Origins of Low Quantum Efficiencies in Quantum Dot LEDs

The promise for next generation light‐emitting device (LED) technologies is a major driver for research on nanocrystal quantum dots (QDs). The low efficiencies of current QD‐LEDs are often attributed to luminescence quenching of charged QDs through Auger‐processes. Although new QD chemistries successfully suppress Auger recombination, high performance QD‐LEDs with these materials have yet to be demonstrated. Here, QD‐LED performance is shown to be significantly limited by the electric field. Experimental field‐dependent photoluminescence decay studies and tight‐binding simulations are used to show that independent of charging, the electric field can strongly quench the luminescence of QD solids by reducing the electron and hole wavefunction overlap, thereby lowering the radiative recombination rate. Quantifying this effect for a series of CdSe/CdS QD solids reveals a strong dependence on the QD band structure, which enables the outline of clear design strategies for QD materials and device architectures to improve QD‐LED performance.     

Rational Design of Colloidal Core/Shell Quantum Dots for Optoelectronic Applications

Colloidal core/shell quantum dots (QDs) are promising for solar technologies because of their excellent optoelectronic properties including tunable light absorption/emission spectra, high photoluminescence quantum yield (PLQY), suppressed Auger recombination, efficient charge separation/transfer, and outstanding photo-/thermal-/chemical stability. In this review, engineered core/shell QDs with various types of band structures and corresponding device performance in luminescent solar concentrators (LSCs), light-emitting diodes (LEDs), solar-driven photoelectrochemical (PEC) devices, and QDs-sensitized solar cells (QDSCs) are summarized. In particular, the applications of interfacial layer engineering and eco-friendly, heavy metal-free core/shell QDs in optoelectronic devices are highlighted. Finally, strategies towards the developments and practical perspectives of core/shell QDs are briefly mentioned to offer guidelines for achieving prospective high-efficiency and long-term stable QD devices.     

Light‐Emitting Electrochemical Cells Based on Color‐Tunable Inorganic Colloidal Quantum Dots

Large‐area, ultrathin light‐emitting devices currently inspire architects and interior and automotive designers all over the world. Light‐emitting electrochemical cells (LECs) and quantum dot light‐emitting diodes (QD‐LEDs) belong to the most promising next‐generation device concepts for future flexible and large‐area lighting technologies. Both concepts incorporate solution‐based fabrication techniques, which makes them attractive for low cost applications based on, for example, roll‐to‐roll fabrication or inkjet printing. However, both concepts have unique benefits that justify their appeal. LECs comprise ionic species in the active layer, which leads to the omission of additional organic charge injection and transport layers and reactive cathode materials, thus LECs impress with their simple device architecture. QD‐LEDs impress with purity and opulence of available colors: colloidal quantum dots (QDs) are semiconducting nanocrystals that show high yield light emission, which can be easily tuned over the whole visible spectrum by material composition and size. Emerging technologies that unite the potential of both concepts (LEC and QD‐LED) are covered, either by extending a typical LEC architecture with additional QDs, or by replacing the entire organic LEC emitter with QDs or perovskite nanocrystals, still keeping the easy LEC setup featured by the incorporation of mobile ions.     

Transparent InP Quantum Dot Light‐Emitting Diodes with ZrO2 Electron Transport Layer and Indium Zinc Oxide Top Electrode

