A new route towards polarized luminescence: 0D/2D nanocomposites.

Combining wide bandgap 2D inorganic materials and blue-light-emitting 0D carbon dots in 0D/2D heterojunction nanocomposites was shown to give rise to unique optical properties and a multifunctional prototype device was developed, capable of polarized light luminescence, modulation and detection.

Shedding Light on Host-to-Yb3+ Energy Transfer in Cs2AgBiBr6:Yb3+ (nano)crystals.

The optical properties of Cs2AgBiBr6 double perovskite nanocrystals have attracted considerable attention as lead-free alternatives to lead halide perovskites. A promising strategy to create additional flexibility in the emission color is doping lanthanide ions into Cs2AgBiBr6. Incorporating Yb3+ in the lattice has been shown to give rise to near-infrared (NIR) emission, but the energy transfer mechanism remained unclear. Here, we report on the luminescence and sensitization mechanism of Yb3+ in Cs2AgBiBr6 nano- and microcrystals. We observe that the incorporation of Yb3+ in the host lattice does not strongly affect the broadband red emission of the Cs2AgBiBr6 host but does give rise to an additional and characteristic ∼1000 nm NIR line emission from Yb3+. Temperature-dependent and time-resolved photoluminescence studies of undoped and Yb-doped Cs2AgBiBr6 reveal that the energy transfer does not take place through the red emissive state of the Cs2AgBiBr6 host. Instead, there is a competition between relaxation to the red-emitting state and trapping of the photoexcited charge carriers on Yb3+. Trapping on Yb3+ subsequently results in a charge transfer state that relaxes to the 2F5/2 excited state of Yb3+, followed by NIR narrow line f-f emission to the 2F7/2 ground state.

Luminescence and Formation of Cubic and Hexagonal (K,Rb)2SiF6:Mn4.

The efficient red-emitting phosphor K2SiF6:Mn4+ (KSF) is widely used for low-power LED applications. The saturated red color and sharp line emission are ideal for application in backlight LEDs for displays. However, the long excited state lifetime lowers the external quantum yield (EQY) at high photon flux, limiting the application in (higher power density) lighting. Here, we report the synthesis of a new crystalline phase: hexagonal (K,Rb)SiF6:Mn4+ (h-KRSF). Due to the lower local symmetry, the Mn4+ emission in this new host material shows a pronounced zero phonon line, which is different from Mn4+ in the cubic KSF. The lower symmetry reduces the excited state lifetime, and thus, the loss of EQY under high photon fluxes, and the spectral change also increases the lumen/W output. Temperature-dependent emission and lifetime measurements reveal a high luminescence quenching temperature of ∼500 K, similar to that of KSF. The formation mechanism of h-KRSF was studied in situ by measuring the emission spectra of the precipitate in solution over time. Initially, nanocrystalline cubic KRSF (c-KRSF) is formed, which transforms into a microcrystalline hexagonal precipitate with a surprising exponential increase in the transformation rate with time. The stability of the new phase was studied by temperature-dependent XRD, and an irreversible transition back to the cubic phase was seen upon heating to temperatures above 200 °C.

High-sensitivity luminescent temperature sensors: MFX:1%Sm2+ (M = Sr, Ba, X = Cl, Br).

The use of lanthanide luminescence has advanced the field of remote temperature sensing. Luminescence intensity ratio methods relying on emission from two thermally coupled energy levels are popular but suffer from a limited temperature range. Here, we present a versatile luminescent thermometer: Ba(Sr)FBr(Cl):Sm2+. The Sm2+ ion benefits from multiple thermally coupled excited states to extend the temperature range and has strong parity-allowed 4f6→4f55d1 absorption to increase brightness. We conduct a comparative analysis of the temperature sensing performance of Sm2+ in BaFBr, BaFCl, SrFBr, and SrFCl and address the role of concentration, host, and Boltzmann equilibration. Different thermal coupling schemes, 5D1-5D0 and 4f55d1-5D0, and temperature-dependent lifetimes enable accurate sensing between 350 and 800 kelvin. Differences in 4f55d1-5D0 energy gap allows optimization for a temperature range of interest. This type of Sm2+-based thermometer holds great potential for temperature monitoring in the wide and relevant range up to 500°C.

New Insights in Luminescence and Quenching Mechanisms of Ag2S Nanocrystals through Temperature-Dependent Spectroscopy.

Bright near-infrared-emitting Ag2S nanocrystals (NCs) are used for in vivo temperature sensing relying on a reversible variation in intensity and photoluminescence lifetime within the physiological temperature range. Here, to gain insights into the luminescence and quenching mechanisms, we investigated the temperature-dependent luminescence of Ag2S NCs from 300 to 10 K. Interestingly, both emission and lifetime measurements reveal similar and strong thermal quenching from 200 to 300 K, indicating an intrinsic quenching process that limits the photoluminescence quantum yield at room temperature, even for perfectly passivated NCs. The low thermal quenching temperature, broadband emission, and multiexponential microsecond decay behavior suggest the optical transition involves strong lattice relaxation, which is consistent with the recombination of a Ag+-trapped hole with a delocalized conduction band electron. Our findings offer valuable insights for understanding the optical properties of Ag2S NCs and the thermal quenching mechanism underlying their temperature-sensing capabilities.