Colloidal Quantum Dots Research Articles

Planar Cation Passivation on Colloidal Quantum Dots Enables High-Performance 0.35-1.8µm Broadband TFT Imager.

Solution-processed colloidal quantum dots (CQDs) are promising candidates for broadband photodetectors from visible light to shortwave infrared (SWIR). However, large-size PbS CQDs sensitive to longer SWIR are mainly exposed with nonpolar (100) facets on the surface, which lack robust passivation strategies. Herein, an innovative passivation strategy that employs planar cation, is introduced to enable face-to-face coupling on (100) facets and strengthen halide passivation on (111) facets. The defect density of CQDs film (Eg ≈ 0.74eV) is reduced from 2.74×1015 to 1.04×1015 cm-3, coupled with 0.1eV reduction in the activation energy of defects. The resultant CQDs photodiodes exhibit a low dark current density of 14 nA cm-2 with a high external quantum efficiency (EQE) of 62%, achieving a linear dynamic range of 98dB, a -3dB bandwidth of 103kHz and a detectivity of 4.7×1011 Jones. The comprehensive performance of the CQDs photodiodes outperforms previously reported CQDs photodiodes operating at >1.6µm. By monolithically integrated with thin-film transistor (TFT) readout circuit, the broadband CQDs imager covering 0.35-1.8µm realizes the functions including silicon wafer perspectivity and material discrimination, showing its potential for wide range of applications.

Direct Visualization of Confinement and Many‐Body Correlation Effects in 2D Spectroscopy of Quantum Dots

AbstractThe size tunable color of colloidal semiconductor quantum dots (QDs) is probably the most elegant illustration of the quantum confinement effect. As explained by the simple “particle‐in‐a‐box” model, the transition energies between the levels increase when the “box” becomes smaller. To investigate quantum confinement effects, typically a well‐defined narrow size distribution of the nanoparticles is needed. In this contribution, how coherent electronic two‐dimensional spectroscopy (2DES) can directly visualize the quantum size effect in a sample with broad size distribution of QDs is demonstrated. The method is based on two features of the 2DES – the ability to resolve inhomogeneous broadening and the capability to reveal correlations between the states. In QD samples, inhomogeneous spectral broadening is mainly caused by the size distribution and leads to elongated diagonal peaks of the spectra. Since the cross peaks correlate the energies of two states, they allow drawing conclusions about the size dependence of the corresponding states. It is also found that the biexciton binding energy changes between 3 and 8 meV with the QD size. Remarkably, the size dependence is non‐monotonic with a clear minimum.

Multi-Interfacial Confined Assembly of Colloidal Quantum Dots Quasisuperlattice Microcavities for High-Resolution Full-Color Microlaser Arrays.

Colloidal quantum dots (CQDs) are considered a promising material for the next generation of integrated display devices due to their designable optical bandgap and low energy consumption. Owing to their dispersibility in solvents, CQD micro/nanostructures are generally fabricated by solution-processing methods. However, the random mass transfer in liquid restricts the programmable construction in macroscopy and ordered assembly in microscopy for the integration of CQD optical structures. Herein, a multi-interfacial confined assembly strategy is developed to fabricate CQDs programmable microstructure arrays with a quasisuperlattice configuration through controlling the dynamics of three-phase contact lines (TPCLs). The motion of TPCLs dominates the division of liquid film for precise positioning of CQD microstructures, while pinned TPCLs control the solvent evaporation and concentration gradient to directionally drive the mass transfer and packing of CQDs. Owing to their long-range order and adjustable structural dimensions, CQD microring arrays function as high-quality-factor (high-Q) lasing resonant cavities with low thresholds and tunable lasing emission modes. Through the further surface treatment and liquid dynamics control, the on-chip integration of red (R), green (G), and blue (B) multicomponent CQD microlaser arrays are demonstrated. The technique establishes a new route to fabricate large-area, ultrahigh-definition, and full-color CQD laser displays.

