The formation of a protective layer from (3-mercaptopropyl)trimethoxysilane (MPTMS) on commercial Sunselect, cermet-based spectrally selective coating (Alanod, DE), was studied by non-electrochemical (infrared reflection-absorption-IR RA, X-ray photoelectron spectroscopy-XPS), electrochemical (cyclic voltammetry (CV) in the presence of a redox probe (Cd(+2)), and potentiodynamic (PD)) techniques. By simple immersion and subsequent dip coating of the Sunselect substrate in the MPTMS sol, the hydrolyzed MPTMS precursor was adsorbed on the substrate, forming a protective layer imparting corrosion stability to Sunselect in a salt spray chamber for at least 20 days, outperforming any other sol-gel coating used so far for the corrosion protection of Sunselect. This was attributed to the penetration of MPTMS into the porous cermet structure through the upper antireflective Sn-oxide layer, as shown from XPS depth profile. Detailed analysis of the hydrolysis and condensation reactions of the MPTMS precursor by (29)Si NMR and IR spectroscopic techniques is reported. The most important finding was the observation that the applied MPTMS layer did not affect the spectral selectivity, as inferred from the solar absorptance increase of 1% and thermal emittance increase of not more than 2%. (C) 2009 Elsevier B.V. All rights reserved.