Near-Unity Emitting, Widely Tailorable, and Stable Exciton Concentrators Built from Doubly Gradient 2D Semiconductor Nanoplatelets.

The strength of electrostatic interactions (EIs) between electrons and holes within semiconductor nanocrystals profoundly affects the performance of their optoelectronic systems, and different optoelectronic devices demand distinct EI strength of the active medium. However, achieving a broad range and fine-tuning of the EI strength for specific optoelectronic applications is a daunting challenge, especially in quasi two-dimensional core-shell semiconductor nanoplatelets (NPLs), as the epitaxial growth of the inorganic shell along the direction of the thickness that solely contributes to the quantum confined effect significantly undermines the strength of the EI. Herein we propose and demonstrate a doubly gradient (DG) core-shell architecture of semiconductor NPLs for on-demand tailoring of the EI strength by controlling the localized exciton concentration via in-plane architectural modulation, demonstrated by a wide tuning of radiative recombination rate and exciton binding energy. Moreover, these exciton-concentration-engineered DG NPLs also exhibit a near-unity quantum yield, high photo- and thermal stability, and considerably suppressed self-absorption. As proof-of-concept demonstrations, highly efficient color converters and high-performance light-emitting diodes (external quantum efficiency: 16.9%, maximum luminance: 43,000 cd/m2) have been achieved based on the DG NPLs. This work thus provides insights into the development of high-performance colloidal optoelectronic device applications.

On the Rational Design of Core/(Multi)-Crown Type-II Heteronanoplatelets.

Solution-processed two-dimensional nanoplatelets (NPLs) allowing lateral growth of a shell (crown) by not affecting the pure confinement in the vertical direction provide unprecedented opportunities for designing heterostructures for light-emitting and -harvesting applications. Here, we present a pathway for designing and synthesizing colloidal type-II core/(multi-)crown hetero-NPLs and investigate their optical properties. Stoke's shifted broad photoluminescence (PL) emission and long PL lifetime (∼few 100 ns) together with our wavefunction calculations confirm the type-II electronic structure in the synthesized CdS/CdSe1-xTex core/crown hetero-NPLs. In addition, we experimentally obtained the band-offsets between CdS, CdTe, and CdSe in these NPLs. These results helped us designing hetero-NPLs with near-unity PL quantum yield in the CdSe/CdSe1-xTex/CdSe/CdS core/multicrown architecture. These core/multicrown hetero-NPLs have two type-II interfaces unlike traditional type-II NPLs having only one and possess a CdS ending layer for passivation and efficient suppression of stacking required for optoelectronic applications. The light-emitting diode (LED) obtained using multicrown hetero-NPLs exhibits a maximum luminance of 36,612 cd/m2 and external quantum efficiency of 9.3%, which outcompetes the previous best results from type-II NPL-based LEDs. These findings may enable designs of future advanced heterostructures of NPLs which are anticipated to show desirable results, especially for LED and lasing platforms.

High External Quantum Efficiency Light-Emitting Diodes Enabled by Advanced Heterostructures of Type-II Nanoplatelets.

Colloidal quantum wells (CQWs), also known as nanoplatelets (NPLs), are exciting material systems for numerous photonic applications, including lasers and light-emitting diodes (LEDs). Although many successful type-I NPL-LEDs with high device performance have been demonstrated, type-II NPLs are not fully exploited for LED applications, even with alloyed type-II NPLs with enhanced optical properties. Here, we present the development of CdSe/CdTe/CdSe core/crown/crown (multi-crowned) type-II NPLs and systematic investigation of their optical properties, including their comparison with the traditional core/crown counterparts. Unlike traditional type-II NPLs such as CdSe/CdTe, CdTe/CdSe, and CdSe/CdSexTe1-x core/crown heterostructures, here the proposed advanced heterostructure reaps the benefits of having two type-II transition channels, resulting in a high quantum yield (QY) of 83% and a long fluorescence lifetime of 73.3 ns. These type-II transitions were confirmed experimentally by optical measurements and theoretically using electron and hole wave function modeling. Computational study shows that the multi-crowned NPLs provide a better-distributed hole wave function along the CdTe crown, while the electron wave function is delocalized in the CdSe core and CdSe crown layers. As a proof-of-concept demonstration, NPL-LEDs based on these multi-crowned NPLs were designed and fabricated with a record high external quantum efficiency (EQE) of 7.83% among type-II NPL-LEDs. These findings are expected to induce advanced designs of NPL heterostructures to reach a fascinating level of performance, especially in LEDs and lasers.

