Fermi Energy Research Articles

Transition metals tailoring of phosphorus-doped gallium nitride nanotubes as sensors for N-butenyl homoserine lactone (BHL): A computational study

This investigation is focused on the impact of transition metals (Ag, Au, and Cu) encapsulations of phosphorus-doped gallium nitride nanotubes (P@GaNNTs) to achieve precise detection and sensing of N-Butenyl homoserine lactone (BHL), which is a biomarker for urinary tract infection, within the framework of density functional theory (DFT) computation at the B3LYP-D3(BJ)/def2SVP method. Adsorption studies unveil the adsorption energies for BHL detection across the systems, with BHL_Cu_P@GaNNT displaying the most favorable adsorption energy of −1.79247 eV and BSSE correction (−1.7685 eV). Additionally, sensor mechanisms are elucidated through Fermi energy level (EFL) calculations, revealing distinct values of 4.748, 4.242, 5.052, and 3.864 for BHL_Ag_P@GaNNT, BHL_Au_P@GaNNT, BHL_Cu_P@GaNNT, and BHL_P@GaNNT, respectively. These values signify variances in charge transfer dynamics upon BHL interaction. In essence, this study lays the foundation for the development of highly efficient biosensors with exceptional biomarker detection capabilities, particularly in the context of urinary tract infections (UTIs). It opens new avenues in the realm of biosensing technology, promising innovative solutions for healthcare and diagnostics.

D-Band-Center-Engineered Platinum-Based Nanozyme for Personalized Pharmacovigilance.

A high-efficiency PtZnCd nanozyme was screened with density functional theory (DFT) and unique d-orbital coupling features for sensitive enrichment and real-time analysis of CO-releasing molecule-3 (CORM-3). Multicatalytic sites in the nanozyme showed a high reactivity of up to 72.89 min-1 for peroxidase (POD)-like reaction, which was 2.2, 4.07, and 14.67 times higher than that of PtZn (32.67 min-1), PtCd (17.89 min-1), and Pt (4.97 min-1), respectively. Normalization of the catalytic sites showed that the catalytic capacity of the active site in PtZnCd was 2.962 U μmol-1, which was four times higher than that of a pure Pt site (0.733 U μmol-1). DFT calculations showed that improved d-orbital coupling between different metals reduces the position of the center of the shifted whole d-band relative to the Fermi energy level, thereby increasing the contribution of the sites to the electron transfer from the active center, accompanied by enhanced substrate adsorption and intermediate conversion in the catalytic process. The potential adsorption principle and color development mechanism of CORM-3 on PtZnCd were determined, and its practical application in drug metabolism was validated in vitro and in zebrafish and mice models, demonstrating that transition-metal doping effectively engineers high-performance nanozymes and optimizes artificial enzymes.

D‐Band‐Center‐Engineered Platinum‐Based Nanozyme for Personalized Pharmacovigilance

AbstractA high‐efficiency PtZnCd nanozyme was screened with density functional theory (DFT) and unique d‐orbital coupling features for sensitive enrichment and real‐time analysis of CO‐releasing molecule‐3 (CORM‐3). Multicatalytic sites in the nanozyme showed a high reactivity of up to 72.89 min−1 for peroxidase (POD)‐like reaction, which was 2.2, 4.07, and 14.67 times higher than that of PtZn (32.67 min−1), PtCd (17.89 min−1), and Pt (4.97 min−1), respectively. Normalization of the catalytic sites showed that the catalytic capacity of the active site in PtZnCd was 2.962 U μmol−1, which was four times higher than that of a pure Pt site (0.733 U μmol−1). DFT calculations showed that improved d‐orbital coupling between different metals reduces the position of the center of the shifted whole d‐band relative to the Fermi energy level, thereby increasing the contribution of the sites to the electron transfer from the active center, accompanied by enhanced substrate adsorption and intermediate conversion in the catalytic process. The potential adsorption principle and color development mechanism of CORM‐3 on PtZnCd were determined, and its practical application in drug metabolism was validated in vitro and in zebrafish and mice models, demonstrating that transition‐metal doping effectively engineers high‐performance nanozymes and optimizes artificial enzymes.

