Deep-Red-Emitting Colloidal Quantum Well Light-Emitting Diodes Enabled through a Complex Design of Core/Crown/Double Shell Heterostructure.

Extending the emission peak wavelength of quasi-2D colloidal quantum wells has been an important quest to fully exploit the potential of these materials, which has not been possible due to the complications arising from the partial dissolution and recrystallization during growth to date. Here, the synthetic pathway of (CdSe/CdS)@(1-4 CdS/CdZnS) (core/crown)@(colloidal atomic layer deposition shell/hot injection shell) hetero-nanoplatelets (NPLs) using multiple techniques, which together enable highly efficient emission beyond 700 nm in the deep-red region, is proposed and demonstrated. Given the challenges of using conventional hot injection procedure, a method that allows to obtain sufficiently thick and passivated NPLs as the seeds is developed. Consequently, through the final hot injection shell coating, thick NPLs with superior optical properties including a high photoluminescence quantum yield of 88% are achieved. These NPLs emitting at 701 nm exhibit a full-width-at-half-maximum of 26 nm, enabled by the successfully maintained quasi-2D shape and minimum defects of the resulting heterostructure. The deep-red light-emitting diode (LED) device fabricated with these NPLs has shown to yield a high external quantum efficiency of 6.8% at 701 nm, which is on par with other types of LEDs in this spectral range.

Self-Resonant Microlasers of Colloidal Quantum Wells Constructed by Direct Deep Patterning.

Here, the first account of self-resonant fully colloidal µ-lasers made from colloidal quantum well (CQW) solution is reported. A deep patterning technique is developed to fabricate well-defined high aspect-ratio on-chip CQW resonators made of grating waveguides and in-plane reflectors. The fabricated waveguide-coupled laser, enabling tight optical confinement, assures in-plane lasing. CQWs of the patterned layers are closed-packed with sharp edges and residual-free lifted-off surfaces. Additionally, the method is successfully applied to various nanoparticles including colloidal quantum dots and metal nanoparticles. It is observed that the patterning process does not affect the nanocrystals (NCs) immobilized in the attained patterns and the different physical and chemical properties of the NCs remain pristine. Thanks to the deep patterning capability of the proposed method, patterns of NCs with subwavelength lateral feature sizes and micron-scale heights can possibly be fabricated in high aspect ratios.

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.

Thickness-Tunable Self-Assembled Colloidal Nanoplatelet Films Enable Ultrathin Optical Gain Media.

We propose and demonstrate construction of highly uniform, multilayered superstructures of CdSe/CdZnS core/shell colloidal nanoplatelets (NPLs) using liquid interface self-assembly. These NPLs are sequentially deposited onto a solid substrate into slabs having monolayer-precise thickness across tens of cm2 areas. Because of near-unity surface coverage and excellent uniformity, amplified spontaneous emission (ASE) is observed from an uncharacteristically thin film having 6 NPL layers, corresponding to a mere 42 nm thickness. Furthermore, systematic studies on optical gain of these NPL superstructures having thicknesses ranging from 6 to 15 layers revealed the gradual reduction in gain threshold with increasing number of layers, along with a continuous spectral shift of the ASE peak (∼18 nm). These observations can be explained by the change in the optical mode confinement factor with the NPL waveguide thickness and propagation wavelength. This bottom-up construction technique for thickness-tunable, three-dimensional NPL superstructures can be used for large-area device fabrication.

Optical Gain in Ultrathin Self-Assembled Bi-Layers of Colloidal Quantum Wells Enabled by the Mode Confinement in their High-Index Dielectric Waveguides.

This study demonstrates an ultra-thin colloidal gain medium consisting of bi-layers of colloidal quantum wells (CQWs) with a total film thickness of 14 nm integrated with high-index dielectrics. To achieve optical gain from such an ultra-thin nanocrystal film, hybrid waveguide structures partly composed of self-assembled layers of CQWs and partly high-index dielectric material are developed and shown: in asymmetric waveguide architecture employing one thin film of dielectric underneath CQWs and in the case of quasi-symmetric waveguide with a pair of dielectric films sandwiching CQWs. Numerical modeling indicates that the modal confinement factor of ultra-thin CQW films is enhanced in the presence of the adjacent dielectric layers significantly. The active slabs of these CQW monolayers in the proposed waveguide structure are constructed with great care to obtain near-unity surface coverage, which increases the density of active particles, and to reduce the surface roughness to sub-nm scale, which decreases the scattering losses. The excitation and propagation of amplified spontaneous emission (ASE) along these active waveguides are experimentally demonstrated and numerically analyzed. The findings of this work offer possibilities for the realization of ultra-thin electrically driven colloidal laser devices, providing critical advantages including single-mode lasing and high electrical conduction.

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.

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.

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.

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.

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.