Room-Temperature Fiber-Coupled Single-Photon Sources based on Colloidal Quantum Dots and SiV Centers in Back-Excited Nanoantennas.

We demonstrate an important step toward on-chip integration of single-photon sources at room temperature. Excellent photon directionality is achieved with a hybrid metal-dielectric bullseye antenna, while back-excitation is permitted by placement of the emitter in a subwavelength hole positioned at its center. The unique design enables a direct back-excitation and very efficient front coupling of emission either to a low numerical aperture (NA) optics or directly to an optical fiber. To show the versatility of the concept, we fabricate devices containing either a colloidal quantum dot or a nanodiamond containing silicon-vacancy centers, which are accurately positioned using two different nanopositioning methods. Both of these back-excited devices display front collection efficiencies of ∼70% at NAs as low as 0.5. The combination of back-excitation with forward directionality enables direct coupling of the emitted photons into a proximal optical fiber without any coupling optics, thereby facilitating and simplifying future integration.

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.

Self-Assembled and Wavelength-Tunable Quantum Dot Whispering-Gallery-Mode Lasers for Backlight Displays.

Thanks to the narrow line width and high brightness, colloidal quantum dot (CQD) lasers show promising applications in next-generation displays. However, CQD laser-based displays have yet to be demonstrated because of two challenges in integrating red, green, and blue (RGB) lasers: absorption from red CQDs deteriorates the optical gain of blue and green CQDs, and imbalanced white spectra lack blue lasing due to the high lasing threshold of blue CQDs. Herein, we introduce a facile surfactant-free self-assembly method to assemble RGB CQDs into high-quality whispering-gallery-mode (WGM) RGB lasers with close lasing thresholds among them. Moreover, these RGB lasers can lase nearly independently even when they are closely integrated, and they can construct an ultrawide color space whose color gamut is 105% of that of the BT.2020 standard. These combined strategies allow us to demonstrate the first full-color liquid crystal displays using CQD lasers as the backlight source.

Slow Auger Recombination in Ag2Se Colloidal Quantum Dots.

Efficient Auger recombination (AR) presents a significant challenge for the advancement of colloidal quantum dot (QD)-based devices involving multiexcitons. Here, the AR dynamics of near-infrared Ag2Se QDs were studied through transient absorption experiments. As the QD radius increases from 0.9 to 2.5 nm, the biexciton lifetime (τ2) of Ag2Se QDs increases from 35 to 736 ps, which is approximately 10 times longer than that of comparable-sized CdSe and PbSe QDs. A qualitative analysis based on observables indicates that the slow Auger rate is primarily attributed to the low density of the final states. The biexciton lifetime and triexciton lifetime (τ3) of Ag2Se QDs follow R3 and R2.6 dependence, respectively. Moreover, the ratio of τ2/τ3 is ∼2.3-3.2, which is markedly lower than the value expected from statistical scaling (4.5). These findings suggest that environmentally friendly Ag2Se QDs can serve as excellent candidates for low-threshold lasers and third-generation photovoltaics utilizing carrier multiplication.

Infrared HOT Photodetectors: Status and Outlook.

At the current stage of long-wavelength infrared (LWIR) detector technology development, the only commercially available detectors that operate at room temperature are thermal detectors. However, the efficiency of thermal detectors is modest: they exhibit a slow response time and are not very useful for multispectral detection. On the other hand, in order to reach better performance (higher detectivity, better response speed, and multispectral response), infrared (IR) photon detectors are used, requiring cryogenic cooling. This is a major obstacle to the wider use of IR technology. For this reason, significant efforts have been taken to increase the operating temperature, such as size, weight and power consumption (SWaP) reductions, resulting in lower IR system costs. Currently, efforts are aimed at developing photon-based infrared detectors, with performance being limited by background radiation noise. These requirements are formalized in the Law 19 standard for P-i-N HgCdTe photodiodes. In addition to typical semiconductor materials such as HgCdTe and type-II AIIIBV superlattices, new generations of materials (two-dimensional (2D) materials and colloidal quantum dots (CQDs)) distinguished by the physical properties required for infrared detection are being considered for future high-operating-temperature (HOT) IR devices. Based on the dark current density, responsivity and detectivity considerations, an attempt is made to determine the development of a next-gen IR photodetector in the near future.

