Pt–Cu Interaction Induced Construction of Single Pt Sites for Synchronous Electron Capture and Transfer in Photocatalysis

Single-atom photocatalysts have shown their fascinating strengths in enhancing charge transfer dynamics; however, rationally designing coordination sites by metal doping to stabilize isolated atoms is still challenging. Here, a one-unit-cell ZnIn₂S₄ (ZIS) nanosheet with abundant Cu dopants serving as the suitable support to achieve a single atom Pt catalyst (Pt₁/Cu–ZIS) is reported, and hence the metal single atom–metal dopant interaction at an atomic level is disclosed. Experimental results and density functional theory calculations highlight the unique stabilizing effect (Pt–Cu interaction) of single Pt atoms in Cu-doped ZIS, while apparent Pt clusters are observed in pristine ZIS. Specifically, Pt–Cu interaction provides an extra coordination site except three S sites on the surface, which induces a higher diffusion barrier and makes the single atom more stable on the surface. Apart from stabilizing Pt single atoms, Pt–Cu interaction also serves as the efficient channel to transfer electrons from Cu trap states to Pt active sites, thereby enhancing the charge separation and transfer efficiency. Remarkably, the Pt₁/Cu–ZIS exhibits a superb activity, giving a photocatalytic hydrogen evolution rate of 5.02 mmol g⁻¹ h⁻¹, nearly 49 times higher than that of pristine ZIS.     

Ultrafast Dynamics of Photoinduced Electron–Hole Plasma in Semiconductor Nanowires

Experimental results obtained in a study of the effect of electron–hole plasma on the generation of terahertz (THz) radiation in semiconductor nanowires grown by metal-organic vapor-phase epitaxy (MOVPE) are presented. It is shown that the temporal dynamics of photoexcited charge carriers in semiconductor nanowires is determined by the transport of carriers, both electrons and holes, and by the time of capture of electrons and holes at surface levels.     

Widening the Length Distributions in Irregular Arrays of Self-Catalyzed III–V Nanowires

Semiconductors - In this work, we account the local variations of nanowire number density to extend the previous approaches to modeling of III–V nanowire length distributions in...     

Integration of Alloy Segregation and Surface Co?O Hybridization in Carbon-Encapsulated CoNiPt Alloy Catalyst for Superior Alkaline Hydrogen Evolution

Constructing an efficient alkaline hydrogen evolution reaction (HER) catalyst with low platinum (Pt) consumption is crucial for the cost reduction of energy devices, such as electrolyzers. Herein, nanoflower-like carbon-encapsulated CoNiPt alloy catalysts with composition segregation are designed by pyrolyzing morphology-controlled and Pt-proportion-tuned metal–organic frameworks (MOFs). The optimized catalyst containing 15% CoNiPt NFs (15%: Pt mass percentage, NFs: nanoflowers) exhibits outstanding alkaline HER performance with a low overpotential of 25 mV at a current density of 10 mA cm⁻², far outperforming those of commercial Pt/C (47 mV) and the most advanced catalysts. Such superior activity originates from an integration of segregation alloy and Co-O hybridization. The nanoflower-like hierarchical structure guarantees the full exposure of segregation alloy sites. Density functional theory calculations suggest that the segregation alloy components not only promote water dissociation but also facilitate the hydrogen adsorption process, synergistically accelerating the kinetics of alkaline HER. In addition, the activity of alkaline HER is volcanically distributed with the surface oxygen content, mainly in the form of Co_3d O_2p hybridization, which is another reason for enhanced activity. This work provides feasible insights into the design of cost-effective alkaline HER catalysts by coordinating kinetic reaction sites at segregation alloy and adjusting the appropriate oxygen content.     

Local neutrality and pinning of the chemical potential in III–V solid solutions: Interfaces and radiation effects

In the virtual crystal approximation the mole fraction (X) of the local neutrality level E _lnl: E _lnl(X)^ABC = XE _lnl ^AC + (1 - X) E _lnl ^BC - C _ABC X(1 - X has been calculated in ABC solid solutions for 18 pairs of III–V semiconductors. An interpolation formula is proposed for the nonlinear coefficient C _ABC (in eV): C _ABC= - 0.03 + 0.04|Δa| + 1.4|Δa|₂ as a function of the lattice mismatch |Δa| (in Å) for boundary compositions of the solid solutions. It is shown that the numerical values of E _lnl obtained provide good agreement with the experimental values of the heights of the Schottky barriers (F _bS) and the limiting Fermi level positions (F _lim) in irradiated III–V solid solutions.     

