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One of the key phenomena that determine the fluorescence of nanocrystals is the nonradiative Auger-Meitner recombination of excitons. This nonradiative rate affects the nanocrystals' fluorescence intensity, excited state lifetime, and quantum yield. Whereas most of the above properties can be directly measured, the quantum yield is the most difficult to assess. Here we place semiconductor nanocrystals inside a tunable plasmonic nanocavity with subwavelength spacing and modulate their radiative de-excitation rate by changing the cavity size. This allows us to determine absolute values of their fluorescence quantum yield under specific excitation conditions. Moreover, as expected considering the enhanced Auger-Meitner rate for higher multiple excited states, increasing the excitation rate reduces the quantum yield of the nanocrystals.

Nanophotonics relies on precise control of refractive index (RI) which can be designed with metamaterials. Plasmonic superstructures of nanoparticles (NPs) can suggest a versatile way of tuning RI. However, the plasmonic effects in the superstructures demand 1 nm-level exquisite control over the interparticle gap, which is challenging in a sub-wavelength NPs. Thus far, a large-area demonstration has been mostly discouraged. Here, heteroligand AuNPs are prepared, which are stable in oil but become Janus particles at the oil-water interface, called "adaptive Janus particles." NPs are bound at the interface and assembled into 2D arrays over square centimeters as toluene evaporates, which distinctively exhibits the RI tunability. In visible and NIR light, the 2D superstructures exhibit the highest-ever RI (≈7.8) with varying the size and interparticle gap of NPs, which is successfully explained by a plasmonic percolation model. Furthermore, fully solution-processable 2D plasmonic superstructures are proved to be advantageous in flexible photonic devices such as distributed Bragg reflectors.

Semiconductor nanocrystals with an anisotropic morphology exhibit unique properties, most notably their linear polarization. The colloidal growth of semiconductor nanorods with core dots inside, also referred to as dot-in-rod (DIR) structure, has enabled the synthesis of anisotropic nanocrystals with better stability and controllable fluorescence polarization. In this study, we synthesize CdSe/CdS DIR nanocrystals, in which the position of the CdSe core particle can be controlled by using different ligand compositions during the CdS growth. Varying the core position within the DIR structure, e.g., from the center to the end of the DIR particles, results in a change in the degree of linear polarization. When the core is positioned at the center of the nanorod, the linear polarization turns out to be higher compared with tip-core DIRs. Time-resolved photoluminescence analysis reveals that the center-core DIRs have higher electron–hole interaction than tip-core DIRs because of weak uniaxial strain in center-core DIR that arises from lattice dislocations at the interface to relieve accumulated strain.

Wide interest in quantum dot (QD) light-emitting diodes (QLEDs) for potential application to display devices and light sources has led to their rapid advancement in device performance. Despite such progress, detailed operation mechanisms of QLEDs, which are necessary for the fundamental understanding and further improvements, have been still uncertain because of the intricate interaction between charges and excitons in electrical operation. In this work, the transient electroluminescence (TREL) signals of dichromatic QLEDs which are purposely designed to consist of two different color-emitting QD layers are analyzed. As a result, not only can the charge injection and exciton recombination processes be visualized but the electron mobility of the QD layer can also be estimated. Furthermore, the effects of Förster resonant energy transfer between two QDs and exciton quenching near the QD layer are quantitatively measured in QLED operation. The authors believe that their results based on TREL analyses will contribute to the understanding and development of high-performance QLEDs.

Colloidal quantum dots (QDs) stand at the forefront of a variety of photonic applications given their narrow spectral bandwidth and near-unity luminescence efficiency. Integrating desired forms of QD films into photonic systems without compromising their optical or transport characteristics is the key to bridging the gap between expectations and outcomes. Here, we devise a dual-ligand passivation system comprising photocrosslinkable ligands and dispersing ligands to enable QDs to be universally compatible with solution-based patterning techniques. The successful control on the structure of both ligands allows multiscale, direct patterning of the dual-ligand QDs on various substrates via commercialized photolithography (i-line) or inkjet printing systems without compromising the optical properties of QDs or the optoelectronic performances of the devices implementing them. Our approach offers a versatile way of creating various structures of luminescent QDs in a cost-effective and non-destructive manner, and thus enables the implementation of QDs in a range of photonic applications.

