This work reports a detailed study of the processing and photo-patterning of two chalcogenide glasses (ChGs) − arsenic trisulfide (As2S3) and a new composition of germanium-doped arsenic triselenide Ge5(As2Se3)95 − as well as their use for creating functional optical structures. ChGs are materials with excellent infrared (IR) transparency, large index of refraction, low coefficient of thermal expansion, and low change in refractive index with temperature. These features make them well suited for a wide range of commercial and industrial applications including detectors, sensors, photonics, and acousto-optics. Photo-patternable films of As2S3 and Ge5(As2Se3)95 were prepared by thermally depositing the ChGs onto silicon substrates. For some As2S3 samples, an anti-reflection layer of arsenic triselenide (As2Se3) was first added to mitigate the effects of standing-wave interference during laser patterning. The ChG films were photo-patterned by multi-photon lithography (MPL) and then chemically etched to remove the unexposed material, leaving free-standing structures that were negative-tone replicas of the photo-pattern in networked-solid ChG. The chemical composition and refractive index of the unexposed and photo-exposed materials were examined using Raman spectroscopy and near-IR ellipsometry. Nano-structured arrays were photo-patterned and the resulting nano-structure morphology and chemical composition were characterized and correlated with the film compositions, conditions of thermal deposition, patterned irradiation, and etch processing. Photo-patterned Ge5(As2Se3)95 was found to be more resistant than As2S3 toward degradation by formation of surface oxides.
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