Extended Short-Wavelength Infrared Photoluminescence and Photocurrent of Nonstoichiometric Silver Telluride Colloidal Nanocrystals.

Demands on nontoxic nanomaterials in the short-wavelength infrared (SWIR) have rapidly grown over the past decade. Here, we present the nonstoichiometric silver chalcogenide nanocrystals of AgxTe (x > 2) and Ag2Te/Ag2S CQDs with a tunable bandgap across the SWIR region. When the atomic percent of the metal and chalcogenide elements are varied, the emission frequency of the excitonic peak is successfully extended to 2.7 µm. Surprisingly, the AgxTe CQD film responds to the SWIR light with a responsivity of 2.1 A/W at 78 K. Also, the Ag2S shell growth over the Ag2Te core enhances not only the emission intensity but also the structural rigidity, preventing crystal morphology deformation under the electron beam. The origin of the enhancement in the emission intensity and air stability of AgxTe and Ag2Te/Ag2S CQDs is carefully investigated by X-ray photoelectron spectroscopy (XPS). The optical properties and infrared photocurrent of AgxTe CQDs will provide new opportunities for solution-based SWIR applications.

Enhancement of the Modulation Response of Quantum-Dot-Based Down-Converted Light through Surface Plasmon Coupling.

In this paper, we first elaborate on the effects of surface plasmon (SP) coupling on the modulation responses of the emission of a light-emitting diode (LED) and its down-converted lights through colloidal quantum dots (QDs). The results of our past efforts for this subject are briefly discussed. The discussions lay the foundation for the presentation of the new experimental data of such down-converted lights in this paper. In particular, the enhancement of the modulation bandwidth (MB) of a QD-based converted light through SP coupling is demonstrated. By linking green-emitting QDs (GQDs) and/or red-emitting QDs (RQDs) with synthesized Ag nano-plates via surface modifications and placing them on a blue-emitting LED, the MBs of the converted green and red emissions are significantly increased through the induced SP coupling of the Ag nano-plates. When both GQD and RQD exist and are closely spaced in a sample, the energy transfer processes of emission-reabsorption and Förster resonance energy transfer from GQD into RQD occur, leading to the increase (decrease) in the MB of green (red) light. With SP coupling, the MB of a mixed light is significantly enhanced.

Compact Quantum-Dot Microbeads with Sub-Nanometer Emission Linewidth.

Fluorescent microbeads are widely used for applications in life sciences and medical diagnosis. The spectral contrast and sharpness of photoluminescence are critical in the utilities of microbeads for imaging and multiplexing. Here, we demonstrate microbeads capable of generating single-peak laser emission with a sub-nanometer linewidth. The microbeads are made of quantum dots that are tightly packed and crosslinked via ligand exchange for high optical gain and refractive index as well as material stability. Bright single-mode lasing with no photobleaching is achieved with particle diameters as small as 1.5 µm in the air. Sub-nm lasing emission is maintained even inside high-index surroundings, such as organic solvents and biological tissues. Feasibility of intracellular tagging and multi-color imaging in vivo is demonstrated.

Hybrid cube-in-cup nanoantenna: towards ordered photonics.

The most significant goal of nanophotonics is the development of high-speed quantum emitting devices operating at ambient temperature. In this regard, plasmonic nanoparticles-on-mirror are potential candidates for designing high-speed photon sources. We introduce a novel hybrid nanoantenna (HNA) with CdSe/CdS colloidal quantum dots (QDs) based on a silver nanocube in a metal cup that presents a nanoparticle-in-cavity coupled with an emitters system. We use focused ion beam nanolithography to fabricate an ordered array of cups, which were then filled with colloidal nanoparticles using the most simple drop-casting and spin coating methods. The spectral and time-resolved studies of the samples with one or more nanocubes in the cup reveal a significant change in the radiation characteristics of QDs inside the nanoantenna. The Purcell effect causes an increase in the fluorescence decay rate (≥30) and an increase in the fluorescence intensity (≥3) of emitters in the HNA. Using the finite element method simulations, we have discovered that the proximity of the cups wall affects the oscillation modes of the gap plasmon, which, in turn, leads to changes in the electric field enhancement inside the nanoantenna gap. Additionally, substantial variations in the behavior of the gap plasmons at different polarizations of the exciting radiation have been revealed. The proposed nanoantenna can be useful in the development of plasmonic sensors, display pixels, and single-photon sources.