The efficiency and operational lifetime of quantum dot (QD) based light-emitting diodes (QLEDs) are essentially affected by the electron–hole charge balance. Although various methods have been reported to improve the charge balance, these methods cause issues at the same time, such as increasing a driving voltage and complicating a device structure. In this work, we introduce hybrid InP/ZnSeS/ZnS QDs, in which the oleic acid ligands are substituted with semiconducting diblock copolymer units possessing hole-transporting carbazole groups, to facilitate hole injection and to reduce electron leakage. As a result, the efficiency and the operational lifetime were improved by 1.4-fold and 4-fold, respectively, with lower driving voltages. Origins of the results were systematically investigated, and we found that the diblock copolymer units surrounding the QDs made the inter-dot distance farther apart from one another, leading to reduced Forster resonance energy transfer between QDs which can cause reduced photoluminescence quantum yields. Also, the hole transporting ability of carbazole groups facilitated hole injection into QDs and blocked excess electron leakage at the same time. The impedance spectroscopy on the devices with the pristine and hybrid QDs before and after bias stress revealed that hole accumulation at the hole transport layer/QD interface significantly affected the operational lifetime of the QLEDs. This work offers a design for the QD emission layer to achieve efficient and stable QLEDs with systematic understanding of the origins.

Due to the strong confinement of carriers, electronic interactions play a major role on the performance of colloidal nanocrystals (NCs) as material for optical gain. Therefore, understanding how to...

Colloidal semiconductor nanocrystals (NCs) are on the vanguard of nonlinear optical materials due to their superb optical properties including tunable multiphoton absorption (MPA) with large absorp...

The rising demand for eradicating hazardous substances in the workplace has motivated vigorous researches on environmentally sustainable manufacturing processes of colloidal quantum dots (QDs) for their optoelectronic applications. Despite remarkable achievements witnessed in QD materials (e.g., Pb- or Cd-free QDs), the progress in the eco-friendly process is far falling behind and thus the practical use of QDs. Herein, a complete "green" process of QDs, which excludes environmentally unfriendly elements from QDs, ligands, or solvents, is presented. The implant of mono-2-(methacryloyloxy)ethyl succinate (MMES) ligands renders InP/ZnSexS1-x QDs dispersed in eco-friendly polar solvents that are widely accepted in the industry while keeping the photophysical properties of QDs unchanged. The MMES-capped QDs show exceptional colloidal stabilities in a range of green polar solvents that permit uniform inkjet printing of QD dispersion. In addition, MMES-capped QDs are also compatible with commercially available photo-patternable resins, and the cross-linkable moiety within MMES further facilitates the achievement in the formation of well-defined, micrometer-scale patterning of QD optical films. The presented materials, all composed of simple, scalable, and environmentally safe compounds, promise low environmental impact during the processing of QDs and thus will catalyze the practicable use of QDs in a variety of optoelectronic devices.

The state-of-the-art quantum dot (QD) based light-emitting diodes (QD-LEDs) reach near-unity internal quantum efficiency thanks to organic materials used for efficient hole transportation within the devices. However, toward high-current-density LEDs, such as augmented reality, virtual reality, and head-up display, thermal vulnerability of organic components often results in device instability or breakdown. The adoption of a thermally robust inorganic hole transport layer (HTL), such as NiO, becomes a promising alternative, but the large energy offset between the NiO HTL and the QD emissive layer impedes the efficient operation of QD-LEDs. Here, we demonstrate bright and stable all-inorganic QD-LEDs by steering the orientation of molecular dipoles at the surfaces of both the NiO HTL and QDs. We show that the molecular dipoles not only induce the vacuum level shift that helps alleviate the energy offset between the NiO HTL and QDs but also passivate the surface trap states of the NiO HTL that act as nonradiative recombination centers. With the facilitated hole injection into QDs and suppressed electron leakage toward trap sites in the NiO HTL, we achieve all-inorganic QD-LEDs with high external quantum efficiency (6.5% at peak) and brightness (peak luminance exceeding 77 000 cd/m

