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.

Interface roughness effects and relaxation dynamics of an amorphous semiconductor oxide-based analog resistance switching memory.

The analog resistive switching properties of amorphous InGaZnOx (a-IGZO)-based devices with Al as the top and bottom electrodes and an Al-Ox interface layer inserted on the bottom electrode are presented here. The influence of the electrode deposition rate on the surface roughness was established and proposed as the cause of the observed unusual anomalous switching effects. The DC electrical characterization of the optimized Al/a-IGZO/AlOx/Al devices revealed an analog resistive switching with a satisfactory value for retention levels, but the endurance was found to decrease after 200 cycles. The predominant conduction mechanism in these devices was found to be thermionic emission. An in-depth analysis was performed to explore the relaxation kinetics of the device and it was found that the current has a lower decay rate. The current level stability was tested and found reliable even after 5 h. The cost-effective and precious metal-free nature of the a-IGZO memristor investigated in this study makes it a highly desirable candidate for neuromorphic computing applications.

Thermoelectric performance of novel single-layer ZrTeSe4.

In energy conversion techniques, two-dimensional (2D) thermoelectric materials with high performance are strongly required. This study scrutinizes the electronic and thermoelectric properties of 2D single-layer (1L) ZrTeSe4 based on first-principles calculations combined with Boltzmann transport theory. First-principles molecular dynamics simulations and phonon calculations confirm the thermodynamic stability of 1L-ZrTeSe4. Furthermore, the electron mobility of 1L-ZrTeSe4 is calculated to be ∼5706 cm2 V-1 s-1, which is much higher than that of the typical 2D semiconducting materials. Intriguingly, the calculated lattice thermal conductivity of 1L-ZrTeSe4 is found to be 3.16 W m-1 K-1 at room temperature, which is relatively smaller than that of 2D transition metal dichalcogenides. The maximum figure of merit ZT of 1L-ZrTeSe4 at 900 K is ∼0.8 for both p- and n-type doping at optimal carrier concentrations. As ZT could be improved through the manipulation of its electronic structure, this is an important clue indicating the enormous potential of 1L-ZrTeSe4 in thermoelectric application.

Hydrogen diffusion and its electrical properties variation as a function of the IGZO stacking structure.

The oxygen vacancies and hydrogen in oxide semiconductors are regarded as the primary sources of charge carriers and various studies have investigated the effect of hydrogen on the properties of oxide semiconductors. However, the carrier generation mechanism between hydrogen and oxygen vacancies in an a-IGZO semiconductor has not yet been clearly examined. In this study we investigated the effect of hydrogen and the variation mechanisms of electrical properties of a thin film supplied with hydrogen from the passivation layer. SiOx and SiNx, which are used as passivation or gate insulator layers in the semiconductor process, respectively, were placed on the top or bottom of an a-IGZO semiconductor to determine the amount of hydrogen penetrating the a-IGZO active layer. The hydrogen diffusion depth was sufficiently deep to affect the entire thin semiconductor layer. A large amount of hydrogen in SiNx directly affects the electrical resistivity of a-IGZO semiconductor, whereas in SiOx, it induces a different behavior from that in SiNx, such as inducing an oxygen reaction and O-H bond behavior change at the interface of an a-IGZO semiconductor. Moreover, the change in electrical resistivity owing to the contribution of free electrons could be varied based on the bonding method of hydrogen and oxygen.

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.

Parasitic Current Induced by Gate Overlap in Thin-Film Transistors.

As novel applications of oxide semiconductors are realized, various structural devices and integrated circuits are being proposed, and the gate-overlay defect phenomenon is becoming more diverse in its effects. Herein, the electrical properties of the transistor that depend on the geometry between the gate and the semiconductor layer are analyzed, and the specific phenomena associated with the degree of overlap are reproduced. In the semiconductor layer, where the gate electrode is not overlapped, it is experimentally shown that a dual current is generated, and the results of 3D simulations confirm that the magnitude of the current increases as the parasitic current moves away from the gate electrode. The generation and path of the parasitic current are then represented visually through laser-enhanced 2D transport measurements; consequently, the flow of the dual current in the transistor is verified to be induced by the electrical potential imbalance in the semiconductor active layer, where the gate electrodes do not overlap.

