Electronic Behavior Research Articles

Bispericyclic Ambimodal Dimerization of Pentafulvene: The Origin of Asynchronicity and Kinetic Selectivity of the Endo Transition State.

The propensity of fulvenes to undergo dimerization has long been known, although the in-depth mechanism and electronic behavior during dimerization are still elusive. Herein, we made an attempt to gain insights into the reactivity of pentafulvene for Diels-Alder (DA) and [6 + 4]-cycloadditions via conventional and ambimodal routes. The result emphasizes that pentafulvene dimerization preferentially proceeds through a unique bifurcation mechanism where two DA pathways merge together to produce two degenerate [4 + 2]-cycloadducts from a single TS. Despite the [6 + 4]-cycloadduct being thermodynamically preferred, [4 + 2]-cycloaddition reactions are kinetically driven. Singlet biradicaloid is involved in through-space 6e- delocalization as a secondary orbital interaction that originates asynchronicity and stabilizes the bispericyclic transition state (TS). The transformation of various actively participating intrinsic bonding orbitals (IBOs) unambiguously forecasts the formation of multiple products from a single TS and rationalizes the mechanism of ambimodal reactions that are rather difficult to probe with other analyses. The changes in active IBOs clearly distinguish the conventional reactions from bifurcation reactions and can be employed to characterize and confirm the ambimodal mechanism. This report gains a crucial theoretical insight into the mechanism of bifurcation, the origin of asynchronicity, and electronic behavior in ambimodal TS, which will certainly be of enormous value for future studies.

Electronic behavior of organic molecules adsorbed on monolayer SiC

Studying the adsorption of organic molecules is a good approach for exploring the electronic conducts of two-dimensional (2D) materials. We utilized density functional theory (DFT) to research the structure and electronic behaviors of organic molecules (Tetracyanoquinodimethane(TCNQ), Tetracyanoethylene(TCNE), Tetrathiafulvalene (TTF)) in the SiC adsorption system. After organic molecules are adsorbed on monolayer SiC, the charge difference density (CDD) and the plane average CDD indicate the presence of charge transfer between monolayer SiC and organic molecules. The research results indicate that the impurity energy level appears in the band structure and is contributed by organic molecules. Facts prove that the TCNQ, TCNE, and TTF molecules may inject additional carriers into the SiC layer. TCNQ and TCNE molecules are the electron acceptors, while TTF molecule is the electron donor. The p-type doping and n-type doping were achieved in monolayer SiC, and induce effective p-type doping behavior. Because TCNQ, TCNE, and TTF molecules inject additional holes or electrons into the monolayer SiC, the dimension of the work function can be regulated, expanding the field emission capability range of SiC-based electronic devices. The current-voltage (I-V) curves reveal that after organic molecules adsorbed on monolayer SiC, the transport current capability of the n-type doping system is stronger than the p-type doping system. Therefore, SiC system electrical characteristics may be regulated by organic molecule adsorption. Our work provides a theoretical foundation for SiC application in nano electronic device.

Characterizing Local Electronic States of Twin Boundaries in Copper.

Grain boundaries (GBs) and twin boundaries (TBs) in copper (Cu) are two major planar defects that influence electrical conductivity due to their complex electron transport characteristics, involving electron scattering and electron concentration. Understanding their local electronic states is crucial for the design of future conductor materials. In this study, we characterized electron behaviors at TBs and GBs within one Cu grain using atomic force microscopy. Our findings revealed that, compared with GBs, TBs exhibit better current transport capability (direct-current mode) and larger electromagnetic loss (high-frequency microwave mode). Both kelvin probe force microscopy and theoretical analysis suggested that TBs with smaller lattice disorder possess lower density of states at the Fermi level. The reduced density of states may result in decreased electron scattering and a lower electron concentration at TBs. The latter can be highlighted by the high-frequency skinning effect, manifested as larger electromagnetic loss and weaker high-frequency conductivity.