Quantum dot light-emitting diodes (QLEDs) are one of the most promising candidates for next-generation displays and lighting sources, but they are barely used because vulnerability to electrical and thermal stresses precludes high brightness, efficiency, and stability at high current density (J) regimes. Here, bright and stable QLEDs on a Si substrate are demonstrated, expanding their potential application boundary over the present art. First, a tailored interface is granted to the quantum dots, maximizing the quantum yield and mitigating nonradiative Auger decay of the multiexcitons generated at high-J regimes. Second, a heat-endurable, top-emission device architecture is employed and optimized based on optical simulation to enhance the light outcoupling efficiency. The multilateral approaches realize that the red top-emitting QLEDs exhibit a maximum luminance of 3 300 000 cd m-2 , a current efficiency of 75.6 cd A-1 , and an operational lifetime of 125 000 000 h at an initial brightness of 100 cd m-2 , which are the highest of the values reported so far.

The past decade has witnessed remarkable progress in the device efficiency of quantum dot light-emitting diodes based on the framework of organic-inorganic hybrid device structure. The striking improvement notwithstanding, the following conundrum remains underexplored: state-of-the-art devices with seemingly unfavorable energy landscape exhibit barrierless hole injection initiated even at sub-band gap voltages. Here, we unravel that the cause of barrierless hole injection stems from the Fermi level alignment derived by the surface states. The reorganized energy landscape provides macroscopic electrostatic potential gain to promote hole injection to quantum dots. The energy level alignment surpasses the Coulombic attraction induced by a charge employed in quantum dots which adjust the local carrier injection barrier of opposite charges by a relatively small margin. Our finding elucidates how quantum dots accommodate barrierless carrier injection and paves the way to a generalized design principle for efficient electroluminescent devices employing nanocrystal emitters., Hybrid quantum dot light-emitting diodes exhibit barrier-less carrier injection despite a seemingly unfavourable energy landscape. Here, Lee et al. unravel the origin of this barrier-less carrier injection, showing the critical role of surface states of quantum dots.

Colloidal quantum dots (QDs) are nanosized semiconductors whose electronic features are dictated by the quantum confinement effect. The optical, electrical, and chemical properties of QDs are influenced by their dimensions and surface landscape. The surface of II–VI and IV–VI QDs has been extensively explored; however, in-depth investigations on the surface of III–V QDs are still lagging behind. This Perspective discusses the current understanding of the surface of III–V QDs, outlines deep trap states presented by surface defects, and suggests strategies to overcome challenges associated with deep traps. Lastly, we discuss a route to create well-defined facets in III–V QDs by providing a platform for surface studies and a recently reported approach in atomistic understanding of covalent III–V QD surfaces using the electron counting model with fractional dangling bonds., Unveiling the atomistic surface structure of colloidal quantum dots may provide the route to rational design of highly performing III–V nanocrystals with control over energy levels position, surface energy, trap passivation, and heterojunction interface.

