Why Do Relative Intensities of Charge Transfer and Intra-4f Transitions of Eu³⁺ Ion Invert in Yttrium Germanate...

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 (O_tetra) and yttrium atom as first and second neighbors, respectively (Eu³⁺-O_tetra-Y³⁺ linkages). Conversely, in Y₂Ge₂O₇ host, the Eu³⁺ ion mostly has tricoordinated oxygen (O_tri) as its nearest neighbor and germanium ions next to O_tri (Eu³⁺-O_tri-Ge⁴⁺ linkage). Theoretical calculations reveal that while Y₂GeO₅:Eu has O_tetra(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 O_tri(2Y + 1Ge) with significant mixing with 4f states of Eu. The dominant control of Eu³⁺-O_tri-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⁺-O_tri-Ge⁴⁺ linkages play a dual role: First, it induces electronic rigidity to hinder excitation of electron at bridging (O_tri) oxygen by highly charged small Ge⁴⁺ cation; second, the covalent character in Eu-O bond is achieved by intermixing of Eu's 4f and O_tri 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 EuO 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.