Raman Study of Visible-Light Photooxidation of As2S3 : Ag Glasses
DOI:
https://doi.org/10.15407/ujpe70.3.206Keywords:
amorphous semiconductors, X-ray diffraction, Raman spectroscopy, photochemical reactions, oxidationAbstract
As2S3 : Ag glasses (up to 10 at.% Ag) were prepared by the melt quenching. Their amorphous structure is confirmed by X-ray diffraction and Raman spectroscopy. No noticeable changes in the Raman spectra with increasing Ag content are revealed at the excitation by a 671 nm laser or by a near-bandgap laser (λexc = 532 nm) at the low power density Pexc = 4 kW/cm2. Meanwhile, for the samples with Ag content above 4 at.% at the excitation by λexc = 532 nm at a higher Pexc = 40 kW/cm2, new narrow peaks emerge and are clearly identified as Raman features of arsenolite (As2O3) formed on the As2S3 : Ag glass surface under the intense illumination. This is the first Raman spectroscopic evidence of the visible-light photooxidation of As2S3-based glasses which previously was observed only under the illumination by ultraviolet light strongly absorbed by the surface layer leading to thermal decomposition of As2S3 in the illuminated area and oxidation of the vaporized arsenic atoms by oxygen from the ambient air. Most likely, the photooxidation is facilitated by the effect of silver on the glass network, reducing its rigidity, or, alternatively, the enhancement of photochemical reaction due to the plasmonic interaction of the incident light with residual ultrasmall silver nanoparticles existing in the glass sample.
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