Ultrafast Cascade Charge Transfer in Multibandgap Colloidal Quantum Dot Solids Enables Threshold Reduction for Optical Gain and Stimulated Emission.

Achieving low-threshold infrared stimulated emission in solution-processed quantum dots is critical to enable real-life applications including photonic integrated circuits (PICs), LIDAR application, and optical telecommunication. However, realization of low threshold infrared gain is fundamentally challenging due to high degeneracy of the first emissive state (e.g., 8-fold) and fast Auger recombination. In this Letter, we demonstrate ultra-low-threshold infrared stimulated emission with an onset of 110 µJ cm-2 employing cascade charge transfer (CT) in Pb-chalcogenide colloidal quantum dot (CQD) solids. In doing so, we investigate this idea in two different architectures including a mixture of multiband gap CQDs and a layer-by-layer (LBL) configuration. Using transient absorption spectroscopy, we show ultrafast cascade CT from large band gap PbS CQD to small band gap PbS/PbSSe core/shell CQDs in LBL (∼2 ps) and mixture (∼9 ps) configurations. These results indicate the feasibility of using cascade CT as an efficient method to reduce the optical gain threshold in CQD solid films.

Colloidal Quantum Dot Infrared Lasers Featuring Sub-Single-Exciton Threshold and Very High Gain.

The use of colloidal quantum dots (CQDs) as a gain medium in infrared laser devices has been underpinned by the need for high pumping intensities, very short gain lifetimes, and low gain coefficients. Here, PbS/PbSSe core/alloyed-shell CQDs are employed as an infrared gain medium that results in highly suppressed Auger recombination with a lifetime of 485 ps, lowering the amplified spontaneous emission (ASE) threshold down to 300 µJ cm-2 , and showing a record high net modal gain coefficient of 2180 cm-1 . By doping these engineered core/shell CQDs up to nearly filling the first excited state, a significant reduction of optical gain threshold is demonstrated, measured by transient absorption, to an average-exciton population-per-dot 〈Nth 〉g of 0.45 due to bleaching of the ground state absorption. This in turn have led to a fivefold reduction in ASE threshold at 〈Nth 〉ASE  = 0.70 excitons-per-dot, associated with a gain lifetime of 280 ps. Finally, these heterostructured QDs are used to achieve near-infrared lasing at 1670 nm at a pump fluences corresponding to sub-single-exciton-per-dot threshold (〈Nth 〉Las  = 0.87). This work brings infrared CQD lasing thresholds on par to their visible counterparts, and paves the way toward solution-processed infrared laser diodes.

Colloidal Quantum Dot Light Emitting Diodes at Telecom Wavelength with 18% Quantum Efficiency and Over 1 MHz Bandwidth.

Developing high performance, low-cost solid-state light emitters in the telecom wavelength bandwidth is of paramount importance for infrared light-based communications. Colloidal quantum dot (CQD) based light emitting diodes (LEDs) have shown tremendous advances in recent times through improvement in synthesis chemistry, surface property, and device structures. Despite the tremendous advancements of CQD based LEDs in the visible range with efficiency reaching theoretical limits, their short-wave infrared (SWIR) counterparts mainly based on lead chalcogenide CQDs, have shown lower performance (≈8%). Here the authors report on highly efficient SWIR CQD LEDs with a recorded EQE of 11.8% enabled by the use of a binary CQD matrix comprising QD populations of different bandgaps at the emission wavelength of 1550 nm. By further optimizing the optical out-coupling via the use of a hemispherical lens to reduce optical waveguide loss, the EQE of the LED increased to 18.6%. The CQD LED has an electrical bandwidth of 2 MHz, which motivated them to demonstrate its use in the first SWIR free-space optical transmission link based entirely on CQD technology (photodetector and light emitter) opening a new window of applications for CQD optoelectronics.

Low-Threshold, Highly Stable Colloidal Quantum Dot Short-Wave Infrared Laser enabled by Suppression of Trap-Assisted Auger Recombination.

Pb-chalcogenide colloidal quantum dots (CQDs) are attractive materials to be used as tuneable laser media across the infrared spectrum. However, excessive nonradiative Auger recombination due to the presence of trap states outcompetes light amplification by rapidly annihilating the exciton population, leading to high gain thresholds. Here, a binary blend is employed of CQDs and ZnO nanocrystals in order to passivate the in-gap trap states of PbS-CQD gain medium. Using transient absorption, a fivefold increase is measured in Auger lifetime demonstrating the suppression of trap-assisted Auger recombination. By doing so, a twofold reduction is achieved in amplified spontaneous emission (ASE) threshold. Finally, by integrating the proposed binary blend to a distributed feedback (DFB) resonator, single-mode lasing emission is demonstrated at 1650 nm with a linewidth of 1.23 nm (0.62 meV), operating at a low lasing threshold of ≈385 µJ cm-2 . The Auger suppression in this system has allowed to achieve unprecedented lasing emission stability for a CQD laser with recorded continuous operation of 5 h at room temperature and ambient conditions.

Solid-State Thin-Film Broadband Short-Wave Infrared Light Emitters.