Electron Temperature Measurement of Argon Capacitive Coupling Plasma by Optical-Emission Spectroscopy

The study of electron interaction with the electric field in low temperature plasmas is a current area of research with various practical applications. Specifically, in the context of low pressure (< 1 mtorr), electrons can travel distances comparable to the size of the reactor without experiencing collisions. The primary objective of this work is to investigate the basic physics of electron behaviors in an argon discharge at low pressure regime. The main aim of the current study is the investigation the electron temperature (Te). Optical emission spectroscopy was used as diagnostic tool to find the electron temperature based on line ratio method. The link between the fundamental plasma parameter (Te) and its spatial dynamics is analyzed. The study also looks into how the Te is affected by the input plasma radio frequency power throughout the electrode distance.

Nanoscale single-electron box with a floating lead for quantum sensing: Modeling and device characterization

We present an in-depth analysis of a single-electron box (SEB) biased through a floating node technique that is common in charge-coupled devices. The device is analyzed and characterized in the context of single-electron charge sensing techniques for integrated silicon quantum dots (QD). The unique aspect of our SEB design is the incorporation of a metallic floating node, strategically employed for sensing and precise injection of electrons into an electrostatically formed QD. To analyze the SEB, we propose an extended multi-orbital Anderson impurity model (MOAIM), adapted to our nanoscale SEB system, that is used to predict theoretically the behavior of the SEB in the context of a charge sensing application. The validation of the model and the sensing technique has been carried out on a QD fabricated in a fully depleted silicon on insulator process (FD-SOI) on a 22-nm CMOS technology node. We demonstrate the MOAIM's efficacy in predicting the observed electronic behavior and elucidating the complex electron dynamics and correlations in the SEB. The results of our study reinforce the versatility and precision of the model in the realm of nanoelectronics and highlight the practical utility of the metallic floating node as a mechanism for charge injection and detection in integrated QDs. Finally, we identify the limitations of our model in capturing higher order effects observed in our measurements and propose future outlooks to reconcile some of these discrepancies.

Exploring Electrostatic Confinement Transport in MoS2/WSe2 Heterostructure via Triple‐Gated Point Contact Device

AbstractThe exponential development in quantum phenomena is directly correlated with the decreasing size of nano‐semiconductor transistors. Consequently, the use of a quantum structure that deviates from traditional transistor types becomes imperative. Electrostatically defined nanoscale devices within 2D semiconductor heterostructures serve as foundational elements for diverse quantum electrical circuits. Van der Waals heterostructures, distinguished by atomically flat interfaces and inherent 2D characteristics, offer advantages such as large‐scale uniformity, flexibility, and portability over conventional bulk semiconductor heterostructures. Herein, the intricate electronic behavior of a MoS2/WSe2 encapsulated heterostructure governed by split‐gate and middle‐gate configurations is investigated, revealing a distinctive step‐like current profile at a low temperature of 77 K. The observed four regimes in the current highlight the impact of quantum confinement induced by reduced lateral dimensions, coupled with precise electrostatic confinement controlled by gate voltages. The temperature dependence of the phenomena emphasizes the role of thermal effects on carrier scattering mechanisms. In addition, the pinch‐off characteristics with different temperatures, middle‐gate voltages, and drain biases are explored. This study contributes to a deeper understanding of electrostatic effects in 2D transition metal dichalcogenide heterostructures and holds promise for the development of advanced electronic devices with tailored confinement for enhanced functionalities.

Synthesis, Cytotoxicity, and Photophysical Investigations of 2-Amino-4,6-diphenylnicotinonitriles: An Experimental and Theoretical Study.

In this study, we present a comprehensive investigation of 2-amino-4,6-diphenylnicotinonitriles (APNs, 1-6), including their synthesis, cytotoxicity against breast cancer cell lines, and photophysical properties. Compound 3 demonstrates exceptional cytotoxicity, surpassing the potency of Doxorubicin. The fluorescence spectra of the synthesized 1-6 in different solvents reveal solvent-dependent shifts in the emission maximum values, highlighting the influence of the solvent environment on their fluorescence properties. A quantum chemical TD-DFT analysis provides insights into the electronic structure and fluorescence behavior of 1-6, elucidating HOMO-LUMO energy gaps, electronegativity values, and dipole moments, contributing to a deeper understanding of their electronic properties and potential reactivity. These findings provide valuable knowledge for the development of APNs (1-6) as fluorescent sensors and potential anticancer agents.

