Role of electron transfer in Ce3+ sensitized Yb3+ luminescence in borate glass

In a Ce3+-Yb3+ system, two mechanisms are proposed so far namely, the quantum cutting mechanism and the electron transfer mechanism explaining Yb3+ infrared luminescence under Ce3+ excitation. Among them, the quantum cutting mechanism, where one Ce3+ photon (ultraviolet/blue) gives rise to two Yb3+ photons (near infrared) is widely sought for because of its huge potential in enhancing the solar cell efficiency. In present study on Ce3+-Yb3+ codoped borate glasses, Ce3+ sensitized Yb3+ luminescence at ∼1 μm have been observed on Ce3+ 5d state excitation. However, the intensity of sensitized Yb3+ luminescence is found to be very weak compared to the strong quenching occurred in Ce3+ luminescence in Yb3+ codoped glasses. Moreover, the absolute luminescence quantum yield also showed a decreasing trend with Yb3+ codoping in the glasses. The overall behavior of the luminescence properties and the quantum yield is strongly contradicting with the quantum cutting phenomenon. The results are attributed to the energetically favorable electron transfer interactions followed by Ce3+-Yb3+ ⇌ Ce4+-Yb2+ inter-valence charge transfer and successfully explained using the absolute electron binding energies of dopant ions in the studied borate glass. Finally, an attempt has been presented to generalize the electron transfer mechanism among opposite oxidation/reduction property dopant ions using the vacuum referred electron binding energy (VRBE) scheme for lanthanide series.