Tuning the Shades of Red Emission in InP/ZnSe/ZnS Nanocrystals with Narrow Full Width for Fabrication of Light-Emitting Diodes.

While Cd-based luminescent nanocrystals (NCs) are the most mature NCs for fabricating efficient red light-emitting diodes (LEDs), their toxicity related limitation is inevitable, making it necessary to find a promising alternative. From this point of view, multishell-coated, red-emissive InP-based NCs are excellent luminescent nanomaterials for use as an emissive layer in electroluminescent (EL) devices. However, due to the presence of oxidation states, they suffer from a wide emission spectrum, which limits their performance. This study uses tris(dimethylamino)phosphine (3DMA-P) as a low-cost aminophosphine precursor and a double HF treatment to suggest an upscaled, cost-effective, and one-pot hot-injection synthesis of purely red-emissive InP-based NCs. The InP core structures were coated with thick layers of ZnSe and ZnS shells to prevent charge delocalization and to create a narrow size distribution. The purified NCs showed an intense emission signal as narrow as 43 nm across the entire red wavelength range (626-670 nm) with an emission quantum efficiency of 74% at 632 nm. The purified samples also showed an emission quantum efficiency of 60% for far-red wavelengths of 670 nm with a narrow full width of 50 nm. The samples showed a relatively long average emission lifetime of 50-70 ns with a biexponential decay profile. To demonstrate the practical ability of the prepared NCs in optoelectronics, we fabricated a red-emissive InP-based LEDs. The best-performing device showed an external quantum efficiency (EQE) of 1.16%, a luminance of 1039 cd m-2, and a current efficiency of 0.88 cd A-1.

Osmotic-Pressure-Induced Nematic Ordering in Suspensions of Laponite and Carboxy Methyl Cellulose.

Laponite is a synthetic clay that is known to form gels in aqueous suspensions at low concentrations (0.01 g/cm3). Although it is expected to form lyotropic liquid crystals, such phases usually do not form, as a consequence of laponite's tendency to form gels at concentrations below the threshold for liquid crystal formation. Here we show that macroscopic, birefringent phases of laponite can be prepared through osmotic compression of a laponite solution by an aqueous solution of carboxy methyl cellulose (CMC). We present polarization imaging studies showing how the initially dilute, isotropic laponite phase shrinks while developing typical birefringence colors between crossed polarizers. Using the Michel-Lévy interference charts, we were able to extract the refractive index and orientation of the laponite nanodisks in the compressed region. Our observations allow us to propose a tentative state diagram, indicating the concentration regions for which we obtain optically anisotropic gels.

Transparent Films Made of Highly Scattering Particles.

Today, colloids are widely employed in various products from creams and coatings to electronics. The ability to control their chemical, optical, or electronic features by controlling their size and shape explains why these materials are so widely preferred. Nevertheless, altering some of these properties may also lead to some undesired side effects, one of which is an increase in optical scattering upon concentration. Here, we address this strong scattering issue in films made of binary colloidal suspensions. In particular, we focus on raspberry-type polymeric particles made of a spherical polystyrene core decorated by small hemispherical domains of acrylate with an overall positive charge, which display an unusual stability against aggregation in aqueous solutions. Their solid films display a brilliant red color due to Bragg scattering but appear completely white on account of strong scattering otherwise. To suppress the scattering and induce transparency, we prepared films by hybridizing them with oppositely charged PS particles with a size similar to that of the bumps on the raspberries. We report that the smaller PS particles prevent raspberry particle aggregation in solid films and suppress scattering by decreasing the spatial variation of the refractive index inside the film. We believe that the results presented here provide a simple strategy to suppress strong scattering of larger particles to be used in optical coatings.

Writing chemical patterns using electrospun fibers as nanoscale inkpots for directed assembly of colloidal nanocrystals.