EMF Induced in a p–n Junction under a Strong Microwave Field and Light

Semiconductors - The effect of a strong electromagnetic field on currents and electromotive forces in a p–n junction is considered. It is shown that a p–n junction upon exposure to an...     

Atomic-Precision Tailoring of Au–Ag Core–Shell Composite Nanoparticles for Direct Electrochemical-Plasmonic Hydrogen Evolution in Water Splitting

Traditionally, bandgap materials are a prerequisite to photocatalysis since they can harness a reasonable range of the solar spectrum. However, the high impedance across the bandgap and the low concentration of intrinsic charge carriers have limited their energy conversion. By contrast, metallic nanoparticles possess a sea of free electrons that can effectively promote the transition to the excited state for reactions. Here, an atomic layer of a bimetallic concoction of silver–gold shells is precisely fabricated onto an Au core via a sonochemical dispersion approach to form a core–shell of Au–Ag that exploits the wide availability of excited states of Ag while maintaining an efficient localized surface plasmon resonance (LSPR) of Au. Catalytic results demonstrate that this mix of Ag and Au can convert solar energy to hydrogen at high efficiency with an increase of 112.5% at an optimized potential of −0.5 V when compared to light-off conditions under the electrochemical LSPR. This outperforms the commercial Pt catalysts by 62.1% with a hydrogen production rate of 1870 µmol g⁻¹ h⁻¹ at room temperature. This study opens a new route for tuning the range of light capture of hydrogen evolution reaction catalysts using fabricated core–shell material through the combination of LSPR with electrochemical means.     

A Dual-Enzyme–Responsive DNA-Based Nanoframework Enables Controlled Co-Delivery of CRISPR-Cas9 and Antisense Oligodeoxynucleotide for Synergistic Gene Therapy

CRISPR-Cas9 has demonstrated potential in inhibiting tumor growth by downregulating target gene expression, and the efficiency is expected to be enhanced with other nucleic acid drugs. Herein, a dual-enzyme–responsive DNA-based nanoframework (NF) that enables controlled co-delivery of Cas9 ribonucleoprotein (RNP) and antisense oligodeoxynucleotide (ASO) for synergistic gene therapy is reported. NF is synthesized with acrylamide DNA (acDNA) as a cross-linker and loading site. A ternary complex containing sgRNA, ASO, and Cas9 that bound to acDNA is designed. The phase transition property of NF allows to reversibly swell and aggregate thermo-responsively for the high-capacity loading of ternary complex. RNA is cleaved from DNA–RNA complex by the overexpressed ribonuclease H for the controlled release of Cas9 RNP, and the bifurcated DNA is cleaved by the overexpressed flap structure-specific endonuclease 1 for the controlled release of overhanging ASO. The combination of gene editing with Cas9 RNP and gene silencing with ASO allows simultaneous manipulation of target gene in nucleus and its mRNA in cytoplasm, and this synergistic gene therapy has shown remarkable therapeutic effect in a breast cancer mouse model, making it a promising therapeutic strategy for future cancer treatment.     

Molecular Engineering for Shortening the Pt···Pt Distances in Pt(II) Dinuclear Complexes and Enhancing the Efficiencies of these Complexes for Application in Deep-Red and Near-IR OLEDs

Deep-red (DR)-to-near-infrared (NIR) phosphorescent organic light-emitting diodes (OLEDs) have potentials for application in various fields ranging from phototherapy to sensing. Accordingly, herein, phenylpyridazine-based bidentate ligands are synthesized and subsequently utilized for the preparation of dinuclear Pt(II) complexes ( 1 – 6 ). The molecular structures of 1 – 3 is investigated by single-crystal X-ray diffraction, and the results suggest that these complexes have substantially shortened Pt···Pt distances (2.906–2.911 Å). Complexes 1 – 6 exhibit intense emissions in the NIR region (700–726 nm), high photoluminescence quantum yield (PLQY) (0.11–0.18), and short phosphorescence decay lifetimes (τ = 0.64–0.95 µs) in a CH₂Cl₂ solution. To examine the effect of N-substitution on the dinuclear Pt complexes, the phenylpyrimidine-based Pt(II) emitters 7 and 8 are prepared and discovered to have Pt···Pt distances of 2.933 Å. 7 and 8 demonstrate strong emissions in the 628–650 nm range with high PLQY of 0.52–0.65. Theoretical studies indicate that the functional groups or atoms in the ligands play crucial roles in the formation of emitters with significantly shortened Pt···Pt distances. 3 and 7 are employed as non-doped emitters to fabricate NIR OLEDs, and the resulting OLEDs exhibit electroluminescence peaks at 754 and 692 nm with maximum external quantum efficiencies of 3.0 and 4.4%, respectively.     

