Identification and elimination of surface emission in lanthanide (Co)doped zirconia nanocrystals
Reichholf N, Horta S, Van Der Heggen D, Seno C, Pulparayil Mathew J, Ibáñez M, Smet PF, De Roo J. 2025. Identification and elimination of surface emission in lanthanide (Co)doped zirconia nanocrystals. ACS Nano. 19(33), 30371–30382.
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Author
Reichholf, Nico;
Horta, SharonaISTA;
Van Der Heggen, David;
Seno, Carlotta;
Pulparayil Mathew, Jikson;
Ibáñez , MariaISTA
;
Smet, Philippe F.;
De Roo, Jonathan

Department
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.
Publishing Year
Date Published
2025-08-26
Journal Title
ACS Nano
Publisher
American Chemical Society
Acknowledgement
N.R. and C.S. thank the SNSF Eccellenza funding scheme (Project 194172) for funding. D.V.d.H. is supported by the Research Foundation Flanders (FWO) through a Senior Postdoctoral Research Fellowship (N° 1237825N). P.F.S. acknowledges the Special Research Fund at UGent (bof/baf/4y/2024/01/037). M.I. acknowledges financial support from ISTA and the Werner Siemens Foundation. This research was supported by the Scientific Service Units (SSU) of ISTA Austria through resources provided by the electron microscopy facility (EMF). We thank Tommaso Costanzo for providing assistance during STEM measurements. We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out using beamline P21.1 at PETRA III, and the authors thank Ann-Christin Dippel, Jiatu Liu, and Fernando Igoa for assistance in using the beamline for PDF acquisition (Proposal I-20231114 EC). The authors thank Daniel Häussinger for help with the analysis of NMR spectra.
Acknowledged SSUs
Volume
19
Issue
33
Page
30371-30382
eISSN
IST-REx-ID
Cite this
Reichholf N, Horta S, Van Der Heggen D, et al. Identification and elimination of surface emission in lanthanide (Co)doped zirconia nanocrystals. ACS Nano. 2025;19(33):30371-30382. doi:10.1021/acsnano.5c09137
Reichholf, N., Horta, S., Van Der Heggen, D., Seno, C., Pulparayil Mathew, J., Ibáñez, M., … De Roo, J. (2025). Identification and elimination of surface emission in lanthanide (Co)doped zirconia nanocrystals. ACS Nano. American Chemical Society. https://doi.org/10.1021/acsnano.5c09137
Reichholf, Nico, Sharona Horta, David Van Der Heggen, Carlotta Seno, Jikson Pulparayil Mathew, Maria Ibáñez, Philippe F. Smet, and Jonathan De Roo. “Identification and Elimination of Surface Emission in Lanthanide (Co)Doped Zirconia Nanocrystals.” ACS Nano. American Chemical Society, 2025. https://doi.org/10.1021/acsnano.5c09137.
N. Reichholf et al., “Identification and elimination of surface emission in lanthanide (Co)doped zirconia nanocrystals,” ACS Nano, vol. 19, no. 33. American Chemical Society, pp. 30371–30382, 2025.
Reichholf N, Horta S, Van Der Heggen D, Seno C, Pulparayil Mathew J, Ibáñez M, Smet PF, De Roo J. 2025. Identification and elimination of surface emission in lanthanide (Co)doped zirconia nanocrystals. ACS Nano. 19(33), 30371–30382.
Reichholf, Nico, et al. “Identification and Elimination of Surface Emission in Lanthanide (Co)Doped Zirconia Nanocrystals.” ACS Nano, vol. 19, no. 33, American Chemical Society, 2025, pp. 30371–82, doi:10.1021/acsnano.5c09137.
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