We report a systematic study of photoluminescence (PL) intensity and lifetime fluctuations in individual CdSe/CdS core/shell nanocrystal quantum dots (NQDs) as a function of shell thickness. We show that while at low pump intensities PL blinking in thin-shell (4–7 monolayers, MLs) NQDs can be described by random switching between two states of high (ON) and low (OFF) emissivities, it changes to the regime with a continuous distribution of ON intensity levels at high pump powers. A similar behavior is observed in samples with a medium shell thickness (10–12 MLs), without however, the PL intensity ever switching to a complete “OFF” state and maintaining ca. 30% emissivity (“gray” state). Further, our data indicate that highly stable, blinking-free PL of thick-shell (15–19 MLs) NQDs (“giant” or g-NQDs) is characterized by nearly perfect Poisson statistics, corresponding to a narrow, shot-noise limited PL intensity distribution. Interestingly, in this case the PL lifetime shortens with increasing pump power and the PL decay may deviate from mono-exponential. However, the PL intensity distribution remains shot-noise limited, indicating the absence of significant quantum yield fluctuations at a given pump power intensity during the experimental time window.

Thick-shell CdSe/nCdS (n >10) nanocrystals were recently reported that show remarkably suppressed fluorescence intermittency or "blinking" at the single-particle level as well as slow rates of Auger decay. Unfortunately, whereas CdSe/nCdS nanocrystal synthesis is well-developed up to n < 6 CdS monolayers (MLs), reproducible syntheses for n > 10 MLs are less understood. Known procedures sometimes result in homogeneous CdS nucleation instead of heterogeneous, epitaxial CdS nucleation on CdSe, leading to broad and multimodal particle size distributions. Critically, obtained core/shell sizes are often below those desired. This article describes synthetic conditions specific to thick-shell growth (n> 10 and n> 20 MLs) on both small (sub2 nm) and large (>4.5 nm) CdSe cores. We find added secondary amine and low concentration of CdSe cores and molecular precursors give desired core/shell sizes. Amine-induced, partial etching of CdSe cores results in apparent shell-thicknesses slightly beyond those desired, especially for very-thick shells (n >20 MLs). Thermal ripening and fast precursor injection lead to undesired homogeneous CdS nucleation and incomplete shell growth. Core/shells derived from small CdSe (1.9 nm) have longer PL lifetimes and more pronounced blinking at single-particle level compared with those derived from large CdSe (4.7 nm). We expect our new synthetic approach will lead to a larger throughput of these materials, increasing their availability for fundamental studies and applications.

Ultrafast transient pump-probe measurements of thin CH3NH3PbI3 perovskite films over a wide spectral range from 350 nm to 800 nm reveal a family of photoinduced bleach (PB) and absorption (PA) features unequivocally pointing to the fundamentally multi-band character of the underlying electronic structure. Excitation pump-energy dependent kinetics of three long-lived PB peaks at 1.65, 2.55 and 3.15 eV along with a broad PA band shows the involvement of band-edge thermalized carriers in all transitions and at least four, possibly more, electronic bands. The evolution of the transient signatures is described in terms of the redistribution of the conserved oscillator strength of the whole system. The multi-band perspective opens up new directions for understanding and controlling photoexcitations in hybrid perovskites.

Nonradiative Auger recombination is the primary exciton loss mechanism in colloidal nanocrystals and an impediment for prospective optoelectronic applications. Recent development of new core/shell nanocrystals with suppressed Auger recombination rates has opened the possibility for studying multicarrier states using time-resolved photoluminescence (PL) spectroscopy. An important aspect not addressed in previous works is the scaling of radiative and nonradiative decay rates with the increasing number and type of excitons in individual nanocrystals. Here we conduct extensive single-dot PL spectroscopy of emissive states in PL blinking trajectories of giant silica-coated CdSe/CdS nanocrystals. At low fluences, we observe the appearance of neutral and charged exciton (trion) states. Both negative and positive trions show strongly suppressed Auger recombination rates resulting in PL quantum yields close to 50%. At higher excitation powers, we observe consecutive emergence of lower efficiency states, indicative of higher order excitons. We employ a scaling model for Auger and radiative decay rates and attribute these states to doubly charged excitons, biexcitons, and a triexciton. Simultaneous analysis of the second-order correlation statistics proves that the biexciton Auger recombination channel can be represented in terms of the superposition of independent recombination channels of trions. Analysis of the PL emission of the triexciton state suggests nonstatistical scaling, likely due to the involvement of the transitions between different symmetries. Finally, measurements at high excitation fluence of nanocrystals with low trion quantum yields does not reveal any higher order excitonic states, corroborating the validity of the scaling model and confirming Auger-related mechanisms responsible for blinking behavior in such core/shell nanocrystals.

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We present a systematic study of photoluminescence (PL) emission intensity and biexciton (BX) quantum yields (QYBX) in individual "giant" CdSe/CdS nanocrystals (g-NCs) as a function of g-NC core size and shell thickness. We show that g-NC core size significantly affects QYBX and can be utilized as an effective tuning parameter towards higher QYBX while keeping the total volume of the g-NC constant. Specifically, we observe that small-core (2.2 nm diameter) CdSe/CdS NCs with a volume of ∼200 nm(3) (shell comprises 4 CdS monolayers) show very low average and maximum QYBX's of ∼3 and 7%, respectively. In contrast, same-volume medium-core (3 nm diameter) NCs afford higher average values of ∼10%, while QYBX's of ∼30% are achieved for same-volume large-core (5.5 nm diameter) CdSe/CdS NCs, with some approaching ∼80%. These observations underline the influence of the g-NC core size on the evolution of PL emissive states in multi-shell NCs. Moreover, our study also reveals that the use of long anneal times in the growth of CdS shells plays a critical role in achieving high QYBX.

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We investigate nonradiative energy transfer (NRET) between CdSe/CdS core/shell "giant" nanocrystal quantum dots (gNQDs) and monolayer domains of molybdenum disulfide (MoS 2 ) grown by chemical vapor deposition. We employ three sets of gNQDs with varied core/shell parameters that exhibit radiative emission from neutral and charged excitons (trions) at different spectral positions from 590 to 660 nm as confirmed by photon statistics of individual nanocrystals. Strong photoluminescence (PL) emission quenching is observed for the donor gNQDs placed on MoS 2 domains, indicative of the efficient NRET. Analysis of the double-component PL decays reveals NRET from both neutral excitons and charged trions with the same efficiency. Applying a macroscopic electrodynamics model for the decay of electric-dipole emitters in the vicinity of an ultrathin semiconducting layer with a strong in-plane excitonic polarizability, we confirm high NRET efficiencies from >95% to 85% for dots with diameters from 10 to 20 nm. This demonstration opens new possibilities for studies of energy transfer between zero-dimensional emitters and two-dimensional absorbers, potentially enabling new avenues for multiexciton harvesting and utilization.