Because of outstanding optical properties and non‐vacuum solution processability of colloidal quantum dot (QD) semiconductors, many researchers have developed various light emitting diodes (LEDs) using QD materials. Until now, the Cd‐based QD‐LEDs have shown excellent properties, but the eco‐friendly QD semiconductors have attracted many attentions due to the environmental regulation. And, since there are many issues about the reliability of conventional QD‐LEDs with organic charge transport layers, a stable charge transport layer in various conditions must be developed for this reason. This study proposes the organic/inorganic hybrid QD‐LEDs with Cd‐free InP QDs as light emitting layer and inorganic ZrO₂ nanoparticles as electron transport layer. The QD‐LED with bottom emission structure shows the luminescence of 530 cd m^?2 and the current efficiency of 1 cd/A. To realize the transparent QD‐LED display, the two‐step sputtering process of indium zinc oxide (IZO) top electrode is applied to the devices and this study could fabricate the transparent QD‐LED device with the transmittance of more than 74% for whole device array. And when the IZO top electrode with high work‐function is applied to top transparent anode, the device could maintain the current efficiency within the driving voltage range without well‐known roll‐off phenomenon in QD‐LED devices.     

Synergistic enhancement of charge generation and transfer in organic solar cells via a separate PbS quantum dot layer

The major impediment to the high photovoltaic performance of organic solar cells (OSCs) involves deficient photon harvesting and ineffective charge transfer from the photoactive layer to the electrodes. To improve these constraints, in this study, a new OSC device architecture is demonstrated by incorporating PbS colloidal quantum dots (QDs) between the organic photoactive layer and the top electrode. PbS QDs were spin-coated on top of an organic blend via a layer-by-layer deposition process, which formed a separate PbS QD layer with high density and uniformity. The PbS QD layer reinforced the optical property of the OSC by harvesting photons that were not absorbed by the underlying organic photoactive layer. In addition, the OSC employing the QD layer showed the enhanced charge transfer and suppressed recombination loss through the hybrid organic-inorganic interfacial contacts. Thus, a significant increase in the efficiency was achieved compared with the OSC with no PbS QD layer (10.12 vs 8.84%). Accompanied with the improved optoelectronic properties, a superior stability of the proposed architecture advances the practical viability of OSCs in various applications.     

Hybrid Perovskite Quantum Dot/Non-Fullerene Molecule Solar Cells with Efficiency Over 15%

Organic-inorganic hybrid film using conjugated materials and quantum dots (QDs) are of great interest for solution-processed optoelectronic devices, including photovoltaics (PVs). However, it is still challenging to fabricate conductive hybrid films to maximize their PV performance. Herein, for the first time, superior PV performance of hybrid solar cells consisting of CsPbI₃ perovskite QDs and Y6 series non-fullerene molecules is demonstrated and further highlights their importance on hybrid device design. In specific, a hybrid active layer is developed using CsPbI₃ QDs and non-fullerene molecules, enabling a type-II energy alignment for efficient charge transfer and extraction. Additionally, the non-fullerene molecules can well passivate the QDs, reducing surface defects and energetic disorder. The champion CsPbI₃ QD/Y6-F hybrid device has a record-high efficiency of 15.05% for QD/organic hybrid PV devices, paving a new way to construct solution-processable hybrid film for efficient optoelectronic devices.     

Quantum Junction Solar Cells: Development and Prospects

Nanocrystals, called semiconductor quantum dots (QDs), contain excitons that are three-dimensionally bound. QDs exhibit a discontinuous electronic energy level structure that is similar to that of atoms and exhibit a distinct quantum confinement effect. As a result, QDs have unique electrical, optical, and physical characteristics that can be used in a variety of optoelectronic device applications, including solar cells. In this review article, the stable and controllable synthesis of QD materials is outlined for upscaling solar cells, including material development and device performance enhancement. It includes a systematic variety of device structures for the fabrication of solar cells, such as QD, hybrid QD/organic, hybrid QD/inorganic, perovskite QD, and hybrid 2D MXene QD/perovskite. The mechanisms for the improvement of stability by QD treatment are examined. For example, the 2D MXene QD and/or Cu_1.8S nanocrystal doping significantly increases the long-term light and ambient stability of perovskite solar cells, resulting from improved perovskite crystallization, reduced hole transport layer (HTL) aggregation and crystallization of films, and reduced UV-induced photocatalytic activity of the electron transport layer (ETL). For the advancement of QD solar cells and their interaction with various materials, the conclusions from this review are crucial. Finally, future prospects for the development of QD solar cells as well as current challenges are discussed.     

