Stacking in Colloidal Nanoplatelets: Tuning Excitonic Properties

Cataloged from PDF version of article.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 Forster 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 Forster radius of similar to 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

Lateral Size-Dependent Spontaneous and Stimulated Emission Properties in Colloidal CdSe Nanoplatelets

Cataloged from PDF version of article.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 10(6) 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

Temperature-Dependent Emission Kinetics of Colloidal Semiconductor Nanoplatelets Strongly Modified by Stacking

We systematically studied temperature-dependent emission kinetics in solid films of solution-processed CdSe nanoplatelets (NPLs) that are either intentionally stacked or nonstacked. We observed that the steady-state photoluminescence (PL) intensity of nonstacked NPLs considerably increases with decreasing temperature, whereas there is only a slight increase in stacked NPLs. Furthermore, PL decay time of the stacked NPL ensemble is comparatively much shorter than that of the nonstacked NPLs, and this result is consistent at all temperatures. To account for these observations, we developed a probabilistic model that describes excitonic processes in a stack using Markov chains, and we found excellent agreement between the model and experimental results. These findings develop the insight that the competition between the radiative channels and energy transfer-assisted hole trapping leads to weakly temperature-dependent PL intensity in the case of the stacked NPL ensembles as compared to the nonstacked NPLs lacking strong energy transfer. This study shows that it is essential to account for the effect of NPL stacking to understand their resulting PL emission properties. © 2016 American Chemical Society

Low-threshold optical gain and lasing of colloidal nanoplatelets

Semiconductor nanocrystals, which are also known as colloidal quantum dots (CQDs), are highly attractive materials for high performance optoelectronic device applications such as lasers. With their size, shape and composition tunable electronic structure and optical properties, CQDs are highly desired for achieving full-color, temperature-insensitive, low-threshold and solution-processed lasers [1, 2]. However, due to their small size, they suffer from the nonradiative multiexciton Auger Recombination (AR), where energy of a bound electron-hole pair is transferred to a third particle of either an electron or a hole instead of radiative recombination. Therefore, CQDs having suppressed AR are strongly required for achieving high quality CQD-based lasers. To address this issue, CQDs having different size, shape and electronic structure have been synthesized and studied extensively [3-5]. Generally, suppression of AR and lower optical gain thresholds are achieved via reducing the wavefunction overlap of the electron and hole in a CQD. However, the separation of the electron and hole wavefunctions will dramatically decrease the oscillator strength and optical gain coefficient, which is highly critical for achieving high performance lasers. Therefore, colloidal materials with suppressed AR and high gain coefficients are highly welcomed. Here, we study optical gain performance of colloidal quantum wells [6] of CdSe-core and CdSe/CdS core/crown nanoplatelets (NPLs) that demonstrate remarkable optical properties with ultra-low threshold one- and two-photon optical pumping. As a result of their giant oscillator strength, superior optical gain and lasing performance are achieved from these colloidal NPLs with greatly enhanced gain coefficient [7]. © 2014 IEEE

Highly Efficient Nonradiative Energy Transfer from Colloidal Semiconductor Quantum Dots to Wells for Sensitive Noncontact Temperature Probing

This study develops and shows highly efficient exciton-transferring hybrid semiconductor nanocrystal films of mixed dimensionality comprising quasi 0D and 2D colloids. Through a systematic study of time-resolved and steady-state photoluminescence spectroscopy as a function of the donor-to-acceptor molar concentration ratio and temperature, a high-efficiency nonradiative energy transfer (NRET) process from CdZnS/ZnS core/shell quantum dots (QDs) directed to atomically flat CdSe nanoplatelets (NPLs) in their solid-state thin films is uncovered. The exciton funneling in this system reaches transfer efficiency levels as high as 90% at room temperature. In addition, this study finds that with decreasing temperature exciton transfer efficiency is increased to a remarkable maximum level of ≈94%. The enhancement in the dipole-dipole coupling strength with decreasing temperature is well accounted by increasing photoluminescence quantum yield of the donor and growing spectral overlap between the donor and the acceptor. Furthermore, NRET efficiency exhibits a highly linear monotonic response with changing temperature. This makes the proposed QD-NPL composites appealing for noncontact sensitive temperature probing based on NRET efficiencies as a new metric. These findings indicate that combining colloidal nanocrystals of different dimensionality enables efficient means of temperature probing at an unprecedented sensitivity level at nanoscale through almost complete exciton transfer. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Platelet-in-Box Colloidal Quantum Wells: CdSe/CdS@CdS Core/Crown@Shell Heteronanoplatelets