Reversible Charge-Carrier Trapping Slows Förster Energy Transfer in CdSe/CdS Quantum-Dot Solids.

The dynamics of photoluminescence (PL) from nanocrystal quantum dots (QDs) is significantly affected by the reversible trapping of photoexcited charge carriers. This process occurs after up to 50% of the absorption events, depending on the type of QD considered, and can extend the time between the photoexcitation and relaxation of the QD by orders of magnitude. Although many optoelectronic applications require QDs assembled into a QD solid, until now, reversible trapping has been studied only in (ensembles of) spatially separated QDs. Here, we study the influence of reversible trapping on the excited-state dynamics of CdSe/CdS core/shell QDs when they are assembled into close-packed "supraparticles". Time- and spectrally resolved photoluminescence (PL) measurements reveal competition among spontaneous emission, reversible charge-carrier trapping, and Förster resonance energy transfer between the QDs. While Förster transfer causes the PL to red-shift over the first 20-50 ns after excitation, reversible trapping stops and even reverses this trend at later times. We can model this behavior with a simple kinetic Monte Carlo simulation by considering that charge-carrier trapping leaves the QDs in a state with zero oscillator strength in which no energy transfer can occur. Our results highlight that reversible trapping significantly affects the energy and charge-carrier dynamics for applications in which QDs are assembled into a QD solid.

Effects of Direct Solvent-Quantum Dot Interaction on the Optical Properties of Colloidal Monolayer WS2 Quantum Dots.

Because of the absence of native dangling bonds on the surface of the layered transition metal dichalcogenides (TMDCs), the surface of colloidal quantum dots (QDs) of TMDCs is exposed directly to the solvent environment. Therefore, the optical and electronic properties of TMDCS QDs are expected to have stronger influence from the solvent than usual surface-passivated QDs due to more direct solvent-QD interaction. Study of such solvent effect has been difficult in colloidal QDs of TMDC due to the large spectroscopic heterogeneity resulting from the heterogeneity of the lateral size or (and) thickness in ensemble. Here, we developed a new synthesis procedure producing the highly uniform colloidal monolayer WS2 QDs exhibiting well-defined photoluminescence (PL) spectrum free from ensemble heterogeneity. Using these newly synthesized monolayer WS2 QDs, we observed the strong influence of the aromatic solvents on the PL energy and intensity of monolayer WS2 QD beyond the simple dielectric screening effect, which is considered to result from the direct electronic interaction between the valence band of the QDs and molecular orbital of the solvent. We also observed the large effect of stacking/separation equilibrium on the PL spectrum dictated by the balance between inter QD and QD-solvent interactions. The new capability to probe the effect of the solvent molecules on the optical properties of colloidal TMDC QDs will be valuable for their applications in various liquid surrounding environments.

Current-Induced Magnetic Polarons in a Colloidal Quantum-Dot Device.

Electrical spin manipulation remains a central challenge for the realization of diverse spin-based information processing technologies. Motivated by the demonstration of confinement-enhanced sp-d exchange interactions in colloidal diluted magnetic semiconductor (DMS) quantum dots (QDs), such materials are considered promising candidates for future spintronic or spin-photonic applications. Despite intense research into DMS QDs, electrical control of their magnetic and magneto-optical properties remains a daunting goal. Here, we report the first demonstration of electrically induced magnetic polaron formation in any DMS, achieved by embedding Mn2+-doped CdSe/CdS core/shell QDs as the active layer in an electrical light-emitting device. Tracing the electroluminescence from cryogenic to room temperatures reveals an anomalous energy shift that reflects current-induced magnetization of the Mn2+ spin sublattice, that is, excitonic magnetic polaron formation. These electrically induced magnetic polarons exhibit an energy gain comparable to their optically excited counterparts, demonstrating that magnetic polaron formation is achievable by current injection in a solid-state device.

Infrared Photodetection Based on Colloidal Quantum-Dot Films with High Mobility and Optical Absorption up to THz.

