Multi-modal luminescence properties of RE3+ (Tm3+, Yb3+) and Bi3+ activated GdNbO4 phosphors—upconversion, downshifting and quantum cutting for spectral conversion

Abstract

This work investigates the promising multi-modal luminescence (upconversion (UC), downshifting (DS) and quantum cutting (QC)) properties of RE3+ (Tm3+, Yb3+) and Bi3+ activated GdNbO4 phosphors synthesized using the well-known solid state reaction method. Structural characterization using x-ray diffraction measurements confirms the formation of the pure phase of the GdNbO4 host with no impurities. The optical band gap (Eg) of GdNbO4 (with and without RE3+ ions) calculated from UV–Vis–near-infrared (NIR) measurements was found to be the same ~4.44 eV which indicates that GdNbO4 is a wide band gap material. Further, Bi3+ doping presents an interesting Eg tuning of the GdNbO4 phosphor, i.e. Eg increases up to 5.38 eV. In terms of luminescence, this material produces intense blue and NIR emission via multi-modal optical processes. On NIR excitation (λexc = 980 nm), Gd0.94Tm0.01Yb0.05NbO4 produces intense upconverted blue and NIR and relatively weak red emission. In addition to the UC process, Gd0.94Tm0.01Yb0.05NbO4 also exhibits pump power dependent variation in fluorescence intensity ratio for I472/I477 showing the applicability of this material as an optical heater. On UV excitation (λexc = 265 nm), Gd0.99Tm0.01NbO4 produces intense DS blue emission due to the Tm3+ ion, overlapped with the emission of the (NbO4)3− ion through strong energy transfer (ET) from (NbO4)3− to Tm3+ ions. Interestingly, NIR QC has also been successfully observed in Gd0.9Yb0.1NbO4, Gd0.89Bi0.01Yb0.1NbO4 and Gd0.79Tm0.01Yb0.2NbO4 phosphors through cooperative ET from the (NbO4)3− group to the Yb3+ ion, Bi(6s)–Nb(4d) to the Yb3+ ion and the Tm3+ ion to the Yb3+ ion, respectively. The mechanisms involved in these processes are explained in detail in this work. The QC efficiency in this work has been found to be ~177%. Thus, the multi-modal luminescence (UC, DS and QC) property of this material makes it a promising candidate for display devices, spectral converters for enhancing the efficiency of silicon solar cells, etc.