Local structure and defect analysis of KVO3 doped BiFeO3–BaTiO3 ceramics facing conductivity, permittivity, and magnetic properties

This study discovers the effects of KVO3 doping on BiFeO3–BaTiO3 regarding phase transitions, defect formation, and changes in electronic and magnetic behavior. The synthesized material (1-x-y)BiFeO3-xBaTiO3-yKVO3 with (x = 0.33, 0.38 and y = 0, 0.01) have pseudo-cubic structure, where the FeO6 octahedron was elongated in the z-axis, and Fe has an oxidation state of 3+ and 4+. The electrons in the 3d subshell initially showed a high spin state, transitioning to a low state after KVO3 doping. Further investigation identified phase transition Rhombohedral + Pseudo Cubic to Rhombohedral for FT33 at T∼100°C and Pseudo Cubic phase to Cubic phase for FT38 at T∼200°C. Conductivity at low temperatures ascribed to unbinding electrons, while the presence of defect-creating dipole strengthened the dipole polarization. The magnetization hysteresis of KVO3-doped samples significantly decreased due to the high spin state transformed to the low spin state of the 3d subshell of Fe in the octahedron FeO6.

Ultralow Glassy Thermal Conductivity and Controllable, Promising Thermoelectric Properties in Crystalline o-CsCu5S3.

We thoroughly investigated the anharmonic lattice dynamics and microscopic mechanisms of the thermal and electronic transport characteristics in orthorhombic o-CsCu5S3 at the atomic level. Taking into account the phonon energy shifts and the wave-like tunneling phonon channel, we predict an ultralow κL of 0.42 w/mK at 300 K with an extremely weak temperature dependence following ∼T-0.33. These findings agree well with experimental values along with the parallel to the Bridgman growth direction. The κL in o-CsCu5S3 is suppressed down to the amorphous limit, primarily due to the unconventional Cu-S bonding induced by the p-d hybridization antibonding state coupled with the stochastic oscillation of Cs atoms. The nonstandard temperature dependence of κL can be traced back to the critical or dominant role of wave-like tunneling of phonon contributions in thermal transport. Moreover, the p-d hybridization of Cu(3)-S bonding results in the formation of a valence band with "pudding-mold" and high-degeneracy valleys, ensuring highly efficient electron transport characteristics. By properly adjusting the carrier concentration, excellent thermoelectric performance is achieved with a maximum thermoelectric conversion efficiency of 18.4% observed at 800 K in p-type o-CsCu5S3. Our work not only elucidates the anomalous electronic and thermal transport behavior in the copper-based chalcogenide o-CsCu5S3 but also provides insights for manipulating its thermal and electronic properties for potential thermoelectric applications.

Kinetic behavior of secondary electrons in a magnetized voltage-driven discharge using combined rf/dc sources

This study employed particle-in-cell/Monte Carlo simulations, along with test particle methods, to examine the characteristics of secondary electrons (SEs) in a voltage-driven discharge using combined rf/dc sources and operates in the presence of a magnetic field. The behavior of SEs is significantly influenced by the magnetic field, leading to the emergence of complex branches in temporal electron energy probability distributions and spatiotemporal electron density distributions within the sheath. The number of branches is directly correlated to the cyclotron period. Moreover, the application of a direct current (dc) source thickens the sheath at the dc biased electrode while attenuating the sheath on the opposite side. This leads to an asymmetrical modulation of the kinetic behavior of SEs in the two sheaths, ultimately resulting in a substantial increase in electron energy on the side of the dc biased electrode.

