Luminescence properties of Tb3+-doped CaMoO4nanoparticles: annealing effect, polar medium dispersible, polymer film and core–shell formation

Abstract

Tb³⁺-doped CaMoO₄ (Tb³⁺ = 1, 3, 5, 7, 10, 15 and 20 atom%) core and core–shell nanoparticles have been prepared by urea hydrolysis in ethylene glycol (EG) as capping agent as well as reaction medium at low temperature ∼150 °C. As-prepared samples were annealed at 500 and 900 °C for 4 h to eliminate unwanted hydrocarbons and/or H₂O present in the sample and to improve crystallinity. The synthesised nanophosphors show tetragonal phase structure. The crystallite size of as-prepared sample is found to be ∼18 nm. The luminescence intensity of the ⁵D₄ → ⁷F₅ transition at 547 nm of Tb³⁺ is much higher than that of the ⁵D₄ → ⁷F₆ transition at 492 nm. 900 °C annealed samples show the highest luminescence intensity. The intensity ratio R (I[⁵D₄ → ⁷F₆]/I[⁵D₄ → ⁷F₅]) lies between 0.3–0.6 for as-prepared, 500 and 900 °C annealed samples. The luminescence decay of ⁵D₄ level under 355 nm excitation shows biexponential behaviour indicating availability of Tb³⁺ ions on surface and core regions of particle; whereas, contribution of Mo–O charge transfer to lifetime is obtained under 250 nm excitation. The CIE coordinates of as-prepared, 500 and 900 °C annealed 5 atom% Tb³⁺-doped CaMoO₄ samples under 250 nm excitation are (0.28, 0.32), (0.22, 0.28) and (0.25, 0.52), respectively. The dispersed particles in polar medium and its polymer film show green light emission. The luminescence intensity is improved significantly after core–shell formation due to extent of decrease of non-radiative rates arising from surface dangling bonds and capping agent. Quantum yields of as-prepared samples of 1, 5 and 7 atom% Tb³⁺-doped CaMoO₄ samples are found to be 10, 3 and 2, respectively.