Memristive Switching Mechanism in Colloidal InP/ZnSe/ZnS Quantum Dot-Based Synaptic Devices for Neuromorphic Computing.

Quantum dots (QDs) have garnered a significant amount of attention as promising memristive materials owing to their size-dependent tunable bandgap, structural stability, and high level of applicability for neuromorphic computing. Despite these advantageous properties, the development of QD-based memristors has been hindered by challenges in understanding and adjusting the resistive switching (RS) behavior of QDs. Herein, we propose three types of InP/ZnSe/ZnS QD-based memristors to elucidate the RS mechanism, employing a thin poly(methyl methacrylate) layer. This approach not only allows us to identify which carriers (electron or hole) are trapped within the QD layer but also successfully demonstrates QD-based synaptic devices. Furthermore, to utilize the QD memristor as a synapse, long-term potentiation/depression (LTP/LTD) characteristics are measured, resulting in a low nonlinearity of LTP/LTD at 0.1/1. On the basis of the LTP/LTD characteristics, single-layer perceptron simulations were performed using the Extended Modified National Institute of Standards and Technology, verifying a maximum recognition rate of 91.46%.

Electrically Tunable Single Polaritonic Quantum Dot at Room Temperature.

Exciton-polaritons confined in plasmonic cavities are hybridized light-matter quasiparticles, with distinct optical characteristics compared to plasmons and excitons alone. Here, we demonstrate the electric tunability of a single polaritonic quantum dot operating at room temperature in electric-field tip-enhanced strong coupling spectroscopy. For a single quantum dot in the nanoplasmonic tip cavity with variable dc local electric field, we dynamically control the Rabi frequency with the corresponding polariton emission, crossing weak to strong coupling. We model the observed behaviors based on the quantum confined Stark effect in the strong coupling regime.

Oligomeric Zinc Thiolates Tethering Multidentate Carboxylates for Nondestructive Aqueous Phase Transfer of Quantum Dots.

Functionalization of quantum dots (QDs) via ligand exchange is prone to debase their photoluminescence quantum yield (PL QY) owing to the unavoidable surface damage by excess reactants, and even worse in aqueous medium. Herein, the oligomeric zinc thiolate as the multidentate hydrophilic ligand featuring facile synthetic protocol is proposed. A simple reaction between ZnCl2 and 3-mercaptopropionic acid produces oligomeric ligands containing 3-6 zinc thiolate units, where the terminal moieties provide multidentate anchoring to the surface as well as hydrophilicity. 2D proton nuclear Overhauser effect spectroscopy (2D 1 H NOESY) and X-ray photoelectron spectroscopy (XPS) reveal that the oligomeric zinc thiolate ligands adsorb on the surface via multidentate metal carboxylate bindings without destruction of molecular structure, regardless of partial dissociation of thiolate branches in aqueous phase. Enhanced binding affinity granted by the multidentate nature allows for the effective exchange of original surface ligands without considerable surface deterioration. The zinc thiolate-capped Cd-free aqueous QDs exhibit a high photoluminescence quantum yield of ≈90% and extended stability against long-term storage and photochemical stress.

Gate Controlled Excitonic Emission in Quantum Dot Thin Films.

Formation of charged trions is detrimental to the luminescence quantum efficiency of colloidal quantum dot (QD) thin films as they predominantly undergo nonradiative recombination. In this regard, control of charged trion formation is of interest for both fundamental characterization of the quasi-particles and performance optimization. Using CdSe/CdS QDs as a prototypical material system, here we demonstrate a metal-oxide-semiconductor capacitor based on QD thin films for studying the background charge effect on the luminescence efficiency and lifetime. The concentration ratio of the charged and neutral quasiparticles in the QDs is reversibly controlled by applying a gate voltage, while simultaneous steady-state and time-resolved photoluminescence measurements are performed. Notably, the photoluminescence intensity is modulated by up to 2 orders of magnitude with a corresponding change in the effective lifetime. In addition, chip-scale modulation of brightness is demonstrated, where the photoluminescence is effectively turned on and off by the gate, highlighting potential applications in voltage-controlled electrochromics.

Evaporation-driven Supraparticle Synthesis by Self-Lubricating Colloidal Dispersion Microdrops.

