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Quantifying stimulated emission in semiconductor nanocrystals (NCs) remains challenging due to masking of its effects on pump-probe spectra by excited state absorption and ground state bleaching signals. The absence of this defining photophysical parameter in turn impedes assignment of band edge electronic structure in many of these important fluorophores. Here we employ a generally applicable 3-pulse ultrafast spectroscopic method coined the "Spectator Exciton" (SX) approach to measure stimulated-emission efficiency in quantum confined inorganic perovskite CsPbBr3 NCs, the band edge electronic structure of which is the subject of lively ongoing debate. Our results show that in 5-6 nm CsPbBr3 NCs, a single exciton bleaches more than half of the intense band edge absorption band, while the cross section for stimulated emission from the same state is nearly 6 times weaker. Discussion of these findings in light of several recent electronic structure models for this material proves them unable to simultaneously explain both measures, proving the importance of this new input to resolving this debate. Along with femtosecond time-resolved photoluminescence measurements on the same sample, SX results also verify that biexciton interaction energy is intensely attractive with a magnitude of â¼80 meV. In light of this observation, our previous suggestion that biexciton interaction is repulsive is reassigned to hot phonon induced slowdown of carrier relaxation leading to direct Auger recombination from an excited state. The mechanism behind the extreme slowing of carrier cooling after several stages of exciton recombination remains to be determined.
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Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent colloidal nanocrystals, as well as their tunable and intriguing optical and electronic properties, has attracted researchers from different disciplines of science and technology. In the last few years, there has been a significant progress in the shape-controlled synthesis of perovskite nanocrystals and understanding of their properties and applications. In this comprehensive review, researchers having expertise in different fields (chemistry, physics, and device engineering) of metal-halide perovskite nanocrystals have joined together to provide a state of the art overview and future prospects of metal-halide perovskite nanocrystal research.
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The lack of long-term stability, the presence of toxic lead, and a low photoluminescence (PL) efficiency are the major obstacles to the commercialization of lead-halide perovskite-based optoelectronic and photovoltaic devices. Herein we report a facile ambient condition doping protocol that addresses all three issues of the CsPbX3 perovskite nanocrystals (NCs) to a substantial extent. We show that the room-temperature treatment of these NCs with MgX2 results in the partial (18-23%) replacement of toxic lead, enhances the PL quantum yield of green-emitting CsPbBr3 (to â¼100% from â¼51%) and violet-emitting CsPbCl3 NCs (to â¼79% from â¼1%), and improves the stability under ambient conditions and in the presence of light and a polar solvent. Ultrafast pump-probe and temperature-dependent PL studies reveal that curing of the intrinsic structural disorder, introduction of some shallow energy levels close to the conduction band edge, and effective passivation of the halide deficiency contribute to the improved properties of the doped systems.
Assuntos
Compostos de Cálcio/química , Magnésio/química , Nanopartículas Metálicas/química , Óxidos/química , Titânio/química , Hexanos/química , Íons/química , Luminescência , TemperaturaRESUMO
Perovskite nanocrystals (NCs), especially those based on cesium lead halides, have emerged in recent years as highly promising materials for efficient solar cells and photonic applications. The key to realization of full potential of these materials lies however in the molecular level understanding of the processes triggered by light. Herein we highlight the knowledge gained from photophysical investigations on these NCs of various sizes and compositions employing primarily the femtosecond pump-probe technique. We show how spectral and temporal characterization of the photo-induced transients provide insight into the mechanism and dynamics of relaxation of hot and thermalized charge carriers through their recombination and trapping. We discuss how the multiple excitons including the charged ones (trions), generated using high pump fluence or photon energy, recombine through the Auger-assisted process. We discussed the harvesting of hot carriers prior to their cooling and band-edge carriers from these perovskite NCs to wide band-gap metal oxides, metal chalcogenide NCs and molecular acceptors. How perovskites can influence the charge carrier dynamics in composites of organic and inorganic semiconductors is also discussed.
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Recent studies show that perovskites (ABX3-type) comprising mixed A or B cation and/or mixed halide (X) are more stable and efficient materials for photovoltaic applications than their respective pure forms. Herein we report how doping of a small quantity of formamidinium and/or chloride ion influences the single and multiexciton dynamics of CsPbI3 nanocrystals (NCs). With the help of ultrafast pump-probe spectroscopic measurements, we show that chloride doping can enhance the biexciton lifetime of the system significantly by slowing down the Auger recombination (AR) process. The measured biexciton AR time scale (â¼195-205 ps) in some of these NCs is the longest among those reported to date for any similar size perovskites. We further demonstrate that suppression of the AR rate and consequent lengthening of biexciton lifetime allow harvest of these species for their utilization through rapid (18-45 ps) electron transfer to fullerene. The insights obtained from this study are expected to help design more efficient doped perovskites for energy conversion purposes.
