Red-emitting Mn4+-doped fluorides are a promising class of materials to improve the color rendering and luminous efficacy of white light-emitting diodes (w-LEDs). For w-LEDs, the luminescence quenching temperature is very important, but surprisingly no systematic research has been conducted to understand the mechanism for thermal quenching in Mn4+-doped fluorides. Furthermore, concentration quenching of the Mn4+ luminescence can be an issue but detailed investigations are lacking. In this work, we study thermal quenching and concentration quenching in Mn4+-doped fluorides by measuring luminescence spectra and decay curves of K2TiF6:Mn4+ between 4 and 600 K and for Mn4+ concentrations from 0.01% to 15.7%. Temperature-dependent measurements on K2TiF6:Mn4+ and other Mn4+-doped phosphors show that quenching occurs through thermally activated crossover between the 4T2 excited state and 4A2 ground state. The quenching temperature can be optimized by designing host lattices in which Mn4+ has a high 4T2 state energy. Concentration-dependent studies reveal that concentration quenching effects are limited in K2TiF6:Mn4+ up to 5% Mn4+. This is important, as high Mn4+ concentrations are required for sufficient absorption of blue LED light in the parity-forbidden Mn4+ d–d transitions. At even higher Mn4+ concentrations (>10%), the quantum efficiency decreases, mostly due to direct energy transfer to quenching sites (defects and impurity ions). Optimization of the synthesis to reduce quenchers is crucial for developing more efficient highly absorbing Mn4+ phosphors. The present systematic study provides detailed insights into temperature and concentration quenching of Mn4+ emission and can be used to realize superior narrow-band red Mn4+ phosphors for w-LEDs.
Förster resonance energy transfer (ET) between luminescent species is applied in bioimaging, lighting and photovoltaics, and has an important role in photosynthesis. However, the fundamental question of whether ET rates and efficiencies can be tuned by the photonic environment remains under debate. Here we show that ET rates are independent of the photonic environment, using the model system of LaPO 4 nanocrystals co-doped with Ce 3 þ donors and Tb 3 þ acceptors. Although the radiative emission rate of the Ce 3 þ excited state increases with the refractive index of the solvent in which the nanocrystals are dispersed, the Ce 3 þ -to-Tb 3 þ ET rate does not. We demonstrate that, as a result, lower refractive index solvents enable higher ET efficiencies leading to higher Tb 3 þ emission intensities. Furthermore, an analytical model for ET in (nano)crystalline host materials is presented, able to predict the dependence of ET efficiencies on the photonic environment and the concentration of acceptor ions.
Nanocrystals (NCs) doped with luminescent ions form an emerging class of materials. In contrast to excitonic transitions in semiconductor NCs, the optical transitions are localized and not affected by quantum confinement. The radiative decay rates of the dopant emission in NCs are nevertheless different from their bulk analogues due to photonic effects, and also the luminescence quantum yield (QY, important for applications) is affected. In the past, different theoretical models have been proposed to describe the photonic effects for dopant emission in NCs, with little experimental validation. In this work we investigate the photonic effects on the radiative decay rate of luminescent doped NCs using 4 nm LaPO4 NCs doped with Ce(3+) or Tb(3+) ions in different refractive index solvents and bulk crystals. We demonstrate that the measured influence of the refractive index on the radiative decay rate of the Ce(3+) emission, having near unity QY, is in excellent agreement with the theoretical nanocrystal-cavity model. Furthermore, we show how the nanocrystal-cavity model can be used to quantify the nonunity QY of Tb(3+)-doped LaPO4 NCs and demonstrate that, as a general rule, the QY is higher in media with higher refractive index.
A novel two-step approach for quantum dot (QD) functionalization and bioconjugation is presented, which yields ultra-compact, stable, and highly luminescent antibody-QD conjugates suitable for use in FRET immunoassays. Hydrophobic InPZnS/ZnSe/ZnS (emission wavelength: 530 nm), CdSe/ZnS (605 nm), and CdSeTe/ZnS (705 nm) QDs were surface functionalized with zwitterionic penicillamine, enabling aqueous phase transfer under conservation of the photoluminescence properties. Post-functionalization with a heterobifunctional crosslinker, containing a lipoic acid group and a maleimide function, enabled the subsequent coupling to sulfhydryl groups of proteins. This was demonstrated by QD conjugation with fragmented antibodies (F(ab)). The obtained F(ab)-QD conjugates range among the smallest antibody-functionalized nanoprobes ever reported, with a hydrodynamic diameter <13 nm, PL quantum yield up to 66% at 705 nm, and colloidal stability of several months in various buffers. They were applied as FRET acceptors in homogeneous, time-gated immunoassays using Tb-antibodies as FRET donors, both coupled by an immunological sandwich complex between the two antibodies and a PSA (prostate specific antigen) biomarker. The advantages of the compact surface coating for FRET could be demonstrated by an 6.2 and 2.5 fold improvement of the limit of detection (LOD) for PSA compared to commercially available hydrophilic QDs emitting at 605 and 705 nm, respectively. While the commercial QDs contain identical inorganic cores responsible for their fluorescence, they are coated with a comparably thick amphiphilic polymer layer leading to much larger hydrodynamic diameters (>26 nm without biomolecules). The LODs of 0.8 and 3.7 ng mL(-1) obtained in 50 μL serum samples are below the clinical cut-off level of PSA (4 ng mL(-1)) and demonstrate their direct applicability in clinical diagnostics.
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