Infrared thermal imaging devices rely on narrow band gap semiconductors grown by physical methods such as molecular beam epitaxy and chemical vapor deposition. These technologies are expensive, and infrared detectors remain limited to defense and scientific applications. Colloidal quantum dots (QDs) offer a low cost alternative to infrared detector by combining inexpensive synthesis and an ease of processing, but their performances are so far limited, in terms of both wavelength and sensitivity. Herein we propose a new generation of colloidal QD-based photodetectors, which demonstrate detectivity improved by 2 orders of magnitude, and optical absorption that can be continuously tuned between 3 and 20 µm. These photodetectors are based on the novel synthesis of n-doped HgSe colloidal QDs whose size can be tuned continuously between 5 and 40 nm, and on their assembly into solid nanocrystal films with mobilities that can reach up to 100 cm(2) V(-1) s(-1). These devices can be operated at room temperature with the same level of performance as the previous generation of devices when operated at liquid nitrogen temperature. HgSe QDs can be synthesized in large scale (>10 g per batch), and we show that HgSe films can be processed to form a large scale array of pixels. Taken together, these results pave the way for the development of the next generation mid- and far-infrared low-cost detectors and camera.

Delayed Exciton Emission and Its Relation to Blinking in CdSe Quantum Dots.

The efficiency and stability of emission from semiconductor nanocrystal quantum dots (QDs) is negatively affected by "blinking" on the single-nanocrystal level, that is, random alternation of bright and dark periods. The time scales of these fluctuations can be as long as many seconds, orders of magnitude longer than typical lifetimes of exciton states in QDs. In this work, we investigate photoluminescence from QDs delayed over microseconds to milliseconds. Our results prove the existence of long-lived charge-separated states in QDs. We study the properties of delayed emission as a direct way to learn about charge carrier separation and recovery of the exciton state. A new microscopic model is developed to connect delayed emission to exciton recombination and blinking from which we conclude that bright periods in blinking are in fact not characterized by uninterrupted optical cycling as often assumed.

Dynamic Charge Carrier Trapping in Quantum Dot Field Effect Transistors.

Noncrystalline semiconductor materials often exhibit hysteresis in charge transport measurements whose mechanism is largely unknown. Here we study the dynamics of charge injection and transport in PbS quantum dot (QD) monolayers in a field effect transistor (FET). Using Kelvin probe force microscopy, we measured the temporal response of the QDs as the channel material in a FET following step function changes of gate bias. The measurements reveal an exponential decay of mobile carrier density with time constants of 3-5 s for holes and ∼10 s for electrons. An Ohmic behavior, with uniform carrier density, was observed along the channel during the injection and transport processes. These slow, uniform carrier trapping processes are reversible, with time constants that depend critically on the gas environment. We propose that the underlying mechanism is some reversible electrochemical process involving dissociation and diffusion of water and/or oxygen related species. These trapping processes are dynamically activated by the injected charges, in contrast with static electronic traps whose presence is independent of the charge state. Understanding and controlling these processes is important for improving the performance of electronic, optoelectronic, and memory devices based on disordered semiconductors.

Interface Engineering to Drive High-Performance MXene/PbS Quantum Dot NIR Photodiode.

The realization of a controllable transparent conducting system with selective light transparency is crucial for exploring many of the most intriguing effects in top-illuminated optoelectronic devices. However, the performance is limited by insufficient electrical conductivity, low work function, and vulnerable interface of traditional transparent conducting materials, such as tin-doped indium oxide. Here, it is reported that two-dimensional (2D) titanium carbide (Ti3 C2 Tx ) MXene film acts as an efficient transparent conducting electrode for the lead sulfide (PbS) colloidal quantum dots (CQDs) photodiode with controllable near infrared transmittance. The solution-processed interface engineering of MXene and PbS layers remarkably reduces the interface defects of MXene/PbS CQDs and the carrier concentration in the PbS layer. The stable Ti3 C2 Tx /PbS CQDs photodiodes give rise to a high specific detectivity of 5.51 × 1012  cm W-1  Hz1/2 , a large dynamic response range of 140 dB, and a large bandwidth of 0.76 MHz at 940 nm in the self-powered state, ranking among the most exceptional in terms of comprehensive performance among reported PbS CQDs photodiodes. In contrast with the traditional photodiode technologies, this efficient and stable approach opens a new horizon to construct widely used infrared photodiodes with CQDs and MXenes.