Applications that range from electronics to biotechnology will greatly benefit from low-cost, scalable and multiplex fabrication of spatially defined arrays of colloidal inorganic nanocrystals. In this work, we present a novel additive patterning approach based on the use of electrospun nanofibers (NFs) as inkpots for end-functional polymers. The localized grafting of end-functional polymers from spatially defined nanofibers results in covalently bound chemical patterns. The main factors that determine the width of the nanopatterns are the diameter of the NF and the extent of spreading during the thermal annealing process. Lowering the surface energy of the substrates via silanization and a proper choice of the grafting conditions enable the fabrication of nanoscale patterns over centimeter length scales. The fabricated patterns of end-grafted polymers serve as the templates for spatially defined assembly of colloidal metal and metal oxide nanocrystals of varying sizes (15 to 100 nm), shapes (spherical, cube, rod), and compositions (Au, Ag, Pt, TiO2), as well as semiconductor quantum dots, including the assembly of semiconductor nanoplatelets.

Record High External Quantum Efficiency of 19.2% Achieved in Light-Emitting Diodes of Colloidal Quantum Wells Enabled by Hot-Injection Shell Growth.

Colloidal quantum wells (CQWs) are regarded as a highly promising class of optoelectronic materials, thanks to their unique excitonic characteristics of high extinction coefficients and ultranarrow emission bandwidths. Although the exploration of CQWs in light-emitting diodes (LEDs) is impressive, the performance of CQW-LEDs lags far behind other types of soft-material LEDs (e.g., organic LEDs, colloidal-quantum-dot LEDs, and perovskite LEDs). Herein, high-efficiency CQW-LEDs reaching close to the theoretical limit are reported. A key factor for this high performance is the exploitation of hot-injection shell (HIS) growth of CQWs, which enables a near-unity photoluminescence quantum yield (PLQY), reduces nonradiative channels, ensures smooth films, and enhances the stability. Remarkably, the PLQY remains 95% in solution and 87% in film despite rigorous cleaning. Through systematically understanding their shape-, composition-, and device-engineering, the CQW-LEDs using CdSe/Cd0.25 Zn0.75 S core/HIS CQWs exhibit a maximum external quantum efficiency of 19.2%. Additionally, a high luminance of 23 490 cd m-2 , extremely saturated red color with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.715, 0.283), and stable emission are obtained. The findings indicate that HIS-grown CQWs enable high-performance solution-processed LEDs, which may pave the path for future CQW-based display and lighting technologies.

Giant Alloyed Hot Injection Shells Enable Ultralow Optical Gain Threshold in Colloidal Quantum Wells.

As an attractive materials system for high-performance optoelectronics, colloidal nanoplatelets (NPLs) benefit from atomic-level precision in thickness, minimizing emission inhomogeneous broadening. Much progress has been made to enhance their photoluminescence quantum yield (PLQY) and photostability. However, to date, layer-by-layer growth of shells at room temperature has resulted in defects that limit PLQY and thus curtail the performance of NPLs as an optical gain medium. Here, we introduce a hot-injection method growing giant alloyed shells using an approach that reduces core/shell lattice mismatch and suppresses Auger recombination. Near-unity PLQY is achieved with a narrow full-width-at-half-maximum (20 nm), accompanied by emission tunability (from 610 to 650 nm). The biexciton lifetime exceeds 1 ns, an order of magnitude longer than in conventional colloidal quantum dots (CQDs). Reduced Auger recombination enables record-low amplified spontaneous emission threshold of 2.4 µJ cm-2 under one-photon pumping. This is lower by a factor of 2.5 than the best previously reported value in nanocrystals (6 µJ cm-2 for CdSe/CdS NPLs). Here, we also report single-mode lasing operation with a 0.55 mJ cm-2 threshold under two-photoexcitation, which is also the best among nanocrystals (compared to 0.76 mJ cm-2 from CdSe/CdS CQDs in the Fabry-Pérot cavity). These findings indicate that hot-injection growth of thick alloyed shells makes ultrahigh performance NPLs.

Highly Stable, Near-Unity Efficiency Atomically Flat Semiconductor Nanocrystals of CdSe/ZnS Hetero-Nanoplatelets Enabled by ZnS-Shell Hot-Injection Growth.

