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Polarized Luminescence of Anisotropic LaPO₄:Eu Nanocrystal Polymorphs

Chaudan, Elodie, Kim, Jongwook, Tusseau-Nenez, Sandrine, Goldner, Philippe, Malta, Oscar L., Peretti, Jacques, Gacoin, Thierry
Journal of the American Chemical Society 2018 v.140 no.30 pp. 9512-9517
X-ray diffraction, anisotropy, europium, luminescence, nanocrystals, phase transition, spectral analysis, spectroscopy
Lanthanide elements exhibit highly appealing spectroscopic properties that are extensively used for phosphor applications. Their luminescence contains precise information on the internal structure of the host materials. Especially, the polarization behavior of the transition sublevel peaks is a fingerprint of the crystal phase, symmetry, and defects. However, this unique feature is poorly explored in current research on lanthanide nanophosphors. We here report on a detailed investigation of the evolution of Eu³⁺ luminescence during the thermally induced phase transition of LaPO₄ nanocrystal hosts. By means of c-axis-aligned nanocrystal assemblies, we demonstrate a dramatic change of the emission polarization feature corresponding to the distinct Eu³⁺ site symmetries in different LaPO₄ polymorphs. We also show that changes of the nanocrystal structure can be identified by this spectroscopic method, with a much higher sensitivity than the X-ray diffraction analysis. This new insight into the nanostructure-luminescence relationship, associated with the unprecedented polarization characterizations, provides a new methodology to investigate phase transitions in nanomaterials. It also suggests a novel function of lanthanide emitters as orientation-sensing nanoprobes for innovative applications such as in bioimaging or microfluidics.