Stability of Quantum Dots,Quantum Dot Films,and Quantum Dot Light‐Emitting Diodes for Display Applications

Quantum dots (QDs) are being highlighted in display applications for their excellent optical properties, including tunable bandgaps, narrow emission bandwidth, and high efficiency. However, issues with their stability must be overcome to achieve the next level of development. QDs are utilized in display applications for their photoluminescence (PL) and electroluminescence. The PL characteristics of QDs are applied to display or lighting applications in the form of color‐conversion QD films, and the electroluminescence of QDs is utilized in quantum dot light‐emitting diodes (QLEDs). Studies on the stability of QDs and QD devices in display applications are reviewed herein. QDs can be degraded by oxygen, water, thermal heating, and UV exposure. Various approaches have been developed to protect QDs from degradation by controlling the composition of their shells and ligands. Phosphorescent QDs have been protected by bulky ligands, physical incorporation in polymer matrices, and covalent bonding with polymer matrices. The stability of electroluminescent QLEDs can be enhanced by using inorganic charge transport layers and by improving charge balance. As understanding of the degradation mechanisms of QDs increases and more stable QDs and display devices are developed, QDs are expected to play critical roles in advanced display applications.     

Tailoring the Heterostructure of Colloidal Quantum Dots for Ratiometric Optical Nanothermometry

Colloidal quantum dots (QDs) are a fascinating class of semiconducting nanocrystals, thanks to their optical properties tunable through size and composition, and simple synthesis methods. Recently, colloidal double‐emission QDs have been successfully applied as competitive optical temperature sensors, since they exhibit structure‐tunable double emission, temperature‐dependent photoluminescence, high quantum yield, and excellent photostability. Until now, QDs have been used as nanothermometers for in vivo biological thermal imaging, and thermal mapping in complex environments at the sub‐microscale to nanoscale range. In this Review, recent progress for QD‐based nanothermometers is highlighted and perspectives for future work are described.     

Temperature‐Dependent Exciton and Trap‐Related Photoluminescence of CdTe Quantum Dots Embedded in a NaCl Matrix: Implication in Thermometry

Temperature‐dependent optical studies of semiconductor quantum dots (QDs) are fundamentally important for a variety of sensing and imaging applications. The steady‐state and time‐resolved photoluminescence properties of CdTe QDs in the size range from 2.3 to 3.1 nm embedded into a protective matrix of NaCl are studied as a function of temperature from 80 to 360 K. The temperature coefficient is found to be strongly dependent on QD size, with the highest sensitivity obtained for the smallest size of QDs. The emission from solid‐state CdTe QD‐based powders is maintained with high color purity over a wide range of temperatures. Photoluminescence lifetime data suggest that temperature dependence of the intrinsic radiative lifetime in CdTe QDs is rather weak, and it is mostly the temperature‐dependent nonradiative decay of CdTe QDs which is responsible for the thermal quenching of photoluminescence intensity. By virtue of the temperature‐dependent photoluminescence behavior, high color purity, photostability, and high photoluminescence quantum yield (26%–37% in the solid state), CdTe QDs embedded in NaCl matrices are useful solid‐state probes for thermal imaging and sensing over a wide range of temperatures within a number of detection schemes and outstanding sensitivity, such as luminescence thermochromic imaging, ratiometric luminescence, and luminescence lifetime thermal sensing.     

Site‐Controlled InGaAs Quantum Dots with Tunable Emission Energy

Semiconductor quantum‐dot (QD) systems offering perfect site control and tunable emission energy are essential for numerous nanophotonic device applications involving spatial and spectral matching of dots with optical cavities. Herein, the properties of ordered InGaAs/GaAs QDs grown by organometallic chemical vapor deposition on substrates patterned with pyramidal recesses are reported. The seeded growth of a single QD inside each pyramid results in near‐perfect (<10 nm) control of the QD position. Moreover, efficient and uniform photoluminescence (inhomogeneous broadening <10 meV) is observed from ordered arrays of such dots. The QD emission energy can be finely tuned by varying 1) the pyramid size and 2) its position within specific patterns. This tunability is brought about by the patterning of both the chemical properties and the surface curvature features of the substrate, which allows local control of the adatom fluxes that determine the QD thickness and composition.     