Revealing oxygen effect on efficiency and stability of quantum dot photovoltaics.

Colloidal quantum dot solar cells (CQDSCs) have received great attention in the development of scalable and stable photovoltaic devices. Despite the high power-conversion-efficiency (PCE) reported, stability investigations are still limited and the exact degradation mechanisms of CQDSCs remain unclear under different atmosphere conditions. In this study, the atmospheric influence on the ZnO electron transport layer material (ETL), halide-passivated lead sulfide CQDs (PbS-PbI2) photoactive layer material and 1,2-ethanedithiol-PbS CQDs (PbS-EDT) hole transport material on device stability in PbS CQDSCs is investigated. It was found that O2 had negligible influence on PbS-PbI2, but it did induce the increase in work function of ZnO ETL and PbS-EDT layers. Notably, the increase of the ZnO work function (WFZnO) induces the formation of interface barrier between ZnO and PbS-PbI2, leading to a deterioration in device efficiency. By further replacing ZnO ETL with SnO2, a multi-interface collaborative CQDSC was constructed to realize the PCE with high stability. This study identifies the efficiency evolution that is inherent in CQDSCs under different atmospheric conditions.

Field Manipulations in On-Chip Micro/Nanoscale Lasers Based on Colloid Nanocrystals.

Owning to merits such as bandgap tunability, solution processability, large absorption coefficients, and high photoluminescence quantum yields, colloidal quantum dots (CQDs) emerged as a promising gain material to make on-chip micro/nanoscale lasers with high silicon compatibility. In this paper, we review the recent progress in CQD on-chip micro/nanoscale lasers, with a special focus on the physical properties achieved through field manipulation schemes in different types of cavities. Key aspects include manipulating and engineering wavelength, polarization, and direction as well as coupling and light extraction. Finally, we give our prospects for future research directions toward the integration of robust CQD nano/microscale lasers with photonic integrated circuits.

Flexible Amperometric Immunosensor Based on Colloidal Quantum Dots for Detecting the Myeloperoxidase (MPO) Systemic Inflammation Biomarker.

Myeloperoxidase (MPO) has been demonstrated to be a biomarker of neutrophilic inflammation in various diseases. Rapid detection and quantitative analysis of MPO are of great significance for human health. Herein, an MPO protein flexible amperometric immunosensor based on a colloidal quantum dot (CQD)-modified electrode was demonstrated. The remarkable surface activity of CQDs allows them to bind directly and stably to the surface of proteins and to convert antigen-antibody specific binding reactions into significant currents. The flexible amperometric immunosensor provides quantitative analysis of MPO protein with an ultra-low limit of detection (LOD) (31.6 fg mL-1), as well as good reproducibility and stability. The detection method is expected to be applied in clinical examination, POCT (bedside test), community physical examination, home self-examination and other practical scenarios.

High-Performance Colloidal Quantum Dot Photodiodes via Suppressing Interface Defects.

PbS colloidal quantum dot (CQD) infrared photodiodes have attracted wide attention due to the prospect of developing cost-effective infrared imaging technology. Presently, ZnO films are widely used as the electron transport layer (ETL) of PbS CQDs infrared photodiodes. However, ZnO-based devices still suffer from the problems of large dark current and low repeatability, which are caused by the low crystallinity and sensitive surface of ZnO films. Here, we effectively optimized the device performance of PbS CQDs infrared photodiode via diminishing the influence of adsorbed H2O at the ZnO/PbS CQDs interface. The polar (002) ZnO crystal plane showed much higher adsorption energy of H2O molecules compared with other nonpolar planes, which could reduce the interface defects induced by detrimentally adsorbed H2O. Based on the sputtering method, we obtained the [002]-oriented and high-crystallinity ZnO ETL and effectively suppressed the adsorption of detrimental H2O molecules. The prepared PbS CQDs infrared photodiode with the sputtered ZnO ETL demonstrated lower dark current density, higher external quantum efficiency, and faster photoresponse compared with the sol-gel ZnO device. Simulation results further unveiled the relationship between interface defects and device dark current. Finally, a high-performance sputtered ZnO/PbS CQDs device was obtained with a specific detectivity of 2.15 × 1012 Jones at -3 dB bandwidth (94.6 kHz).