Colloidal quantum dots (QDs) combine the superior light-emission characteristics of quantum-confined semiconductors with the chemical flexibility of molecular systems. These properties could, in ...principle, enable solution-processable laser diodes with an ultrawide range of accessible colours. However, the realization of such devices has been hampered by fast optical gain decay due to non-radiative Auger recombination and poor stability of QD solids at the high current densities required for the lasing regime. Recently, these problems have been resolved, which resulted in the development of electrically pumped optical gain devices operating at ultrahigh current densities of around 1,000 A cm−2. The next step is the realization of a QD laser diode (QLD). Here we assess the status of the QD lasing field, examine the remaining challenges on the path to a QLD and discuss practical strategies for attaining electrically pumped QD lasing.Colloidal quantum dots may offer solution-processable lasers, with a wide range of colours available. Technical hurdles and progress towards realization of useful quantum dot laser diodes is reviewed.
Advances in colloidal quantum dots
The confinement found in colloidal semiconductor quantum dots enables the design of materials with tunable properties. García de Arquer
et al
. review the recent ...advances in methods for synthesis and surface functionalization of quantum dots that enable fine tuning of their optical, chemical, and electrical properties. These important developments have driven the commercialization of display and lighting applications and provide promising developments in the related fields of lasing and sensing. —MSL
A review highlights advances in the synthesis of colloidal quantum dots that have enabled numerous applications.
BACKGROUND
Semiconductor materials feature optical and electronic properties that can be engineered through their composition and crystal structure. The use of semiconductors such as silicon gallium arsenide sparked technologies from computers and mobile phones to lasers and satellites. Semiconductor quantum dots (QDs) offer an additional lever: Because their size is reduced to the nanometer scale in all three dimensions, the restricted electron motion leads to a discrete atom-like electronic structure and size-dependent energy levels. This enables the design of nanomaterials with widely tunable light absorption, bright emission of pure colors, control over electronic transport, and a wide tuning of chemical and physical functions because of their large surface-to-volume ratio.
ADVANCES
The bright and narrowband light emission of semiconductor QDs, tunable across the visible and near-infrared spectrum, is attractive to realize more efficient displays with purer colors. QDs are engineered compositionally and structurally to manipulate energy states and charge interactions, leading to optical gain and lasing, relevant to light emission across visible and infrared wavelengths and fiberoptic communication. Their tunable surface chemistry allows application as optical labels in bio-imaging, made possible by tethering QDs with proteins and antibodies. The manipulation of QD surfaces with capping molecules that have different chemical and physical functions can be tailored to program their assembly into semiconducting solids, increasing conductivity and enabling the transduction of photonic and chemical stimuli into electrical signals. Optoelectronic devices such as transistors and photodetectors lead to cameras sensitive to visible and infrared light. Highly crystalline QDs can be grown epitaxially on judiciously chosen substrates by using high-temperature and vacuum conditions, and their use has led to commercially viable high-performance lasers. The advent of colloidal QDs, which can be fabricated and processed in solution at mild conditions, enabled large-area manufacturing and widened the scope of QD application to markets such as consumer electronics and photovoltaics.
OUTLOOK
From a chemistry perspective, further advances in QD fabrication are needed to sustain and improve desired chemical and optoelectronic properties and to do so with high reproducibility. This entails the use of inexpensive synthesis methods and precursors that are able to retain laboratory-scale QD properties to market-relevant volumes. A better understanding of the yet-incomplete picture of QD surfaces, atomic arrangement, and metastable character is needed to drive further progress. From a regulatory perspective, added attention is needed to achieve high-quality materials that do not rely on heavy metals such as Cd, Pb, and Hg. The role of nanostructuring in toxicity and life cycle analysis for each application is increasingly important. From a materials and photophysics perspective, exciting opportunities remain in the understanding and harnessing of electrons in highly confined materials, bridging the gap between mature epitaxial QDs and still-up-and-coming colloidal QDs. The yet-imperfect quality of the latter—a price paid today in exchange for their ease of manufacture—remains a central challenge and must be addressed to achieve further-increased performance in devices. From a device perspective, colloidal QD manufacturing must advance to translate from laboratory-scale to large-area applications such as roll-to-roll and inkjet printing. Photocatalysis, in which light is used to drive chemical transformations, is an emerging field in which QDs are of interest. Quantum information technologies, which rely on the transduction of coherent light and electrons, bring new challenges and opportunities to exploit quantum confinement effects. Moving forward, opportunities remain in the design of QD-enabled new device architectures.