Electrically Pumped White‐Light‐Emitting Diodes Based on Histidine‐Doped MoS2 Quantum Dots

MoS₂ quantum dots (QDs)‐based white‐light‐emitting diodes (QD‐WLEDs) are designed, fabricated, and demonstrated. The highly luminescent, histidine‐doped MoS₂ QDs synthesized by microwave induced fragmentation of 2D MoS₂ nanoflakes possess a wide distribution of available electronic states as inferred from the pronounced excitation‐wavelength‐dependent emission properties. Notably, the histidine‐doped MoS₂ QDs show a very strong emission intensity, which exceeds seven times of magnitude larger than that of pristine MoS₂ QDs. The strongly enhanced emission is mainly attributed to nitrogen acceptor bound excitons and passivation of defects by histidine‐doping, which can enhance the radiative recombination drastically. The enabled electroluminescence (EL) spectra of the QD‐WLEDs with the main peak around 500 nm are found to be consistent with the photoluminescence spectra of the histidine‐doped MoS₂ QDs. The enhanced intensity of EL spectra with the current increase shows the stability of histidine‐doped MoS₂ based QD‐WLEDs. The typical EL spectrum of the novel QD‐WLEDs has a Commission Internationale de l'Eclairage chromaticity coordinate of (0.30, 0.36) exhibiting an intrinsic broadband white‐light emission. The unprecedented and low‐toxicity QD‐WLEDs based on a single light‐emitting material can serve as an excellent alternative for using transition metal dichalcogenides QDs as next generation optoelectronic devices.     

Enhanced radiative efficiency in GaN quantum dots grown by molecular beam epitaxy

Self-assembled GaN quantum dots (QDs), grown on AlN by molecular beam epitaxy, were investigated by time-resolved photoluminescence spectroscopy. We investigate the emission mechanism in GaN QDs by comparing the carrier recombination dynamics in single and multiple period QDs. At 100 K, the PL decay time in single period QD structures is considerably shorter than in stacked QDs. Compared to single period QDs, the room temperature PL efficiency is considerably enhanced in 20 period QDs due to the reduction in nonradiative recombination processes.     

Photostability of quantum dots with amphiphilic polymer-based passivation strategies

Quantum dots (QDs) have many appealing properties for biological fluorescence imaging, but exhibit photostabilities that are dependent upon surface passivation to minimize susceptibility to oxygen and light. Here, through spectroscopy and imaging techniques, we compare the photostability of micelle-encapsulated QDs with QDs passivated with either crosslinked amphiphilic polymers or crosslink-free amphiphilic polymers. Both crosslinked and crosslink-free amphiphilic polymer passivation strategies produced QDs with high photoluminescence stability for exposure to light under ambient conditions. In contrast, micelle encapsulation resulted in QDs with photoluminescence emission levels that were highly sensitive to both light exposure and oxygen, exhibiting a reduction of up to 70% in photoluminescence intensity within twenty minutes of exposure. With the addition of reducing agents, the photoluminescence level of the micelle-encapsulated QDs was significantly stabilized. We conclude that amphiphilic polymers provide coatings with considerably higher integrity and stability than micelle encapsulation, reducing the QDs' sensitivities to oxygen and light, both of which are relevant factors in biological imaging applications.     

Structural,optical and morphological studies of undoped and Zn-doped CdSe QDs via aqueous route synthesis

Undoped and Zn-doped CdSe quantum dots (QDs) were successfully synthesized by the chemical precipitation method. The structural, optical and morphological properties of the synthesized undoped and Zn-doped CdSe QDs were studied by X-ray diffraction (XRD), UV–visible absorption spectroscopy, photoluminescence (PL) spectroscopy, fluorescence lifetime spectroscopy, scanning electron microscopy (SEM), field emission transmission electron microscopy (FE-TEM) and FTIR. The synthesized undoped and Zn-doped CdSe QDs were in cubic crystalline phase, which was confirmed by the XRD technique. From the UV–visible absorption spectral analysis, the absorption wavelengths of both undoped and Zn-doped CdSe QDs show blue-shift with respect to their bulk counterpart as a result of quantum confinement effect. The highest luminescence intensity was observed for CdSe QDs doped with 4% Zn by PL studies. TEM analysis shows that the prepared QDs are spherical in shape.     