Solid-state broadband light emitters in the visible have revolutionized today's lighting technology achieving compact footprints, flexible form factors, long lifetimes, and high energy saving, although their counterparts in the infrared are still in the development phase. To date, broadband emitters in the infrared have relied on phosphor-downconverted light emitters based on atomic optical transitions in transition metal or rare earth elements in the phosphor layer resulting in limited spectral bandwidths in the near-infrared and preventing their integration into electrically driven light-emitting diodes (LEDs). Herein, phosphor-converted LEDs based on engineered stacks of multi-bandgap colloidal quantum dots (CQDs) are reported as a novel class of broadband emitters covering a broad short-wave infrared (SWIR) spectrum from 1050-1650 nm with a full-width-half-maximum of 400 nm, delivering 14 mW of optical power with a quantum efficiency of 5.4% and power conversion efficiency of 13%. Leveraging the electrical conductivity of the CQD stacks, further, the first broadband SWIR-active LED is demonstrated, paving the way toward complementary metal-oxide-semiconductor integrated broadband emitters for on-chip spectrometers and low-cost volume manufacturing. SWIR spectroscopy is employed to illustrate the practical relevance of the emitters in food and material identification case studies.

Monitoring the insertion of Pt into Cu2-xSe nanocrystals: a combined structural and chemical approach for the analysis of new ternary phases.

The tuning of the chemical composition in nanostructures is a key aspect to control for the preparation of new multifunctional and highly performing materials. The modification of Cu2-xSe nanocrystals with Pt could provide a good way to tune both optical and catalytic properties of the structure. Although the heterogeneous nucleation of metallic Pt domains on semiconductor chalcogenides has been frequently reported, the insertion of Pt into chalcogenide materials has not been conceived so far. In this work we have explored the experimental conditions to facilitate and enhance the insertion of Pt into the Cu2-xSe nanocrystalline lattice, forming novel ternary phases that show a high degree of miscibility and compositional variability. Our results show that Pt is mainly found as a pure metal or a CuPt alloy at high Pt loads (Pt : Cu atomic ratio in reaction medium >1). However, two main ternary CuPtSe phases with cubic and monoclinic symmetry can be identified when working at lower Pt : Cu atomic ratios. Their structure and chemical composition have been studied by local STEM-EDS and HRTEM analyses. The samples containing ternary domains have been loaded on graphite-like C3N4 (g-C3N4) semiconductor layers, and the resulting nanocomposite materials have been tested as promising photocatalysts for the production of H2 from aqueous ethanolic solutions.

Single-Exciton Gain and Stimulated Emission Across the Infrared Telecom Band from Robust Heavily Doped PbS Colloidal Quantum Dots.

Materials with optical gain in the infrared are of paramount importance for optical communications, medical diagnostics, and silicon photonics. The current technology is based either on costly III-V semiconductors that are not monolithic to silicon CMOS technology or Er-doped fiber technology that does not make use of the full fiber transparency window. Colloidal quantum dots (CQDs) offer a unique opportunity as an optical gain medium in view of their tunable bandgap, solution processability, and CMOS compatibility. The 8-fold degeneracy of infrared CQDs based on Pb-chalcogenides has hindered the demonstration of low-threshold optical gain and lasing, at room temperature. We demonstrate room-temperature, infrared, size-tunable, band-edge stimulated emission with a line width of ∼14 meV. Leveraging robust electronic doping and charge-exciton interactions in PbS CQD thin films, we reach a gain threshold at the single exciton regime representing a 4-fold reduction from the theoretical limit of an 8-fold degenerate system, with a net modal gain in excess of 100 cm-1.

Size- and Temperature-Dependent Intraband Optical Properties of Heavily n-Doped PbS Colloidal Quantum Dot Solid-State Films.

Steady-state access to intraband transitions in colloidal quantum dots (CQDs), via doping, permits exploitation of the electromagnetic spectrum at energies below the band gap. CQD intraband optoelectronics allows envisaging cheap mid- and long-wavelength infrared photodetectors and light-emitting devices, which today employ epitaxial materials. As intraband devices start to emerge, thorough studies of the basic properties of intraband transitions in different CQD materials are needed to guide technological research. In this work, we investigate the size and temperature dependence of the intraband transition in heavily n-doped PbS quantum dot (QD) films. In the studied QD size range (5-8 nm), the intraband energy spans from 209 to 151 meV. We measure the intraband absorption coefficient of heavily doped PbS QD films to be around 2 × 104 cm-1, proving that intraband absorption is as strong as interband absorption. We demonstrate a negative dependence of the intraband energy with temperature, in contrast to the positive dependence of the interband transition. Also opposite to the interband case, the temperature dependence of the intraband energy increases with decreasing size, going from -29 µeV/K to -49 µeV/K in the studied size range.

Facile morphology control of gold(0) structures from aurophilic assemblies.

Different gold microstructures have been synthesized by using supramolecular gold(i) organometallic compounds as templates and Ag nanoparticles as reducing agents. The use of fibers resulting from supramolecular assemblies of neutral gold(i) compounds gives rise to the formation of microrods. The use of supramolecular assemblies from ionic molecules results in spherical or square-based prism gold microstructures, depending on the shape of the supramolecular gold(i) precursor assembly. In addition to temperature and reaction time, solvents exert a strong influence on the formation and morphology of gold structures, as borne out by the example that well-defined star-like morphologies have been obtained in chloroform.