Commercially viable synthesis of InP nanocrystals (NCs) involves highly pyrophoric phosphorus (P) precursor, tris(trimethylsilyl) phosphine (TMS3P). Finding a cheap and safe alternative would be the holy grail. We report the synthesis of InP NCs using triphenyl phosphite, an inexpensive and relatively safe phosphorous source. By reacting indium chloride and triphenyl phosphite, we obtained large-sized and black-colored InP NCs, yet without any distinct feature that shows quantum confinement effect. Addition of ZnCl2 resulted in InP NCs with controlled size, which was manifested in the shift of 1S peak in absorption spectra. By coating ZnS shell on InP NCs, we achieved photoluminescence with some extent of trap emission, showing maximum total quantum yield (QY) of 23% (8% of band-edge emission QY). We used 31P nuclear magnetic resonance (NMR), diffusion-ordered spectroscopy (DOSY), and mass spectrometry (MS) to assign intermediates and following mechanisms of the InP synthesis using triphenyl phosphite. The development of this safe and cost-effective P precursor opens broader opportunity space for large-scale production of InP NC.

Colloidal semiconductor nanocrystals hold great promise in display technologies, as the tunable energy levels and narrow emission bandwidth allow for wide gamut in color space. Impetus for energy-e...

Advance in wet chemistry enables the sophisticated design of nanocrystal quantum dots (QDs) and allows unprecedented color purity and brightness, promising their useful applications in a variety of...

Colloidal semiconductor nanocrystals, referred to as quantum dots (QDs), have unique and superb photophysical properties, promising a variety of applications ranging from optoelectronics and energy harvesting to agriculture. The last decade witnessed a tremendous advance in QDs and their successful debut in displays, and now, QDs are equipped with environmental benignity to expand their territory to everyday life. From this perspective, the current research status and future perspective of environmentally benign QDs as building blocks for light-generating and light-harvesting applications are provided. Also provided is an overview of the progress made in the chemistry (colloidal synthesis, surface chemistry, and heterostructuring) and in their photophysical and electrical properties from the viewpoint of their use in light-emitting or light-harvesting applications. Grounded on the current status of heavy-metal-free QDs compared with cutting-edge technologies, the perspective of environmentally benign QDs for practical use and future research directions is discussed.

Relatively large faces of colloidal CdSe nanoplatelets (NPLs) drive the anisotropic nanomaterials into one-dimensional superstructures through stacking of NPLs when solvent evaporates. We observe that the assembly could result in the formation of twisted ribbon superstructures with varying pitch length depending on lateral dimensions of CdSe NPLs. Transmission electron microscopy images and simulated projection reveal that stacked NPLs are distorted. The estimation of the contact area between distorted NPLs suggests that this distortion leads to lower energy of overall nanoribbon superstructures. The average pitch length of superstructures on the lateral dimension of NPLs depends on the dimension of NPLs as it alters the distortion angle of NPLs and thus the rotation angle between NPLs. We investigate the energy transfer between NPLs in the context of the lateral dimension of NPLs and the geometric structure of their superstructures via transient photoluminescence decay measurements. Our analysis on the e...

Synthesis of colloidal nanocrystals (NCs), which are not readily available via the wet-chemical approach based on arrested precipitation, has often relied on templated growth. Cation exchange, in which guest cations in bulk solution replace host cations in template NCs, has evolved as one of the most powerful examples. Despite its versatility and facileness, there are caveats because most of the cation-exchange processes presuppose the formation of crystalline defects, which are more or less uncontrolled in terms of population and locations. The defect formation is a consequence of the imbalance between extraction and incorporation of host and guest cations. Here, we demonstrate the controlling of ion-exchange balance in the Cu+-to-In3+ cation-exchange reaction of Cu3–xP nanoplatelets (NPLs), which triggers the nanoscale Kirkendall effect, a representative phenomenon of crystal defect generation, clearly shown by morphology change of NPLs. Cation-exchanged NPLs exhibit various morphologies depending on th...

