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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.

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.

Though Pr3+ doped LiYF4 (LiYF4:Pr3+) bulk crystals are a well-known laser gain material with several radiative transitions, their nanocrystal counterparts have not been investigated with regards to these. Through downsizing to the nanoscale, novel applications are expected, especially in composite photonic devices. For example, nanocrystals in stable colloidal form with narrow size distribution are highly desirable to reduce scattering in such composites. Herein, we synthesized monodispersed LiYF4:Pr3+ nanocrystals having a size of 10 nm resulting in colorless clear stable colloidal dispersions and conducted an extensive optical characterization for the first time. We observed unexpected yet intense emission with excited state lifetimes comparable to bulk crystals in the visible spectrum through excitation at 444 nm and 479 nm. In macroscopic bulk crystals, this emission is only exploitable through excitation of a different, subjacent energy level. A comprehensive comparison to the bulk crystals provides deeper insight into the excitation mechanism and performance of these nanocrystals. The presented results pave the way for developing application-oriented LiYF4:Pr3+ nanocrystals as emitters with tailored properties for quantum optics or biomedical applications.

In this work, we investigate the electrical and dielectric response of lead sulfide (PbS) nanoparticle (NP) films with impedance spectroscopy. In particular, the influence of the ligand passivation on the surface trap state density of PbS NPs is demonstrated by comparing two different types of ligands: ethane-1,2-dithiol (EDT) and 3-sulfanylpropanoic acid (MPA). We observe that the MPA treatment passivates the PbS surface more efficiently than EDT. By analyzing the dielectric loss spectra, we are able to visualize shallow trap states in the bulk of PbS-EDT films and correlate this with the dispersive response observed in the impedance spectra. Evidence of deep trap states is revealed for both PbS-EDT and PbS-MPA diodes. Under illumination, the PbS-MPA and PbS-EDT films demonstrate almost identical trap profiles, showing solely the deep trap state densities. We conclude that the deep traps are related to the stoichiometry of the PbS NPs.