Electrically driven amplified spontaneous emission from colloidal quantum dots.

Colloidal quantum dots (QDs) are attractive materials for realizing solution-processable laser diodes that could benefit from size-controlled emission wavelengths, low optical-gain thresholds and ease of integration with photonic and electronic circuits1-7. However, the implementation of such devices has been hampered by fast Auger recombination of gain-active multicarrier states1,8, poor stability of QD films at high current densities9,10 and the difficulty to obtain net optical gain in a complex device stack wherein a thin electroluminescent QD layer is combined with optically lossy charge-conducting layers11-13. Here we resolve these challenges and achieve amplified spontaneous emission (ASE) from electrically pumped colloidal QDs. The developed devices use compact, continuously graded QDs with suppressed Auger recombination incorporated into a pulsed, high-current-density charge-injection structure supplemented by a low-loss photonic waveguide. These colloidal QD ASE diodes exhibit strong, broadband optical gain and demonstrate bright edge emission with instantaneous power of up to 170 µW.

Randomly Disassembled Nanostructure for Wide Angle Light Extraction of Top-Emitting Quantum Dot Light-Emitting Diodes.

The quantum dot light-emitting diode (QLED) represents one of the strongest display technologies and has unique advantages like a shallow emission spectrum and superior performance based on the cumulative studies of state-of-the-art quantum dot (QD) synthesis and interfacial engineering. However, research on managing the device's light extraction has been lacking compared to the conventional LED field. Moreover, relevant studies on top-emitting QLEDs (TE-QLEDs) have been severely lacking compared to bottom-emitting QLEDs (BE-QLEDs). This paper demonstrates a novel light extraction structure called the randomly disassembled nanostructure (RaDiNa). The RaDiNa is formed by detaching polydimethylsiloxane (PDMS) film from a ZnO nanorod (ZnO NR) layer and laying it on top of the TE-QLED. The RaDiNa-attached TE-QLED shows significantly widened angular-dependent electroluminescence (EL) intensities over the pristine TE-QLED, confirming the effective light extraction capability of the RaDiNa layer. Consequently, the optimized RaDiNa-attached TE-QLED achieves enhanced external quantum efficiency (EQE) over the reference device by 60%. For systematic analyses, current-voltage-luminance (J-V-L) characteristics are investigated using scanning electron microscopy (SEM) and optical simulation based on COMSOL Multiphysics. It is believed that this study's results provide essential information for the commercialization of TE-QLEDs.

Interface polarization in heterovalent core-shell nanocrystals.

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 approach to such a control by steering dipole densities at the interface of III-V-II-VI h-NCs. The controllable heterovalency at the interface is responsible for interfacial dipole densities that result in the vacuum-level shift, providing an additional knob for the control of optical and electrical characteristics of h-NCs. The synthesis of h-NCs with atomic precision allows us to correlate interfacial dipole moments with the NCs' photochemical stability and optoelectronic performance.

Transient Dynamics of Charges and Excitons in Quantum Dot Light-Emitting Diodes.

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.

Highly Efficient and Bright Inverted Top-Emitting InP Quantum Dot Light-Emitting Diodes Introducing a Hole-Suppressing Interlayer.

InP quantum dots (QDs) based light-emitting diodes (QLEDs) are considered as one of the most promising candidates as a substitute for the environmentally toxic Cd-based QLEDs for future displays. However, the device architecture of InP QLEDs is almost the same as the Cd-based QLEDs even though the properties of Cd-based and InP-based QDs are quite different in their energy levels and shapes. Thus, it is highly required to develop a proper device structure for InP-based QLEDs to improve the efficiency and stability. In this work, efficient, bright, and stable InP/ZnSeS QLEDs based on an inverted top emission QLED (ITQLED) structure by newly introducing a "hole-suppressing interlayer" are demonstrated. The green-emitting ITQLEDs with the hole-suppressing interlayer exhibit a maximum current efficiency of 15.1-21.6 cd A-1 and the maximum luminance of 17 400-38 800 cd m-2 , which outperform the recently reported InP-based QLEDs. The operational lifetime is also increased when the hole-suppressing interlayer is adopted. These superb QLED performances originate not only from the enhanced light-outcoupling by the top emission structure but also from the improved electron-hole balance by introducing a hole-suppressing interlayer which can control the hole injection into QDs.

Controlled Phase Separation in Poly( p-phenyleneethynylene) Thin Films and Its Relationship to Vapor-Sensing Properties.