Near-Field Energy Transfer into Silicon Inversely Proportional to Distance Using Quasi-2D Colloidal Quantum Well Donors.

Silicon is the most prevalent material system for light-harvesting applications; however, its inherent indirect bandgap and consequent weak absorption limits its potential in optoelectronics. This paper proposes to address this limitation by combining the sensitization of silicon with extraordinarily large absorption cross sections of quasi-2D colloidal quantum well nanoplatelets (NPLs) and to demonstrate excitation transfer from these NPLs to bulk silicon. Here, the distance dependency, d, of the resulting Förster resonant energy transfer from the NPL monolayer into a silicon substrate is systematically studied by tuning the thickness of a spacer layer (of Al2 O3 ) in between them (varied from 1 to 50 nm in thickness). A slowly varying distance dependence of d-1 with 25% efficiency at a donor-acceptor distance of 20 nm is observed. These results are corroborated with full electromagnetic solutions, which show that the inverse distance relationship emanates from the delocalized electric field intensity across both the NPL layer and the silicon because of the excitation of strong in-plane dipoles in the NPL monolayer. These findings pave the way for using colloidal NPLs as strong light-harvesting donors in combination with crystalline silicon as an acceptor medium for application in photovoltaic devices and other optoelectronic platforms.

Tailored Synthesis of Iron Oxide Nanocrystals for Formation of Cuboid Mesocrystals.

In this work, we systematically studied the shape- and size-controlled monodisperse synthesis of iron oxide nanocrystals (IONCs) for their use as building blocks in the formation of mesocrystals. For this aim, on understanding the influence of the oleic acid concentration, iron-oleate concentration, and heating rate on the synthesis of robust and reproducible IONCs with desired sizes and shapes, we synthesized highly monodisperse ∼11 nm sized nanocubes and nanospheres. Magnetic measurements of both cubic and spherical IONCs revealed the presence of mixed paramagnetic and superparamagnetic phases in these nanocrystals. Moreover, we observed that the magnetic moments of the nanocubes are more substantial compared to their spherical counterparts. We then demonstrated a simple magnetic-field-assisted assembly of nanocubes into three-dimensional (3D) cuboid mesocrystals while nanospheres did not form any mesocrystals. These findings indicate that small cubic nanocrystals hold great promise as potential building blocks of 3D magnetic hierarchical structures with their superior magnetic properties and mesocrystal assembly capability, which may have high relevance in various fields ranging from high-density data storage to biomedical applications.

Trion-Mediated Förster Resonance Energy Transfer and Optical Gating Effect in WS2/hBN/MoSe2 Heterojunction.

van der Waals two-dimensional layered heterostructures have recently emerged as a platform, where the interlayer couplings give rise to interesting physics and multifunctionalities in optoelectronics. Such couplings can be rationally controlled by dielectric, separation, and stacking angles, which affect the overall charge or energy-transfer processes, and emergent potential landscape for twistronics. Herein, we report the efficient Förster resonance energy transfer (FRET) in WS2/hBN/MoSe2 heterostructure, probed by both steady-state and time-resolved optical spectroscopy. We clarified the evolution behavior of the electron-hole pairs and free electrons from the trions, that is, ∼59.9% of the electron-hole pairs could transfer into MoSe2 by FRET channels (∼38 ps) while the free electrons accumulate at the WS2/hBN interface to photogate MoSe2. This study presents a clear picture of the FRET process in two-dimensional transition-metal dichalcogenides' heterojunctions, which establishes the scientific foundation for developing the related heterojunction optoelectronic devices.

Persuasive Evidence for Electron-Nuclear Coupling in Diluted Magnetic Colloidal Nanoplatelets Using Optically Detected Magnetic Resonance Spectroscopy.

The incorporation of magnetic impurities into semiconductor nanocrystals with size confinement promotes enhanced spin exchange interaction between photogenerated carriers and the guest spins. This interaction stimulates new magneto-optical properties with significant advantages for emerging spin-based technologies. Here we observe and elaborate on carrier-guest interactions in magnetically doped colloidal nanoplatelets with the chemical formula CdSe/Cd1-xMnxS, explored by optically detected magnetic resonance and magneto-photoluminescence spectroscopy. The host matrix, with a quasi-type II electronic configuration, introduces a dominant interaction between a photogenerated electron and a magnetic dopant. Furthermore, the data convincingly presents the interaction between an electron and nuclear spins of the doped ions located at neighboring surroundings, with consequent influence on the carrier's spin relaxation time. The nuclear spin contribution by the magnetic dopants in colloidal nanoplatelets is considered here for the first time.