Synergistic effects of SPR and FRET on the photoluminescence of ZnO nanorod heterostructures

Solution-grown ZnO nanorods (NRs) were successfully conjugated with CdSe/ZnS quantum dots (QDs) and Ag nanoparticles (NPs) to suppress intrinsic defect emission and to enhance band-edge emission at the same time. First, high-density and high-crystallinity ZnO NRs of diameter 80–90 nm and length 1.2–1.5 μm were grown on glass substrates using a low-temperature seed-assisted solution method. The as-synthesized ZnO NRs showed sharp photoluminescence (PL) band-edge emission centered at ～377 nm together with broad defect emission in the range of ～450–800 nm. The ZnO NRs were decorated with CdSe/ZnS QDs and Ag NPs, respectively, by sequential drop-coating. The PL of CdSe/ZnS QD||ZnO NR conjugates showed that ZnO band-edge emission decreased by 73.8% due to fluorescence resonance energy transfer (FRET) and charge separation between ZnO and CdSe/ZnS by type II energy band structure formation. On the other hand, Ag NP||CdSe/ZnS QD||ZnO NR conjugates showed increased band-edge emission (by 25.8%) and suppressed defect emission compared to bare ZnO NRs. A possible energy transfer mechanism to explain the improved PL properties of ZnO NRs was proposed based upon the combined effects of FRET and surface plasmon resonance (SPR).     

Zinc Thiolate Enables Bright Cu‐Deficient Cu‐In‐S/ZnS Quantum Dots

Copper indium sulfide (CIS) colloidal quantum dots (QDs) are a promising candidate for commercially viable QD‐based optical applications, for example as colloidal photocatalysts or in luminescent solar concentrators (LSCs). CIS QDs with good photoluminescence quantum yields (PLQYs) and tunable emission wavelength via size and composition control are previously reported. However, developing an understanding and control over the growth of electronically passivating inorganic shells would enable further improvements of the photophysical properties of CIS QDs. To improve the optical properties of CIS QDs, the focus is on the growth of inorganic shells via the popular metal‐carboxylate/alkane thiol decomposition reaction. 1) The role of Zn‐carboxylate and Zn‐thiolate on the formation of ZnS shells on Cu‐deficient CIS (CDCIS) QDs is studied, 2) this knowledge is leveraged to yield >90% PLQY CDCIS/ZnS core/shell QDs, and 3) a mechanism for ZnS shells grown from zinc‐carboxylate/alkane thiol decomposition is proposed.     

Direct spectroscopic evidence for the formation of one-dimensional wetting wires during the growth of InGaAs/GaAs quantum dot chains

We report direct spectroscopic evidence for the formation of one-dimensional (1D) wetting wires (WWs) during the Stransky-Krastanov growth of InGaAs/GaAs quantum dot (QD) chains. The wire-like nature of these 1D WWs was demonstrated by their 1D density of states and absorption anisotropies from the photoluminescence excitation measurements. Two groups of QDs were found sitting on top of these 1D WWs and the traditional two-dimensional wetting layers, respectively, with size-dependent emission polarization anisotropies of ca. 6-25% because of their elongated shapes.     

Composition of self-assembled quantum dots

Abstract

Semiconductor quantum dot (QD) nanostructures have attracted increased interest in recent years because of their electronic and optical properties. A common way to make QDs is to grow a thin layer of material on a substrate with a different lattice constant. The strain between the layers induces the formation of three-dimensional islands. The electronic properties of the islands are mainly determined by their size, shape and composition. While the size and shape of QDs have been the focus of many studies, only recently has their composition been investigated. Experimental studies of the composition of QDs are reviewed and compared with the available theoretical models of QD growth. It is found that no model in the literature can satisfactorily predict QD size, shape and composition. Experimental results from studies of QDs grown under similar conditions vary substantially. Most authors, however, agree that the average composition of the QDs is different from the nominal composition of the deposited material. The composition is also found to vary from top to bottom of the QDs, which is found to have a significant influence on the electronic properties.     

