Dual-Resonance Nanostructures for Color Downconversion of Colloidal Quantum Emitters.

We present a dual-resonance nanostructure made of a titanium dioxide (TiO2) subwavelength grating to enhance the color downconversion efficiency of CdxZn1-xSeyS1-y colloidal quantum dots (QDs) emitting at ∼530 nm when excited with a blue light at ∼460 nm. A large mode volume can be created within the QD layer by the hybridization of the grating resonances and waveguide modes, resulting in large absorption and emission enhancements. Particularly, we achieved polarized light emission with a maximum photoluminescence enhancement of ∼140 times at a specific angular direction and a total enhancement of ∼34 times within a 0.55 numerical aperture (NA) of the collecting objective. The enhancement encompasses absorption, Purcell and outcoupling enhancements. We achieved a total absorption of 35% for green QDs with a remarkably thin color conversion layer of ∼400 nm. This work provides a guideline for designing large-volume cavities for absorption/fluorescence enhancement in microLED display, detector, or photovoltaic applications.

Highly-Directional, Highly-Efficient Solution-Processed Light-Emitting Diodes of All-Face-Down Oriented Colloidal Quantum Well Self-Assembly.

Semiconductor colloidal quantum wells (CQWs) provide anisotropic emission behavior originating from their anisotropic optical transition dipole moments (TDMs). Here, solution-processed colloidal quantum well light-emitting diodes (CQW-LEDs) of a single all-face-down oriented self-assembled monolayer (SAM) film of CQWs that collectively enable a supreme level of IP TDMs at 92% in the ensemble emission are shown. This significantly enhances the outcoupling efficiency from 22% (of standard randomly-oriented emitters) to 34% (of face-down oriented emitters) in the LED. As a result, the external quantum efficiency reaches a record high level of 18.1% for the solution-processed type of CQW-LEDs, putting their efficiency performance on par with the hybrid organic-inorganic evaporation-based CQW-LEDs and all other best solution-processed LEDs. This SAM-CQW-LED architecture allows for a high maximum brightness of 19,800 cd m-2 with a long operational lifetime of 247 h at 100 cd m-2 as well as a stable saturated deep-red emission (651 nm) with a low turn-on voltage of 1.7 eV at a current density of 1 mA cm-2 and a high J90 of 99.58 mA cm-2 . These findings indicate the effectiveness of oriented self-assembly of CQWs as an electrically-driven emissive layer in improving outcoupling and external quantum efficiencies in the CQW-LEDs.

Room-Temperature Lasing in Colloidal Nanoplatelets via Mie-Resonant Bound States in the Continuum.

Solid-state room-temperature lasing with tunability in a wide range of wavelengths is desirable for many applications. To achieve this, besides an efficient gain material with a tunable emission wavelength, a high quality-factor optical cavity is essential. Here, we combine a film of colloidal CdSe/CdZnS core-shell nanoplatelets with square arrays of nanocylinders made of titanium dioxide to achieve optically pumped lasing at visible wavelengths and room temperature. The all-dielectric arrays support bound states in the continuum (BICs), which result from lattice-mediated Mie resonances and boast infinite quality factors in theory. In particular, we demonstrate lasing from a BIC that originates from out-of-plane magnetic dipoles oscillating in phase. By adjusting the diameter of the cylinders, we tune the lasing wavelength across the gain bandwidth of the nanoplatelets. The spectral tunability of both the cavity resonance and nanoplatelet gain, together with efficient light confinement in BICs, promises low-threshold lasing with wide selectivity in wavelengths.

Light-Emitting Diodes with Cu-Doped Colloidal Quantum Wells: From Ultrapure Green, Tunable Dual-Emission to White Light.

Copper-doped colloidal quantum wells (Cu-CQWs) are considered a new class of optoelectronic materials. To date, the electroluminescence (EL) property of Cu-CQWs has not been revealed. Additionally, it is desirable to achieve ultrapure green, tunable dual-emission and white light to satisfy the various requirement of display and lighting applications. Herein, light-emitting diodes (LEDs) based on colloidal Cu-CQWs are demonstrated. For the 0% Cu-doped concentration, the LED exhibits Commission Internationale de L'Eclairage 1931 coordinates of (0.103, 0.797) with a narrow EL full-wavelength at half-maximum of 12 nm. For the 0.5% Cu-doped concentration, a dual-emission LED is realized. Remarkably, the dual emission can be tuned by manipulating the device engineering. Furthermore, at a high doping concentration of 2.4%, a white LED based on CQWs is developed. With the management of doping concentrations, the color tuning (green, dual-emission to white) is shown. The findings not only show that LEDs with CQWs can exhibit polychromatic emission but also unlock a new direction to develop LEDs by exploiting 2D impurity-doped CQWs that can be further extended to the application of other impurities (e.g., Mn, Ag).

