods for the production of colloidal Ga nanoparticles (GaNPs) are introduced based on the evaporation of gallium on expendable aluminum zinc oxide (AZO) layer. The nanoparticles can be prepared in aqueous or organic solvents such as tetrahydrofuran in order to be used in different sensing applications. The particles had a quasi mono-modal distribution with diameters ranging from 10 nm to 80 nm, and their aggregation status depended on the solvent nature. Compared to common chemical synthesis, our method assures higher yield with the possibility of tailoring particles size by adjusting the deposition time. The GaNPs have been studied by spectrophotometry to obtain the absorption spectra. The colloidal solutions exhibit strong plasmonic absorption in the ultra violet (UV) region around 280 nm, whose width and intensity mainly depend on the nanoparticles dimensions and their aggregation state. With regard to the colloidal GaNPs flocculate behavior, the water solvent case has been investigated for different pH values, showing UV-visible absorption because of the formation of NPs clusters. Using discrete dipole approximation (DDA) method simulations, a close connection between the UV absorption and NPs with a diameter smaller than ~40 nm was observed.
Core–shell gallium nanoparticles (Ga NPs) have recently been proposed as an ultraviolet plasmonic material for different applications but only at room temperature. Here, the thermal stability as a function of the size of the NPs is reported over a wide range of temperatures. We analyze the chemical and structural properties of the oxide shell by x-ray photoelectron spectroscopy and atomic force microscopy. We demonstrate the inverse dependence of the shell breaking temperature with the size of the NPs. Spectroscopic ellipsometry is used for tracking the rupture and its mechanism is systematically investigated by scanning electron microscopy, grazing incidence x-ray diffraction and cathodoluminescence. Taking advantage of the thermal stability of the NPs, we perform complete oxidations that lead to homogenous gallium oxide NPs. Thus, this study set the physical limits of Ga NPs to last at high temperatures, and opens up the possibility to achieve totally oxidized NPs while keeping their sphericity.