Intraband Exciton Dynamics of n-Doped Silver Selenide Quantum Dots.

AgxSe (x > 2) colloidal quantum dots (CQDs) have recently emerged as a promising environmentally friendly material contender for mid- and long-wave infrared optoelectronics, leveraging their intraband transition (1Se-1Pe). However, multicarrier interactions in CQDs, particularly Auger recombination, have profound implications on the optoelectronic properties of the materials and their potential in device applications. Understanding the intraband excited-state dynamics in n-doped AgxSe is therefore essential for the assessment and successful implementation of this material platform in devices. We, herein, investigate the carrier dynamics of AgxSe in both solution and thin-film states using a femtosecond mid-infrared transient absorption spectrometer. Our observations reveal that the multicarrier Auger process depends on the degree of doping in AgxSe CQDs and accelerates when the Fermi energy (EF) level approaches the 1Pe state. The calculated intraband Auger coefficients (CA) are measured to be on the order of ∼10-28 cm6 s-1, significantly larger compared to analogous n-doped HgS/Se CQDs.

Influence of Subvalent Twin-Rattler for High n-Type Thermoelectric Performance in Bi13S18Br2 Chalcohalide.

Metal chalcohalides, owing to their higher stability over halides and greater tunability of electronic features over chalcogenides, open new avenues for investigating properties of materials. Complex metal chalcohalides can be a good choice for thermoelectric studies for their halide-like low thermal conductivity and chalcogenide-like high electrical conductivity. Here, we have investigated the thermoelectric properties of n-type Bi13S18Br2 and utilized the concept of Fajans' polarization to describe the formation of a dimer and explained how it can help achieve high thermoelectric figure of merit (zT) of ∼1.0 at 748 K. This zT value is so far the highest-reported value for pristine metal chalcohalides. The existence of subunit in Bi13S18Br2 is experimentally verified by synchrotron X-ray pair distribution function (X-PDF) analysis. The complex structure of Bi13S18Br2 having a large unit cell exhibits simultaneous dimer-cation rattler (i.e., "twin-rattler"), which decreases the lattice thermal conductivity drastically. We observed evidence of such low-energy rattling vibrations from DFT-calculated eigen mode visualizations of the phonon dispersion. The subvalent nature of accommodates an extra electron in Bi(6pz) orbital, which helps form a weakly dispersed donor band just below the Fermi energy (EF), leading to a significant reduction in band gap (0.77 eV), which is favorable for high thermoelectric performance. Consequently, we obtained a semiconducting nature of n-type Bi13S18Br2 with moderate electrical conductivity, as well as a high Seebeck coefficient. Our investigation presents the importance of fundamental chemistry in thermoelectrics and demonstrates the influence of subvalent twin-rattler in triggering high thermoelectric performance in metal chalcohalides.

Magneto-optical properties of heavily Fe-doped GaAs: a density functional approach.

The magneto-optical properties of heavily iron-doped GaAs are investigated. Complex permittivity, optical conductivity and absorption coefficients are mainly discussed using spin-polarized electronic band structures close to the Fermi energy level. Furthermore, prominent magneto-optical properties in visible light and ultraviolet regions, including magnetic circular dichroism as well as complex Kerr and Faraday rotation angles, are presented and discussed. A density functional approach corroborated by some experimental results indicates that GaAs with 25% Fe dopants either in As or Ga sites is a promising ferromagnetic material and a useful platform for optoelectronic and spintronic device applications.

Self-Powered Infrared-Detectable BP/Ta2NiS5 Heterojunction and Its Application in Energy-Efficient Optoelectronic Synapses.

