ABSTRACT
Metal halide perovskites are attracting great interest for the fabrication of light-emitting devices encompassing light-emitting diodes, lasers, and scintillators. As the field develops, perovskite doping emerges as a promising way to enrich the material functionalities and enhance the luminescence yield and tunability. While Mn+2 addition has been well explored, doping with lanthanides has received less attention, even though their intense and line-like luminescence is interesting for a wide range of applications. In this work, we study the doping of NMA2PbBr4 layered perovskites with Eu3+ and Eu3+ tetrakis ß-diketonate complex. By exploiting the antenna effect of the naphthalene-based functional cation (NMA = 1-naphtylmethylammonium), direct sensitization of Eu3+ is obtained; nevertheless, it is not very efficient due to the non-optimal energy level alignment with the resonance acceptor level of the lanthanide. Protection of Eu3+ in the form of tetrakis ß-diketonate complex grants a more ideal coordination geometry and energetic landscape for the energy transfer to europium in the perovskite matrix, allowing for a nearly 30-fold improvement in luminescence yield. This work sets the basis for new synthetic strategies for the design of functional perovskite/lanthanide host-guest systems with improved luminescence properties.
ABSTRACT
Published studies of layered (2D) (100)-oriented hybrid lead-bromide perovskites evidence a correlation between increased inter-octahedral (Pb-Br-Pb) distortions and the appearance of broadband white light emission. However, the impact of distortions within their constituent [PbBr6 ]4- octahedra has yet to be assessed. Herein, we report two new (100)-oriented 2D Pb-Br perovskites, whose structures display unusually high intra-octahedral distortions, whilst retaining minimal inter-octahedral distortions. Using a combination of temperature-dependent, power-dependent and time-resolved photoluminescence spectroscopic measurements, we show that increased intra-octahedral distortion induces exciton localization processes and leads to formation of multiple photoinduced emissive colour centres. Ultimately, this leads to highly Stokes-shifted, ultrabroad white light emission at room temperature.
ABSTRACT
Semiconducting transition metal dichalcogenides (TMDs) have been applied as the active layer in photodetectors and solar cells, displaying substantial charge photogeneration yields. However, their large exciton binding energy, which increases with decreasing thickness (number of layers), as well as the strong resonance peaks in the absorption spectra suggest that excitons are the primary photoexcited states. Detailed time-domain studies of the photoexcitation dynamics in TMDs exist mostly for MoS2. Here, we use femtosecond optical spectroscopy to study the exciton and charge dynamics following impulsive photoexcitation in few-layer WS2. We confirm excitons as the primary photoexcitation species and find that they dissociate into charge pairs with a time constant of about 1.3 ps. The better separation of the spectral features compared to MoS2 allows us to resolve a previously undetected process: these charges diffuse through the samples and get trapped at defects, such as flake edges or grain boundaries, causing an appreciable change of their transient absorption spectra. This finding opens the way to further studies of traps in TMD samples with different defect contents.