In this paper, we report the synthesis and mesoporous film formation of hydrophobic rodlike poly( p-phenyleneethynylene)s (PPEs) and present porosity-dependent quenching studies using 1,3,5-trinitrotoluene (TNT) vapors. Nonsolvent vapor-induced phase separation was used to induce pore formation during film casting, and the concentration of PPEs in the casting solution was controlled carefully to prevent excimer formation. We found that the structures of the sidechains of the PPEs strongly influence the range of relative humidity at which controlled pore generation occurs, which could be rationalized from interfacial energies calculated from contact angle measurements. Porosity of the PPE films resulted in increased efficiency of fluorescence quenching toward TNT vapors, which previously required very thin films (below 5 nm) for sensing applications. The control of the porous structure as well as film thickness constitutes a promising strategy for enhancing the efficiency of chemosensors and in more general applications requiring fine-tuned polymer-gas interactions.

Assemblies of Colloidal CdSe Tetrapod Nanocrystals with Lengthy Arms for Flexible Thin-Film Transistors.

Herein, we report unique features of the assemblies of tetrapod-shaped colloidal nanocrystals (TpNCs) with lengthy arms applicable to flexible thin-film transistors. Due to the extended nature of tetrapod geometry, films made of the TpNC assemblies require reduced numbers of inter-NC hopping for the transport of charge carriers along a given channel length; thus, enhanced conductivity can be achieved compared to those made of typical spherical NCs without arms. Moreover, electrical conduction through the assemblies is tolerant against mechanical bending because interconnections between TpNCs can be well-preserved under bending. Interestingly, both the conductivity of the assemblies and their mechanical tolerance against bending are improved with an increase in the length of tetrapod arms. The arm length-dependency was demonstrated in a series of CdSe TpNC assemblies with different arm lengths (l = 0-90 nm), whose electrical conduction was modulated through electrolyte gating. From the TpNCs with the longest arm length included in the study (l = 90 nm), the film conductivity as high as 20 S/cm was attained at 3 V of gate voltage, corresponding to electron mobility of >10 cm2/(V s) even when evaluated conservatively. The high channel conductivity was retained (∼90% of the value obtained from the flat geometry) even under high bending (bending radius = 5 mm). The results of the present study provide new insights and guidelines for the use of colloidal nanocrystals in solution-processed flexible electronic device applications.

Quantum Dot-Based Three-Stack Tandem Near-Infrared-to-Visible Optoelectric Upconversion Devices.

Quantum dots (QDs) exhibit size-tunable optical properties, making them suitable for efficient light-sensing and light-emitting devices. Tandem devices that can convert near-infrared (NIR) to visible (Vis) signals can be fabricated by integrating an NIR-sensing QD device with a Vis electroluminescence (EL) QD device. However, these devices require delicate control of the QD layer during processing to prevent damage to the predeposited QD layers in tandem devices during the subsequent deposition of other functional layers. This has restricted attainable device structures for QD-based upconversion devices. Herein, we present a modular approach for fabricating QD-based optoelectric upconversion devices. This approach involves using NIR QD-absorbing (Abs) and Vis QD-EL units as building modules, both of which feature cross-linked functional layers that exhibit structural tolerance to dissolution during subsequent solution-based processes. Tandem devices are fabricated in both normal (EL unit on Abs unit) and inverted (Abs unit on EL unit) structures using the same set of NIR QD-Abs and Vis QD-EL units stacked in opposite sequences. The tandem device in the normal structure exhibits a high NIR photon-to-Vis-photon conversion efficiency of up to 1.9% in a practical transmissive mode. By extending our modular approach, we also demonstrate a three-stack tandem device that incorporates a single NIR-absorbing unit coupled with two EL units, achieving an even higher conversion efficiency of up to 3.2%.

Impact of Alternating-Current Operation on All-Inorganic Quantum Dot Light-Emitting Diodes.

In colloidal quantum dot light-emitting diodes (QD-LEDs), replacing organic hole transport layers (HTLs) with their inorganic counterparts is expected to yield distinct advantages due to their inherent material robustness. However, despite the promising characteristics of all-inorganic QD-LEDs, some challenges persist in achieving stable operation; for example, the electron overflow toward the inorganic HTL and charge accumulation within working devices return a temporal inconsistency in device characteristics. To address these challenges, we propose an operational approach that employs an alternating-current (AC) in all-inorganic QD-LEDs. We carry out comprehensive studies on the optoelectrical characteristics of all-inorganic QD-LEDs under direct-current (DC) or AC operation and demonstrate that AC operation can facilitate efficient charge carrier recombination within the QD emissive layer, leading to improved device efficiency and temporally invariant optoelectronic characteristics. Leveraging the intrinsic material robustness of inorganic charge transport layers (CTLs), our current study suggests a promising pathway toward enhancing the performance and stability of QD-LEDs, particularly for futuristic display applications.

Heteroepitaxial chemistry of zinc chalcogenides on InP nanocrystals for defect-free interfaces with atomic uniformity.