Near-Unity Efficiency Energy Transfer from Colloidal Semiconductor Quantum Wells of CdSe/CdS Nanoplatelets to a Monolayer of MoS2.

A hybrid structure of the quasi-2D colloidal semiconductor quantum wells assembled with a single layer of 2D transition metal dichalcogenides offers the possibility of highly strong dipole-to-dipole coupling, which may enable extraordinary levels of efficiency in Förster resonance energy transfer (FRET). Here, we show ultrahigh-efficiency FRET from the ensemble thin films of CdSe/CdS nanoplatelets (NPLs) to a MoS2 monolayer. From time-resolved fluorescence spectroscopy, we observed the suppression of the photoluminescence of the NPLs corresponding to the total rate of energy transfer from ∼0.4 to 268 ns-1. Using an Al2O3 separating layer between CdSe/CdS and MoS2 with thickness tuned from 5 to 1 nm, we found that FRET takes place 7- to 88-fold faster than the Auger recombination in CdSe-based NPLs. Our measurements reveal that the FRET rate scales down with d-2 for the donor of CdSe/CdS NPLs and the acceptor of the MoS2 monolayer, d being the center-to-center distance between this FRET pair. A full electromagnetic model explains the behavior of this d-2 system. This scaling arises from the delocalization of the dipole fields in the ensemble thin film of the NPLs and full distribution of the electric field across the layer of MoS2. This d-2 dependency results in an extraordinarily long Förster radius of ∼33 nm.

sp-d Exchange Interactions in Wave Function Engineered Colloidal CdSe/Mn:CdS Hetero-Nanoplatelets.

In two-dimensional (2D) colloidal semiconductor nanoplatelets, which are atomically flat nanocrystals, the precise control of thickness and composition on the atomic scale allows for the synthesis of heterostructures with well-defined electron and hole wave function distributions. Introducing transition metal dopants with a monolayer precision enables tailored magnetic exchange interactions between dopants and band states. Here, we use the absorption based technique of magnetic circular dichroism (MCD) to directly prove the exchange coupling of magnetic dopants with the band charge carriers in hetero-nanoplatelets with CdSe core and manganese-doped CdS shell (CdSe/Mn:CdS). We show that the strength of both the electron as well as the hole exchange interactions with the dopants can be tuned by varying the nanoplatelets architecture with monolayer accuracy. As MCD is highly sensitive for excitonic resonances, excited level spectroscopy allows us to resolve and identify, in combination with wave function calculations, several excited state transitions including spin-orbit split-off excitonic contributions. Thus, our study not only demonstrates the possibility to expand the extraordinary physical properties of colloidal nanoplatelets toward magneto-optical functionality by transition metal doping but also provides an insight into the excited state electronic structure in this novel two-dimensional material.

Plasmon-Enhanced Energy Transfer in Photosensitive Nanocrystal Device.

Förster resonance energy transfer (FRET) interacted with localized surface plasmon (LSP) gives us the ability to overcome inadequate transfer of energy between donor and acceptor nanocrystals (NCs). In this paper, we show LSP-enhanced FRET in colloidal photosensors of NCs in operation, resulting in substantially enhanced photosensitivity. The proposed photosensitive device is a layered self-assembled colloidal platform consisting of separated monolayers of the donor and the acceptor colloidal NCs with an intermediate metal nanoparticle (MNP) layer made of gold interspaced by polyelectrolyte layers. Using LBL assembly, we fabricated and comparatively studied seven types of such NC-monolayer devices (containing only donor, only acceptor, Au MNP-donor, Au MNP-acceptor, donor-acceptor bilayer, donor-Au MNP-acceptor trilayer, and acceptor-Au MNP-donor reverse trilayer). In these structures, we revealed the effect of LSP-enhanced FRET and exciton interactions from the donor NCs layer to the acceptor NCs layer. Compared to a single acceptor NC device, we observed a significant extension in operating wavelength range and a substantial photosensitivity enhancement (2.91-fold) around the LSP resonance peak of Au MNPs in the LSP-enhanced FRET trilayer structure. Moreover, we present a theoretical model for the intercoupled donor-Au MNP-acceptor structure subject to the plasmon-mediated nonradiative energy transfer. The obtained numerical results are in excellent agreement with the systematic experimental studies done in our work. The potential to modify the energy transfer through mastering the exciton-plasmon interactions and its implication in devices make them attractive for applications in nanophotonic devices and sensors.

Cascaded plasmon-plasmon coupling mediated energy transfer across stratified metal-dielectric nanostructures.