Colloidal semiconductor nanoplatelets (NPLs) offer important benefits in nanocrystal optoelectronics with their unique excitonic properties. For NPLs, colloidal atomic layer deposition (c-ALD) provides the ability to produce their core/shell heterostructures. However, as c-ALD takes place at room temperature, this technique allows for only limited stability and low quantum yield. Here, highly stable, near-unity efficiency CdSe/ZnS NPLs are shown using hot-injection (HI) shell growth performed at 573 K, enabling routinely reproducible quantum yields up to 98%. These CdSe/ZnS HI-shell hetero-NPLs fully recover their initial photoluminescence (PL) intensity in solution after a heating cycle from 300 to 525 K under inert gas atmosphere, and their solid films exhibit 100% recovery of their initial PL intensity after a heating cycle up to 400 K under ambient atmosphere, by far outperforming the control group of c-ALD shell-coated CdSe/ZnS NPLs, which can sustain only 20% of their PL. In optical gain measurements, these core/HI-shell NPLs exhibit ultralow gain thresholds reaching ≈7 µJ cm-2 . Despite being annealed at 500 K, these ZnS-HI-shell NPLs possess low gain thresholds as small as 25 µJ cm-2 . These findings indicate that the proposed 573 K HI-shell-grown CdSe/ZnS NPLs hold great promise for extraordinarily high performance in nanocrystal optoelectronics.

CdSe/ZnS quantum dot films for high performance flexible lighting and display applications.

Colloidal quantum dots have attracted significant interest in recent years for lighting and display applications and have recently appeared in high-end market products. The integration of quantum dots with light emitting diodes has made them promising candidates for superior lighting applications with tunable optical characteristics. In this work we propose and demonstrate high quality colloidal quantum dots in their novel free-standing film forms to allow high quality white light generation to address flexible lighting and display applications. High quality quantum dots have been characterized using transmission electron microscopy, x-ray diffraction, x-ray photoelectron spectroscopy, steady state and time resolved photoluminescence and dynamic light scattering methods. The engineering of colloidal quantum dot composition and its optical properties in stand-alone film form has led to the experimentally high NTSC color gamut of 122.5 (CIE-1931) for display applications, color rendering index of 88.6, luminous efficacy of optical radiation value of 290 lm/Wopt and color temperature of 2763 K for lighting applications.

Observation of polarized gain from aligned colloidal nanorods.

In recent years, colloidal semiconductor nanorods have attracted great interest for polarized spontaneous emission. However, their polarized gain has not been possible to achieve so far. In this work we show the highly polarized stimulated emission from the densely packed ensembles of core-seeded nanorods in a cylindrical cavity. Here CdSe/CdS dot-in-rods were coated and aligned on the inner wall of a capillary tube, providing optical feedback for the nanorod gain medium. Results show that the polarized gain originates intrinsically from the aligned nanorods and not from the cavity and that the optical anisotropy of the nanorod ensemble was amplified with the capillary tube, resulting in highly polarized whispering gallery mode lasing. The highly polarized emission and lasing, together with easy fabrication and flexible incorporation, make this microlaser a promising candidate for important color conversion and enrichment applications including liquid crystal display backlighting and laser lighting.

Highly flexible, electrically driven, top-emitting, quantum dot light-emitting stickers.

Flexible information displays are key elements in future optoelectronic devices. Quantum dot light-emitting diodes (QLEDs) with advantages in color quality, stability, and cost-effectiveness are emerging as a candidate for single-material, full color light sources. Despite the recent advances in QLED technology, making high-performance flexible QLEDs still remains a big challenge due to limited choices of proper materials and device architectures as well as poor mechanical stability. Here, we show highly efficient, large-area QLED tapes emitting in red, green, and blue (RGB) colors with top-emitting design and polyimide tapes as flexible substrates. The brightness and quantum efficiency are 20,000 cd/m(2) and 4.03%, respectively, the highest values reported for flexible QLEDs. Besides the excellent electroluminescence performance, these QLED films are highly flexible and mechanically robust to use as electrically driven light-emitting stickers by placing on or removing from any curved surface, facilitating versatile LED applications. Our QLED tapes present a step toward practical quantum dot based platforms for high-performance flexible displays and solid-state lighting.

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.

Stimulated emission and lasing from CdSe/CdS/ZnS core-multi-shell quantum dots by simultaneous three-photon absorption.