The surface-templated evaporation-driven (S-TED) method that uses liquid-repellent surfaces has attracted considerable attention for its use in fabricating supraparticles of defined shape, size, and porosity. However, challenges in achieving mass production have impeded the widespread adoption of the S-TED method. To overcome this limit, we introduce an evaporation-driven "multiple supraparticle" synthesis by drying arrays of self-lubricating colloidal dispersion microdrops. To facilitate this synthetic method, a hydrophilic micropattern is prepared on a hydrophobic substrate as a template. During the removal of the substrate out of a dispersion, liquid drops are trapped and generate a microdrop array. To produce supraparticles, the contact lines of the trapped drops must be able to recede freely during evaporation. However, hydrophilic micropatterns induce strong contact line pinning for microdrops that hinders supraparticle formation. Herein, we solve this contradiction by employing an Ouzo-like colloidal dispersion, where we can control the wettability of the drop trapping domain. The self-lubrication effect provided by the Ouzo-like solution enables smooth movement of the drops' contact lines during evaporation, thereby resulting in the successful fabrication of supraparticle arrays even within the trapping domain. This strategy offers a promising and scalable approach for large-scale evaporation-driven supraparticle synthesis with a potential for extension to various primary colloidal particles, further broadening its applicability.

All-Solution-Processed Quantum Dot Light-Emitting Diode Using Phosphomolybdic Acid as Hole Injection Layer.

In this study, we investigate phosphomolybdic acid (PMA), which allows solution processing of quantum dot light-emitting diodes. With its low cost, easy solution processes, and excellent physical and optical properties, PMA is a potential candidate as the hole injection layer (HIL) in optoelectronic devices. We evaluate the physical and electrical properties of PMA using various solvents. The surface morphology of the PMA film was improved using a solvent with appropriate boiling points, surface tension, and viscosity to form a smooth, pinhole-free film. The energy level was regulated according to the solvent, and PMA with the appropriate electronic structure provided balanced charge carrier transport in quantum dot electroluminescent (QD-EL) devices with enhanced efficiency. A device using PMA dissolved in cyclohexanone was demonstrated to exhibit improved efficiency compared to a device using PEDOT:PSS, which is a conventional solution HIL. However, the stability of PMA was slightly poorer than PEDOT:PSS; there needs to be further investigation.

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%.

Environmental management education using immersive virtual reality in asthmatic children in Korea: a randomized controlled study (secondary publication)

Awareness of environmental control is considered a significant influence on the performance of asthma self-management behaviors, which are involved in maintaining effective asthma control. This study aimed to investigate whether immersive virtual reality (VR) education is effective in environmental control education for asthmatic children in Korea. Thirty asthmatic children aged 9 to 13 years with aeroallergen sensitization were enrolled. Environmental control education for asthmatic participants was performed using immersive VR (VR group) or conventional leaflets provided by asthma specialists (control group). Five questionnaires, on awareness of environmental control, memory, assessment of intent to act, a satisfaction test, and an Asthma Control Test (ACT), were used to estimate the effects of education. The scores for awareness of environmental control, memory, and intent to act significantly increased after education in both groups, and the scores remained high until 4 weeks after education. Both groups' ACT scores were consistently high before and 4 weeks after education. Satisfaction scores were very high in the VR group. The increased scores in awareness of environmental control and intent to act indicate that the environmental control education using VR is worthy of attention as an effective educational tool for asthma management. Further developed techniques, including active environmental interventions by participants in VR, could be applied to effective asthma management.

Two-band optical gain and ultrabright electroluminescence from colloidal quantum dots at 1000 A cm-2.

Colloidal quantum dots (QDs) are attractive materials for the realization of solution-processable laser diodes. Primary challenges towards this objective are fast optical-gain relaxation due to nonradiative Auger recombination and poor stability of colloidal QD solids under high current densities required to obtain optical gain. Here we resolve these challenges and achieve broad-band optical gain spanning the band-edge (1S) and the higher-energy (1P) transitions. This demonstration is enabled by continuously graded QDs with strongly suppressed Auger recombination and a current-focusing device design, combined with short-pulse pumping. Using this approach, we achieve ultra-high current densities (~1000 A cm-2) and brightness (~10 million cd m-2), and demonstrate an unusual two-band electroluminescence regime for which the 1P band is more intense than the 1S feature. This implies the realization of extremely large QD occupancies of up to ~8 excitons per-dot, which corresponds to complete filling of the 1S and 1P electron shells.

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.

Surface state-induced barrierless carrier injection in quantum dot electroluminescent devices.

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.

High-Resolution Colloidal Quantum Dot Film Photolithography via Atomic Layer Deposition of ZnO.