The development of energy-efficient and high-performance optoelectronic devices is crucial for the advancement of modern optoelectronic and microelectronic systems. Although the self-powered devices and optoelectronic synapses based on 2D heterojunction show great application prospects, the high energy consumption and infrared band detection of self-powered optoelectronic synapses are still an urgent problem to be solved. In this report, a BP/Ta2NiS5 heterojunction is constructed to achieve infrared detection by leveraging differences in Fermi energy levels. This heterojunction exhibits a high specific detectivity of 6.57×1010, 2.6×1010, and 1.12×1010 Jones and responsivity of 20, 10.6, and 5.9mAW-1 for 1064, 1550, and 2200nm infrared light at 0 bias voltage, respectively. In addition, under the 2200nm light, by applying an ultra-low bias voltage of 800µV, the heterojunction exhibits ultra-low power and energy consumption of 28.8pW and 0.64pJ, successfully simulates a variety of synaptic behaviors under infrared light, and demonstrates its image perception and image memory capabilities. These findings position the BP/Ta2NiS5 heterojunction as an ideal candidate for a multifunctional optoelectronic device crucial for advanced photodetection, neuromorphic computing, and artificial intelligence.

Incoherence-to-coherence crossover observed in charge-density-wave material 1T-TiSe2

Analogous to the condensation of Cooper pairs in superconductors, the Bose–Einstein condensation (BEC) of electron–hole pairs in semiconductors and semimetals leads to an emergence of an exotic ground state — the excitonic insulator state. In this paper, we study the electronic structure of 1T-TiSe2 utilizing angle-resolved photoemission spectroscopy and alkali-metal deposition. Alkali-metal adatoms are deposited in-situ on the sample surface, doping the system with electrons. The conduction bands of 1T-TiSe2 are thereby pushed down below the Fermi energy, which enables us to characterize its temperature dependence with precision. We found that the formation of the charge density wave (CDW) in 1T-TiSe2 at ~ 205 K is accompanied by a significant increase of the band gap, supporting the existence of excitonic pairing in the CDW state of 1T-TiSe2. More importantly, by analyzing the linewidth of the single-particle excitation spectrum, we unveiled an incoherence-to-coherence crossover at 165 K, which could be attributed to a possible exciton condensation that occurs beneath the CDW transition in 1T-TiSe2. Our results not only explain the exotic transport properties of 1T-TiSe2, but also highlight the possible existence of an excitonic condensate in this semiconducting material.

New Comprehensive Stability and Sensitivity Analysis on Graphene Nanoribbon Interconnects Parameters

Based on the transmission line modeling for multilayer graphene nanoribbon (MGNR) interconnects, system stability was studied on intrinsic parameters. In addition to width,length and height variation, dielectric constant, permeability and Fermi velocity path change in multilayer graphene nanoribbon (MGNR) interconnects are analyzed. In thispaper, the obtained results show with increasing dielectric constant and decreasing permeability, Fermi velocity system becomes more stable. Nyquist diagram and stepresponse method results confirm these and are matched with physical parameter variation like resistance, capacitance and inductance in the following sensitivity analysis results where it shows with increasing width and length, sensitivity will decrease and increase respectively. Impulse response diagram results show with increasing 50% width, sensitivity will be zero but with increasing 50% length, amplitude will decrease and the time of setting will increase. On the other hand, from the step response of the transfer function, both width and length increase cause more stability for a system but the width parameter will be a better choice for manipulating the dimension of MGNR to reach a stable system.

Atomically dispersed Ir Lewis acid sites on (111)-oriented CeO2 enable enhanced reaction kinetics for Li-O2 batteries

Non-aqueous lithium-oxygen batteries are widely regarded as one of the most promising electrochemical energy storage systems, with their ultra-high theoretical energy density and environmental friendliness. However, the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics hinder their practical application. In this study, we tailored an atomically dispersed Ir site on a CeO2 support (Ir@CeO2) with {111} facet-dependent activity to enhance cathode reaction kinetics. The charge interaction between Ir and Ce atoms results in the appropriate regulation of the d-band center of Ir sites leaping into the Fermi energy level, demonstrating a stronger Lewis acidity, which enables easier electron injection from the Ir d-orbitals into O 2p-orbitals of LiO2. This facilitates the conversion kinetics, and as a result, the lithium-oxygen battery with Ir@CeO2 catalyst delivers a minimal discharge/charge polarization and long-term cycle stability, outperforming most traditional catalysts reported. Our promising findings offer compelling insights into the precise manipulation of d orbital structures and the optimization of Lewis acidity, paving the way for advanced electrocatalyst design.

