Behaviour of electric and magnetic dipole transitions of Eu3+, 5D0 → 7F0 and Eu–O charge transfer band in Li+ co-doped YPO4:Eu3+

The effect of Li+ co-doping on the photoluminescence properties of YPO4:Eu is discussed. Interesting behaviours, such as the presence of intermediate bands, shifting of the Eu–O charge transfer band (Eu–O CTB) to a lower wavelength, variation in intensities of magnetic (5D0 → 7F1) and electric dipole (5D0 → 7F2) transitions of Eu3+ and shift of 5D0 → 7F0 to higher energy with increasing excitation wavelengths are observed. The Eu3+ ion does not have an absorption band in the range 340–350 nm, but after excitation at these wavelengths, a broad emission band (370–570 nm), as well as sharp peaks of Eu3+, could be observed. This is due to strong energy transfer from the intermediate band of the host to the Eu3+ ion. X-ray photoelectron spectroscopy (XPS) study also confirms that intermediate band emission is not due to Eu2+ ion emission. The blue shifting of Eu–O CTB is because of the increase in the optical electronegativity of the Eu3+ ion on Li+ co-doping. The variation in intensities of the 5D0 → 7F2 and 5D0 → 7F1 dipole transitions is related to (i) overlapping interaction parameters within the ground and excited states, (ii) exchange interaction among atoms/ions and (iii) density of the incoming photons. Shift of 5D0 → 7F0 to a higher energy with increasing excitation wavelengths is because of change in the second order crystal field parameter B20 with excitation wavelength. The significant enhancement of luminescence intensity is found with Li+ co-doping due to the increase in crystallinity.