Size-induced variations in bulk/surface structures and their impact on photoluminescence properties of GdVO4:Eu3+ nanoparticles

Abstract

This work explores the size-induced lattice modification and its relevance to photoluminescence properties of tetragonal zircon-type GdVO₄:Eu³⁺ nanostructures. GdVO₄:Eu³⁺ nanoparticles with crystallite sizes ranging from 14.4 to 24.7 nm were synthesized by a hydrothermal method using sodium citrate as a capping agent. Regardless of the reaction temperatures, all samples retained an ellipsoidal-like morphology. Nevertheless, as the crystallite size reduces, there appears a tensile strain and lattice distortion, which is accompanied by a lattice expansion and a decreased symmetry of structural units. These lattice modifications could be associated with the changes in the interior chemical bonding due to the interactions of surface defect dipoles that have imposed an increased negative pressure with crystallite size reduction. Furthermore, crystallite size reduction also led to a significant increase in the amounts of surface hydroxyl groups and citric species, as well as the concentration of the surface Eu³⁺ ions. When Eu³⁺ was taken as a structural probe, it was found that the asymmetric ratio (I₀₂/I₀₁) of Eu³⁺ gradually declined to show a remarkable decrease in color chromaticity as crystallite size reduces, which could be interpreted as due to the change of local environments of Eu³⁺ ions from the interior to the surface of the nanoparticles.