Mid- and Long-Wave Infrared Optoelectronics via Intraband Transitions in PbS Colloidal Quantum Dots.

Optical sensing in the mid- and long-wave infrared (MWIR, LWIR) is of paramount importance for a large spectrum of applications including environmental monitoring, gas sensing, hazard detection, food and product manufacturing inspection, and so forth. Yet, such applications to date are served by costly and complex epitaxially grown HgCdTe quantum-well and quantum-dot infrared photodetectors. The possibility of exploiting low-energy intraband transitions make colloidal quantum dots (CQD) an attractive low-cost alternative to expensive low bandgap materials for infrared applications. Unfortunately, fabrication of quantum dots exhibiting intraband absorption is technologically constrained by the requirement of controlled heavy doping, which has limited, so far, MWIR and LWIR CQD detectors to mercury-based materials. Here, we demonstrate intraband absorption and photodetection in heavily doped PbS colloidal quantum dots in the 5-9 µm range, beyond the PbS bulk band gap, with responsivities on the order of 10-4 A/W at 80 K. We have further developed a model based on quantum transport equations to understand the impact of electron population of the conduction band in the performance of intraband photodetectors and offer guidelines toward further performance improvement.

Origin of the Below-Bandgap Turn-On Voltage in Light-Emitting Diodes and the High VOC in Solar Cells Comprising Colloidal Quantum Dots with an Engineered Density of States.

The turn-on voltage of a light-emitting diode (LED) is an important parameter as it determines the power consumption of the LED and influences the effective power conversion efficiency. LEDs based on nanoscale engineering of the blended PbS [mixture of quantum dots (QDs) with two different bandgaps] colloidal QDs have recently shown record performance in the infrared region. One of the most intriguing findings for these blended devices is the substantially lower-than-bandgap turn-on voltage and the achievement of an open circuit voltage ( VOC), approaching the radiative limit. In this work, we provide new insight into the origin of these phenomena. We posit that the decrease in the effective density of states in the conduction and valence band of the emitter QDs in the blended structures modifies the chemical potential, which controls the turn-on voltage for LEDs through the modification of the photon flux and VOC for photovoltaic devices with quasi-Fermi level modification.

Preparation and Antitumoral Activity of Au-Based Inorganic-Organometallic Nanocomposites.

The synergy between gelator molecules and nanostructured materials is currently a novel matter of study. The possibility to carefully design the skeleton of the molecular entity as well as the nanostructure's morphological and chemical features offers the possibility to prepare a huge variety of nanocomposites with properties potentially different than just the sum of those of the individual building blocks. Here we describe the synthesis and characterization of nanocomposites made by the unconventional combination of phosphine-Au(I)-alkynyl-based organometallic gelating molecules and plasmonic Au nanoparticles. Our results indicate that the interaction between the two moieties leads to a significant degree of aggregation in both hydrophilic and hydrophobic media, either when using DAPTA or PTA-based organometallic molecules, with the formation of a sponge-like hybrid powder upon solvent evaporation. The biological activity of the nanocomposites was assessed, suggesting the existence of a synergetic effect evidenced by the higher cytotoxicity of the hybrid systems with respect to that of any of their isolated counterparts. These results represent a preliminary proof-of-concept for the exploitation of these novel nanocomposites in the biomedical field.

Highly water-stable rare ternary Ag-Au-Se nanocomposites as long blood circulation time X-ray computed tomography contrast agents.

X-ray computed tomography (CT) is a powerful and widely used medical non-invasive technique that often requires intravenous administration of contrast agents (CAs) to better visualize soft tissues. In this work, we have developed a novel CT contrast agent based on ternary Ag-Au-Se chalcogenide nanoparticles (NP). A facile ligand exchange by using a 3 kDa PEGylated ligand with a dithiol dihydrolipoic acid as an anchor group resulted in highly water-soluble and monodisperse nanoparticles. These PEGylated ternary NPs were tested in vivo in mice, showing slow uptake by the mononuclear phagocyte system, long blood circulation times, low toxicity, and very good X-ray contrast, thus being promising candidates as CT contrast agents for clinical applications.

Exploiting Metallophilicity for the Assembly of Inorganic Nanocrystals and Conjugated Organic Molecules.

The accurate engineering of interfaces between inorganic nanocrystals and semiconducting organic molecules is currently viewed as key for further developments in critical fields such as photovoltaics and photocatalysis. In this work, a new and unconventional source of interface interaction based on metal-metal bonds is presented. With this aim, an Au(I) organometallic gelator was exploited for the formation of hydrogel-like nanocomposites containing inorganic nanoparticles and conjugated organic molecules. Noteworthy, the establishment of metallophilic interactions at the interface between the two moieties greatly enhances interparticle coupling in the composites. Thus, we believe that this new hybrid system might represent a promising alternative in several fields, such as in the fabrication of improved light-harvesting devices.