Heteroepitaxy on colloidal semiconductor nanocrystals is an essential strategy for manipulating their optoelectronic functionalities. However, their practical synthesis typically leads to scattered and unexpected outcomes due to the intervention of multiple reaction pathways associated with complicated side products of reactants. Here, the heteroepitaxy mechanism of zinc chalcogenide initiated on indium phosphide (InP) colloidal nanocrystals is elucidated using the precursors, zinc carboxylate and trialkylphosphine selenide. The high magnetic receptivity of 77Se and the characteristic longitudinal optical phonon mode of ZnSe allowed for monitoring the sequence of epilayer formation at the molecular level. The investigation revealed the sterically hindered acyloxytrialkylphosphonium and diacyloxytrialkylphosphorane to be main intermediates in the surface reaction, which retards the metal ion adsorption by a large steric hindrance. The transformation of adsorbates to the crystalline epilayer was disturbed by surface oxides. Raman scattering disclosed the pathway of secondary surface oxidation triggered by carboxylate ligands migrated from zinc carboxylate. The surface-initiated heteroepitaxy protocol is proposed to fabricate core/shell heterostructured nanocrystals with atomic-scale uniformity of epilayers. Despite the large lattice mismatch of ZnS to InP, we realised a uniform and interface defect-free ZnS epilayer (~0.3 nm thickness) on InP nanocrystals, as evidenced by a high photoluminescence quantum yield of 97.3%.

Optimum Design Configuration of Thin-Film Transistors and Quantum-Dot Light-Emitting Diodes for Active-Matrix Displays.

Active matrix (AM) quantum-dot light-emitting diodes (QLEDs) driven by thin-film transistors (TFTs) have attracted significant attention for use in next-generation displays. Several challenges remain for the realisation of AM-QLEDs, such as device design, fabrication process, and integration between QLEDs and TFTs, depending on their device structures and configurations. Herein, efficient and stable AM-QLEDs are demonstrated using conventional and inverted structured QLEDs (C- and I-QLEDs, respectively) combined with facile type-convertible (p- and n-type) single-walled carbon nanotube (SWNT)-based TFTs. Based on the four possible configurations of the QLED-TFT subpixel, the performance of the SWNT TFT-driven QLEDs and the fabrication process to determine the ideal configuration are compared, taking advantage of each structure for AM-QLEDs. The QLEDs and TFTs are also optimized to maximise the performance of the AM-QLEDs-the inner shell composition of quantum dots and carrier type of TFTs-resulting in a maximum external quantum efficiency and operational lifetime (at an initial luminance of 100 cd m2 ) of 21.2% and 38 100 000 h for the C-QLED, and 19.1% and 133100000 h for the I-QLED, respectively. Finally, a 5×5 AM-QLED display array controlled using SWNT TFTs is successfully demonstrated. This study is expected to contribute to the development of advanced AM-QLED displays.

Bright and Stable Quantum Dot Light-Emitting Diodes.

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.

Impact of Morphological Inhomogeneity on Excitonic States in Highly Mismatched Alloy ZnSe1-XTeX Nanocrystals.

ZnSe1-XTeX nanocrystals (NCs) are promising photon emitters with tunable emission across the violet to orange range and near-unity quantum yields. However, these NCs suffer from broad emission line widths and multiple exciton decay dynamics, which discourage their practicable use. Here, we explore the excitonic states in ZnSe1-XTeX NCs and their photophysical characteristics in relation to the morphological inhomogeneity of highly mismatched alloys. Ensemble and single-dot spectroscopic analysis of a series of ZnSe1-XTeX NC samples with varying Te ratios coupled with computational calculations shows that, due to the distinct electronegativity between Se and Te, nearest-neighbor Te pairs in ZnSe1-XTeX alloys create localized hole states spectrally distributed approximately 130 meV above the 1Sh level of homogeneous ZnSe1-XTeX NCs. This forms spatially separated excitons (delocalized electron and localized hole in trap), accounting for both inhomogeneous and homogeneous line width broadening with delayed recombination dynamics. Our results identify photophysical characteristics of excitonic states in NCs made of highly mismatched alloys and provide future research directions with potential implications for photonic applications.

Direct patterning of colloidal quantum dots with adaptable dual-ligand surface.

Colloidal quantum dots (QDs) stand at the forefront of a variety of photonic applications given their narrow spectral bandwidth and near-unity luminescence efficiency. However, integrating luminescent QD films into photonic devices without compromising their optical or transport characteristics remains challenging. 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 over the structure of both ligands allows the direct patterning of dual-ligand QDs on various substrates using commercialized photolithography (i-line) or inkjet printing systems at a resolution up to 15,000 pixels per inch without compromising the optical properties of the QDs or the optoelectronic performance of the device. We demonstrate the capabilities of our approach for QD-LED applications. Our approach offers a versatile way of creating various structures of luminescent QDs in a cost-effective and non-destructive manner, and could be implemented in nearly all commercial photonics applications where QDs are used.