Non-equilibrium chiral domain wall dynamics excited by transverse magnetic field pulses.

Non-equilibrium domain wall dynamics on a perpendicularly magnetized nanowire manipulated by the transverse magnetic field pulse are numerically investigated. We systematically observe the large displacements of the chiral domain wall and the domain wall tilting angles generated by Dzyaloshinskii-Moriya interaction during the competition between the precession torque and the magnetic damping process. The magnetic-property-dependent domain wall displacements exhibit that the lower magnetic damping constants and Dzyaloshinskii-Moriya energy densities generate the longer transition times and the significant larger domain wall displacements for the non-equilibrium magnetization dynamics. Compare with the spin-polarized-current-driven domain wall dynamics, the transverse magnetic field pulses guarantee faster domain wall movements without Walker breakdown and lower energy consumptions because it is free from the serious Joule heating issue. Finally, we demonstrate successive chiral domain wall displacements, which are necessary to develop multilevel resistive memristors for next-generation artificial intelligent devices based on magnetic domain wall motions.

Measurement of Exciton and Trion Energies in Multistacked hBN/WS2 Coupled Quantum Wells for Resonant Tunneling Diodes.

Quantum confinements, especially quantum in narrow wells, have been investigated because of their controllability over electrical parameters. For example, quantum dots can emit a variety of photon wavelengths even for the same material depending on their particle size. More recently, the research into two-dimensional (2D) materials has shown the availability of several quantum mechanical phenomenon confined within a sheet of materials. Starting with the gapless semimetal properties of graphene, current research has begun into the excitons and their properties within 2D materials. Even for simple 2D systems, experimental results often offer surprising results, unexpected from traditional studies. We investigated a coupled quantum well system using 2D hexagonal boron nitride (hBN) barrier as well as 2D tungsten disulfide (WS2) semiconductor arranged in stacked structures to study the various 2D to 2D interactions. We determined that for hexagonal boron nitride-tungsten disulfide (hBN/WS2) quantum well stacks, the interaction between successive wells resulted in decreasing bandgap, and the effect was pronounced even over a large distance of up to four stacks. Additionally, we observed that a single layer of isolating hBN barriers significantly reduces interlayer interaction between WS2 layers, while still preserving the interwell interactions in the alternative hBN/WS2 structure. The methods we used for the study of coupled quantum wells here show a method for determining the respective exciton energy levels and trion energy levels within 2D materials and 2D materials-based structures. Renormalization energy levels are the key in understanding conductive and photonic properties of stacked 2D materials.

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.

Enhanced thermal stability of InP quantum dots coated with Al-doped ZnS shell.

Colloidal InP quantum dots (QDs) have attracted a surge of interest as environmentally friendly light-emitters in downconversion liquid crystal displays and light-emitting diodes (LEDs). A ZnS shell on InP-based core QDs has helped achieve high photoluminescence (PL) quantum yield (QY) and stability. Yet, due to the difficulty in the growth of a thick ZnS shell without crystalline defects, InP-based core/shell QDs show inferior stability against QY drop compared to Cd chalcogenide precedents, e.g., CdSe/CdS core/thick-shell QDs. In this work, we demonstrate the synthesis of InP-based core/shell QDs coated with an Al-doped ZnS outer shell. QDs with an Al-doped shell exhibit remarkable improvement in thermal and air stability even when the shell thickness is below 2 nm, while the absorption and PL spectra, size, and crystal structure are nearly the same as the case of QDs with a pristine ZnS shell. X-ray photoelectron spectroscopy reveals that Al3+ in Al-doped QDs forms an Al-oxide layer at elevated temperature under ambient atmosphere. The as-formed Al-oxide layer blocks the access of external oxidative species penetrating into QDs and prevents QDs from oxidative degradation. We also trace the chemical pathway of the incorporation of Al3+ into ZnS lattice during the shell growth. Furthermore, we fabricate QD-LEDs using Al-doped and undoped QDs and compare the optoelectronic characteristics and stability.