Surface plasmon (SP) coupling has been successfully applied to nonradiative energy transfer via exciton-plasmon-exciton coupling in conventionally sandwiched donor-metal film-acceptor configurations. However, these structures lack the desired efficiency and suffer poor photoemission due to the high energy loss. Here, we show that the cascaded exciton-plasmon-plasmon-exciton coupling in stratified architecture enables an efficient energy transfer mechanism. The overlaps of the surface plasmon modes at the metal-dielectric and dielectric-metal interfaces allow for strong cross-coupling in comparison with the single metal film configuration. The proposed architecture has been demonstrated through the analytical modeling and numerical simulation of an oscillating dipole near the stratified nanostructure of metal-dielectric-metal-acceptor. Consistent with theoretical and numerical results, experimental measurements confirm at least 50% plasmon resonance energy transfer enhancement in the donor-metal-dielectric-metal-acceptor compared to the donor-metal-acceptor structure. Cascaded plasmon-plasmon coupling enables record high efficiency for exciton transfer through metallic structures.

Critical role of CdSe nanoplatelets in color-converting CdSe/ZnS nanocrystals for InGaN/GaN light-emitting diodes.

Here we report CdSe nanoplatelets that are incorporated into color-converting CdSe/ZnS nanocrystals for InGaN/GaN light-emitting diodes. The critical role of CdSe nanoplatelets as an exciton donor for the color conversion was experimentally investigated. The power conversion efficiency of the hybrid light-emitting diode was found to increase by 23% with the incorporation of the CdSe nanoplatelets. The performance enhancement is ascribed to efficient exciton transfer from the donor CdSe nanoplatelet quantum wells to the acceptor CdSe/ZnS nanocrystal quantum dots through Förster-type nonradiative resonance energy transfer.

Mn(2+)-Doped CdSe/CdS Core/Multishell Colloidal Quantum Wells Enabling Tunable Carrier-Dopant Exchange Interactions.

In this work, we report the manifestations of carrier-dopant exchange interactions in colloidal Mn(2+)-doped CdSe/CdS core/multishell quantum wells. The carrier-magnetic ion exchange interaction effects are tunable through wave function engineering. In our quantum well heterostructures, manganese was incorporated by growing a Cd0.985Mn0.015S monolayer shell on undoped CdSe nanoplatelets using the colloidal atomic layer deposition technique. Unlike previously synthesized Mn(2+)-doped colloidal nanostructures, the location of the Mn ions was controlled with atomic layer precision in our heterostructures. This is realized by controlling the spatial overlap between the carrier wave functions with the manganese ions by adjusting the location, composition, and number of the CdSe, Cd1-xMnxS, and CdS layers. The photoluminescence quantum yield of our magnetic heterostructures was found to be as high as 20% at room temperature with a narrow photoluminescence bandwidth of ∼22 nm. Our colloidal quantum wells, which exhibit magneto-optical properties analogous to those of epitaxially grown quantum wells, offer new opportunities for solution-processed spin-based semiconductor devices.

Macrocrystals of Colloidal Quantum Dots in Anthracene: Exciton Transfer and Polarized Emission.

In this work, centimeter-scale macrocrystals of nonpolar colloidal quantum dots (QDs) incorporated into anthracene were grown for the first time. The exciton transfer from the anthracene host to acceptor QDs was systematically investigated, and anisotropic emission from the isotropic QDs in the anthracene macrocrystals was discovered. Results showed a decreasing photoluminescence lifetime of the donor anthracene, indicating a strengthening energy transfer with increasing QD concentration in the macrocrystals. With the anisotropy study, QDs inside the anthracene host acquired a polarization ratio of ~1.5 at 0° collection angle, and this increases to ~2.5 at the collection angle of 60°. A proof-of-concept application of these excitonic macrocrystals as tunable color converters on light-emitting diodes was also demonstrated.

Study of exciton transfer in dense quantum dot nanocomposites.

Nanocomposites of colloidal quantum dots (QDs) integrated into conjugated polymers (CPs) are key to hybrid optoelectronics, where engineering the excitonic interactions at the nanoscale is crucial. For such excitonic operation, it was believed that exciton diffusion is essential to realize nonradiative energy transfer from CPs to QDs. In this study, contrary to the previous literature, efficient exciton transfer is demonstrated in the nanocomposites of dense QDs, where exciton transfer can be as efficient as 80% without requiring the assistance of exciton diffusion. This is enabled by uniform dispersion of QDs at high density (up to ∼70 wt%) in the nanocomposite while avoiding phase segregation. Theoretical modeling supports the experimental observation of weakly temperature dependent nonradiative energy transfer dynamics. This new finding provides the ability to design hybrid light-emitting diodes that show an order of magnitude enhanced external quantum efficiencies.