One-pot heat-up synthesis of short-wavelength infrared, colloidal InAs quantum dots.

III-V colloidal quantum dots (QDs) promise Pb and Hg-free QD compositions with which to build short-wavelength infrared (SWIR) optoelectronic devices. However, their synthesis is limited by the availability of group-V precursors with controllable reactivities to prepare monodisperse, SWIR-absorbing III-V QDs. Here, we report a one-pot heat-up method to synthesize ∼8nm edge length (∼6.5nm in height) tetrahedral, SWIR-absorbing InAs QDs by increasing the [In3+]:[As3+] ratio introduced using commercially available InCl3 and AsCl3 precursors and by decreasing the concentration and optimizing the volume of the reducing reagent superhydride to control the concentration of In(0) and As(0) intermediates through QD nucleation and growth. InAs QDs are treated with NOBF4, and their deposited films are exchanged with Na2S to yield n-type InAs QD films. We realize the only colloidal InAs QD photoconductors with responsivity at the technologically important wavelength of 1.55μm.

Ligand Mediated Assembly of CdS Colloids in 3D Porous Metal–Organic Framework Derived Scaffold with Multi‐Sites Heterojunctions for Efficient CO2 Photoreduction

AbstractThe inclusion of colloidal particles into 3D porous constructs to realize heterostructure ensembles enhances surface interactions and energy transfer that can transform the catalytic properties of conventional catalysts. However, assembling hydrophobic colloidal nanoparticles within hydrophilic 3D porous matrices to create tailored heterostructures and catalytic properties is particularly challenging. Here, a modified ligand grafting method is presented to spontaneously assemble CdS inorganic colloidal quantum dots within a metal‐organic framework (MOF) derived porous framework for efficient photocatalytic CO2 reduction. The grafted long chain molecular ligands effectively suppress phase separation and endow a molecular‐recognition effect to form ordered assembly microstructures. The proof‐of‐concept assembly of CdS and Prussian blue analogues (PBA) derived Co3O4 facilitates a high density of heterojunctions formation, improving charge transfer and extended lifetimes of photo‐induced electrons. Consequently, CdS/Co3O4 assembly exhibits exceptionally active and stable photocatalytic CO2 reduction activity, with a CO production rate of 73.9 µmol g−1 h−1 and CO selectivity of 98.9%. Importantly, the ligand grafting method can be generalized to achieve spontaneous assembly of quantum dots within various metal organic framework derived porous scaffolds. This work provides a rational strategy for precise self‐assembly of colloidal nanoparticles within porous microstructures, allowing tailored heterointerfaces for functional materials and applications.

Spontaneous crystallization of strongly confined CsSnxPb1-xI3 perovskite colloidal quantum dots at room temperature.

The scalable and low-cost room temperature (RT) synthesis for pure-iodine all-inorganic perovskite colloidal quantum dots (QDs) is a challenge due to the phase transition induced by thermal unequilibrium. Here, we introduce a direct RT strongly confined spontaneous crystallization strategy in a Cs-deficient reaction system without polar solvents for synthesizing stable pure-iodine all-inorganic tin-lead (Sn-Pb) alloyed perovskite colloidal QDs, which exhibit bright yellow luminescence. By tuning the ratio of Cs/Pb precursors, the size confinement effect and optical band gap of the resultant CsSnxPb1-xI3 perovskite QDs can be well controlled. This strongly confined RT approach is universal for wider bandgap bromine- and chlorine-based all-inorganic and iodine-based hybrid perovskite QDs. The alloyed CsSn0.09Pb0.91I3 QDs show superior yellow emission properties with prolonged carrier lifetime and significantly increased colloidal stability compared to the pristine CsPbI3 QDs, which is enabled by strong size confinement, Sn2+ passivation and enhanced formation energy. These findings provide a RT size-stabilized synthesis pathway to achieve high-performance pure-iodine all-inorganic Sn-Pb mixed perovskite colloidal QDs for optoelectronic applications.

