Facet Dependent Photoluminescence Blinking from Perovskite Nanocrystals.

Photoluminescence (PL) blinking of nanoparticles, while detrimental to their imaging applications, may benefit next-generation displays if the blinking is precisely controlled by reversible electron/hole injections from an external source. Considerable efforts are made to create well-characterized charged excitons within nanoparticles through electrochemical charging, which has led to enhanced control over PL-blinking in numerous instances. Manipulating the photocharging/discharging rates in nanoparticles by surface engineering can represent a straightforward method for regulating their blinking behaviors, an area largely unexplored for perovskite nanocrystals (PNCs). This work shows facet engineering leading to different morphologies of PNCs characterized by distinct blinking patterns. For instance, examining the PL intensity trajectories of single PNCs, representing the instantaneous photon count rate over time, reveals that the OFF-state population significantly increases as the number of facets increases from six to twenty-six. This study suggests that extra-faceted PNCs, owing to their polar facets and expanded surface area, render them more susceptible to photocharging, which results in larger OFF-state populations. Furthermore, the fluorescence correlation spectroscopy (FCS) study unveils that the augmented propensity for photocharging in extra-faceted PNCs can also originate from their greater tendency to form complexes with neighboring molecules.

Unveiling the Influence of Brightness Heterogeneity in Fluorescence Correlation Spectroscopy of Perovskite Nanocrystals.

Nanoparticles (NPs), including perovskite nanocrystals (PNCs) with single photon purity, present challenges in fluorescence correlation spectroscopy (FCS) studies due to their distinct photoluminescence (PL) behaviors. In particular, the zero-time correlation amplitude [g2(0)] and the associated diffusion timescale (τD) of their FCS curves show substantial dependency on pump intensity (IP). Optical saturation inadequately explains the origin of this FCS phenomenon in NPs, thus setting them apart from conventional dye molecules, which do not manifest such behavior. This observation is apparently attributed to either photo-brightening or optical trapping, both lead to increased NP occupancy (N) in the excitation volume, consequently reducing the g2(0) amplitude [since g2(0) α 1/N] at high IP. However, an advanced FCS study utilizing alternating laser excitation at two different intensities dismisses such possibilities. Further investigation into single-particle blinking behaviors as a function of IP reveals that the intensity dependence of g2(0) primarily arises from the brightness heterogeneity prevalent in almost all types of NPs. This report delves into the complexities of the photophysical properties of NPs and their adverse impacts on FCS studies.

Facet Engineering for Decelerated Carrier Cooling in Polyhedral Perovskite Nanocrystals.

We report here the hot carrier (HC) cooling time scales within polyhedral CsPbBr3 nanocrystals (NCs) characterized by different numbers of facets (6 to 26) utilizing a femtosecond upconversion setup. Interestingly, the observed cooling time scale slows many-fold (>10 times) upon opening the new facets on the NC surface. Furthermore, a temperature-dependent study reveals that cooling in multifaceted NCs is polaron mediated, where newly opened polar facets and the soft lattice of CsPbBr3 NCs play pivotal roles. Our hallmark result of slow cooling in polyhedral NCs renders an excellent opportunity for harvesting high-energy carriers by a carefully chosen molecular system. To this end, employing the hole scavenger molecule aniline, we successfully extracted hot holes from optically pumped NCs. We believe that several intriguing properties of the polyhedral NCs, including rapid polaron formation, defect-tolerant nature, and the capability of soft lattice to support slow diffusion of charge carriers, resulted in decelerated cooling.

Evidence of carrier diffusion between emission states in CdSe/ZnS core-shell quantum dots: a comprehensive investigation combining fluorescence lifetime correlation spectroscopy (FLCS) and single dot photoluminescence studies.

Investigation of carrier dynamics in CdSe/ZnS core-shell quantum dots (QDs) is performed using fluorescence-lifetime-correlation-spectroscopy (FLCS) and single-dot PL blinking studies. The origin of an emitted photon from a QD in an FLCS study is assigned to either an exciton state or trap state based on its excited state lifetime (τfl). Subsequently, two intrastate autocorrelation functions (ACFs) representing the exciton and trap states and one cross-correlation function (CCF) coupling these two states are constructed. Interestingly, the timescales of carrier diffusion (τR) show striking similarities across all three correlation functions, which further correlate with τR of the conventional FCS. However, ACFs notably deviate from the CCF in their µs progression patterns, with the latter showing growth, whereas the former ones display decay. This implies inter-state carrier diffusions leading to the QD blinking. Further study of single particle PL blinking on a surface-immobilized QD indicates shallow trap states near the band edge cause the blinking at low excitation power, while trion recombination becomes an additional contributing factor at higher pump power. Overall, the results highlight not only an excellent correlation between these two techniques but also the potential of our approach for achieving an accurate and comprehensive understanding of carrier dynamics in CdSe/ZnS QDs.

Dodecahedron CsPbBr3 Perovskite Nanocrystals Enable Facile Harvesting of Hot Electrons and Holes.

This Letter reports the facile harvesting of hot carriers (HCs) in a composite of 12-faceted dodecahedron CsPbBr3 nanocrystal (NC) and a scavenger molecule. We recorded ∼3.3 × 1011 s-1 HC cooling rate in NC when excited with ∼1.4 times the band gap energy (Eg), increasing to >3 × 1012 s-1 in the presence of scavengers at high concentration due to the HC extractions. Since the observed intrinsic charge transfer rate (∼1.7 × 1012 s-1) in our NC-scavenger complex is about an order of magnitude higher than the HC cooling rate (∼3.3 × 1011 s-1), carriers are harvested before their cooling. Further, a fluorescence correlation spectroscopy study reveals NC tends to form a quasi-stable complex with a scavenger molecule, ensuring charge transfer completed (τct ≈ 0.6 ps) much before the complex breaks apart (>600 µs). The overall results of our study highlight the promise shown by 12-faceted NCs and their implications in modern applications, including hot carrier solar cells.

