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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. 

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. 

The excited state dynamics of ligand-passivated PbBr2 molecular clusters (MCs) in solution have been investigated for the first time using femtosecond transient absorption spectroscopy. The results uncover a transient bleach (TB) feature peaked around 404 nm, matching the ground state electronic absorption band peaked at 404 nm. The TB recovery signal can be fitted with a triple exponential with fast (10 ps), medium (350 ps), and long (1.8 ns) time constants. The medium and long time constants are very similar to those observed in the timeresolved photoluminescence (TRPL) decay monitored at 412 nm. The TB fast component is attributed to vibrational relaxation in the excited electronic state while the medium component with dominant amplitude is attributed to recombination between the relaxed electron and hole. The small amplitude slow component is assigned to electrons in a relatively long-lived excited electronic state, e.g., triplet state, or shallow trap state due to defects. This study provides new insights into the excited state dynamics of metal halide MCs. 

Abstract BackgroundResearch into perovskite nanocrystals (PNCs) has uncovered interesting properties compared to their bulk counterparts, including tunable optical properties due to size‐dependent quantum confinement effect (QCE). More recently, smaller PNCs with even stronger QCE have been discovered, such as perovskite magic sized clusters (PMSCs) and ligand passivated PbX₂metal halide molecular clusters (MHMCs) analogous to perovskites. ObjectiveThis review aims to present recent data comparing and contrasting the optical and structural properties of PQDs, PMSCs, and MHMCs, where CsPbBr₃PQDs have first excitonic absorption around 520 nm, the corresponding PMSCS have absorption around 420 nm, and ligand passivated MHMCs absorb around 400 nm. ResultsCompared to normal perovskite quantum dots (PQDs), these clusters exhibit both a much bluer optical absorption and emission and larger surface‐to‐volume (S/V) ratio. Due to their larger S/V ratio, the clusters tend to have more surface defects that require more effective passivation for stability. ConclusionRecent study of novel clusters has led to better understanding of their properties. The sharper optical bands of clusters indicate relatively narrow or single size distribution, which, in conjunction with their blue absorption and emission, makes them potentially attractive for applications in fields such as blue single photon emission.