Efficient Near‐Infrared Light‐Emitting Diodes based on In(Zn)As–In(Zn)P–GaP–ZnS Quantum Dots

Near‐infrared (NIR) lighting plays an increasingly important role in new facial recognition technologies and eye‐tracking devices, where covert and nonvisible illumination is needed. In particular, mobile or wearable gadgets that employ these technologies require electronic lighting components with ultrathin and flexible form factors that are currently unfulfilled by conventional GaAs‐based diodes. Colloidal quantum dots (QDs) and emerging perovskite light‐emitting diodes (LEDs) may fill this gap, but generally employ restricted heavy metals such as cadmium or lead. Here, a new NIR‐emitting diode based on heavy‐metal‐free In(Zn)As–In(Zn)P–GaP–ZnS quantum dots is reported. The quantum dots are prepared with a giant shell structure, enabled by a continuous injection synthesis approach, and display intense photoluminescence at 850 nm with a high quantum efficiency of 75%. A postsynthetic ligand exchange to a shorter‐chain 1‐mercapto‐6‐hexanol (MCH) affords the QDs with processability in polar solvents as well as an enhanced charge‐transport performance in electronic devices. Using solution‐processing methods, an ITO/ZnO/PEIE/QD/Poly‐TPD/MoO₃/Al electroluminescent device is fabricated and a high external quantum efficiency of 4.6% and a maximum radiance of 8.2 W sr^?1 m^?2 are achieved. This represents a significant leap in performance for NIR devices employing a colloidal III–V semiconductor QD system, and may find significant applications in emerging consumer electronic products.     

Low Roll‐Off Perovskite Quantum Dot Light‐Emitting Diodes Achieved by Augmenting Hole Mobility

The external quantum efficiencies (EQEs) of perovskite quantum dot light‐emitting diodes (QD‐LEDs) are close to the out‐coupling efficiency limitation. However, these high‐performance QD‐LEDs still suffer from a serious issue of efficiency roll‐off at high current density. More injected carriers produce photons less efficiently, strongly suggesting the variation of ratio between radiative and non‐radiative recombination. An approach is proposed to balance the carrier distribution and achieve high EQE at high current density. The average interdot distance between QDs is reduced and this facilitates carrier transport in QD films and thus electrons and holes have a balanced distribution in QD layers. Such encouraging results augment the proportion of radiative recombination, make devices with peak EQE of 12.7%, and present a great device performance at high current density with an EQE roll‐off of 11% at 500 mA cm^?2 (the lowest roll‐off known so far) where the EQE is still over 11%.     

Synergistic Effect of Hybrid PbS Quantum Dots/2D‐WSe2 Toward High Performance and Broadband Phototransistors

The transitionmetal dichalcogenides‐based phototransistors have demonstrated high transport mobility but are limited to poor photoresponse, which greatly blocks their applications in optoelectronic fields. Here, light sensitive PbS colloidal quantum dots (QDs) combined with 2D WSe₂ to develop hybrid QDs/2D‐WSe₂ phototransistors for high performance and broadband photodetection are utilized. The device shows a responsivity up to 2 × 10⁵ A W^–1, which is orders of magnitude higher than the counterpart of individual material‐based devices. The detection spectra of hybrid devices can be extended to near infrared similar to QDs' response. The high performance of hybrid 0D‐2D phototransistor is ascribed to the synergistic function of photogating effect. PbS QDs can efficiently absorb the input illumination and 2D WSe₂ supports a transport expressway for injected photocarriers. The hybrid phototransistors obtain a specific detectivity over 10¹³ Jones in both ON and OFF state in contrast to the depleted working state (OFF) for other reported QDs/2D phototransistors. The present device construction strategy, photogating enhanced performance, and robust device working conditions contain high potential for future optoelectronic devices.     

