Probing structural and optical modulations in metal-ion co-doped gadolinium vanadate: a combined spectroscopic and diffraction study

Abstract

Upconversion (UC) luminescence enhancement in trivalent lanthanide-doped materials -particularly the ytterbium (Yb³⁺) / erbium (Er³⁺) ion pair -remains challenging due to complex, interdependent mechanisms involving structural modifications and defect formation. Here, we present a systematic investigation of UC enhancement in relation to defect formation in GdVO₄:Yb³⁺/Er³⁺ microcrystals through strategic co-doping with optically inactive ions (Sc³⁺ ,Cd²⁺, Zn²⁺ ). We employ a novel multi-technique approach combining positron annihilation lifetime spectroscopy (PALS)-to quantify vacancy-type defects in UC materialswith X-ray diffraction and photoluminescence quantum yield (PLQY) measurements to establish direct structure-defect-property relationships. Our results reveal that dopant valence and ionic radius dictate distinct defect formation patterns: isovalent Sc³⁺ substitution primarily induces lattice contraction with minimal point defect generation, while aliovalent Cd²⁺ and Zn²⁺ doping creates extensive Gd vacancy networks through charge compensation mechanisms. Critically, we demonstrate that defect cluster size and spatial distribution, rather than total defect concentration, govern UC efficiency. Zn²⁺ co-doping achieves a remarkable PLQY enhancement through progressive suppression of large vacancy clusters at grain boundaries, coupled with favorable redistribution of oxygen vacancies within crystallite interiors. In contrast, Cd²⁺ doping, despite similar charge compensation requirements, produces extended defect clusters that act as efficient non-radiative quenching centers, limiting PLQY improvement. These findings establish defect engineering as a powerful strategy for UC optimization and provide a quantitative framework for rational design of high-efficiency lanthanide-based photonic materials.