Semiconductor quantum dot technologies.
Quantum dots feature widely tunable and distinctive optical, electrical, chemical, and physical properties. They span energy harvesting, illumination, displays, cameras, sensors, communication and information technology, biology, and medicine, among others. These have been exploited to realize efficient lasers, displays, biotags, and solar harvesting devices available in the market and are emerging in photovoltaics, sensing, and quantum information.
In quantum-confined semiconductor nanostructures, electrons exhibit distinctive behavior compared with that in bulk solids. This enables the design of materials with tunable chemical, physical, electrical, and optical properties. Zero-dimensional semiconductor quantum dots (QDs) offer strong light absorption and bright narrowband emission across the visible and infrared wavelengths and have been engineered to exhibit optical gain and lasing. These properties are of interest for imaging, solar energy harvesting, displays, and communications. Here, we offer an overview of advances in the synthesis and understanding of QD nanomaterials, with a focus on colloidal QDs, and discuss their prospects in technologies such as displays and lighting, lasers, sensing, electronics, solar energy conversion, photocatalysis, and quantum information.
Luminescent solar concentrators (LSCs) can serve as large-area sunlight collectors for terrestrial and space-based photovoltaics. Due to their high emission efficiencies and readily tunable emission ...and absorption spectra, colloidal quantum dots have emerged as a new and promising type of LSC fluorophore. Spectral tunability of the quantum dots also facilitates the realization of stacked multilayered LSCs, where enhanced performance is obtained through spectral splitting of incident sunlight, as in multijunction photovoltaics. Here, we demonstrate a large-area (>230 cm2) tandem LSC based on two types of nearly reabsorption-free quantum dots spectrally tuned for optimal solar-spectrum splitting. This prototype device exhibits a high optical quantum efficiency of 6.4% for sunlight illumination and solar-to-electrical power conversion efficiency of 3.1%. The efficiency gains due to the tandem architecture over single-layer devices quickly increase with increasing LSC size and can reach more than 100% in structures with window sizes of more than 2,500 cm2.
Realization of electrically pumped lasing with solution processable materials will have a revolutionary impact on many disciplines including photonics, chemical sensing, and medical diagnostics. Due ...to readily tunable, size-controlled emission wavelengths, colloidal semiconductor quantum dots (QDs) are attractive materials for attaining this goal. Here we use specially engineered QDs to demonstrate devices that operate as both a light emitting diode (LED) and an optically pumped laser. These structures feature a distributed feedback resonator integrated into a bottom LED electrode. By carefully engineering a refractive-index profile across the device, we are able to obtain good confinement of a waveguided mode within the QD medium, which allows for demonstrating low-threshold lasing even with an ultrathin (about three QD monolayers) active layer. These devices also exhibit strong electroluminescence (EL) under electrical pumping. The conducted studies suggest that the demonstrated dual-function (lasing/EL) structures represent a promising device platform for realizing colloidal QD laser diodes.
Because of the strong spatial confinement of electronic wave functions and reduced dielectric screening, the effects of carrier-carrier Coulomb interactions are greatly enhanced in semiconductor ...nanocrystals (NCs) compared with those in bulk materials. These interactions open a highly efficient decay channel via Auger recombination, which represents a dominant recombination pathway for multiexcitons in NCs. Furthermore, strong Coulomb coupling between charge carriers leads to extremely efficient direct photogeneration of multiexcitons by single photons via carrier (or exciton) multiplication. This review focuses on spectral and dynamical properties of multiexcitons in semiconductor NCs. The specific topics discussed here include the structure of NC electronic states, spectral signatures of multiexcitons in transient absorption and photoluminescence, exciton-exciton interaction energies, Auger recombination, and carrier multiplication. This chapter also briefly reviews the implications of multiexciton effects for practical technologies, such as NC lasing and photovoltaics.