The exceptional quality of light generated from colloidal quantum dots has attracted continued interest from the display and lighting industry, leading to the development of commercial quantum dot displays based on the photoluminescence down-conversion process. Beyond this technical level, quantum dots are being introduced as emissive materials in electroluminescence devices (or quantum dot-based light-emitting diodes), which boast high internal quantum efficiency of up to 100%, energy efficiency, thinness, and flexibility. In this review, we revisit various milestone studies regarding the core/shell heterostructures of colloidal quantum dots from the viewpoint of electroluminescence materials. Development of nanostructured colloidal quantum dots advanced from core/shell heterostructure, core/thick shell formulation, and delicate control of confinement potential shape has demonstrated close correlation of the photophysical properties of quantum dots with the performance of electroluminescence device, which provided useful guidelines on the heterostructured quantum dots for mitigating or eliminating efficiency limiting phenomena in quantum dot light emitting diodes. To enable practical and high performance quantum dot-based electroluminescence devices in the future, integration of design concepts on the heterostructures with environmentally benign systems will be crucial.

We investigate the operational instability of quantum dot (QD)-based light-emitting diodes (QLEDs). Spectroscopic analysis on the QD emissive layer within devices in chorus with the optoelectronic and electrical characteristics of devices discloses that the device efficiency of QLEDs under operation is indeed deteriorated by two main mechanisms. The first is the luminance efficiency drop of the QD emissive layer in the running devices owing to the accumulation of excess electrons in the QDs, which escalates the possibility of nonradiative Auger recombination processes in the QDs. The other is the electron leakage toward hole transport layers (HTLs) that accompanies irreversible physical damage to the HTL by creating nonradiative recombination centers. These processes are distinguishable in terms of the time scale and the reversibility, but both stem from a single origin, the discrepancy between electron versus hole injection rates into QDs. Based on experimental and calculation results, we propose mechanistic models for the operation of QLEDs in individual quantum dot levels and their degradation during operation and offer rational guidelines that promise the realization of high-performance QLEDs with proven operational stability.

Quasi-type II heterostructured nanocrystals (NCs) have been of particular interest due to their great potential for controlling the interplay of charge carriers. However, the lack of material choices for quasi-type II NCs restricts the accessible emission wavelength from red to near-infrared (NIR), which hinders their use in light-emitting applications that demand a wide range of visible colors. Herein, we demonstrate a new class of quasi-type II nanoemitters formulated in ZnSe/ZnSe 1- X Te X /ZnSe seed/spherical quantum well/shell heterostructures (SQWs) whose emission wavelength ranges from blue to orange. In a given geometry, ZnSe 1- X Te X emissive layers grown between the ZnSe seed and the shell layer are strained to fit into the surrounding media, and thus, the lattice mismatch between ZnSe 1- X Te X and ZnSe is effectively alleviated. In addition, composition of the ZnSe 1- X Te X emissive layer and the dimension of the ZnSe shell layer are engineered to tailor the distribution and energy of electron and hole wave functions. Benefitting from the capabilities to tune the charge carriers on demand and to form defect-free heterojunctions, ZnSe/ZnSe 1- X Te X /ZnSe/ZnS NCs show near-unity photoluminescence quantum yield ( PL QY > 90 % ) in a broad range of emission wavelengths (peak PL from 450 nm to 600 nm). Finally, we exemplify dichromatic white NC-based light-emitting diodes (NC-LEDs) employing the mixed layer of blue- and yellow-emitting ZnSe/ZnSe 1- X Te X /ZnSe/ZnS SQW NCs.

The potential profile and the energy level offset of core/shell heterostructured nanocrystals (h-NCs) determine the photophysical properties and the charge transport characteristics of h-NC solids. However, limited material choices for heavy metal-free III-V/II-VI h-NCs pose challenges in comprehensive control of the potential profile. Herein, we present an unprecedented approach to such control by steering dipole moments at the interface of III-V/II-VI h-NCs. The controllable heterovalency at the interface is responsible for interfacial dipole moments that result in the vacuum-level shift, providing an additional knob for the control of optical and electrical characteristics of h-NCs. We capitalize on the atomic precision with which to synthesize h-NCs by correlating interfacial dipole moments to photochemical stability and optoelectronic performance of resulting h-NCs.