Consideration of electronic mean heat transport via a low dimension system

The object of research is the complex realm of energy localization and coherent ballistic electronic transport within low-dimensional silicon quantum wires, specifically those doped with germanium atoms. Unlike their three-dimensional counterparts, low-dimensional systems exhibit unique electronic transport behaviors, necessitating novel analytical approaches for a comprehensive understanding. The core of this investigation leverages the Phase Field Matching Theory (PMFT) and the tight-binding (TB) approximation, sophisticated methodologies that enable a deep dive into the quantum mechanical nuances of these systems. Through this lens, we examine the intricate dynamics of dispersion relationships, phase factors, group velocities, and notably, the impact of defects introduced by the germanium doping. This research meticulously analyzes how these defects affect electronic and thermal conductivities, along with densities of states, offering new insights into the role of Fano resonances in the fluctuation of transmission and reflection spectra. These resonances, we find, are crucially dependent on the nature of the defects, their configuration, and the electronic parameters in their vicinity, underscoring the nuanced interplay between material composition and electronic properties in low-dimensional systems. The implications of our findings extend far beyond the theoretical. They pave the way for significant advancements in nanotechnology and the design of electronic devices, highlighting the potential for creating more efficient, high-performance components. Furthermore, this work proposes a framework for developing non-destructive testing methodologies that could revolutionize material science by enabling the precise analysis of defects in low-dimensional systems without causing damage. This is particularly critical for the ongoing development of materials with optimized properties for various applications, from electronics to energy storage. In essence, this research not only enriches our understanding of the physics governing low-dimensional systems but also offers practical insights into leveraging these properties for technological innovation. By bridging the gap between theoretical physics and material science, our study sets the stage for the next generation of electronic components and non-destructive evaluation techniques, marking a significant step forward in the application of quantum mechanics to real-world challenges.

Simulating charged defects at database scale

Point defects have a strong influence on the physical properties of materials, often dominating the electronic and optical behavior in semiconductors and insulators. The simulation and analysis of point defects is, therefore, crucial for understanding the growth and operation of materials, especially for optoelectronics applications. In this work, we present a general-purpose Python framework for the analysis of point defects in crystalline materials as well as a generalized workflow for their treatment with high-throughput simulations. The distinguishing feature of our approach is an emphasis on a unique, unit cell, structure-only, definition of point defects which decouples the defect definition, and the specific supercell representation used to simulate the defect. This allows the results of first-principles calculations to be aggregated into a database without extensive provenance information and is a crucial step in building a persistent database of point defects that can grow over time, a key component toward realizing the idea of a “defect genome” that can yield more complex relationships governing the behavior of defects in materials. We demonstrate several examples of the approach for three technologically relevant materials and highlight current pitfalls that must be considered when employing these methodologies as well as their potential solutions.

Electronic and half-metallic behavior of copper-doped silicon carbide armchair single-walled nanotubes using density functional theory

Due to their remarkable mechanical, thermal and electrical characteristics, silicon carbide (SiC) single-walled nanotubes (SWNTs) are an unusual and promising class of materials. Density functional theory (DFT) is used in this study to examine the electrical and structural characteristics of copper-doped SiC armchair SWNTs. It has been discovered that copper doping of SiC armchair SWNTs alters the materials’ electrical characteristics. SiC SWNTs band gap plays a significant role in influencing the electrical conductivity and optical characteristics of the substance. The energy bands i.e., valence band and conduction band of SiC armchair SWNTs overlapped as copper doping concentration increased, altering the materials’ electrical conductivity and optical characteristics. Additionally, a continuous density of states plot and a narrower band gap are frequently employed as markers of ferroelectric behaviour which indicates the existence of a polarizable and highly delocalized electronic system. The significance of copper doping in SiC SWNTs is understood by this study, along with the effects of the doping on the material’s electrical properties.

Exotic Magnetism in Perovskite KOsO_{3}.

