Here, we systematically investigated the spontaneous and stimulated emission performances of solution-processed atomically flat quasi-2D nanoplatelets (NPLs) as a function of their lateral size using ...colloidal CdSe core NPLs. We found that the photoluminescence quantum efficiency of these NPLs decreases with increasing lateral size while their photoluminescence decay rate accelerates. This strongly suggests that nonradiative channels prevail in the NPL ensembles having extended lateral size, which is well-explained by the increasing number of the defected NPL subpopulation. In the case of stimulated emission the role of lateral size in NPLs influentially emerges both in the single- and two-photon absorption (1PA and 2PA) pumping. In the amplified spontaneous emission measurements, we uncovered that the stimulated emission thresholds of 1PA and 2PA exhibit completely opposite behavior with increasing lateral size. The NPLs with larger lateral sizes exhibited higher stimulated emission thresholds under 1PA pumping due to the dominating defected subpopulation in larger NPLs. On the other hand, surprisingly, larger NPLs remarkably revealed lower 2PA-pumped amplified spontaneous emission thresholds. This is attributed to the observation of a “giant” 2PA cross-section overwhelmingly growing with increasing lateral size and reaching record levels higher than 106 GM, at least an order of magnitude stronger than colloidal quantum dots and rods. These findings suggest that the lateral size control in the NPLs, which is commonly neglected, is essential to high-performance colloidal NPL optoelectronic devices in addition to the vertical monolayer control.
We proposed and showed strongly orientation-controlled Förster resonance energy transfer (FRET) to highly anisotropic CdSe nanoplatelets (NPLs). For this purpose, we developed a liquid–air interface ...self-assembly technique specific to depositing a complete monolayer of NPLs only in a single desired orientation, either fully stacked (edge-up) or fully nonstacked (face-down), with near-unity surface coverage and across large areas over 20 cm2. These NPL monolayers were employed as acceptors in an energy transfer working model system to pair with CdZnS/ZnS core/shell quantum dots (QDs) as donors. We found the resulting energy transfer from the QDs to be significantly accelerated (by up to 50%) to the edge-up NPL monolayer compared to the face-down one. We revealed that this acceleration of FRET is accounted for by the enhancement of the dipole–dipole interaction factor between a QD-NPL pair (increased from 1/3 to 5/6) as well as the closer packing of NPLs with stacking. Also systematically studying the distance-dependence of FRET between QDs and NPL monolayers via varying their separation (d) with a dielectric spacer, we found out that the FRET rate scales with d –4 regardless of the specific NPL orientation. Our FRET model, which is based on the original Förster theory, computes the FRET efficiencies in excellent agreement with our experimental results and explains well the enhancement of FRET to NPLs with stacking. These findings indicate that the geometrical orientation of NPLs and thereby their dipole interaction strength can be exploited as an additional degree of freedom to control and tune the energy transfer rate.
Doping of bulk semiconductors has revealed widespread success in optoelectronic applications. In the past few decades, substantial effort has been engaged for doping at the nanoscale. Recently, doped ...colloidal quantum dots (CQDs) have been demonstrated to be promising materials for luminescent solar concentrators (LSCs) as they can be engineered for providing highly tunable and Stokes‐shifted emission in the solar spectrum. However, existing doped CQDs that are aimed for full solar spectrum LSCs suffer from moderately low quantum efficiency, intrinsically small absorption cross‐section, and gradually increasing absorption profiles coinciding with the emission spectrum, which together fundamentally limit their effective usage. Here, the authors show the first account of copper doping into atomically flat colloidal quantum wells (CQWs). In addition to Stokes‐shifted and tunable dopant‐induced photoluminescence emission, the copper doping into CQWs enables near‐unity quantum efficiencies (up to ≈97%), accompanied by substantially high absorption cross‐section and inherently step‐like absorption profile, compared to those of the doped CQDs. Based on these exceptional properties, the authors have demonstrated by both experimental analysis and numerical modeling that these newly synthesized doped CQWs are excellent candidates for LSCs. These findings may open new directions for deployment of doped CQWs in LSCs for advanced solar light harvesting technologies.
