Why Do Relative Intensities of Charge Transfer and Intra-4f Transitions of Eu³⁺ Ion Invert in Yttrium Germanate Hosts? Unravelling the Underlying Intricacies from Experimental and Theoretical Investigations

The dominant intensity of parity-forbidden intra-4f transitions of europium(III) over O → Eu charge-transfer band (CTB) intensity is against common perceptions, yet this trend is observed in many germanate hosts and has not been rationalized so far. In search of a plausible explanation for this unusual trend, present work reports an experimental and theoretical investigations in conjunction on two sibling germanate host, namely, Y2GeO5 and Y2Ge2O7 having dopant Eu3+ in their respective YO7 polyhedra. Whereas for Y2GeO5:Eu3+, the CTB is more intense than the intra-4f transitions in the excitation spectrum, in the case of Y2Ge2O7:Eu3+, the relative intensities of CTB and intra-4f transitions are reversed. Comparative structural analysis reveals that Eu3+ present in YO7 of Y2GeO5 has a greater number of tetra-coordinated oxygen (Otetra) and yttrium atom as first and second neighbors, respectively (Eu3+-Otetra-Y3+ linkages). Conversely, in Y2Ge2O7 host, the Eu3+ ion mostly has tricoordinated oxygen (Otri) as its nearest neighbor and germanium ions next to Otri (Eu3+-Otri-Ge4+ linkage). Theoretical calculations reveal that while Y2GeO5:Eu has Otetra(4Y) dominating at the Fermi level and the 4f state of Eu3+ remains inert toward mixing, in Y2Ge2O7:Eu, the Fermi level has major contribution from Otri(2Y + 1Ge) with significant mixing with 4f states of Eu. The dominant control of Eu3+-Otri-Ge4+ linkages in geometrical and electronic structure of Y2Ge2O7:Eu owing to the GeO4 surrounding has been attributed to relative poor intensity of O → Eu CTB. Siege of Eu3+ by GeO4 and subsequent occurrence of Eu3+-Otri-Ge4+ linkages play a dual role: First, it induces electronic rigidity to hinder excitation of electron at bridging (Otri) oxygen by highly charged small Ge4+ cation; second, the covalent character in Eu-O bond is achieved by intermixing of Eu's 4f and Otri 2p orbital which facilitates relaxing of the parity-selection rule thus enhancing the probability of intra-4f transitions. The inferences drawn remain valid when extrapolated to other inorganic oxides having EuOx polyhedra surrounded by covalent units like PO4, SiO4, etc. and have a prevailing number of low-coordinated oxygen atoms and highly charged small cation in the first and second coordination shells, respectively. The optical basicity concept is also found to endorse our explanation. These remarkable generic inferences will pave the rational way for designing efficient phosphors for solid-state lighting.