Unraveling the Interaction of Diflunisal with Cyclodextrin and Lysozyme by Fluorescence Spectroscopy.

Understanding the interaction between the drug:carrier complex and protein is essential for the development of a new drug-delivery system. However, the majority of reports are based on an understanding of interactions between the drug and protein. Here, we present our findings on the interaction of the anti-inflammatory drug diflunisal with the drug carrier cyclodextrin (CD) and the protein lysozyme, utilizing steady-state and time-resolved fluorescence spectroscopy. Our findings reveal a different pattern of molecular interaction between the inclusion complex of ß-CD (ß-CD) or hydroxypropyl-ß-CD (HP-ß-CD) (as the host) and diflunisal (as the guest) in the presence of protein lysozyme. The quantum yield for the 1:2 guest:host complex is twice that of the 1:1 guest:host complex, indicating a more stable hydrophobic microenvironment created in the 1:2 complex. Consequently, the nonradiative decay pathway is significantly reduced. The interaction is characterized by ultrafast solvation dynamics and time-resolved fluorescence resonance energy transfer. The solvation dynamics of the lysozyme becomes 10% faster under the condition of binding with the drug, indicating a negligible change in the polar environment after binding. In addition, the fluorescence lifetime of diflunisal (acceptor) is increased by 50% in the presence of the lysozyme (donor), which indicates that the drug molecule is bound to the binding pocket on the surface of the protein, and the average distance between active tryptophan in the hydrophobic region and diflunisal is calculated to be approximately 50 Å. Excitation and emission matrix spectroscopy reveals that the tryptophan emission increases 3-5 times in the presence of both diflunisal and CD. This indicates that the tryptophan of lysozyme may be present in a more hydrophobic environment in the presence of both diflunisal and CD. Our observations on the interaction of diflunisal with ß-CD and lysozyme are well supported by molecular dynamics simulation. Results from this study may have an impact on the development of a better drug-delivery system in the future. It also reveals a fundamental molecular mechanism of interaction of the drug-carrier complex with the protein.

Subpicosecond Hot Hole Transfer in a Graphene Quantum Dot Composite with High Efficiency.

Extraction of hot carriers is of prime importance because of its potential to overcome the energy loss that limits the efficiency of an optoelectronic device. Employing a femtosecond upconversion setup, herein we report a few picoseconds carrier cooling time of colloidal graphene quantum dots (GQDs) is at least an order of magnitude slower compared to that in its bulk form. A slower carrier cooling time of GQDs compared to that of the other semiconductor quantum dots and their bulk materials is indeed a coveted property of GQDs that would allow one easy harvesting of high energy species employing a suitable molecular system as shown in this study. A subpicosecond hot hole transfer time scale has been achieved in a GQD-molecular system composite with high transfer efficiency. Our finding suggests a dramatic enhancement of the efficiency of GQD based optoelectronic devices can possibly be a reality.

Multifunctional Lanthanide-Doped Binary Fluorides and Graphene Oxide Nanocomposites Via a Task-Specific Ionic Liquid.

Graphene oxide-based nanocomposites (NCMs) exhibit diverse photonic and biophotonic applications. Innovative nanoengineering using a task-specific ionic liquid (IL), namely, 1-butyl-3-methyl tetrafluoroborate [C4mim][BF4], allows one to access a unique class of luminescent nanocomposites formed between lanthanide-doped binary fluorides and graphene oxide (GO). Here the IL is used as a solvent, templating agent, and as a reaction partner for the nanocomposite synthesis, that is, "all three in one". Our study shows that GO controls the size of the NCMs; however, it can tune the luminescence properties too. For example, the excitation spectrum of Ce3+ is higher-energy shifted when GO is attached. In addition, magnetic properties of GdF3:Tb3+ nanoparticles (NPs) and GdF3:Tb3+-GO NCMs are also studied at room temperature (300 K) and very low temperature (2 K). High magnetization results for the NPs (e.g., 6.676 emu g-1 at 300 K and 184.449 emu g-1 at 2 K in the applied magnetic field from +50 to -50 kOe) and NCMs promises their uses in many photonic and biphotonic applications including magnetic resonance imaging, etc.

Femtosecond Upconversion Study of Interfacial Electron Transfer from Photoexcited CsPbBr3 Perovskite Nanocrystal to Rhodamine 6G.

Photoinduced electron transfer (PET) from an excited-state CsPbBr3 nanocrystal (NC) to rhodamine 6G (r6G) is studied in toluene using different fluorescence-based techniques. Because of weak solubility of r6G in toluene, excess r6G molecules adsorb at NC surface which result in a much slower rotational diffusion time scale of r6G in the presence of NCs. Study of intrinsic PET benefits from the soft molecular interactions leading to donor (NC)-acceptor (r6G) complex formation, where solvent diffusion parameters would not play any role in the PET kinetics. Femtosecond transients of NCs are nicely fit to a Poisson expression originally proposed by Tachiya. Conclusive fittings to the temperature dependence quenching data reveal two interesting observations: (1) Even though the average number of surface trap state in a NC does not change with temperature (5-60 °C), the trap-state-induced quenching time scale is accelerated with increase in temperature, pointing toward a more efficient trapping at higher temperature. (ii) In the presence of r6G, a fast (∼150 ps per r6G molecule) interfacial PET time scale is observed, which remains unaffected by temperature (5-60 °C). Our findings demonstrate that even a simple "perovskite NC-electron acceptor" composite like that in the present study can ensure a rapid interfacial charge separation. Such information will help us to realize the actual potential of perovskites NCs in their real applications.