A new perovskite KOsO_{3} has been stabilized under high-pressure and high-temperature conditions. It is cubic at 500K (Pm-3m) and undergoes subsequent phase transitions to tetragonal at 320K (P4/mmm) and rhombohedral (R-3m) at 230K as shown from refining synchrotron x-ray powder diffraction (SXRD) data. The larger orbital overlap integral and the extended wave function of 5d electrons in the perovskite KOsO_{3} allow to explore physics from the regime where Mott and Hund's rule couplings dominate to the state where the multiple interactions are on equal footing. We demonstrate an exotic magnetic ordering phase found by neutron powder diffraction along with physical properties via a suite of measurements including magnetic and transport properties, differential scanning calorimetry, and specific heat, which provide comprehensive information for a system at the crossover from localized to itinerant electronic behavior.

Layer-number parity-dependent oscillatory spin transport in β -Ga2O3 magnetic tunnel junctions

Spintronics devices have been a research hotspot due to their rich theoretical and application value. The widebandgap semiconductor β-Ga2O3 has excellent application potential in spintronics due to the controllability of its electron behavior via ultraviolet light. This paper employs first-principles calculations and the Wenzel–Kramers–Brillouin (WKB) approximation to comprehensively investigate spin transport based on magnetic tunnel junctions (MTJs) comprising β-Ga2O3 nanosheets. The magnetic moment of the ferromagnetic layer in β-Ga2O3 MTJs is found to be positively correlated with tunnel magnetoresistance (TMR). Interestingly, layer-number parity-dependent oscillation of TMR in β-Ga2O3 MTJs is observed, which is explained by the non-equilibrium Green function and the WKB approximation. TMR reaches a maximum of 1077% at five layers, and bias-dependent stability is observed in the monolayer model under biases of 0–20 mV. This study not only expands the application potential of β-Ga2O3 and predicts its superiority in spintronics but also enriches the related condensed matter theory.

Unraveling Broadband Near-Infrared Luminescence in Cr3+-Doped Ca3Y2Ge3O12 Garnets: Insights from First-Principles Analysis.

In this study, we conducted an extensive investigation into broadband near-infrared luminescence of Cr3+-doped Ca3Y2Ge3O12 garnet, employing first-principles calculations within the density functional theory framework. Our initial focus involved determining the site occupancy of Cr3+ activator ions, which revealed a pronounced preference for the Y3+ sites over the Ca2+ and Ge4+ sites, as evidenced by the formation energy calculations. Subsequently, the geometric structures of the excited states 2E and 4T2, along with their optical transition energies relative to the ground state 4A2 in Ca3Y2Ge3O12:Cr3+, were successfully modeled using the ΔSCF method. Calculation convergence challenges were effectively addressed through the proposed fractional particle occupancy schemes. The constructed host-referred binding energy diagram provided a clear description of the luminescence kinetics process in the garnet, which explained the high quantum efficiency of emission. Furthermore, the accurate prediction of thermal excitation energy yielded insights into the thermal stability of the compound, as illustrated in the calculated configuration coordinate diagram. More importantly, all calculated data were consistently aligned with the experimental results. This research not only advances our understanding of the intricate interplay between geometric and electronic structures, optical properties, and thermal behavior in Cr3+-doped garnets but also lays the groundwork for future breakthroughs in the high-throughput design and optimization of luminescent performance and thermal stability in Cr3+-doped phosphors.

Many-body Effects on Electronic Transport in Molecular Junctions: A Quantum Perspective.

This concept delves into quantum particle transport at the nanoscale, with a particular focus on how electrons move through molecular circuits. The thriving field of single molecular electronics benefits from the unique electrical and other properties of nanostructures. It concentrates on single molecular junctions that serve as bridges between electrodes. In this context, the electronic correlation-induced many-body effect gives rise to resonant states. These states, along with conductance, depend on electron spin. Thus, the field acts as a bridge between quantum and macroscopic worlds, unveiling unique behaviors of electrons. Additionally, external factors, such as magnetic fields and voltages, offer means to control the electron correlation in these junctions.

DFT and TDDFT exploration on electronic transitions and bonding aspect of DPA and PTDC ligated transition metal complexes.