Deep-learning-based inverse design of colloidal quantum dots

Because optical properties of colloidal quantum dots (QDs) greatly depend on their layer thicknesses at the sub-nanometer scale, accurately predicting optical properties based on these structural parameters can help streamline the development process. However, most of traditional inverse design approaches require time-consuming numerical simulations and optimization processes. In this simulation-only paper, we propose a deep-learning-based inverse design model for colloidal InP/ZnSe/ZnS QDs based on the structure parameters of layer thicknesses and optical properties of the emission and absorption spectrum. Four different deep neural network (DNN) structures are implemented and compared. A tandem DNN structure with the simultaneous use of both emission and absorption spectra as input data shows the best accuracy due to its ability to alleviate the non-uniqueness problem in the inverse design of colloidal QDs. Our inverse design model enables the prediction of layer thicknesses for QDs that exhibit on-demand optical emission/absorption spectra, which are particularly enhanced at the specific target wavelength region. Moreover, the weights and biases of the well-trained tandem DNN for InP/ZnSe/ZnS QDs can be transferred and tuned to implement a transfer-learning-assisted inverse design model for CdSe/ZnSe/ZnS QDs, where the amount of training data to achieve the average prediction accuracy of 99.3 % is reduced by a maximum of 71.4 %.

Unveiling the Nanocluster Conversion Pathway for Highly Monodisperse InAs Colloidal Quantum Dots.

Colloidal quantum dots (CQDs) have garnered significant attention in nanoscience and technology, with a particular emphasis on achieving high monodispersity in their synthesis. Recent advances in understanding the chemistry of reaction intermediates such as magic-sized nanoclusters (MSC) have paved the way for innovative synthetic strategies. Notably, monodisperse CQDs of various compositions, including indium phosphide, indium arsenide, and cadmium chalcogenide, have been successfully prepared using nanocluster intermediates as single-source precursors. Still, the early stage conversion chemistry of these nanoclusters preceding CQD formation has not been fully unveiled yet. Herein, we report the first-order conversion of amorphous nanoclusters (AMCs) to InAs MSCs prior to the formation of CQDs. We find that MSC, isolated via gel-permeation chromatography, is more stable than purified AMCs, as demonstrated in various chemical and thermolytic reactions. While the surface of InAs AMCs and MSC is similarly bound with carboxylate ligands, detailed structural analyses employing synchrotron X-ray scattering and X-ray absorption spectroscopy unveil subtle distinctions arising from the distinct surface properties and structural disorder characteristics of InAs nanoclusters. We propose that InAs AMCs undergo a surface reduction and structural ordering process, resulting in the formation of an InAs MSC in a thermodynamically local minimum state. Furthermore, we demonstrate that both types of nanoclusters serve as viable precursors, providing a similar monomer supply rate at elevated temperatures of around 300 °C. This study offers invaluable insights into the interplay of structure and chemical stability in binary nanoclusters, enhancing our ability to design these nanoclusters as precursors for highly monodisperse CQDs.

Ligand Exchange of Quantum Dots: A Thermodynamic Perspective.

Colloidal quantum dots (QDs) consist of an inorganic core and organic surface ligands. Surface ligands play a dominant role in maintaining the colloidal stability of QDs and passivating the surface defects of QDs. However, the original ligands introduced in the synthetic process of QDs cannot meet the requirements for diverse applications; therefore, ligand exchanges with functional ligands are mandatory. Understanding the ligand exchange process requires a comprehensive combination of the concepts and techniques of surface chemistry. In this Perspective, the ligand exchange process is discussed in detail. Specifically, we elaborate on the thermodynamics that can reveal the feasibility and mechanism of ligand exchange. It depicts a critical physical picture of the surface of QDs along with the following ligand exchange.

