TY - JOUR

T1 - Predicting the Excitation Dynamics in Lanthanide Nanoparticles

AU - Spelthann, Simon

AU - Thiem, Jonas

AU - Melchert, Oliver

AU - Komban, Rajesh

AU - Gimmler, Christoph

AU - Demicran, Ayhan

AU - Ruehl, Axel

AU - Ristau, Detlev

N1 - Funding Information: Funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy – EXC‐2123 Quantum Frontiers – 390837967. O.M., A.D., and D. R. would like to thank the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) for partly funding this work under Germany's Excellence Strategy within the Cluster of Excellence PhoenixD (EXC‐2122, Project ID 390833453). R. K. and C. G. would like to thank the Free and Hanseatic City of Hamburg, Germany for the financial support. The numerical results presented here were achieved by computations carried out on the LUH cluster system funded by the Leibniz Universität Hannover, the Niedersächsisches Ministerium für Wissenschaft und Kultur (MWK, Lower Saxony Ministry of Science and Culture), and the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation). Dr. Christian Kraenkel and Dr. Sascha Kalusniak, Leibniz‐Institut für Kristallzüchtung Berlin, Germany provided absorption and emission data for the overlap spectra. S.S. thanks Tamara Grossmann, University of Cambridge, and Dr. Torben Sell, University of Edinburgh, for helpful discussions on probability theory. The authors thank Dan Huy Chau for the graphic realization of the ToC figure.

PY - 2023/7/18

Y1 - 2023/7/18

N2 - With their dipole-forbidden 4f transitions, lanthanides doped in nanoparticles promise high excited state lifetimes and quantum yields that are required for applications such as composite lasers or nanoscale quantum memories. Quenching at the nanoparticle surface, however, severely reduces the lifetime and quantum yield and requires resource-consuming experimental optimization that could not be replaced by simulations due to the limitations of existing approaches until now. Here, a versatile approach is presented that fully accounts for spatiotemporal dynamics and reliably predicts the lifetimes and quantum yields of lanthanide nanoparticles. LiYF4:Pr3+nanoparticles are synthesized as a model system, and the lifetimes of a concentration series (≈10 nm, 0.7−1.47 at%) are used to match the model parameters to the experimental conditions. Employing these parameters, the lifetimes and quantum yields of a size series (≈5 at%, 12−21 nm) are predicted with a maximum uncertainty of 12.6%. To demonstrate the potential of the model, a neutral shell is added around the core particles in the model which extends the lifetime by up to 44%. Furthermore, spatiotemporal analysis of single nanoparticles points toward a new type of energy trapping in lanthanide nanoparticles. Consequently, the numerical optimization brings applications such as efficient nanoparticle lasers or quantum memories within reach.

AB - With their dipole-forbidden 4f transitions, lanthanides doped in nanoparticles promise high excited state lifetimes and quantum yields that are required for applications such as composite lasers or nanoscale quantum memories. Quenching at the nanoparticle surface, however, severely reduces the lifetime and quantum yield and requires resource-consuming experimental optimization that could not be replaced by simulations due to the limitations of existing approaches until now. Here, a versatile approach is presented that fully accounts for spatiotemporal dynamics and reliably predicts the lifetimes and quantum yields of lanthanide nanoparticles. LiYF4:Pr3+nanoparticles are synthesized as a model system, and the lifetimes of a concentration series (≈10 nm, 0.7−1.47 at%) are used to match the model parameters to the experimental conditions. Employing these parameters, the lifetimes and quantum yields of a size series (≈5 at%, 12−21 nm) are predicted with a maximum uncertainty of 12.6%. To demonstrate the potential of the model, a neutral shell is added around the core particles in the model which extends the lifetime by up to 44%. Furthermore, spatiotemporal analysis of single nanoparticles points toward a new type of energy trapping in lanthanide nanoparticles. Consequently, the numerical optimization brings applications such as efficient nanoparticle lasers or quantum memories within reach.

KW - core/shell nanoparticles

KW - luminescence

KW - Monte Carlo simulations

KW - praseodymium

UR - http://www.scopus.com/inward/record.url?scp=85152678856&partnerID=8YFLogxK

U2 - 10.1002/adom.202300096

DO - 10.1002/adom.202300096

M3 - Article

AN - SCOPUS:85152678856

VL - 11

JO - Advanced optical materials

JF - Advanced optical materials

SN - 2195-1071

IS - 14

M1 - 2300096

ER -