Nondestructive Photopatterning of Heavy-Metal-Free Quantum Dots.

Electroluminescence from quantum dots (QDs) is a suitable photon source for futuristic displays offering hyper-realistic images with free-form factors. Accordingly, a nondestructive and scalable process capable of rendering multicolored QD patterns on a scale of several micrometers needs to be established. Here, nondestructive direct photopatterning for heavy-metal-free QDs is reported using branched light-driven ligand crosslinkers (LiXers) containing multiple azide units. The branched LiXers effectively interlock QD films via photo-crosslinking native aliphatic QD surface ligands without compromising the intrinsic optoelectronic properties of QDs. Using branched LiXers with six sterically engineered azide units, RGB QD patterns are achieved on the micrometer scale. The photo-crosslinking process does not affect the photoluminescence and electroluminescence characteristics of QDs and extends the device lifetime. This nondestructive method can be readily adapted to industrial processes and make an immediate impact on display technologies, as it uses widely available photolithography facilities and high-quality heavy-metal-free QDs with aliphatic ligands.

Electronic Skin Based on a Cellulose/Carbon Nanotube Fiber Network for Large-Area 3D Touch and Real-Time 3D Surface Scanning.

Electronic skin (E-skin) based on tactile sensors has great significance in next-generation electronics such as biomedical application and artificial intelligence that requires interaction with humans. To mimic the properties of human skin, high flexibility, excellent sensing capability, and sufficient spatial resolution through high-level sensor integration are required. Here, we report a highly sensitive pressure sensor matrix based on a piezoresistive cellulose/single-walled carbon nanotube-entangled fiber network, which forms its own porous structure enabling a superior pressure sensor with a high sensitivity (9.097 kPa-1), a fast response speed (<2 ms), and orders of magnitude detection range with a detection limit of 1 Pa. Furthermore, the remarkable device expandability based on the ease of patterning and scalability allows easy implementation of a large-area pressure sensor matrix which has 2304 (48 × 48) pixels. Combined with a real-time pressure distribution monitoring system, a flexible 3D touch sensor that simultaneously displays plane coordinates and pressure information and a scanning device that detects the morphology of the soft body 3D surface are successfully demonstrated.

Steering Interface Dipoles for Bright and Efficient All-Inorganic Quantum Dot Based Light-Emitting Diodes.

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/m2) along with prolonged operational stability. The approaches and results in the present study provide the design principles for high-performance all-inorganic QD-LEDs suited for next-generation light sources.

A Bioinspired Stretchable Sensory-Neuromorphic System.

Conventional stretchable electronics that adopt a wavy design, a neutral mechanical plane, and conformal contact between abiotic and biotic interfaces have exhibited diverse skin-interfaced applications. Despite such remarkable progress, the evolution of intelligent skin prosthetics is challenged by the absence of the monolithic integration of neuromorphic constituents into individual sensing and actuating components. Herein, a bioinspired stretchable sensory-neuromorphic system, comprising an artificial mechanoreceptor, artificial synapse, and epidermal photonic actuator is demonstrated; these three biomimetic functionalities correspond to a stretchable capacitive pressure sensor, a resistive random-access memory, and a quantum dot light-emitting diode, respectively. This system features a rigid-island structure interconnected with a sinter-free printable conductor, which is optimized by controlling the evaporation rate of solvent (≈160% stretchability and ≈18 550 S cm-1 conductivity). Devised design improves both areal density and structural reliability while avoiding the thermal degradation of heat-sensitive stretchable electronic components. Moreover, even in the skin deformation range, the system accurately recognizes various patterned stimuli via an artificial neural network with training/inferencing functions. Therefore, the new bioinspired system is expected to be an important step toward implementing intelligent wearable electronics.

Surface Engineered Colloidal Quantum Dots for Complete Green Process.

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.

Tailoring the Electronic Landscape of Quantum Dot Light-Emitting Diodes for High Brightness and Stable Operation.

The charge injection imbalance into the quantum dot (QD) emissive layer of QD-based light-emitting diodes (QD-LEDs) is an unresolved issue that is detrimental to the efficiency and operation stability of devices. Herein, an integrated approach to harmonize the charge injection rates for bright and stable QD-LEDs is proposed. Specifically, the electronic characteristics of the hole transport layer (HTL) is delicately designed in order to facilitate the hole injection from the HTL into QDs and confine the electron overflow toward the HTL. The well-defined exciton recombination zone by the engineered QDs and HTL results in high performance with a peak luminance exceeding 410 000 cd/m2, suppressed efficiency roll-off characteristics (ΔEQE < 5% between 200 and 200 000 cd/m2), and prolonged operational stability. The electric and optoelectronic analyses reveal the charge carrier injection mechanism at the interface between the HTL and QDs and provides the design principle of QD heterostructures and charge transport layers for high-performance QD-LEDs.