Copper‐doped colloidal semiconductor quantum wells are successfully synthesized by nucleation doping technique. These newly synthesized doped nanoplatelets are successfully shown to be applied in luminescent solar concentrators thanks to their near‐unity photoluminescence quantum efficiencies (≈97%), profoundly step‐like absorption profiles, and higher absorption cross‐sections along with highly Stokes‐shifted tunable emission in visible‐to‐near‐infrared.
An all‐solution processed and all‐colloidal laser is demonstrated using tailored CdSe/CdS core/shell quantum dots, which exhibit highly stable and low‐threshold optical gain owing to substantially ...suppressed non‐radiative Auger recombination.
A new type of light-emitting hybrid device based on colloidal quantum dots (QDs) and an ionic transition metal complex (iTMC) light-emitting electrochemical cell (LEC) is introduced. The developed ...hybrid devices show light emission from both active layers, which are combined in a stacked geometry. Time-resolved photoluminescence experiments indicate that the emission is controlled by direct charge injection into both the iTMC and the QD layer. The turn-on time (time to reach 1 cd/m2) at constant voltage operation is significantly reduced from 8 min in the case of the reference LEC down to subsecond in the case of the hybrid device. Furthermore, luminance and efficiency of the hybrid device are enhanced compared to reference LEC directly after device turn-on by a factor of 400 and 650, respectively. We attribute these improvements to an increased electron injection efficiency into the iTMC directly after device turn-on.
The distinct optical properties and electronic structures of two-dimensional colloidal nanoplatelets (NPLs) have garnered significant scientific and practical interest. However, concerns regarding ...the toxicity of cadmium-based NPLs and their limited spectral coverage show the importance of developing nontoxic alternatives. In this study, we devised a new synthetic approach for the direct synthesis of zinc-blende (ZB) ZnSe NPLs. By introducing two different zinc precursors, short-chain metal carboxylate- zinc acetate, and metal halide-zinc chloride, we successfully synthesized two-dimensional ZB ZnSe NPLs. By modifying the reaction parameters, we obtained two different populations of ZnSe NPLs, characterized by the first absorption peak at “343” and “367 nm”. Ostwald ripening experiments further confirmed the formation of 2D ZnSe NPLs by the observed discrete growth mechanism. Lastly, we investigated the impact of surface ligands on the excitonic properties of ZB ZnSe NPLs by treating their initially carboxylic acid-capped surface with oleylamine. Remarkably, we observed significant red-shifting in the first excitonic peaks, up to 130 meV, in a reversible manner, demonstrating further tunability of excitonic features in ZnSe NPLs. We anticipate that our findings will serve as a catalyst for further exploration of nontoxic two-dimensional materials, fostering their investigation and application in various fields.
In nanocrystal quantum dots (NQDs), generating multiexcitons offers an enabling tool for enhancing NQD-based devices. However, the photocharging effect makes understanding multiexciton kinetics in ...NQD solids fundamentally challenging, which is critically important for solid-state devices. To date, this lack of understanding and the spectral–temporal aspects of the multiexciton recombination still remain unresolved in solid NQD ensembles, which is mainly due to the confusion with recombination of carriers in charged NQDs. In this work, we reveal the spectral–temporal behavior of biexcitons (BXs) in the presence of photocharging using near-unity quantum yield CdSe/CdS NQDs exhibiting substantial suppression of Auger recombination. Here, recombinations of biexcitons and single excitons (Xs) are successfully resolved in the presence of trions in the ensemble measurements of time-correlated single-photon counting at variable excitation intensities and varying emission wavelengths. The spectral behaviors of BXs and Xs are obtained for three NQD samples with different core sizes, revealing the strength tunability of the X–X interaction energy in these NQDs. The extraction of spectrally resolved X, BX, and trion kinetics, which are otherwise spectrally unresolved, is enabled by our approach introducing integrated time-resolved fluorescence. The results are further experimentally verified by cross-checking excitation intensity and exposure time dependencies as well as the temporal evolutions of the photoluminescence spectra, all of which prove to be consistent. The BX and X energies are also confirmed by theoretical calculations. These findings fill an important gap in understanding the spectral dynamics of multiexcitons in such NQD solids under the influence of photocharging effects, paving the way to engineering of multiexciton kinetics in nanocrystal optoelectronics, including NQD-based lasing, photovoltaics, and photodetection.