Green InP/ZnSeS/ZnS Core Multi-Shelled Quantum Dots Synthesized with Aminophosphine for Effective Display Applications

InP quantum dots (QDs) are emerging as promising materials for replacing cadmium-based QDs in view of their heavy metal-free and tunable luminescence. However, the development of InP QD materials still lags due to the expensive and flammable phosphorus precursors, and also the unsatisfactory repeatability caused by the fast nucleation rate. Adopting lowly reactive P precursor aminophosphine can overcome this issue, but their low photoluminescence quantum yield (PLQY) and widening line widths do not apply to the practical application. Through engineering, the core-shell structure of QD, significantly promoted green emissions of QDs were obtained with PLQY of 95% and full width and half maximum (FWHM) of 45 nm, which demonstrated the highest PLQY record obtained from the aminophosphine system. Moreover, due to the residue halogen atoms on the QD surface as inorganic ligands to prevent further oxidization, these InP QDs demonstrated the ultra-long operational lifetime (over 1000 h) for QDs based color enhancement film. By optimizing the device structure, an inverted green InP quantum dot light-emitting diode (QLED) with external quantum efficiency (EQE) of 7.06% was also demonstrated, which showed a significant promise of these InP QDs in highly effective optoelectronic devices.     

Facet Control for Trap‐State Suppression in Colloidal Quantum Dot Solids

Trap states in colloidal quantum dot (QD) solids significantly affect the performance of QD solar cells, because they limit the open‐circuit voltage and short circuit current. The {100} facets of PbS QDs are important origins of trap states due to their weak or missing passivation. However, previous investigations focused on synthesis, ligand exchange, or passivation approaches and ignored the control of {100} facets for a given dot size. Herein, trap states are suppressed from the source via facet control of PbS QDs. The {100} facets of ≈3 nm PbS QDs are minimized by tuning the balance between the growth kinetics and thermodynamics in the synthesis. The PbS QDs synthesized at a relatively low temperature with a high oversaturation follow a kinetics‐dominated growth, producing nearly octahedral nanoparticles terminated mostly by {111} facets. In contrast, the PbS QDs synthesized at a relatively high temperature follow a thermodynamics‐dominated growth. Thus, a spherical shape is preferred, producing truncated octahedral nanoparticles with more {100} facets. Compared to PbS QDs from thermodynamics‐dominated growth, the PbS QDs with less {100} facets show fewer trap states in the QD solids, leading to a better photovoltaic device performance with a power conversion efficiency of 11.5%.     

Enhancing Resistive Switching Performance and Ambient Stability of Hybrid Perovskite Single Crystals via Embedding Colloidal Quantum Dots

Hybrid organic‐inorganic halide perovskites are actively pursued for optoelectronic technologies, but the poor stability is the Achilles’ heel of these materials that hinders their applications. Very recently, it has been shown that lead sulfide (PbS) quantum dots (QDs) can form epitaxial interfaces with the perovskite matrix and enhance the overall stability. In this work, it is demonstrated that embedding QDs can significantly modify the transport property of pristine perovskite single crystals, endowing them with new functionalities besides being structurally robust and free from grain boundaries. Resistive switching memory devices are constructed using solution‐processed CH₃NH₃PbBr₃ (MAPbBr₃) perovskite single crystals and the QD‐embedded counterparts. It is found that QDs could significantly enhance the charge transport and reduce the current–voltage hysteresis. The pristine singe crystal device exhibits negative differential resistance, while the QD‐embedded crystals are featured with filament‐type switching behavior and much improved device stability. This study underscores the potential of QD‐embedded hybrid perovskites as a new media for advanced electronic devices.     