Analysis of the hump phenomenon and needle defect states formed by driving stress in the oxide semiconductor.

The reduction in current ability accompanied by the hump phenomenon in oxide semiconductor thin-film transistors to which high DC voltages and AC drive voltages are applied has not been studied extensively, although it is a significant bottleneck in the manufacture of integrated circuits. Here, we report on the origin of the hump and current drop in reliability tests caused by the degradation in the oxide semiconductor during a circuit driving test. The hump phenomenon and current drop according to two different driving stresses were verified. Through a numerical computational simulation, we confirmed that this issue can be caused by an additional "needle", a shallow (~0.2 eV) and narrow (<0.1 eV), defect state near the conduction band minimum (CBM). This is also discussed in terms of the dual current path caused by leakage current in the channel edge.

Reliable Multivalued Conductance States in TaO x Memristors through Oxygen Plasma-Assisted Electrode Deposition with in Situ-Biased Conductance State Transmission Electron Microscopy Analysis.

Transition metal oxide-based memristors have widely been proposed for applications toward artificial synapses. In general, memristors have two or more electrically switchable stable resistance states that device researchers see as an analogue to the ion channels found in biological synapses. The mechanism behind resistive switching in metal oxides has been divided into electrochemical metallization models and valence change models. The stability of the resistance states in the memristor vary widely depending on: oxide material, electrode material, deposition conditions, film thickness, and programming conditions. So far, it has been extremely challenging to obtain reliable memristors with more than two stable multivalued states along with endurances greater than ∼1000 cycles for each of those states. Using an oxygen plasma-assisted sputter deposition method of noble metal electrodes, we found that the metal-oxide interface could be deposited with substantially lower interface roughness observable at the nanometer scale. This markedly improved device reliability and function, allowing for a demonstration of memristors with four completely distinct levels from ∼6 × 10-6 to ∼4 × 10-8 S that were tested up to 104 cycles per level. Furthermore through a unique in situ transmission electron microscopy study, we were able to verify a redox reaction-type model to be dominant in our samples, leading to the higher degree of electrical state controllability. For solid-state synapse applications, the improvements to electrical properties will lead to simple device structures, with an overall power and area reduction of at least 1000 times when compared to SRAM.

Electron-blocking by the potential barrier originated from the asymmetrical local density of state in the oxide semiconductor.

Defect generation in oxide semiconductor thin-film transistors under high-voltage driving has not been studied in depth despite being a crucial bottleneck in the making of the integrated circuit utilized in an oxide semiconductor. Here we report on the origin of the asymmetrical transport characteristics caused by the degradation in the oxide semiconductor during integrated circuit driving. The variation of the current profiles based on test conditions is related to the generation of local defect states in the oxide material; this generation could be caused by the structural change of the material. The numerical calculations show that the flow of the electron is blocked by the "electrical pocket" formed by the electric-field distortion due to the local defect states near the edge of the electrode.

Impact of transient currents caused by alternating drain stress in oxide semiconductors.

Reliability issues associated with driving metal-oxide semiconductor thin film transistors (TFTs), which may arise from various sequential drain/gate pulse voltage stresses and/or certain environmental parameters, have not received much attention due to the competing desire to characterise the shift in the transistor characteristics caused by gate charging. In this paper, we report on the reliability of these devices under AC bias stress conditions because this is one of the major sources of failure. In our analysis, we investigate the effects of the driving frequency, pulse shape, strength of the applied electric field, and channel current, and the results are compared with those from a general reliability test in which the devices were subjected to negative/positive bias, temperature, and illumination stresses, which are known to cause the most stress to oxide semiconductor TFTs. We also report on the key factors that affect the sub-gap defect states, and suggest a possible origin of the current degradation observed with an AC drive. Circuit designers should apply a similar discovery and analysis method to ensure the reliable design of integrated circuits with oxide semiconductor devices, such as the gate driver circuits used in display devices.

