Search for: All records

Mn²⁺doping of CsPbBr₃perovskite magic‐sized clusters (PMSCs) has been reported previously, where PMSCs with first excitonic absorption and photoluminescence (PL) around 425 nm were reported originally, followed by Mn²⁺‐doped PMSCs with host absorption and PL around 400 nm. There, the observed 25 nm blueshift was attributed to smaller PMSCs or the Cl⁻ions introduced by MnCl₂as dopant precursor. However, subsequent studies suggest that the 400 nm band may instead be due to ligand‐assisted metal halide molecular clusters (MHMCs), which lack the A component of perovskite. This raises the question whether the originally claimed Mn²⁺‐doped PMSCs are actually MHMCs. To unambiguously address this issue, Mn²⁺‐doped CH₃NH₃PbBr₃PMSCs were synthesized with PL at both 440 nm, attributed to the PMSC, and at 600 nm, attributed to Mn²⁺. Blueshifting of the host absorption and PL bands due to Cl⁻codoping is avoided by selecting MnBr₂as dopant precursor rather than MnCl₂. Dopant incorporation into PMSCs is further supported by PL excitation, time‐resolved PL, and electron paramagnetic resonance studies. This work provides direct and strong evidence of successful Mn²⁺doping in PMSCs. 

In the audio modality, state-of-the-art watermarking methods leverage deep neural networks to allow the embedding of human-imperceptible signatures in generated audio. The ideal is to embed signatures that can be detected with highaccuracy when the watermarked audio is altered via compression, filtering, or other transformations. Existing audio watermarking techniques operate in a post-hoc manner, manipulating “low-level” features of audio recordings after generation (e.g. through the addition of a low-magnitude watermark signal). We show that this post-hoc formulation makes existing audio watermarks vulnerable to transformation-based removal attacks. Focusing on speech audio, we (1) unify and extend existing evaluations of the effect of audio transformations on watermark detectability, and (2) demonstrate that state-of-the-art post-hoc audio watermarks can be removed with no knowledge of the watermarking scheme and minimal degradation in audio quality 

A solid-state synthesis of blue-emitting lead halide nanoclusters has been demonstrated for the first time. 

We have synthesized L-cysteine and oleylamine stabilized CsPbBr3 perovskite quantum dots (PQDs) and coupled them with gold nanoparticles (AuNPs). The PQDs and AuNPs, as well as their hybrid nanostructures (HNS), were characterized using UV–visible (UV–vis) and photoluminescence (PL) spectroscopy. The UV–vis spectra show absorption bands of the HNS at 503 and 520 nm, attributed mainly to PQDs and AuNPs, respectively. The PQDs show a strong excitonic PL band peaked at 513 nm from PQDs. The HR-TEM results show the formation of hybrid structures between PQDs and AuNPs, which is also supported by the PL quenching of the PQDs by the coupled AuNPs. Ultrafast dynamics of the exciton and charge carriers in the HNS and pristine PQD were studied using femtosecond transient absorption. Multiexponential fitting of the dynamic data revealed the existence of shallow and deep trap states in pristine PQDs and ultrafast electron transfer from PQDs to AuNPs in the HNS. A kinetic model was proposed to account for the key dynamic processes involved and to extract the time for electron transfer from PQDs to AuNPs in the HNS, found to be ∼2 ps. Dynamic processes in pristine PQDs are largely unchanged by HNS formation with AuNPs. 

We have synthesized inherently chiral cesium lead halide perovskite magic-sized clusters (PMSCs) and ligand-assisted metal halide molecular clusters (MHMCs) using the achiral ligands octanoic acid (OCA) and octylamine (OCAm). UV–vis electronic absorption was used to confirm characteristic absorption bands while circular dichroism (CD) spectroscopy was utilized to determine their chiroptical activity in the 412–419 and 395–405 nm regions, respectively. In contrast, the larger sized counterpart of PMSCs, namely, perovskite quantum dots (PQDs), do not show chirality. The inherent chirality of the clusters is tentatively attributed to a twisted chiral layered structure, defect-induced chiral structure, or twisted Pb–Br octahedra 

Exciton dynamics o perovskite nanoclusters has been investigated or the rst time using emtosecond transient absorption (TA) and time-resolved photoluminescence (TRPL) spectroscopy. The TA results show two photoinduced absorption signals at 420 and 461 nm and a photoinduced bleach (PB) signal at 448 nm. The analysis o the PB recovery kinetic decay and kinetic model uncovered multiple processes contributing to electron−hole recombination. The ast component (∼8 ps) is attributed to vibrational relaxation within the initial excited state, and the medium component (∼60 ps) is attributed to shallow carrier trapping. The slow component is attributed to deep carrier trapping rom the initial conduction band edge (∼666 ps) and the shallow trap state (∼40 ps). The TRPL reveals longer time dynamics, with modeled lietimes o 6.6 and 93 ns attributed to recombination through the deep trap state and direct band edge recombination, respectively. The signicant role o exciton trapping processes in the dynamics indicates that these highly conned nanoclusters have deect-rich suraces.