Quantum dots on vertically aligned gold nanorod monolayer: plasmon enhanced fluorescence.

CTAB-coated Au nanorods were directly self-assembled into a vertically aligned monolayer with highly uniform hot spots through a simple but robust approach. By coupling with CdSe/ZnS quantum dots, a maximum enhancement of 10.4 is achieved due to: increased excitation transition rate, radiative rate, and coupling efficiency of emission to the far field.

Phonon-assisted exciton transfer into silicon using nanoemitters: the role of phonons and temperature effects in Förster resonance energy transfer.

We study phonon-assisted Förster resonance energy transfer (FRET) into an indirect band-gap semiconductor using nanoemitters. The unusual temperature dependence of this energy transfer, which is measured using the donor nanoemitters of quantum dot (QD) layers integrated on the acceptor monocrystalline bulk silicon as a model system, is predicted by a phonon-assisted exciton transfer model proposed here. The model includes the phonon-mediated optical properties of silicon, while considering the contribution from the multimonolayer-equivalent QD film to the nonradiative energy transfer, which is derived with a d(-3) distance dependence. The FRET efficiencies are experimentally observed to decrease at cryogenic temperatures, which are well explained by the model considering the phonon depopulation in the indirect band-gap acceptor together with the changes in the quantum yield of the donor. These understandings will be crucial for designing FRET-enabled sensitization of silicon based high-efficiency excitonic systems using nanoemitters.

Bio-nanohybrids of quantum dots and photoproteins facilitating strong nonradiative energy transfer.

Utilization of light is crucial for the life cycle of many organisms. Also, many organisms can create light by utilizing chemical energy emerged from biochemical reactions. Being the most important structural units of the organisms, proteins play a vital role in the formation of light in the form of bioluminescence. Such photoproteins have been isolated and identified for a long time; the exact mechanism of their bioluminescence is well established. Here we show a biomimetic approach to build a photoprotein based excitonic nanoassembly model system using colloidal quantum dots (QDs) for a new bioluminescent couple to be utilized in biotechnological and photonic applications. We concentrated on the formation mechanism of nanohybrids using a kinetic and thermodynamic approach. Finally we propose a biosensing scheme with an ON/OFF switch using the QD-GFP hybrid. The QD-GFP hybrid system promises strong exciton-exciton coupling between the protein and the quantum dot at a high efficiency level, possessing enhanced capabilities of light harvesting, which may bring new technological opportunities to mimic biophotonic events.

Observation of selective plasmon-exciton coupling in nonradiative energy transfer: donor-selective versus acceptor-selective plexcitons.

We report selectively plasmon-mediated nonradiative energy transfer between quantum dot (QD) emitters interacting with each other via Förster-type resonance energy transfer (FRET) under controlled plasmon coupling either to only the donor QDs (i.e., donor-selective) or to only the acceptor QDs (i.e., acceptor-selective). Using layer-by-layer assembled colloidal QD nanocrystal solids with metal nanoparticles integrated at carefully designed spacing, we demonstrate the ability to enable/disable the coupled plasmon-exciton (plexciton) formation distinctly at the donor (exciton departing) site or at the acceptor (exciton feeding) site of our choice, while not hindering the donor exciton-acceptor exciton interaction but refraining from simultaneous coupling to both sites of the donor and the acceptor in the FRET process. In the case of donor-selective plexciton, we observed a substantial shortening in the donor QD lifetime from 1.33 to 0.29 ns as a result of plasmon-coupling to the donors and the FRET-assisted exciton transfer from the donors to the acceptors, both of which shorten the donor lifetime. This consequently enhanced the acceptor emission by a factor of 1.93. On the other hand, in the complementary case of acceptor-selective plexciton we observed a 2.70-fold emission enhancement in the acceptor QDs, larger than the acceptor emission enhancement of the donor-selective plexciton, as a result of the combined effects of the acceptor plasmon coupling and the FRET-assisted exciton feeding. Here we present the comparative results of theoretical modeling of the donor- and acceptor-selective plexcitons of nonradiative energy transfer developed here for the first time, which are in excellent agreement with the systematic experimental characterization. Such an ability to modify and control energy transfer through mastering plexcitons is of fundamental importance, opening up new applications for quantum dot embedded plexciton devices along with the development of new techniques in FRET-based fluorescence microscopy.

Observation of biexcitons in nanocrystal solids in the presence of photocharging.

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.