Matrix Manipulation of Directly-Synthesized PbS Quantum Dot Inks Enabled by Coordination Engineering

The direct-synthesis of conductive PbS quantum dot (QD) ink is facile, scalable, and low-cost, boosting the future commercialization of optoelectronics based on colloidal QDs. However, manipulating the QD matrix structures still is a challenge, which limits the corresponding QD solar cell performance. Here, for the first time a coordination-engineering strategy to finely adjust the matrix thickness around the QDs is presented, in which halogen salts are introduced into the reaction to convert the excessive insulating lead iodide into soluble iodoplumbate species. As a result, the obtained QD film exhibits shrunk insulating shells, leading to higher charge carrier transport and superior surface passivation compared to the control devices. A significantly improved power-conversion efficiency from 10.52% to 12.12% can be achieved after the matrix engineering. Therefore, the work shows high significance in promoting the practical application of directly synthesized PbS QD inks in large-area low-cost optoelectronic devices.     

Modeling of a Room-Temperature Silicon Quantum Dot-Based Single-Electron Transistor and the Effect of Energy-Level Broadening on Its Performance

In this work, we have modeled silicon quantum dot (QD)-based single-electron transistors (SETs) operating at room temperature and investigated the effect of the QD’s energy-level broadening on the performance of the SET. First we obtained the energy levels and corresponding wave functions for spherical Si QDs by solving the coupled Schrödinger–Poisson equations in three dimensions. Then, we demonstrated different tunneling current rates for separated energy levels by considering nonequal energy-level broadenings. Accordingly, an expression for the corresponding tunneling rates in the quantum Coulomb blockade regime was derived. In the next step, the transconductance characteristics of the Si QD SET device with Coulomb oscillations were simulated, and their differences from previously investigated metal-based SETs were demonstrated. Finally, by applying different bias voltages, we determined the effect of temperature variations on the transconductance characteristics.     

Progress in Epitaxial Growth and Performance of Quantum Dot and Quantum Wire Lasers

We report on interplay of epitaxial growth phenomena and device performance in quantum dot (QD) and quantum wire (QWW) lasers based on self-organized nanostructures. InAs QDs are the most explored model system for basic understanding of "near-ideal" QD devices. Vertically-coupled growth of QDs and activated phase separation allow ultimate QD wavefunction engineering enabling GaAs lasers beyond 1400 nm and polarization-insensitive optical amplification. A feasibility of QD semiconductor optical amplifiers at terabit frequencies using InAs QDs is manifested at 1300 and 1500 nm. 1250-1300 nm QD GaAs edge emitters and VCSELs operate beyond 10 Gb/s with ultimate temperature robustness. Furthermore, temperature-insensitive operation without current or modulation voltage adjustment at >20 Gb/s is demonstrated up to ~90 degC. Light-emitting devices based on InGaN-QDs cover ultraviolet (UV) and visible blue-green spectral ranges. In these applications, InN-rich nanodomains prevent diffusion of nonequilibrium carries towards crystal defects and result in advanced degradation robustness of the devices. All the features characteristic to QDs are unambiguously confirmed for InGaN structures. For the red spectral range InGaAlP lasers are used. Growth on misoriented surfaces, characteristic to these devices, leads to nano-periodi- cally-step-bunched epitaxial surfaces resulting in two principal effects: 1) step-bunch-assisted alloy phase separation, leading to a spontaneous formation of ordered natural super lattices; 2) formation of quantum wire-like structures in the active region of the device. A high degree of polarization is revealed in the luminescence recorded from the top surface of the structures, in agreement with the QWW nature of the gain medium. QD and QWW lasers are remaining at the frontier of the modern optoelectronics penetrating into the mainstream applications in key industries.     

Mechanism of electronic-excitation transfer in organic light-emitting devices based on semiconductor quantum dots

The results of an experimental study of organic light-emitting diodes (LEDs) with luminescent layers based on two types of CdSe/CdS semiconductor quantum dots (QDs) with an average CdSe core diameter of 3 and 5 nm and a characteristic CdS shell thickness of 0.5 nm are presented. The dependences of the LED efficiency on the QD concentration are determined. The experimental data are used to determine the mechanism of electronic-excitation transfer from the organic matrix to the semiconductor QDs. Ways of optimizing the design of the LEDs in order to improve their efficiency are suggested on this basis.     