Angle‐Independent Top‐Emitting Quantum‐Dot Light‐Emitting Diodes Using a Solution‐Processed Subwavelength Scattering–Capping Layer

AbstractOwing to the excellent optoelectronic properties of colloidal quantum dots (QDs), light‐emitting diodes based on QDs (QLEDs) have been considered one of the most promising electroluminescence (EL) devices for full‐color displays with a wide color gamut. Particularly, top‐emission device architecture has been of interest to both academia and industry, because of the advantages in light outcoupling, aperture ratios, and integration with conventional backplanes. In this structure, however, angle‐dependent color shifts originating from a variation in microcavity length are a critical issue that needs to be resolved. Here, a solution‐processed dual‐functional scattering–capping layer (SCPL) using ZnO nanoparticles on top‐emitting QLEDs with ZnSeTe/ZnSe/ZnS QDs to modulate the optical interference is presented. By precisely controlling the thickness of the SCPL, the EL intensity and spectrum can be redistributed to produce a uniform color from any viewing angle. It is discovered that, unlike conventional CPLs, the formation of random nanocracks and nanoclusters in the SCPL adds subwavelength light‐scattering capabilities, which promotes light extraction. The QLEDs with the solution‐processed SCPL exhibit a 44% increase in the maximum external quantum efficiency, with completely imperceptible angle‐dependent spectral shifts. The SCPL is expected to be applied to the development of high‐performance and next‐generation QLED displays.

Tailoring p-Type Behavior in ZnO Quantum Dots through Enhanced Sol-Gel Synthesis: Mechanistic Insights into Zinc Vacancies.

The synthesis and control of properties of p-type ZnO is crucial for a variety of optoelectronic and spintronic applications; however, it remains challenging due to the control of intrinsic midgap (defect) states. In this study, we demonstrate a synthetic route to yield colloidal ZnO quantum dots (QD) via an enhanced sol-gel process that effectively eliminates the residual intermediate reaction molecules, which would otherwise weaken the excitonic emission. This process supports the creation of ZnO with p-type properties or compensation of inherited n-type defects, primarily due to zinc vacancies under oxygen-rich conditions. The in-depth analysis of carrier recombination in the midgap across several time scales reveals microsecond carrier lifetimes at room temperature which are expected to occur via zinc vacancy defects, supporting the promoted p-type character of the synthesized ZnO QDs.

Enhancement of Optical Gain in Colloidal CdSe/CdS/ZnS Quantum Dots through Nanosecond Optical Pumping.

Optical gain and lasing in colloidal nanocrystals are often hindered by sub-nanosecond rapid Auger non-radiative recombination, especially under continuous wave optical or electrical excitation. This study demonstrates amplified spontaneous emission (ASE) from CdSe/CdS/ZnS quantum dot (QD) solids through prolonged pulsed optical pumping over 10 ns. The incorporation of CdS and ZnS double shells on CdSe QDs effectively decelerates the Auger process in multiexcitonic states by extending the electron wave function and enhancing dielectric screening. Furthermore, we engineer smooth, densely packed QD solid films that efficiently guide the optical mode, achieving substantial net gain values under nanosecond pumping. The proposed approach helps observe ASE with gain thresholds of 0.84 and 1.5 mJ/cm2 under optical pumping pulse widths of 6 and 15 ns, respectively. This advancement can promote continuous pumping in colloidal QD gain systems, opening new avenues for optoelectronic applications.

Fast Organic Cation Exchange in Colloidal Perovskite Quantum Dots toward Functional Optoelectronic Applications.