Organic–inorganic lead-halide perovskites have been the subject of recent intense interest due to their unusually strong photovoltaic performance. A new addition to the perovskite family is ...all-inorganic Cs–Pb-halide perovskite nanocrystals, or quantum dots, fabricated via a moderate-temperature colloidal synthesis. While being only recently introduced to the research community, these nanomaterials have already shown promise for a range of applications from color-converting phosphors and light-emitting diodes to lasers, and even room-temperature single-photon sources. Knowledge of the optical properties of perovskite quantum dots still remains vastly incomplete. Here we apply various time-resolved spectroscopic techniques to conduct a comprehensive study of spectral and dynamical characteristics of single- and multiexciton states in CsPbX3 nanocrystals with X being either Br, I, or their mixture. Specifically, we measure exciton radiative lifetimes, absorption cross-sections, and derive the degeneracies of the band-edge electron and hole states. We also characterize the rates of intraband cooling and nonradiative Auger recombination and evaluate the strength of exciton–exciton coupling. The overall conclusion of this work is that spectroscopic properties of Cs–Pb-halide quantum dots are largely similar to those of quantum dots of more traditional semiconductors such as CdSe and PbSe. At the same time, we observe some distinctions including, for example, an appreciable effect of the halide identity on radiative lifetimes, considerably shorter biexciton Auger lifetimes, and apparent deviation of their size dependence from the “universal volume scaling” previously observed for many traditional nanocrystal systems. The high efficiency of Auger decay in perovskite quantum dots is detrimental to their prospective applications in light-emitting devices and lasers. This points toward the need for the development of approaches for effective suppression of Auger recombination in these nanomaterials, using perhaps insights gained from previous studies of II–VI nanocrystals.
One consequence of strong spatial confinement of electronic wave functions in ultrasmall semiconductor nanocrystals is a great enhancement of carrier−carrier interactions, which has a dramatic effect ...on the spectral and dynamical properties of both single and multiexciton states. Strong carrier−carrier interactions open new nanocrystal-specific energy relaxation and recombination channels associated, e.g., with electron−hole energy transfer and ultrafast nonradiative Auger recombination. Further, they lead to extremely efficient direct photogeneration of multiple electron−hole pairs (excitons) by single photons known as carrier (or exciton) multiplication. This review focuses on the effect of Coulomb interactions on carrier recombination and photogeneration mechanisms in nanocrystals based on II−VI (e.g., CdSe) and IV−VI (e.g., PbSe) compounds. The specific topics discussed here include the fine structure of the band-edge optical transitions and its effect on temperature-dependent single-exciton recombination dynamics, Auger recombination of multiexcitons in size- and shape-controlled nanocrystals with a specific emphasis on optical-gain properties of nanocrystalline materials (including quantum rods and multicomponent core−shell heterostructures), and the direct generation of multiple excitons via carrier multiplication and its implications in photovoltaic technologies.
Colloidal semiconductor quantum dots are attractive materials for the realization of solution-processable lasers. However, their applications as optical-gain media are complicated by a non-unity ...degeneracy of band-edge states, because of which multiexcitons are required to achieve the lasing regime. This increases the lasing thresholds and leads to very short optical gain lifetimes limited by nonradiative Auger recombination. Here, we show that these problems can be at least partially resolved by employing not neutral but negatively charged quantum dots. By applying photodoping to specially engineered quantum dots with impeded Auger decay, we demonstrate a considerable reduction of the optical gain threshold due to suppression of ground-state absorption by pre-existing carriers. Moreover, by injecting approximately one electron per dot on average, we achieve a more than twofold reduction in the amplified spontaneous emission threshold, bringing it to the sub-single-exciton level. These measurements indicate the feasibility of 'zero-threshold' gain achievable by completely blocking the band-edge state with two electrons.
Chemically synthesized semiconductor quantum dots (QDs) can potentially enable solution-processable laser diodes with a wide range of operational wavelengths, yet demonstrations of lasing from the ...QDs are still at the laboratory stage. An important challenge-realization of lasing with electrical injection-remains unresolved, largely due to fast nonradiative Auger recombination of multicarrier states that represent gain-active species in the QDs. Here we present population inversion and optical gain in colloidal nanocrystals realized with direct-current electrical pumping. Using continuously graded QDs, we achieve a considerable suppression of Auger decay such that it can be outpaced by electrical injection. Further, we apply a special current-focusing device architecture, which allows us to produce high current densities (j) up to ∼18 A cm
without damaging either the QDs or the injection layers. The quantitative analysis of electroluminescence and current-modulated transmission spectra indicates that with j = 3-4 A cm
we achieve the population inversion of the band-edge states.
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