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@ARTICLE{Reichholf:639100,
author = {Reichholf, Nico and Horta, Sharona and Van der Heggen,
David and Seno, Carlotta and Pulparayil Mathew, Jikson and
Ibáñez, Maria and Smet, Philippe F. and De Roo, Jonathan},
title = {{I}dentification and {E}limination of {S}urface {E}mission
in {L}anthanide ({C}o)doped {Z}irconia {N}anocrystals},
journal = {ACS nano},
volume = {19},
number = {33},
issn = {1936-0851},
address = {Washington, DC},
publisher = {Soc.},
reportid = {PUBDB-2025-04303},
pages = {30371 - 30382},
year = {2025},
abstract = {Zirconia nanocrystals (ZrO2 NCs) are a stable host material
for lanthanides, but their performance lags behind that of
the leading NaYF4 nanomaterials. Here, we leverage surface
chemistry and core/shell architectures to uncover the
contribution of dopants at the nanocrystal surface and of
dopants in the nanocrystal bulk. We first assess the doping
efficiency by ICP and find that, while Eu is almost
quantitatively incorporated, the other lanthanides (La, Ce,
Tb, Tm, Er, Yb) have about $50\%$ incorporation efficiency
over the studied doping range of $1–10\%.$ We then
determine the nanocrystal surface chemistry using NMR
spectroscopy, despite the additional spectral line
broadening caused by the paramagnetic lanthanide dopants. By
varying the surface ligands and measuring the
photoluminescence, we resolve the spectroscopic signals that
are sensitive to a change in surface chemistry.
Time-resolved emission spectra further reinforce the notion
of a bulk component with a long luminescent lifetime and a
surface component with a fast lifetime. Upon shelling Eu- or
Tb-doped zirconia NCs with pure zirconia, the surface
component disappears, and the photoluminescence quantum
yield increases. We further functionalized the surface of
the core/shell particles with oleylphosphonic acid ligands
to obtain excellent dispersibility. These results show that
lanthanide-doped zirconia NCs can be engineered to eliminate
deactivation pathways.},
cin = {FS DOOR-User},
ddc = {540},
cid = {$I:(DE-H253)FS_DOOR-User-20241023$},
pnm = {6G3 - PETRA III (DESY) (POF4-6G3) / FS-Proposal: I-20231114
EC (I-20231114-EC)},
pid = {G:(DE-HGF)POF4-6G3 / G:(DE-H253)I-20231114-EC},
experiment = {EXP:(DE-H253)P-P21.1-20150101},
typ = {PUB:(DE-HGF)16},
doi = {10.1021/acsnano.5c09137},
url = {https://bib-pubdb1.desy.de/record/639100},
}