Thermoluminescence Study of Persistent Luminescence Materials:  Eu2+- and R3+-Doped Calcium Aluminates, CaAl2O4:Eu2+,R3

• Published in: The journal of physical chemistry. B 2006-03, Vol.110 (10), p.4589-4598
• Main Authors: Aitasalo, Tuomas, Hölsä, Jorma, Jungner, Högne, Lastusaari, Mika, Niittykoski, Janne
• Format: Article
• Language: English
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp057185m

Thermoluminescence properties of the Eu2+-, R3+-doped calcium aluminate materials, CaAl2O4:Eu2+,R3+, were studied above room temperature. The trap depths were estimated with the aid of the preheating and initial rise methods. The seemingly simple glow curve of CaAl2O4:Eu2+ peaking at ca. 80 °C was found to correspond to several traps. The Nd3+ and Tm3+ ions, which enhance most the intensity of the high-temperature TL peaks, form the most suitable traps for intense and long-lasting persistent luminescence, too. The location of the 4f and 5d ground levels of the R3+ and R2+ ions were deduced in relation to the band structure of CaAl2O4. No clear correlation was found between the trap depths and the R3+ or R2+ level locations. The traps may thus involve more complex mechanisms than the simple charge transfer to (or from) the R3+ ions. A new persistent luminescence mechanism presented is based on the photoionization of the electrons from Eu2+ to the conduction band followed by the electron trapping to an oxygen vacancy, which is aggregated with a calcium vacancy and a R3+ ion. The migration of the electron from one trap to another and also to the aggregated R3+ ion forming R2+ (or R3+−e-) is then occurring. The reverse process of a release of the electron from traps to Eu2+ will produce the persistent luminescence. The ability of the R3+ ions to trap electrons is probably based on the different reduction potentials and size of the R3+ ions. Hole trapping to a calcium vacancy and/or the R3+ ion may also occur. The mechanism presented can also explain why Na+, Sm3+, and Yb3+ suppress the persistent luminescence.