In this study, we have investigated the structure, reactivity, bonding, and electronic transitions ofDPAandPDTC along with theirNi-Zncomplexes usingDFT/TD-DFT methods. The energy gap between the frontier orbitals was computed to understand the reactivity pattern of the ligands and metal complexes. From the energies of FMO's, the global reactivity descriptors such as electron affinity, ionization potential, hardness (η), softness (S), chemical potential (μ), electronegativity (χ), and electrophilicity index (ω) have been calculated. The complexes show a strong NLO properties due to easily polarization as indicated by the narrow HOMO-LUMO gap. The polarizability and hyperpolarizabilities of the complexes indicate that they are good candidates for NLO materials. Molecular electrostatic potential (MEP) maps identified electrophilic and nucleophilic sites on the surfaces of the complexes. TDDFT and NBO analyses provided insights into electronic transitions, bonding, and stabilizing interactions within the studied complexes. DPA and PDTC exhibited largerHOMO-LUMO gapsand more negative electrostatic potentials compared to their metal complexes suggesting the higher reactivity. Ligands (DPA and PDTC) had absorption spectra in the range of250nm to 285nm while their complexes spanned250nm to 870nm. These bands offer valuable information on electronic transitions, charge transfer and optical behavior. This work enhances our understanding of the electronic structure and optical properties of these complexes. Gaussian16 program was used for the optimization of all the compounds. B3LYP functional in combination with basis sets, such as LanL2DZ for Zn, Ni and Cu while 6-311G** for other atoms like C, H, O, N, and S was used. Natural bond orbital (NBO) analysis is carried out to find out how the filled orbital of one sub-system interacts with the empty orbital of another sub-system. The ORCA software is used for computing spectral features along with the zeroth order regular approximation method (ZORA) to observe its relativistic effects. TD-DFT study is carried out to calculate the excitation energy by using B3LYP functional.

Electronic phase transformations and energy gap variations in uniaxial and biaxial strained monolayer VS[formula omitted] TMDs: A comprehensive DFT and beyond-DFT study

In the rapidly evolving field of 2D materials, transition metal dichalcogenides (TMDs) have emerged as compelling candidates for electronic applications. This study investigates the electronic structure of the H-phase monolayer VS2 belonging to TMD family and the influence of strain on its band structure through Density Functional Theory (DFT). We employ two different pseudopotential approximations and a suite of computational methods including DFT+U, GAUPBE, G0W0, and self-GW to provide a nuanced understanding of its electronic band structure. A highlight of the study is its focus on how both uniaxial and biaxial strains, ranging from -5% to +5%, affect the electronic properties of the H-phase monolayer VS2. Our comprehensive analysis reveals that these tensile strains significantly widen the energy gap, with uniaxial strains having a more pronounced effect than their biaxial counterparts. Additionally, we identify an intriguing phase transition from a semiconducting to a metallic state under compressive strains, this transition is attributed to both symmetry breaking and bond length variation in the uniaxial case, the bond length in biaxial. These key findings not only enrich our understanding of the intricate electronic behavior of monolayer VS2 under different strains but also pave the way for the design of innovative electronic devices using strain engineering.

Electronic transport evolution across the successive structural transitions in Ni50–xFexTi50 shape memory alloys

Abstract TiNi-based shape memory alloys have been extensively investigated due to their significant applications, but a comprehensive understanding of the evolution of electronic structure and electrical transport in a system with martensitic transformations (MT) is still lacking. In this work, we focused on the electronic transport behavior of three phases in Ni50−x Fe x Ti50 across the MT. A phase diagram of Ni50−x Fe x Ti50 was established based on x-ray diffraction, calorimetric, magnetic, and electrical measurements. To reveal the driving force of MT, phonon softening was revealed using first-principles calculations. Notably, the transverse and longitudinal transport behavior changed significantly across the phase transition, which can be attributed to the reconstruction of electronic structures. This work promotes the understanding of phase transitions and demonstrates the sensitivity of electron transport to phase transition.