Here, the CdSe/CdS@CdS core/crown@shell heterostructured nanoplatelets (NPLs) resembling a platelet-in-box structure are developed and successfully synthesized. It is found that the core/crown@shell NPLs exhibit consistently substantially improved photoluminescence quantum yield compared to the core@shell NPLs regardless of their CdSe-core size, CdS-crown size, and CdS-shell thickness. This enhancement in quantum yield is attributed to the passivation of trap sites resulting from the critical peripheral growth with laterally extending CdS-crown layer before the vertical shell growth. This is also verified with the disappearance of the fast nonradiative decay component in the core/crown NPLs from the time-resolved fluorescence spectroscopy. When compared to the core@shell NPLs, the core/crown@shell NPLs exhibit relatively symmetric emission behavior, accompanied with suppressed lifetime broadening at cryogenic temperatures, further suggesting the suppression of trap sites. Moreover, constructing both the CdS-crown and CdS-shell regions, significantly enhanced absorption cross-section is achieved. This, together with the suppressed Auger recombination, enables the achievement of the lowest threshold amplified spontaneous emission (≈20 μJ cm−2) from the core/crown@shell NPLs among all different architectures of NPLs. These findings indicate that carefully heterostructured NPLs will play a critical role in building high-performance colloidal optoelectronic devices, which may even possibly challenge their traditional epitaxially grown thin-film based counterparts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinhei

High-Efficiency Optical Gain in Type-II Semiconductor Nanocrystals of Alloyed Colloidal Quantum Wells

Colloidal nanocrystals having controlled size, tailored shape, and tuned composition have been explored for optical gain and lasing. Among these, nanocrystals having Type-II electronic structure have been introduced toward low-threshold gain. However, to date, their performance has remained severely limited due to diminishing oscillator strength and modest absorption cross-section. Overcoming these problems, here we realize highly efficient optical gain in Type-II nanocrystals by using alloyed colloidal quantum wells. With composition-tuned core/alloyed-crown CdSe/CdSexTe1-x quantum wells, we achieved amplified spontaneous emission thresholds as low as 26 μJ/cm2, long optical gain lifetimes (τgain ≈ 400 ps), and high modal gain coefficients (gmodal ≈ 930 cm-1). We uncover that the optical gain in these Type-II quantum wells arises from the excitations localized to the alloyed-crown region that are electronically coupled to the charge-transfer state. These alloyed heteronanostructures exhibiting remarkable optical gain performance are expected to be highly appealing for future display and lighting technologies. © 2017 American Chemical Society

Experimental Determination of the Absorption Cross-Section and Molar Extinction Coefficient of Colloidal CdSe Nanoplatelets

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. © 2015 American Chemical Society

Colloidal Nanoplatelet/Conducting Polymer Hybrids: Excitonic and Material Properties

Here we present the first account of conductive polymer/colloidal nanoplatelet hybrids. For this, we developed DEH-PPV-based polymers with two different anchor groups (sulfide and amine) acting as surfactants for CdSe nanoplatelets, which are atomically flat semiconductor nanocrystals. Hybridization of the polymers with the nanoplatelets in the solution phase was observed to cause strong photoluminescence quenching in both materials. Through steady-state photoluminescence and excitation spectrum measurements, photoluminescence quenching was shown to result from dominant exciton dissociation through charge transfer at the polymer/nanoplatelet interfaces that possess a staggered (i.e., type II) band alignment. Importantly, we found out that sulfide-based anchors enable a stronger emission quenching than amine-based ones, suggesting that the sulfide anchors exhibit more efficient binding to the nanoplatelet surfaces. Also, shorter surfactants were found to be more effective for exciton dissociation as compared to the longer ones. In addition, we show that nanoplatelets are homogeneously distributed in the hybrid films owing to the functional polymers. These nanocomposites can be used as building blocks for hybrid optoelectronic devices, such as solar cells. © 2016 American Chemical Society

Near-Unity Emitting Copper-Doped Colloidal Semiconductor Quantum Wells for Luminescent Solar Concentrators

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. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinhei