Unraveling the site-specific energy transfer driven tunable emission characteristics of Eu3+ & Tb3+ co-doped Ca10(PO4)6F2 phosphors

Abstract

In this study we have explored Ca₁₀(PO₄)₆F₂ as host to develop a variety of phosphor materials with tunable emission and lifetime characteristics based on Eu³⁺ and Tb³⁺ as co-dopant ions and the energy transfer process involved with them. The energy transfer from the excited state of Tb³⁺ ion to the ⁵D₀ state of Eu³⁺ makes it possible to tune the colour characteristics from yellow to orange to red. Further, such energy transfer process is highly dependent on the concentration of Eu³⁺ and Tb³⁺ ions and their site-selective distribution among the two different Ca-sites (CaO₉ and CaO₆F) available. We have carried out DFT based theoretical calculation for both Eu³⁺ and Tb³⁺ ions in order to understand their distribution. It was observed that in cases of co-doped sample, Tb³⁺ ions prefer to occupy the Ca2 site in the CaO₆F network while Eu³⁺ ions prefer Ca1 site in the CaO₉ network. This distribution has significant impact on the lifetime values and the energy transfer process as observed in the experimental photoluminescence lifetime values. We have observed that for the 1^st series of compounds, wherein the concentration Tb³⁺ ions are fixed, the energy transfer from Tb³⁺ ion at Ca2 site to Eu³⁺ ion at Ca1 site is dominating (Tb³⁺@Ca2 → Eu³⁺@Ca1). However, for the 2^nd series of compounds, wherein the concentration Eu³⁺ ions are fixed, the energy transfer process was found to occur from the excited Tb³⁺ ion at Ca1 site to Eu³⁺ ions at both Ca1 and Ca2 (Tb³⁺@Ca1 → Eu³⁺@Ca1 and Tb³⁺@Ca1 → Eu³⁺@Ca2). This is the first reports of its kind on site-specific energy transfer driven colour tunable emission characteristics in Eu³⁺ and Tb³⁺ co-doped Ca₁₀(PO₄)₆F₂ phosphor and it will pave the way for the future development of effective colour tunable phosphor materials based on a single host and same co-dopant ions.