There has been a strong interest in solution-processed two-dimensional nanomaterials because of their great potential in optoelectronics. Here, the absorption cross-section and molar extinction ...coefficient of four and five monolayer thick colloidal CdSe nanoplatelets (NPLs) having various lateral sizes are reported. The absorption cross-section of these NPLs and their corresponding molar extinction coefficients are found to strongly depend on the lateral area. An excellent agreement is observed between the experimental results and the calculated values based on the small-particle light absorption model. With these optical properties, NPLs hold great promise for optoelectronic applications.
Colloidal semiconductor quantum wells, also commonly known as nanoplatelets (NPLs), have arisen among the most promising materials for light generation and harvesting applications. Recently, NPLs ...have been found to assemble in stacks. However, their emerging characteristics essential to these applications have not been previously controlled or understood. In this report, we systematically investigate and present excitonic properties of controlled column-like NPL assemblies. Here, by a controlled gradual process, we show that stacking in colloidal quantum wells substantially increases exciton transfer and trapping. As NPLs form into stacks, surprisingly we find an order of magnitude decrease in their photoluminescence quantum yield, while the transient fluorescence decay is considerably accelerated. These observations are corroborated by ultraefficient Förster resonance energy transfer (FRET) in the stacked NPLs, in which exciton migration is estimated to be in the ultralong range (>100 nm). Homo-FRET (i.e., FRET among the same emitters) is found to be ultraefficient, reaching levels as high as 99.9% at room temperature owing to the close-packed collinear orientation of the NPLs along with their large extinction coefficient and small Stokes shift, resulting in a large Förster radius of ∼13.5 nm. Consequently, the strong and long-range homo-FRET boosts exciton trapping in nonemissive NPLs, acting as exciton sink centers, quenching photoluminescence from the stacked NPLs due to rapid nonradiative recombination of the trapped excitons. The rate-equation-based model, which considers the exciton transfer and the radiative and nonradiative recombination within the stacks, shows an excellent match with the experimental data. These results show the critical significance of stacking control in NPL solids, which exhibit completely different signatures of homo-FRET as compared to that in colloidal nanocrystals due to the absence of inhomogeneous broadening.
Semiconductor nanoplatelets (NPLs) have emerged as a very promising class of colloidal nanocrystals for light-emitting devices owing to their quantum-well-like electronic and optical characteristics. ...However, their lower photoluminescence quantum yield (PLQY) and limited stability have hampered the realization of their outstanding luminescent properties in device applications. Here, to address these deficiencies, we present a two-step synthetic approach that enables the synthesis of core/shell NPLs with precisely controlled shell composition for engineering their excitonic properties. The proposed CdSe colloidal quantum wells possess a graded shell, which is composed of a CdS buffer layer and a Cd x Zn1–x S gradient layer, and exhibit bright emission (PLQY 75–89%) in the red spectral region (634–648 nm) with a narrow emission line width (21 nm). These enhanced optical properties allowed us to attain low thresholds for amplified spontaneous emission (down to ∼40 μJ/cm2) under nanosecond laser excitation. We also studied the electroluminescent performance of these NPLs by fabricating solution-processed light-emitting diodes (LEDs). In comparison to NPL-LEDs with CdSe/CdS core/shell NPLs, which exhibit an external quantum efficiency (EQE) value of only 1.80%, a significantly improved EQE value of 9.92% was obtained using graded-shell NPLs, the highest value for colloidal NPL-based-LEDs. In addition, the low efficiency roll-off characteristics of NPL-LEDs enabled a high brightness of up to ∼46 000 cd/m2 with an electroluminescence peak centered at 650 nm. These findings demonstrate the paramount role that heterostructure engineering occupies in enhancing the optoelectronic characteristics of semiconductor NPLs toward practically relevant levels.
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