Three-photon pumped stimulated emission and coherent random lasing from colloidal CdSe/CdS/ZnS core-multishell quantum dots are achieved for the first time. These results can offer new possibilities in biology and photonics, as well as at their intersection of biophotonics.

Stable, efficient, and all-solution-processed quantum dot light-emitting diodes with double-sided metal oxide nanoparticle charge transport layers.

An efficient and stable quantum dot light-emitting diode (QLED) with double-sided metal oxide (MO) nanoparticle (NP) charge transport layers is fabricated by utilizing the solution-processed tungsten oxide (WO3) and zinc oxide (ZnO) NPs as the hole and electron transport layers, respectively. Except for the electrodes, all other layers are deposited by a simple spin-coating method. The resulting MO NP-based QLEDs show excellent device performance, with a peak luminance of 21300 cd/m(2) at the emission wavelength of 516 nm, a maximal current efficiency of 4.4 cd/A, and a low turn-on voltage of 3 V. More importantly, with the efficient design of the device architecture, these devices exhibit a significant improvement in device stability and the operational lifetime of 95 h measured at room temperature can be almost 20-fold longer than that of the standard device.

Colloidal Quantum Dot Light-Emitting Diodes Employing Phosphorescent Small Organic Molecules as Efficient Exciton Harvesters.

Nonradiative energy transfer (NRET) is an alternative excitation mechanism in colloidal quantum dot (QD) based electroluminescent devices (QLEDs). Here, we develop hybrid highly spectrally pure QLEDs that facilitate energy transfer pumping via NRET from a phosphorescent small organic molecule-codoped charge transport layer to the adjacent QDs. A partially codoped exciton funnelling electron transport layer is proposed and optimized for enhanced QLED performance while exhibiting very high color purity of 99%. These energy transfer pumped hybrid QLEDs demonstrate a 6-fold enhancement factor in the external quantum efficiency over the conventional QLED structure, in which energy transfer pumping is intrinsically weak.

Solution processed tungsten oxide interfacial layer for efficient hole-injection in quantum dot light-emitting diodes.

A highly efficient and stable QLED using an inorganic WO3 nanoparticle film as a hole injection layer is demonstrated.The resulting WO3 nanoparticle-based QLEDs also exhibit superior performance compared to that of the present PEDOT:PSS-based QLEDs. The results indicate that WO3 nanoparticles are promising solution-processed buffer layer materials and serve as a strong candidate for QLED technology towards the practical applications in the next-generation lighting and displays.

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.

Quantum dot light-emitting diode with quantum dots inside the hole transporting layers.

We report a hybrid, quantum dot (QD)-based, organic light-emitting diode architecture using a noninverted structure with the QDs sandwiched between hole transporting layers (HTLs) outperforming the reference device structure implemented in conventional noninverted architecture by over five folds and suppressing the blue emission that is otherwise observed in the conventional structure because of the excess electrons leaking towards the HTL. It is predicted in the new device structure that 97.44% of the exciton formation takes place in the QD layer, while 2.56% of the excitons form in the HTL. It is found that the enhancement in the external quantum efficiency is mainly due to the stronger confinement of exciton formation to the QDs.

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 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.

Plasmonic light-sensitive skins of nanocrystal monolayers.

We report plasmonically coupled light-sensitive skins of nanocrystal monolayers that exhibit sensitivity enhancement and spectral range extension with plasmonic nanostructures embedded in their photosensitive nanocrystal platforms. The deposited plasmonic silver nanoparticles of the device increase the optical absorption of a CdTe nanocrystal monolayer incorporated in the device. Controlled separation of these metallic nanoparticles in the vicinity of semiconductor nanocrystals enables optimization of the photovoltage buildup in the proposed nanostructure platform. The enhancement factor was found to depend on the excitation wavelength. We observed broadband sensitivity improvement (across 400-650 nm), with a 2.6-fold enhancement factor around the localized plasmon resonance peak. The simulation results were found to agree well with the experimental data. Such plasmonically enhanced nanocrystal skins hold great promise for large-area UV/visible sensing applications.