4.6 Article

Stabilization of Eu2+ in Li2B4O7 with the BO3 network through U6+ co-doping and defect engineering

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PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 25, 期 3, 页码 1889-1902

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ROYAL SOC CHEMISTRY
DOI: 10.1039/d2cp04672e

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A co-doping strategy with hexavalent uranium ions was used to stabilize divalent europium ions in the Li2B4O7 host at low hydrogen flux, providing a possibility for luminescent materials in technological applications like phosphor-converted light emitting diodes (pc-LEDs).
Owing to the unique 4f-5d transitions and the involvement of 5d electrons, the divalent europium (Eu2+) ion is extensively used as a dopant ion in luminescent materials for phosphor-converted light emitting diodes (pc-LEDs) and other technological applications. Earlier reports in most of the cases have shown that the reduction of Eu3+ to Eu2+ requires very high temperatures and large hydrogen flux. In this study, a co-doping strategy with higher valent U6+ ions was utilized to successfully stabilize Eu2+ ions in the Li2B4O7 (LTB) host with both the BO3 and BO4 network in low H-2 flux of only 8%. It is postulated that charge transfer occurs from U to Eu, resulting in the reduction of the charged state of Eu and the reaction probably proceeds via the formation of paramagnetic transient [U5+-Eu3+] species in the co-doped LTB. The same is also believed to be facilitated by the enhanced formation of Li-O type vacancy clusters in co-doped samples and enhanced oxygen vacancies in a reducing atmosphere. We believe this work will pave a new pathway for stabilizing the unusual oxidation state of lanthanides and transition metal ions through co-doping with hexavalent uranium ions.

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