Tunable mid-infrared absorber based on Dirac metamaterials

Abstract In this paper, a tunable metamaterial absorber based on Dirac semimetal is proposed, which consists of three different structures, from top to bottom, namely a double semicircular Dirac semimetal resonator, a silicon dioxide (SiO2) substrate, and a continuous vanadium dioxide (VO2) reflector layer. When the Fermi energy level of the Dirac semimetal is 10\ meV, the absorber absorbs more than 90% in the 39.06-84.76\ THz range. Firstly, taking advantage of the tunability of the conductivity of the Dirac semimetal, the dynamic tuning of the absorption frequency can be achieved by changing the Fermi energy level of the Dirac semimetal without the need to optimise the geometry and remanufacture the structure. Secondly, the structure has been improved by the addition of the phase change material VO2, resulting in a much higher absorption performance of the absorber. Since vanadium dioxide is a temperature-sensitive metal oxide with an insulating phase below the phase transition temperature (about 68℃) and a metallic phase above the phase transition temperature, this paper also analyses the effect of vanadium dioxide on the absorptive performance at different temperatures, with the aim of further improving the absorber performance.

Implementing Lattice and Energy Level Matching to Optimize Buried Interfaces for High-Performance Perovskite Solar Cells.

In n-i-p type perovskite solar cells (PSCs), mismatches in energy level and lattice at the buried interface is highly detrimental to device performance. Here, thin PbS interconnect layer in situ coating on the SnO2 surface is grown. The function of PbS at the interface is different from the commonly used function of crystalline seeds in perovskite bulk. The theoretical calculation show that it helps construct an interconnect structure of SnO2/PbS/Perovskite with matched energy level and lattice. This not only increases conductivity of SnO2, but also upshifts Fermi energy levels (EF) of both SnO2 and buried perovskite due to charge transfer and perovskite's internal defect changes. Such a suitable energy level arrangement ensures a better energy level match at the interface, favoring efficient charge transfer and less open circuit voltage (Voc) loss. Additionally, in situ PL reveals that the template effect of PbS enable perovskite grain to grow bottom-up because of their highly matched lattice parameters. This growth mode optimizes buried interface contact and crystallinity of perovskite. Ultimately, after PbS modification, a remarkable power conversion efficiency (PCE) exceeding 24% and better device stability are obtained. This work demonstrates an effective interconnect layers strategy to realize ideal interface contact toward high-performance PSCs.

Gate voltage dependence on the density of state of 30° twisted bilayer graphene using Trotter–Suzuki tight-binding time propagation method

Abstract Twisted multilayer structures are considered a helpful framework for exploring strongly correlated many-particle systems, where phenomena of physics correlation emerge. Here, we present the Trotter–Suzuki tight-binding time propagation method for computing the density of states (DOS) in a 30° twisted bilayer graphene (TBG). This method solves the time-dependent Schrödinger equation by decomposing Hamiltonian matrices to derive the correlation function. The Fourier transform of this correlation function yields the DOS of the system up to ≈ 1000 000 atoms. Our calculation proves that geometry makes an outstanding contribution to our final results. Additionally, applying additional gate voltage induces shifts in Van Hove singularities, potentially leading to the emergence of new states at the Fermi energy level. The results demonstrate that TBG systems can be easily adjusted and modified for further investigation of optoelectronic features.

A Diphosphonic Acid-Based Interlayer for Highly Efficient and Stable Inverted Perovskite Solar Cells.