The evaluation of implementing smart patient controlled analgesic pump with a different infusion rate for different time duration on postoperative pain management.

BACKGROUND: Control of postoperative pain is an important aspect of postoperative patient management. Among the methods of postoperative pain control, patient-controlled analgesia (PCA) has been the most commonly used. This study tested the convenience and safety of a PCA method in which the dose adjusted according to time. METHODS: This study included 100 patients who had previously undergone orthognathic surgery, discectomy, or total hip arthroplasty, and wished to control their postoperative pain through PCA. In the test group (n = 50), the rate of infusion was changed over time, while in the control group (n = 50), drugs were administered at a fixed rate. Patients' pain scores on the visual analogue scale, number of rescue analgesic infusions, side effects, and patients' satisfaction with analgesia were compared between the two groups. RESULTS: The patients and controls were matched for age, gender, height, weight, and body mass index. No significant difference in the mount of drug administered was found between the test and control groups at 0-24 h after the operation; however, a significant difference was observed at 24-48 h after the operation between the two groups. No difference was found in the postoperative pain score, number of side effects, and patient satisfaction between the two groups. CONCLUSIONS: Patient-controlled anesthesia administered at changing rates of infusion has similar numbers of side effects as infusion performed at a fixed rate; however, the former allows for efficient and safe management of postoperative pain even in small doses.

Effects of light-emitting diode irradiation on RANKL-induced osteoclastogenesis.

BACKGROUND AND OBJECTIVE: Bone homeostasis is maintained by a balance between osteoblastic bone formation and osteoclastic bone resorption, where intracellular reactive oxygen species (ROS) are crucial mediators of osteoclastogenesis. Recently, low-level light therapy (LLLT), a form of laser medicine used in various clinical fields, was shown to alleviate oxidative stress by scavenging intracellular ROS. The present study aimed to investigate the impact of 635 nm irradiation from a light-emitting diode (LED) on osteoclastogenesis from receptor activator of nuclear factor kappa-B (NF-κB) ligand (RANKL)-stimulated mouse bone marrow-derived macrophages (BMMs). STUDY DESIGN/MATERIALS AND METHODS: The effects of LED irradiation on osteoclastogenesis were assessed in tartrate-resistant acid phosphatase (TRAP), 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT), cell viability, and resorption pit formation, respectively. Quantitative real-time polymerase chain reaction (qPCR) and Western blot analyses were also performed to assess mRNA expression of osteoclastogenesis-related genes and phosphorylation of extracellular signal-regulated kinase 1/2 (ERK 1/2), p38, and c-Jun-N-terminal kinase (JNK). NF-κB activity was assayed by luciferase reporter assay and Intracellular ROS generation was investigated by the 2',7'-dichlorodihydrofluorescein diacetate (H2 DCF-DA) detection method. RESULTS: LED irradiation significantly inhibited RANKL-mediated osteoclast differentiation from BMMs and mRNA expression of TRAP, osteoclast-associated immunoglobulin-like receptor (OSCAR), and dendrocyte-expressed seven-transmembrane protein (DC-STAMP). Exposure to LED light likewise significantly decreased RANKL-facilitated NF-κB activity, p38 and ERK phosphorylation and intracellular ROS generation, and increased gene expression of nuclear factor E2-related factor 2 (Nrf2). CONCLUSIONS: Taken together, the results presented herein show that LED irradiation downregulates osteoclastogenesis by reducing ROS production. Therefore, LED irradiation/LLLT might be useful as an alternative, conservative approach to osteoporosis management.