Plasmonic Ga nanoparticles (NPs) were thermally oxidized at low temperature in order to increase the native Ga2O3 shell thickness and to improve their stability during the chemical functionalization. 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 with the increasing annealing time due to the Ga2O3 thickness increase, and barely affecting the intensity of the plasmon resonance. This oxide layer enhances the stability of the NPs upon immersion in ethanol or water. The surface sensitivity properties of the as-grown and oxidized NPs were investigated by linking a thiol group from 6-Mercapto-1-hexanol through immersion. Ellipsometric spectra at the reversal polarization handedness (RPH) condition are in agreement with the Langmuir absorption model, indicating the formation of a thiol monolayer on the NPs.
A new method for the synthesis of colloidal gallium nanoparticles (Ga NPs) based on the thermal evaporation of Ga on an expendable aluminum zinc oxide (AZO) layer is presented here. The growth of AZO layers was investigated on different substrates at room temperature and 300 °C. By means of physical evaporation process, nanoparticles were deposited with a distribution ranging from 10 nm to 80 nm in diameter. A study of their endurance in acidic environment was carried out in order to assure the NPs shape and size stability during the etching process. Smaller particles start to disappear between 1h and 2h immersion time in a pH=1 solution, while bigger particles reduce their dimension. The NPs were dispersed in tetrahydrofuran (THF) organic solvent and optically characterized, showing strong UV absorption with a band centered at 280 nm. The colloids size distribution of as-evaporated samples was compared with the distribution obtained in droplets of the solution after drop-casting. By Dipole Discrete Approximation simulations, a close relationship between the UV absorption and the NPs with diameter smaller than ~40 nm was found. Because of the gallium oxide (Ga1-xOx) outer shell that surrounds the Ga NPs, an enhancement of their hydrophobicity occurs. Hence, the low agglomeration state between NPs in tetrahydrofuran allows to obtain narrow absorption band in the optical spectrum.
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