High-Frequency EPR and ENDOR Spectroscopy of Mn2+ Ions in CdSe/CdMnS Nanoplatelets.

Semiconductor colloidal nanoplatelets based of CdSe have excellent optical properties. Their magneto-optical and spin-dependent properties can be greatly modified by implementing magnetic Mn2+ ions, using concepts well established for diluted magnetic semiconductors. A variety of magnetic resonance techniques based on high-frequency (94 GHz) electron paramagnetic resonance in continuous wave and pulsed mode were used to get detailed information on the spin structure and spin dynamics of Mn2+ ions in core/shell CdSe/(Cd,Mn)S nanoplatelets. We observed two sets of resonances assigned to the Mn2+ ions inside the shell and at the nanoplatelet surface. The surface Mn demonstrates a considerably longer spin dynamics than the inner Mn due to lower amount of surrounding Mn2+ ions. The interaction between surface Mn2+ ions and 1H nuclei belonging to oleic acid ligands is measured by means of electron nuclear double resonance. This allowed us to estimate the distances between the Mn2+ ions and 1H nuclei, which equal to 0.31 ± 0.04, 0.44 ± 0.09, and more than 0.53 nm. This study shows that the Mn2+ ions can serve as atomic-size probes for studying the ligand attachment to the nanoplatelet surface.

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.

Optically detected magnetic resonance in CdSe/CdMnS nanoplatelets.

Core/shell CdSe/(Cd,Mn)S colloidal nanoplatelets containing magnetic Mn2+ ions are investigated by the optically detected magnetic resonance technique, combining 60 GHz microwave excitation and photoluminescence detection. Resonant heating of the Mn spin system is observed. We identify two mechanisms of optical detection, via variation of either the photoluminescence polarization or its intensity in an external magnetic field. The spin-lattice relaxation dynamics of the Mn spin system is measured and used for evaluation of the Mn concentration. In CdSe/(Cd,Zn,Mn)S nanoplatelets the addition of Zn in the shells significantly broadens the magnetic resonance, evidencing local strain.

Sub-single exciton optical gain threshold in colloidal semiconductor quantum wells with gradient alloy shelling.

Colloidal semiconductor quantum wells have emerged as a promising material platform for use in solution-processable lasers. However, applications relying on their optical gain suffer from nonradiative Auger decay due to multi-excitonic nature of light amplification in II-VI semiconductor nanocrystals. Here, we show sub-single exciton level of optical gain threshold in specially engineered CdSe/CdS@CdZnS core/crown@gradient-alloyed shell quantum wells. This sub-single exciton ensemble-averaged gain threshold of (Ng)≈ 0.84 (per particle) resulting from impeded Auger recombination, along with a large absorption cross-section of quantum wells, enables us to observe the amplified spontaneous emission starting at an ultralow pump fluence of ~ 800 nJ cm-2, at least three-folds better than previously reported values among all colloidal nanocrystals. Finally, using these gradient shelled quantum wells, we demonstrate a vertical cavity surface-emitting laser operating at a low lasing threshold of 7.5 µJ cm-2. These results represent a significant step towards the realization of solution-processable electrically-driven colloidal lasers.

Magneto-Optics of Excitons Interacting with Magnetic Ions in CdSe/CdMnS Colloidal Nanoplatelets.

Excitons in diluted magnetic semiconductors represent excellent probes for studying the magnetic properties of these materials. Various magneto-optical effects, which depend sensitively on the exchange interaction of the excitons with the localized spins of the magnetic ions can be used for probing. Here, we study core/shell CdSe/(Cd,Mn)S colloidal nanoplatelets hosting diluted magnetic semiconductor layers. The inclusion of the magnetic Mn2+ ions is evidenced by three magneto-optical techniques using high magnetic fields up to 15 T: polarized photoluminescence, optically detected magnetic resonance, and spin-flip Raman scattering. We show that the holes in the excitons play the dominant role in exchange interaction with magnetic ions. We suggest and test an approach for evaluation of the Mn2+ concentration based on the spin-lattice relaxation dynamics of the Mn2+ spin system.

Electrically control amplified spontaneous emission in colloidal quantum dots.

