Synthesis, characterization and luminescence properties of Eu3+-doped hydroxyapatite nanocrystal and the thermal treatment effects

• Published in: Optical materials 2015-09, Vol.47, p.135-142
• Main Authors: Silva, Flávia R.O., de Lima, Nelson B., Bressiani, Ana Helena A., Courrol, Lilia C., Gomes, Laércio
• Format: Article
• Language: English
• Subjects: Energy transfer; Europium luminescence; Hydroxyapatite; Luminescence efficiency; Nanophosphors; Time-resolved luminescence spectroscopy
• ISSN: 0925-3467; 1873-1252
• DOI: 10.1016/j.optmat.2015.07.006

•Luminescence effects of Eu3+ in HAp nanocrystals induced by thermal treatments were investigated.•The energy transfer between Eu3+ (site I) to Eu3+ (site II) was observed and analyzed.•Eu3+ site distribution starts with 100% at site I for non-thermally treated nanocrystal.•Eu3+ ion gradually changes from site I symmetry to site II by thermal treatments.•Our study contributes for understanding the luminescence properties of nanophosphors. In this work, we present the synthesis, characterization and the luminescence properties of Ca10(PO4)6(OH)2 (hydroxyapatite/HAp) nanocrystals doped with europium trivalent ions. The most important processes that lead to europium emissions in the visible region were identified. Eu:HAp nanopowder excited at 394nm (or 460nm) exhibits several emissions: (i) weak emissions at 579nm, 592nm and 616nm due to the 5D0→7F0, 5D0→7F1 and 5D0→7F2 transitions, respectively, with europium ion occupying site I in hydroxyapatite structure and (ii) strong emissions due to the 5D0→7F0 (574nm), 5D0→7F1 (602nm) and 5D0→7F2 (610–630nm) transitions, when Eu3+ is occupying site II. The emission spectrum and the time-resolved luminescence analysis showed that the HAp nanocrystals (nanopowder) thermally treated at temperature (T) between 500 and 800°C have a change in the initial Eu3+ site distribution of 100 % of Eu3+ at site I to a more stable one where the majority of europium ions are at site II: 30% remains at site I and 70% migrates to site II. In addition, an enhancement of the Eu3+ emission intensity is observed due to the increasing crystallite size. A time-resolved luminescence investigation using a short pulse laser excitation at 460nm was employed to measure the luminescence decays and to determine the most important mechanisms involved in the deexcitation process of 5D0 excited state of Eu3+, where it is seen a fast (2.9μs) energy transfer from Eu3+- site I (donor) to Eu3+- site II (acceptor) in the thermally treated nanopowders with T>500°C. The initial presence of 100% of Eu3+ at site I in the synthesized nanocrystals is gradually modified by the thermal treatments with temperatures above 500°C by thermal activation of Ca2+ vacancy (the charge compensator) diffusion through the HAp lattice, which propitiates the Ca2+- vacancies and Eu3+ ions to exchange positions in the lattice. By this thermal activated mechanism, Eu3+ ion migrates through the lattice until get the final distribution of 30% at site I and 70% at site II. As a result,