We observe the seldom reported near infrared (NIR) emissions at 870 nm (FWHM = 53 nm) and 1037 nm (FWHM = 67 nm) which are in the spectral response region of crystalline silicon photovoltaic solar cells. The emissions are much enhanced with the addition of GeO2, and the possible mechanisms for the photoluminescence spectra evolution are discussed. The decay curves are monitored at both the visible and NIR emissions of Pr3+ doped glasses and lifetimes are calculated using a second-order exponential decay model. Raman spectra are used to characterize some interesting structural evolutions which are responsible for the GeO2 induced luminescence property changes. (C) 2013 Elsevier B.V. All rights reserved.