Colloidal quantum dots with lower surface ligand density are desired for preparing the active layer for photovoltaic, lighting, and other potential optoelectronic applications. In emerging perovskite quantum dots (PQDs), the diffusion of cations is thought to have a high energy barrier, relative to that of halide anions. Herein, we investigate the fast cross cation exchange approach in colloidal lead triiodide PQDs containing methylammonium (MA+) and formamidinium (FA+) organic cations, which exhibits a significantly lower exchange barrier than inorganic cesium (Cs+)-FA+ and Cs+-MA+ systems. First-principles calculations further suggest that the fast internal cation diffusion arises due to a lowering in structural distortions and the consequent decline in attractive cation-cation and cation-anion interactions in the presence of organic cation vacancies in mixed MA+-FA+ PQDs. Combining both experimental and theoretical evidence, we propose a vacancy-assisted exchange model to understand the impact of structural features and intermolecular interaction in PQDs with fewer surface ligands. Finally, for a realistic outcome, the as-prepared mixed-cation PQDs display better photostability and can be directly applied for one-step coated photovoltaic and photodetector devices, achieving a high photovoltaic efficiency of 15.05% using MA0.5FA0.5PbI3 PQDs and more precisely tunable detective spectral response from visible to near-infrared regions.

Colloidal Quantum Dots for Explosive Detection: Trends and Perspectives.

Sensitive, accurate, and reliable detection of explosives has become one of the major needs for international security and environmental protection. Colloidal quantum dots, because of their unique chemical, optical, and electrical properties, as well as easy synthesis route and functionalization, have demonstrated high potential to meet the requirements for the development of suitable sensors, boosting the research in the field of explosive detection. Here, we critically review the most relevant research works, highlighting three different mechanisms for explosive detection based on colloidal quantum dots, namely photoluminescence, electrochemical, and chemoresistive sensing. We provide a comprehensive overview and an extensive discussion and comparison in terms of the most relevant sensor parameters. We highlight advantages, limitations, and challenges of quantum dot-based explosive sensors and outline future research directions for the advancement of knowledge in this surging research field.

InSb/InP Core-Shell Colloidal Quantum Dots for Sensitive and Fast Short-Wave Infrared Photodetectors.

Colloidal quantum dot (CQD) technology is considered the main contender toward a low-cost high-performance optoelectronic technology platform for applications in the short-wave infrared (SWIR) to enable 3D imaging, LIDAR night vision, etc. in the consumer electronics and automotive markets. In order to unleash the full potential of this technology, there is a need for a material that is environmentally friendly, thus RoHS compliant, and possesses adequate optoelectronic properties to deliver high-performance devices. InSb CQDs hold great potential in view of their RoHS-compliant nature and─in principle─facile access to the SWIR. However, to date progress in realizing high-performance optoelectronic devices, including photodetectors (PDs), has been limited. Here, we have developed a synthesis method for producing size-tunable InSb CQDs with distinct excitonic peaks spanning a wide range from 900 to 1750 nm. To passivate the surface defects and enhance the photoluminescence (PL) efficiency of InSb CQDs, we further designed an InSb/InP core-shell structure. By employing the InSb/InP core-shell CQDs in a photodiode device stack, we report on robust InSb CQD SWIR photodetectors that exhibit an external quantum efficiency (EQE) of 25% at 1240 nm, a wide linear dynamic range exceeding 128 dB, a photoresponse time of 70 ns, and a specific detectivity of 4.4 × 1011 jones.

High‐performance Photoelectrochemical Hydrogen Production Using Asymmetric Quantum Dots

AbstractSolar‐driven photoelectrochemical (PEC) reactions using colloidal quantum dots (QDs) as photoabsorbers have shown great potential for the production of clean fuels. However, the low H2 evolution rate, consistent with low values of photocurrent density, and their limited operational stability are still the main obstacles. To address these challenges, the heterostructure engineering of asymmetric capsule‐shaped CdSe/CdxZn1‐xSe QDs with broad absorption and efficient charge extraction compared to pure‐shell QDs is reported. By engineering the shell composition from pure ZnSe shells into CdxZn1‐xSe gradient shells, the electron transfer rate increased from 4.0 × 107 s−1 to 32.7 × 107 s−1. Moreover, the capsule‐shaped architecture enables more efficient spatial carrier separation, yielding a saturated current density of average of 25.4 mA cm−2 under AM 1.5 G one sun illumination. This value is the highest ever observed for QDs‐based devices and comparable to the best‐known Si‐based devices, perovskite‐based devices, and metal oxide‐based devices. Furthermore, PEC devices based on heterostructured QDs maintained 96% of the initial current density after 2 h and 82% after 10 h under continuous illumination, respectively. The results represent a breakthrough in hydrogen production using heterostructured asymmetric QDs.