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Excitation of semiconductor quantum dots (QDs) by photons possessing energy higher than the band-gap creates a hot electron-hole pair, which releases its excess energy as waste heat or under certain conditions (when hν > 2Eg) produces multiple excitons. Extraction of these hot carriers and multiple excitons is one of the key strategies for enhancing the efficiency of QD-based photovoltaic devices. However, this is a difficult task as competing carrier cooling and relaxation of multiple excitons (through Auger recombination) are ultrafast processes. Herein, we study the potential of all-inorganic perovskite nanocrystals (NCs) of CsPbX3 (X = Cl, Br) as harvesters of these short-lived species from photo-excited CdTe QDs. The femtosecond transient absorption measurements show CsPbX3 mediated extraction of both hot and thermalized electrons of the QDs (under a low pump power) and (under a high pump fluence) extraction of multiple excitons prior to their Auger assisted recombination. A faster timescale of thermalized electron transfer (â¼2 ps) and a higher extraction efficiency of hot electrons (â¼60%) are observed in the presence of CsPbBr3. These observations demonstrate the potential of all-inorganic perovskite NCs in the extraction of these short-lived energy rich species implying that complexes of the QDs and perovskite NCs are better suited for improving the efficiency of QD-sensitized solar cells.
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Mn-Doped perovskite nanocrystals (NCs) are a new class of materials offering exciting opportunities to control over their optical and magnetic properties. Herein, we report a series of Mn-doped CsPbCl3 NCs exhibiting a tunable Mn photoluminescence (PL) band with a PL peak wavelength pushed up to 625 nm and tuned over a range of 40 nm, the largest achieved so far, by only varying the Mn content. The X-band EPR data and Mn PL decay behaviour of the NCs reveal that the exchange interaction between Mn2+ ions is mainly responsible for a large shift of the Mn PL band. Ultrafast pump-probe measurements show that exciton-dopant energy transfer in these NCs is slower (â¼50-100 ps) than trapping of the carriers (â¼8-10 ps) in the host lattice. The large PL tuning reported here along with the insights into the mechanism of tuning and carrier dynamics are expected to boost the potential of Mn-doped CsPbCl3 NCs in light-powered devices.
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Surface protection using an appropriate ligand is essential for controlling the size, stability and luminescence properties of the quantum dots (QDs). Though 3-mercaptopropanoic acid (3-MPA) is regarded as the most suitable protecting ligand among the mercapto acids for water soluble CdTe QDs, one receives a different picture from recent studies, which report a much higher luminescence efficiency of 3-mercaptobutyric acid (3-MBA) capped QDs compared with those capped by 3-MPA and attribute the observation to the influence of the side methyl group of mercapto acids. Herein we report the luminescence properties and carrier trapping dynamics of four different, but structurally related mercapto acid capped CdTe QDs prepared using a different method. The results show that these QDs are much more fluorescent than those prepared directly in an aqueous environment and surprisingly, no enhanced luminescence for the QDs capped by mercapto acids containing a side methyl group is observed. Ultrafast pump-probe measurements confirm these results in addition to providing insight into the carrier trapping dynamics of these systems. It is shown that our findings, which appear to be in conflict with the recent literature, can be rationalized and the exact role of the side methyl group of the mercapto acids can be understood by careful analysis of the results taking into consideration the difference in the methods of preparation of the QDs in the two cases.
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CONTEXT: Mucuna pruriens Linn. (Fabaceae) is a tropical legume, traditionally used for controlling blood pressure. Inhibition of angiotensin-converting enzyme (ACE) is one of the successful strategies for controlling hypertension. OBJECTIVE: The present study evaluated the ACE inhibition potential of the standardized extract of M. pruriens seeds. MATERIALS AND METHODS: Standardization of the extract and its fractions were carried out by RP-HPLC method [methanol and 1% v/v acetic acid in water (5:95 v/v)] using levodopa as a marker. The ACE inhibition activity of the extract and fractions was evaluated at different concentrations (20, 40, 60, 80, and 100 µg/mL) using the HPLC-DAD and the UV spectrophotometric method. The liberation of hippuric acid (HA) from hippuryl-L-histidyl-L-leucine (HHL) was estimated in the spectrophotometric method and RP-HPLC assay at 228 nm. RESULTS: Methanol extract and aqueous fraction showed a maximum activity with IC50 values of 38.44 ± 0.90 and 57.07 ± 2.90 µg/mL (RP-HPLC), and 52.68 ± 2.02 and 67.65 ± 2.40 µg/mL (spectrophotometry), respectively. DISCUSSION: The study revealed that the aqueous extract contains the highest amount of levodopa. Eventually the methanol extract showed highest ACE inhibition activity except levodopa alone. It was further observed that the inhibition was altered with respect to the change in the content of levodopa in the extract. Thus, it can be assumed that levodopa may be responsible for the ACE inhibition activity of M. pruriens seeds. CONCLUSION: It can be concluded that M. pruriens seed is a potential ACE inhibitor can be explored further as an effective antihypertensive agent.