Measurement and Modeling of DTTV–SFN Propagation in Thailand

Wireless Personal Communications - Digital terrestrial television (DTTV) with a single frequency network (SFN) in Thailand is based on digital video broadcasting-terrestrial second generation...     

Robust Fault Estimation and Accommodation for a Class of T–S Fuzzy Systems with Local Nonlinear Models

This paper focuses on the problems of fault estimation and accommodation for a class of T–S fuzzy systems with local nonlinear models and having an external disturbance and sensor and actuator faults, simultaneously. A fuzzy robust fault estimation observer is designed to estimate the system state and sensor and actuator faults. Compared with existing results, the observer not only is robust to the disturbance but also has a wider application range and more freedom for design. To compensate for the effect of faults and to stabilize the closed-loop system, an observer-based fault-tolerant controller is proposed. The separate design of the observer and controller avoids coupling between them. Finally, a simulation is conducted to demonstrate the effectiveness of the proposed method.     

Effect of the Phase Composition and Local Crystal Structure on the Transport Properties of the ZrO2–Y2O3 and ZrO2–Gd2O3 Solid Solutions

Russian Microelectronics - The results of investigating the crystal structure, ionic conductivity, and local structure of the (ZrO2)1 –x(Gd2O3)x and (ZrO2)1 –x(Y2O3)x (x = 0.04, 0.08,...     

Structural Characterization and Magnetic and Electrical Properties of La0.7Ca0.3MnO3–La1.5Sr0.5NiO4 Nanocomposites

Nanocomposite samples of (1 ? x)La_0.7Ca_0.3MnO₃ + xLa_1.5Sr_0.5NiO₄ (x = 0 to 0.3) were synthesized by a combination of the mechanical milling and solid-state reaction methods. X-ray diffraction analyses and magnetic measurements indicated that no reaction occurred between La_0.7Ca_0.3MnO₃ (LCMO) and La_1.5Sr_0.5NiO₄ (LSNO). The Curie temperature (T _C) was almost independent of x, while the metal–insulator transition temperature (T _MI) shifted from 251 K for x = 0.0 to 65 K for x = 0.2. The samples with x ≥ 0.25 exhibited insulating behavior in the temperature range from 30 K to 300 K. Addition of LSNO substantially increased the resistivity of the composites. This is attributed to enhanced magnetic disorder at LCMO grain boundaries due to the addition of LSNO. The temperature dependence of the resistivity, ρ(T), could be described by the phenomenological percolation model of phase segregation. Fitting the experimental ρ(T) data in the temperature range of 30 K to 300 K indicated that the activation energy of the composites increases as a function of the LSNO doping concentration (x).     

Structural and Thermoelectric Properties of Chimney–Ladder Compounds in the Ru-Mn-Si System

We have investigated phase relationships of the sesquisilicide alloys in the Ru-Mn-Si system. A series of chimney–ladder phases Ru_1−x Mn _x Si _y (0.14 ≤ x ≤ 0.97, 1.584 ≤ y ≤ 1.741) are formed over a wide compositional range between Ru₂Si₃ and Mn₄Si₇. We also investigated thermoelectric properties of the directionally solidified Ru_1−x Mn _x Si _y alloys as a function of Mn content and temperature. The dimensionless figure of merit ZT for alloys with high Mn content (x ≥ 0.75) increases as the Mn content increases. The alloy with x = 0.90 exhibits ZT as high as 0.76 at 874 K.     

Analysis of Phonon Modes and Electron–Phonon Interaction in Quantum-Cascade Laser Heterostructures

Semiconductors - The phonon modes of quantum-cascade heterostructures based on binary and ternary semiconductor compounds are simulated. The dependences of the frequencies of the structure...     