Synthesis and luminescent properties of PbS/SiO2 core-shell quantum dots

The research focuses on the development of techniques for creating core-shell structures, based on colloidal PbS quantum dots (PbS QDs) and establishing the influence of the dielectric SiO2 shell on the luminescent properties of PbS QDs. The objects of the study were PbS QDs with an average size of 3.0±0.5 nm, passivated with thioglycolic acid (TGA) and PbS/SiO2 QDs, based on them with an average size of 6.0±0.5 nm. When we passivated the PbS QD interfaces with thioglycolic acid molecules, there were two luminescence peaks at 1100 and at 1260 nm. It was found that increasing the temperature of the colloidal mixture to 60 °C provides an increase in the intensity of the long-wave peak. An analysis of the luminescence excitation spectra of both bands and the Stokes shift showed that the band at 1100 nm is associated with the radiativeannihilation of an exciton, while the band at 1260 nm is due to recombination at trap levels. The formation of PbS/SiO2 QDs suppresses trap state luminescence, indicating the localization of luminescence centers predominantly at QD interfaces. The exciton luminescence at 1100 nm becomes more intensive

High-directivity far-field radiation of quantum dot-based single-photon emitter coupled to polymeric circular waveguide resonant grating

Solid-state single-photon emitters (SPEs) commonly encounter the limitation of quasi-omnidirectional radiation patterns, which poses challenges in utilizing their emission with conventional optical instruments. In this study, we demonstrate the tailoring of the far-field radiation patterns of SPEs based on colloidal quantum dots (QDs), both theoretically and experimentally, by employing a polymer-based dielectric antenna. We introduce a simple and cost-effective technique, namely low one-photon absorption direct laser writing, to achieve precise coupling of a QD into an all-polymer circular waveguide resonance grating. By optimizing the geometry parameters of the structure using 3D finite-difference time-domain simulations, resonance at the emission wavelength of QDs is achieved in the direction perpendicular to the substrate, resulting in photon streams with remarkably high directivity on both sides of the grating. Theoretical calculations predict beam divergence values below 2°, while experimental measurements using back focal plane imaging yield divergence angles of approximately 8°. Our study contributes to the evaluation of concentric circular grating structures employing low refractive index polymer materials, thereby expanding the possibilities for their application.

Bright Nonblinking Photoluminescence with Blinking Lifetime from a Nanocavity-Coupled Quantum Dot.

Colloidal quantum dots (QDs) are excellent luminescent nanomaterials for many optoelectronic applications. However, photoluminescence blinking has limited their practical use. Coupling QDs to plasmonic nanostructures shows potential in suppressing blinking. However, the underlying mechanism remains unclear and debated, hampering the development of bright nonblinking dots. Here, by deterministically coupling a QD to a plasmonic nanocavity, we clarify the mechanism and demonstrate unprecedented single-QD brightness. In particular, we report for the first time that a blinking QD could obtain nonblinking photoluminescence with a blinking lifetime through coupling to the nanocavity. We show that the plasmon-enhanced radiative decay outcompetes the nonradiative Auger process, enabling similar quantum yields for charged and neutral excitons in the same dot. Meanwhile, we demonstrate a record photon detection rate of 17 MHz from a colloidal QD, indicating an experimental photon generation rate of more than 500 MHz. These findings pave the way for ultrabright nonblinking QDs, benefiting diverse QD-based applications.

High-Affinity Ligand-Enhanced Passivation of Group III–V Colloidal Quantum Dots for Sensitive Near-Infrared Photodetection

High-Affinity Ligand-Enhanced Passivation of Group III–V Colloidal Quantum Dots for Sensitive Near-Infrared Photodetection