Colloidal silicon quantum dots: synthesis and luminescence tuning from the near-UV to the near-IR range

This review describes a series of representative synthesis processes, which have been developed in the last two decades to prepare silicon quantum dots (QDs). The methods include both top-down and bottom-up approaches, and their methodological advantages and disadvantages are presented. Considerable efforts in surface functionalization of QDs have categorized it into (i) a two-step process and (ii) in situ surface derivatization. Photophysical properties of QDs are summarized to highlight the continuous tuning of photoluminescence color from the near-UV through visible to the near-IR range. The emission features strongly depend on the silicon nanostructures including QD surface configurations. Possible mechanisms of photoluminescence have been summarized to ascertain the future challenges toward industrial use of silicon-based light emitters.     

On the quenching of semiconductor quantum dot photoluminescence by proximal gold nanoparticles

Luminescent quantum dots (QDs) were proven to be very effective fluorescence resonance energy transfer donors with an array of organic dye acceptors, and several fluorescence resonance energy transfer based biosensing assemblies utilizing QDs have been demonstrated in the past few years. Conversely, gold nanoparticles (Au-NPs) are known for their capacity to induce strong fluorescence quenching of conventional dye donors. Using a rigid variable-length polypeptide as a bifunctional biological linker, we monitor the photoluminescence quenching of CdSe-ZnS QDs by Au-NP acceptors arrayed around the QD surface, where the center-to-center separation distance was varied over a broad range of values (approximately 50-200 Angstrom). We measure the Au-NP-induced quenching rates for such QD conjugates using steady-state and time-resolved fluorescence measurements and examine the results within the context of theoretical treatments based on the F?rster dipole-dipole resonance energy transfer, dipole-metal particle energy transfer, and nanosurface energy transfer. Our results indicate that nonradiative quenching of the QD emission by proximal Au-NPs is due to long-distance dipole-metal interactions that extend significantly beyond the classical F?rster range, in agreement with previous studies using organic dye-Au-NP donor-acceptor pairs.     

Perovskite Quantum Dots with Near Unity Solution and Neat‐Film Photoluminescent Quantum Yield by Novel Spray Synthesis

In this study, a novel perovskite quantum dot (QD) spray‐synthesis method is developed by combining traditional perovskite QD synthesis with the technique of spray pyrolysis. By utilizing this new technique, the synthesis of cubic‐shaped perovskite QDs with a homogeneous size of 14 nm is demonstrated, which shows an unprecedented stable absolute photoluminescence quantum yield ≈100% in the solution and even in the solid‐state neat film. The highly emissive thin films are integrated with light emission devices (LEDs) and organic light emission displays (OLEDs). The color conversion type QD‐LED (ccQD‐LED) hybrid devices exhibit an extremely saturated green emission, excellent external quantum efficiency of 28.1%, power efficiency of 121 lm W^?1, and extraordinary forward‐direction luminescence of 8 500 000 cd m^?2. The conceptual ccQD‐OLED hybrid display also successfully demonstrates high‐definition still images and moving pictures with a 119% National Television System Committee 1931 color gamut and 123% Digital Cinema Initiatives‐P3 color gamut. These very‐stable, ultra‐bright perovskite QDs have the properties necessary for a variety of useful applications in optoelectronics.     

NIR‐Emitting Quantum Dot‐Encoded Microbeads through Membrane Emulsification for Multiplexed Immunoassays

NIR‐emitting CdSeTe/CdS/ZnS core/shell/shell QD‐encoded microbeads are combined with common flow cytometry with one laser for multiplexed detection of hepatitis B virus (HBV). A facile one‐pot synthetic route is developed to prepare CdSeTe/CdS/ZnS core/shell/shell QDs with high photoluminescence quantum yield and excellent stability in liquid paraffin, and a Shirasu porous glass (SPG) membrane emulsification technique is applied to incorporate the QDs into polystyrene–maleic anhydride (PSMA) microbeads to obtain highly fluorescent QD‐encoded microbeads. The relatively wide NIR photoluminescence full width half maximum of the CdSeTe/CdS/ZnS QDs is used to develop a ‘single wavelength’ encoding method to obtain different optical codes by changing the wavelengh and emission intensity of the QDs incorporated into the microbeads. Moreover, a detection platform combining NIR‐emitting CdSeTe/CdS/ZnS QD‐encoded microbeads and Beckman Coulter FC 500 flow cytometry with one laser of 488 nm is successfully used to conduct a 2‐plex hybridization assay for hepatitis B surface antigen (HBsAg), hepatitis B e antigen (HBeAg), and a 3‐plex hybridization assay for hepatitis B surface antibody (HBsAb), hepatitis B e antibody (HBeAb), and hepatitis B core antibody (HBcAb), which suggests the promising application of NIR QD‐encoded microbeads for multiplex immunoassays.     

