Optical devices such as waveguides and resonators have typically been produced through standard vacuum deposition and photolithography techniques. Solution-derived chalcogenide films are presented as an alternative for devices not easily fabricated through these standard techniques; however, many details of the chemical processes involved in film deposition are still unknown. We present a detailed analysis of the formation of Ge23Sb7S70 films from solution: solvent removal was studied using in situ FTIR and UV-visible absorption spectroscopies during heat treatments at various temperatures, and the glass structure and glass-solvent interactions were studied through analysis of the far- and mid-IR regions, respectively. Correlations have been established between atomic-level structural aspects and macroscopic physical properties such as refractive index, band gap energies, and surface roughness. (C) 2012 Elsevier Ltd. All rights reserved.