Analysis of quantum efficiency and optical enhancement in amorphous Si p–i–n solar cells

The effect of i-layer thickness, tin oxide texture, and back reflector (BR) on optical enhancement has been systematically studied in a series of 20 a-Si p–i–n solar cells. The internal quantum efficiency has been analyzed by a simple model based on the work of Schade and Smith. The enhancement of optical absorption is characterized by m, a wavelength-dependent fitting parameter representing the increase in optical pathlength relative to the i-layer thickness d. Solar cells with an Al BR have negligible optical enhancement, with m < 1.5, consistent with large parasitic absorption at the Al/Si interface as reported by others. Solar cells on highly textured SnO₂ with ZnO/Al or ZnO/Ag BR have peak values of m ∼ 3–4, with ZnO/Ag having slightly larger values than ZnO/Al. It was found that m has a strong dependence on the product αd, and that maximum values of m increase with reflectivity of the BR. It is shown that a major source of parasitic absorption loss at long wavelengths is light trapping in the textured SnO₂ front contact. Copyright © 2002 John Wiley & Sons, Ltd.     

Investigation on the mechanism of charge generation in organic heterojunctions: Analysis of I–V and C–V characteristics

The charge generation mechanism of organic heterojunction (OHJ) consisted of 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HAT-CN) and different hole transporting materials (HTMs) are studied systematically by current-voltage (I–V) and capacitance-voltage measurements. The analysis of I–V characteristics of the devices based on OHJs at forward and reverse voltages by comparing the thickness of HTM layers finds that a forward and reverse symmetrical I–V curve is observed at thin HTM layers and the forward current becomes larger than the reverse current with the increase of HTM thickness, fully illustrating the effectiveness of OHJ charge generation. Moreover, the I–V characteristics at different temperatures indicate that the efficient charge generation is originated from electron tunneling rather than diffusion. And the C–V and capacitance-frequency (C–F)characteristics further illustrate the highly efficient charge generation ability of OHJs so that the charge density is as high as 4.5 × 10¹⁷ cm⁻³, guaranteeing the high conductivity of OHJs, which is very beneficial to developing highly efficient OLEDs using OHJs as charge injector and generator.     

IR photodetectors in the range of λ = 1.5–8 μm, based on silicon with multicharged nanoclusters of manganese atoms

It is demonstrated that infrared photodetectors based on silicon with multicharged nanoclusters of manganese atoms can be designed that operate in the wavelength range of ?? = 1.55?C8 ??m. Photodetectors fabricated on such materials have the following parameters: a spectral sensitivity range of ?? = 1.55?C8 ??m, an operating temperature range of T = 77?C250 K, an optimal electric field of E = 5 V/cm, an optimal size of V = 3 × 2 × 1 mm³, a sensitivity threshold of S = 10^?9 W/cm², and a response time of ?? < 10^?6 s.     

Design and implementation of adaptive slope compensation in current mode DC–DC onverter

To improve the compensation for the inherent instability in a current mode converter, the adaptive slope compensation, giving attention to the problems of the traditional compensation on compensation accuracy, loading capability and turning jitter, is presented. Based on the analysis of current loop, by detecting the input and output voltage, converting the adaptive slope compensation current, the compensation of the current loop is optimized successfully. It can not only improve the compensation accuracy but also eliminate the over compensation, the turning jitter and the poor loading capability in the reported slope compensation. A power supply chip with adaptive slope compensation has been fabricated in a 0.35 μm CMOS process. The measurement results show that the chip starts up and operates steadily with the constant current limit under conditions of 5 V input voltage, from 10% to 100% duty cycle.     

Performance Analysis of Combined mMCSK–mMFSK Modulation in AWGN and Rayleigh Fading Channel

As there are many use cases considered for robotics communications, the data rate variation may be very large. Some sensor applications may require very low data rate, telemetry data may require low-to-medium data rates and e.g. video application will require high data rates. On the other hand, robots may have to operate in very difficult radio propagation environments such as nuclear power plants or industrial facilities. To combat difficult propagation characteristics, an often used and well known mechanism is to use spread spectrum signal structures. Thus in this paper a novel modulation method is considered which offers the inherent signal structure and processing opportunities of spread spectrum signal and at the same time offers an easy mechanism to adapt the data rate from low to high depending on the requirement at hand thus addressing two important communication requirements for robotics. The introduction of $m$ MFSK generated the idea of applying the given approach to other modulation methods. To further enlarge the modulation alphabet sizes (with the price of larger spectrum usage) it was realized that combining the $m$ MFSK and $m$ MCSK would be an interesting choice. The $m$ MCSK– $m$ MFSK modulation is hence considered. A method to analyze this two-component modulation is developed and the performance analyses give results for $m$ MCSK– $m$ MFSK modulation in AWGN and flat Rayleigh fading channels for both coherent and non-coherent receivers. The performance was also assessed with orthogonal and non-orthogonal code constructs for coherent receiver.