High-resolution patterning of quantum dot (QD) films is one of the preconditions for the practical use of QD-based emissive display platforms. Recently, inkjet printing and transfer printing have been actively developed; however, high-resolution patterning is still limited owing to nozzle-clogging issues and coffee ring effects during the inkjet printing and kinetic parameters such as pickup and peeling speed during the transfer process. Consequently, employing direct optical lithography would be highly beneficial owing to its well-established process in the semiconductor industry; however, exposing the photoresist (PR) on top of the QD film deteriorates the QD film underneath. This is because a majority of the solvents for PR easily dissolve the pre-existing QD films. In this study, we present a conventional optical lithography process to obtain solvent resistance by reacting the QD film surface with diethylzinc (DEZ) precursors using atomic layer deposition. It was confirmed that, by reacting the QD surface with DEZ and coating PR directly on top of the QD film, a typical photolithography process can be performed to generate a red/green/blue pixel of 3000 ppi or more. QD electroluminescence devices were fabricated with all primary colors of QDs; moreover, compared to reference QD-LED devices, the patterned QD-LED devices exhibited enhanced brightness and efficiency.

Probiotic mixture reduces gut inflammation and microbial dysbiosis in children with atopic dermatitis.

BACKGROUND: Recent data suggested that dysbiosis of the gut microbiome is associated with childhood allergic diseases. Oral administration of probiotic formulations may improve the severity of atopic dermatitis (AD) by restoring imbalanced gut microbiota and reducing intestinal inflammation in children. OBJECTIVES: The aim of this study was to investigate the effects of a probiotic mixture on the clinical severity of AD, gut inflammatory markers and alterations in microbiome dysbiosis in children with AD. METHODS: A total of 25 subjects were enrolled in this study and administered with a mixture of probiotic strains consisting of Lactobacilli and Bifidobacteria for 4 weeks. The clinical efficacy of the probiotic mixture was assessed using SCORAD index and TEWL. Faecal calprotectin levels were measured as a marker for intestinal inflammation. The composition and diversity of the gut microbiome were analysed using 16S rRNA pyrosequencing. RESULTS: The SCORAD (38.9 ± 17.2 vs 29.0 ± 15.4, P < 0.001) and TEWL (58.3 ± 12.5 vs 27.3 ± 8.7 g/m2 /h, P = 0.028) were significantly decreased after 4 weeks administration of the probiotic mixture. The faecal calprotectin level (121.5 [27.7-292.9] vs 37.0 µg/g [12.6-108.9 µg/g], P = 0.038) was significantly decreased. The α-diversity and composition of the gut microbiome were not significantly changed, but ß-diversity was increased after 4 weeks. CONCLUSIONS: The oral administration of the probiotic mixture was effective in reducing clinical severity and intestinal inflammation in children with AD. Gut microbial diversity was slightly increased after administration of the probiotic mixture. The results of this study suggest that a probiotic mixture can alleviate AD by decreasing inflammation and modulating the gut microbiota in children with AD.

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.

Solution-processable integrated CMOS circuits based on colloidal CuInSe2 quantum dots.

The emerging technology of colloidal quantum dot electronics provides an opportunity for combining the advantages of well-understood inorganic semiconductors with the chemical processability of molecular systems. So far, most research on quantum dot electronic devices has focused on materials based on Pb- and Cd chalcogenides. In addition to environmental concerns associated with the presence of toxic metals, these quantum dots are not well suited for applications in CMOS circuits due to difficulties in integrating complementary n- and p-channel transistors in a common quantum dot active layer. Here, we demonstrate that by using heavy-metal-free CuInSe2 quantum dots, we can address the problem of toxicity and simultaneously achieve straightforward integration of complimentary devices to prepare functional CMOS circuits. Specifically, utilizing the same spin-coated layer of CuInSe2 quantum dots, we realize both p- and n-channel transistors and demonstrate well-behaved integrated logic circuits with low switching voltages compatible with standard CMOS electronics.

High-resolution patterning of colloidal quantum dots via non-destructive, light-driven ligand crosslinking.