Emission properties of colloidal quantum dots on polyelectrolyte multilayers

We present steady state and time-resolved photoluminescence (PL) characteristics of differently charged CdTe quantum dots (QDs) adsorbed onto a polyelectrolyte (PE) multilayer. The PE multilayer is built up using a layer-by-layer assembly technique. We find that the diffusion of the QDs into the PE multilayer is an important factor in the case of 3-mercapto-1, 2-propanediol stabilized QDs (neutral surface charge), resulting in a ～31-fold enhancement in PL intensity accompanied by a blue shift in the PL spectra and an increase in decay lifetime from 3.74?ns to a maximum of 11.65?ns. These modified emission properties are attributed to the enhanced surface related emission resulting from the interaction of the QD's surface with the PE. We find that diffusion does not occur for thioglycolic acid (TGA) stabilized QDs (negative surface charge) or 2-mercaptoethylamine stabilized QDs (positive surface charge), indicating localization of the QDs on top of the PE multilayer. However, the PL lifetime of the TGA stabilized QDs decreases from 9.58 to 5.78?ns with increasing PE multilayer thickness. This provides evidence for increased intrinsic exciton recombination relative to surface related emission, which results in an overall reduction in the average lifetime. Our studies indicate the importance of the QD surface charge in determining the interaction with the PE multilayers and the subsequent modification of the QD emission properties.     

Quantum dot/plasmonic nanoparticle metachromophores with quantum yields that vary with excitation wavelength

Coupled plasmonic/chromophore systems are of interest in applications ranging from fluorescent biosensors to solar photovoltaics and photoelectrochemical cells because near-field coupling to metal nanostructures can dramatically alter the optical performance of nearby materials. We show that CdSe quantum dots (QDs) near single silver nanoprisms can exhibit photoluminescence lifetimes and quantum yields that depend on the excitation wavelength, in apparent violation of the Kasha-Vavilov rule. We attribute the variation in QD lifetime with excitation wavelength to the wavelength-dependent coupling of higher-order plasmon modes to different spatial subpopulations of nearby QDs. At the QD emission wavelength, these subpopulations are coupled to far-field radiation with varying efficiency by the nanoprism dipolar resonance. These results offer an easily accessible new route to design metachromophores with tailored optical properties.     

Bismuth surfactant mediated growth of InAs quantum dots by molecular beam epitaxy

This paper explores the significance of using bismuth as a surfactant during the molecular beam epitaxy growth of InAs quantum dots (QDs). The results show that Bi-mediated growth provides a practical solution towards achieving lower density QDs with high optical quality. The InAs QDs grown using Bi as a surfactant exhibit a 50 % lower QD density, narrower QD size distribution, and a doubled photoluminescence peak intensity at 16 K compared to those grown without Bi.     

Morphology and energy transfer in PbS quantum dot arrays formed with supercritical fluid deposition

Lead sulfide (PbS) quantum dots (QDs) were synthesized in our lab with controllable and tunable sizes. Supercritical fluid CO₂ (sc-CO₂) provides a useful tool to deposit PbS QDs on substrate surfaces with lateral uniformity. Either in the PbS/toluene solution or in the sc-CO₂ fabricated film, the absorbance maxima of the PbS QDs do not show an obvious dependence on the PbS QD concentrations. Fluorescence spectra of PbS QDs obtained from the films prepared by the sc-CO₂ method indicate energy transfer between PbS QDs with different sizes, the small QDs serving as energy donors and large ones as acceptors. Samples formed with sc-CO₂ method measured by photoluminescence (PL) show a red-shift and an enhanced emission intensity with respect to samples formed with solution deposition method (SDM), specifically at cryogenic temperatures.