Voltage-Dependent Charge Storage in Cladded Zn0.56Cd0.44Se Quantum Dot MOS Capacitors for Multibit Memory Applications

As conventional memories approach scaling limitations, new storage methods must be utilized to increase Si yield and produce higher on-chip memory density. Use of II–VI Zn_0.56Cd_0.44Se quantum dots (QDs) is compatible with epitaxial gate insulators such as ZnS-ZnMgS. Voltage-dependent charging effects in cladded Zn_0.56Cd_0.44Se QDs are presented in a conventional metal–oxide–semiconductor capacitor structure. Charge storage capabilities in Si and ZnMgS QDs have been reported by various researchers; this work is focused on II–VI material Zn_0.56Cd_0.44Se QDs nucleated using photoassisted microwave plasma metalorganic chemical vapor deposition. Using capacitance–voltage hysteresis characterization, the multistep charging and discharging capabilities of the QDs at room temperature are presented. Three charging states are presented within a 10 V charging voltage range. These characteristics exemplify discrete charge states in the QD layer, perfect for multibit, QD-functionalized high-density memory applications. Multiple charge states with low operating voltage provide device characteristics that can be used for multibit storage by allowing varying charges to be stored in a QD layer based on the applied “write” voltage.     

Perspective:optically-pumped Ⅲ–Ⅴ quantum dot microcavity lasers via CMOS compatible patterned Si (001) substrates

Direct epitaxial growthⅢ–Ⅴquantum dot(QD)structures on CMOS-compatible silicon substrates is considered as one of the most promising approaches to achieve low-cost and high-yield Si-based lasers for silicon photonic integration.However,epitaxial growth ofⅢ–Ⅴmaterials on Si encounters the following three major challenges:high density of threading dislocations,antiphase boundaries and thermal cracks,which significantly degrade the crystal quality and potential device performance.In this review,we will focus on some recent results related to InAs/GaAs quantum dot lasers on Si(001)substrates byⅢ–Ⅴ/Ⅳhybrid epitaxial growth via(111)-faceted Si hollow structures.Moreover,by using the step-graded epitaxial growth process the emission wavelength of InAs QDs can be extended from O-band to C/L-band.High-performance InAs/GaAs QD microdisk lasers with sub-milliwatts threshold on Si(001)substrates are fabricated and characterized.The above results pave a promising path towards the on-chip lasers for optical interconnect applications.     

Fast,Air‐Stable Infrared Photodetectors based on Spray‐Deposited Aqueous HgTe Quantum Dots

The ability to detect near‐infrared and mid‐infrared radiation has spawned great interest in colloidal HgTe quantum dots (QDs). In contrast to the studies focused on extending the spectral range of HgTe QD devices, the temporal response, another figure of merit for photodetectors, is rarely investigated. In this work, a single layer, aqueous HgTe QD based photoconductor structure with very fast temporal response (up to 1 MHz 3 dB bandwidth) is demonstrated. The device is fabricated using a simple spray‐coating process and shows excellent stability in ambient conditions. The origin of the remarkably fast time response is investigated by combining light intensity‐dependent transient photocurrent, temperature‐dependent photocurrent, and field‐effect transistor (FET) measurements. The charge carrier mobility, as well as the energy levels and carrier lifetimes associated with the trap states in the QDs, are identified. The results suggest that the temporal response is dominated by a fast bimolecular recombination process under high light intensity and by a trap‐mediated recombination process at low light intensity. Interestingly, it was found that the gain and time response of aqueous HgTe QD‐based photoconductors can be tuned by controlling the QD size and surface chemistry, which provides a versatile approach to optimize the photodetectors with selectable sensitivity and operation bandwidth.