Establishing multi-colour patterning technology for colloidal quantum dots is critical for realising high-resolution displays based on the material. Here, we report a solution-based processing method to form patterns of quantum dots using a light-driven ligand crosslinker, ethane-1,2-diyl bis(4-azido-2,3,5,6-tetrafluorobenzoate). The crosslinker with two azide end groups can interlock the ligands of neighbouring quantum dots upon exposure to UV, yielding chemically robust quantum dot films. Exploiting the light-driven crosslinking process, different colour CdSe-based core-shell quantum dots can be photo-patterned; quantum dot patterns of red, green and blue primary colours with a sub-pixel size of 4 µm × 16 µm, corresponding to a resolution of >1400 pixels per inch, are demonstrated. The process is non-destructive, such that photoluminescence and electroluminescence characteristics of quantum dot films are preserved after crosslinking. We demonstrate that red crosslinked quantum dot light-emitting diodes exhibiting an external quantum efficiency as high as 14.6% can be obtained.

Double Metal Oxide Electron Transport Layers for Colloidal Quantum Dot Light-Emitting Diodes.

The performance of colloidal quantum dot light-emitting diodes (QD-LEDs) have been rapidly improved since metal oxide semiconductors were adopted for an electron transport layer (ETL). Among metal oxide semiconductors, zinc oxide (ZnO) has been the most generally employed for the ETL because of its excellent electron transport and injection properties. However, the ZnO ETL often yields charge imbalance in QD-LEDs, which results in undesirable device performance. Here, to address this issue, we introduce double metal oxide ETLs comprising ZnO and tin dioxide (SnO2) bilayer stacks. The employment of SnO2 for the second ETL significantly improves charge balance in the QD-LEDs by preventing spontaneous electron injection from the ZnO ETL and, as a result, we demonstrate 1.6 times higher luminescence efficiency in the QD-LEDs. This result suggests that the proposed double metal oxide ETLs can be a versatile platform for QD-based optoelectronic devices.

Ligands as a universal molecular toolkit in synthesis and assembly of semiconductor nanocrystals.

Successful exploitation of semiconductor nanocrystals (NCs) in commercial products is due to the remarkable progress in the wet-chemical synthesis and controlled assembly of NCs. Central to the cadence of this progress is the ability to understand how NC growth and assembly can be controlled kinetically and thermodynamically. The arrested precipitation strategy offers a wide opportunity for materials selection, size uniformity, and morphology control. In this colloidal approach, capping ligands play an instrumental role in determining growth parameters and inter-NC interactions. The impetus for exquisite control over the size and shape of NCs and orientation of NCs in an ensemble has called for the use of two or more types of ligands in the system. In multiple ligand approaches, ligands with different functionalities confer extended tunability, hinting at the possibility of atomic-precision growth and long-range ordering of desired superlattices. Here, we highlight the progress in understanding the roles of ligands in size and shape control and assembly of NCs. We discuss the implication of the advances in the context of optoelectronic applications.

Effect of Electron Injection Layer on the Parasitic Recombination at the Hole Transport Layer/Quantum Dot Interface in Quantum Dot Light-Emitting Diodes.

Zinc oxide (ZnO) nanoparticles layers are used as a substitute for organic electron transport layer due to high electron mobility, higher thermal stability and less sensitivity to the oxygen/moisture. In this study, we investigated the electron injection properties of ZnO nanoparticles in QLED compared with TPBi commonly used as injection layer in OLEDs. The expected electron injection barrier from energy diagram is similar in both devices, but the current density of the ZnO injection layer was slightly high compared with the TPBi injection layer. The current efficiency of ZnO and TPBi devices were 5.21 cd/A and 2.24 cd/A, respectively. The current efficiency of TPBi device is below half of ZnO device. We found that the electron-hole recombination occurs not only in the QD but also in the poly-TPD for TPBi device.

High Efficiency Quantum Dot Light-Emitting Diode by Solution Printing of Zinc Oxide Nanoparticles.

Quantum dot light-emitting diodes (QLEDs) have attracted considerable attention owing to the narrow emission spectra, wide color gamut, high quantum yield and size-controlled emission wavelength. Zinc oxide nanoparticles have been widely used as an electron transport layer (ETL) in QLEDs due to their excellent electrical properties. In this study, we compared the efficiency of QLEDs with organic and zinc oxide ETLs in viewpoint of the charge balance. The QLEDs were constructed using ZnO nanoparticles with an average particle size of 3 nm or 3TPYMB as the ETL materials. CdSe/ZnS quantum dots and poly-TPD were used as a light-emitting elements and hole transporting material, respectively. The QLED with 3TPYMB ETL exhibited current efficiency of 7.71 cd/A, while the efficiency of the QLED using ZnO nanoparticles was significantly improved to 38.76 cd/A. Such a substantial improvement of emission efficiency in the QLEDs with ZnO ETL was attributed to the much better charge balance by the ZnO.