The structural and optical properties of thin layers based on 70%SiO2–30%HfO2 doped with different concentration of rare earth ions (terbium and ytterbium) have been studied with a view to integrating them in a photovoltaic cell as a spectral conversion layer in order to improve its efficiency, by using down-conversion process. These thin films were synthesized by using sol gel technique and deposited on the pure silica substrate by dip-coating method. The DC layer can be placed on the front side of a solar cell and can enhance the current by converting ultraviolet (UV) photons into a large number of visible photons.In present study two series of samples are compared, the first series corresponds to samples treated at 900 °C (glass- S) while the second series concerns samples treated at 1000 °C (glass-ceramic- SC). These series are based on 70SiO2–30HfO2 activated by different molar concentrations of rare earths [Tb + Yb]/[Si + Hf] = 7%, 9%, 12%, 15%, 17%, 19% and 21%.Photoluminescence results of reference samples (without Yb3+) showed an emission from 5D4 to 7FJ (J = 3, 4, 5, 6) level characteristic transitions of Tb3+, with a maximum peak in the green centered at 543.5 nm corresponding to the 5D4→7F5 transition. For the co-doped samples a clear NIR PL emission around 980 nm was detected, due to the 2F5/2→2F7/2 transition of Yb3+ ions. From luminescence decay curves of Tb3+ maximum emission peak (7F5→5D4 transition at 543.5 nm) we have identified the energy transfer efficiency. The quantum efficiency increases by increasing the total [Tb + Yb] concentration. The most significant yield was achieved with [Tb + Yb]=19%, the maximum quantum transfer efficiency obtained was 190% for glass-ceramic samples and 161% for glassy one.