Colloidal quantum dots (CQDs) are highly promising materials for light amplification thanks to their efficient photoluminescence, tunable emission wavelength and low-cost synthesis. Unfortunately, CQDs are suffering from band-edge state degeneracy which demands multiple excitons to achieve population inversion. As a result, non-radiative Auger recombination increases the lasing threshold and limits the gain lifetime. Here, benefiting from the negative charging, we demonstrate that the amplified spontaneous emission (ASE) threshold is controllable in a device where CQD film is exposed to an external electric field. Specifically, singly charged CQDs lower the threshold due to the preexisting electron in the conduction band, while strongly enhanced Auger recombination in doubly charged CQDs stymies the ASE. Experimental results and kinetic equation model show that ASE threshold reduces 10% even if our device only charges ~17% of the CQD population. Our results open new possibilities for controlling exciton recombination dynamics and achieving electrically pumped CQD lasers.

Ultrahigh-efficiency aqueous flat nanocrystals of CdSe/CdS@Cd1-xZnxS colloidal core/crown@alloyed-shell quantum wells.

Colloidal semiconductor nanoplatelets (NPLs) are highly promising luminescent materials owing to their exceptionally narrow emission spectra. While high-efficiency NPLs in non-polar organic media can be obtained readily, NPLs in aqueous media suffer from extremely low quantum yields (QYs), which completely undermines their potential, especially in biological applications. Here, we show high-efficiency water-soluble CdSe/CdS@Cd1-xZnxS core/crown@shell NPLs formed by layer-by-layer grown and composition-tuned gradient Cd1-xZnxS shells on CdSe/CdS core/crown seeds. Such control of shell composition with monolayer precision and effective peripheral crown passivation, together with the compact capping density of short 3-mercaptopropionic acid ligands, allow for QYs reaching 90% in water, accompanied by a significantly increased photoluminescence lifetime (∼35 ns), indicating the suppression of nonradiative channels in these NPLs. We also demonstrate the controlled attachment of these NPLs without stacking at the nanoscale by taking advantage of their 2D geometry and hydrophilicity. This is a significant step in achieving controlled assemblies and overcoming the stacking process, which otherwise undermines their film formation and performance in optoelectronic applications. Moreover, we show that the parallel orientation of such NPLs achieved by the controlled attachment enables directed emission perpendicular to the surface of the NPL films, which is highly advantageous for light extraction in light-emitting platforms.

Temperature-dependent optoelectronic properties of quasi-2D colloidal cadmium selenide nanoplatelets.

Colloidal cadmium selenide (CdSe) nanoplatelets (NPLs) are a recently developed class of efficient luminescent nanomaterials suitable for optoelectronic device applications. A change in temperature greatly affects their electronic bandstructure and luminescence properties. It is important to understand how and why the characteristics of NPLs are influenced, particularly at elevated temperatures, where both reversible and irreversible quenching processes come into the picture. Here we present a study of the effect of elevated temperatures on the characteristics of colloidal CdSe NPLs. We used an effective-mass envelope function theory based 8-band k·p model and density-matrix theory considering exciton-phonon interaction. We observed the photoluminescence (PL) spectra at various temperatures for their photon emission energy, PL linewidth and intensity by considering the exciton-phonon interaction with both acoustic and optical phonons using Bose-Einstein statistical factors. With a rise in temperature we observed a fall in the transition energy (emission redshift), matrix element, Fermi factor and quasi Fermi separation, with a reduction in intraband state gaps and increased interband coupling. Also, there was a fall in the PL intensity, along with spectral broadening due to an intraband scattering effect. The predicted transition energy values and simulated PL spectra at varying temperatures exhibit appreciable consistency with the experimental results. Our findings have important implications for the application of NPLs in optoelectronic devices, such as NPL lasers and LEDs, operating much above room temperature.

High brightness formamidinium lead bromide perovskite nanocrystal light emitting devices.

Formamidinium lead halide (FAPbX3) has attracted greater attention and is more prominent recently in photovoltaic devices due to its broad absorption and higher thermal stability in comparison to more popular methylammonium lead halide MAPbX3. Herein, a simple and highly reproducible room temperature synthesis of device grade high quality formamidinium lead bromide CH(NH2)2PbBr3 (FAPbBr3) colloidal nanocrystals (NC) having high photoluminescence quantum efficiency (PLQE) of 55-65% is reported. In addition, we demonstrate high brightness perovskite light emitting device (Pe-LED) with these FAPbBr3 perovskite NC thin film using 2,2',2″-(1,3,5-Benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) commonly known as TPBi and 4,6-Bis(3,5-di(pyridin-3-yl)phenyl)-2-methylpyrimidine (B3PYMPM) as electron transport layers (ETL). The Pe-LED device with B3PYMPM as ETL has bright electroluminescence of up to 2714 cd/m2, while the Pe-LED device with TPBi as ETL has higher peak luminous efficiency of 6.4 cd/A and peak luminous power efficiency of 5.7 lm/W. To our knowledge this is the first report on high brightness light emitting device based on CH(NH2)2PbBr3 widely known as FAPbBr3 nanocrystals in literature.