We investigate an interlayer of 6,6'-bis(4-(bis(4-methoxyphenyl)amino)phenyl)-[1,1'-binaphthalene]-(2,2'-diyl)bis(oxy)bis(propane-3,1-diyl)bis(phosphonic acid) (BINOL-PA) with undoped poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) coverage. The incorporation of the 1,10-bi-2-naphthol central core enhances π-π stacking and reduces charge recombination at the interface. Compared to PTAA alone (0.95 eV), BINOL-PA/PTAA exhibits a shorter distance from the Fermi energy (EF) to the valence-band maximum (VBM) (0.36 eV). Two phosphoric acid units in BINOL-PA fine-tune the molecular dipoles. Theoretical calculations reveal electrostatic surface potential differences between BINOL-PA and PTAA in their backbone structure. Open-circuit voltage decay (OCVD) and electrochemical impedance spectroscopy (EIS) results suggest suppressed interface recombination. The photovoltaic conversion efficiency (PCE), short-circuit current density (JSC), open-circuit voltage (VOC), and fill factor (FF) for the BINOL-PA/PTAA device are measured as 21.02%, 22.67 mA cm-2, 1.12 V, and 82.8%, respectively, all higher than those achieved by the PTAA device with a PCE of 18%. BINOL-PA/PTAA significantly elevates VOC and FF values compared with dopant-free PTAA alone. The champion device retains over 89% of its initial PCE after being exposed to an ambient environment without encapsulation for more than 30 days. The thermal aging test conducted under a nitrogen atmosphere demonstrates that the efficiency retention rate for BINOL-PA/PTAA displays 60% of its initial efficiency after 1500 h.

Andreev reflection in topological nodal-line semimetals superconductor junction

Abstract Andreev reflection is an important quantum tunneling phenomenon in the conductor-superconductor junction. The Andreev reflection coefficients TAR of a hybrid system with s-wave superconductor connected by topological nodal-line semimetals (TNLSMs-SC junction system) is calculated theoretically by using the Landauer-Büttiker formula combined with the nonequilibrium Green’s function method. The results show that when the direction of the boundary state electron and the incident electron are the same, only the bulk states of the TNLSMs involve the Andreev reflection of the hybrid system, and the Andreev reflection coefficients TAR enhance with the increase of the Fermi energy EF . We also study the effect of on-site energy µz and mass term m on the Andreev reflection and find that the Andreev reflection in the system decreases rapidly with the increase of on-site energy µz and mass term m. Moreover, we find that only in the presence of a mass term m, the Andreev reflection coefficients TAR of the system changes with the rise of the Fermi energy EF . When a perpendicular magnetic field is applied in the system, the Andreev reflection coefficients TARin the superconducting gap will appear a series of oscillating peaks. For a hybrid system with the large perpendicular magnetic field applied, we find that the maximum Andreev reflection coefficients TAR=7.2 at the Fermi energy EF = 0.0 and the incident electron energy E = ±0.1. The Andreev reflection coefficients TAR is gradually enhanced in the superconducting gap (incident energy |E| ≤ 0.2) when a disorder is applied to the superconductor region of the system. However, the symmetry of the Andreev reflection coefficients TARis broken when the perpendicular magnetic field is applied to the system. These peculiar transport properties of the TNLSMs-SC junction system are expected to provide theoretical guidance for future applications.

Coexistence of anomalous Hall effect and weak magnetization in a nominally collinear antiferromagnet MnTe

In various material systems, an antiferromagnetic phase was found to coexist with a weak ferromagneticlike signal, while symmetry-based theoretical predictions indicate a possibility of a nonzero anomalous Hall effect (AHE) even in the absence of sample magnetization. This is the case of nominally collinear antiferromagnets, in particular, hexagonal MnTe, where the AHE and no detectable magnetization have been recently reported. To clarify the role of magnetization, we present a study of bulk MnTe samples, combining experiment and theory. We demonstrate that the existence of the AHE in the hexagonal MnTe is accompanied by the presence of a weak but detectable ferromagneticlike signal, vanishing at the Néel temperature. In contrast to thin layer samples, we find that the AHE hysteresis loop shows an opposite sign and Barkhausen-like jumps. We introduce a macrospin model involving the Dzyaloshinskii–Moriya type interaction, which explains the existence of a nonzero magnetic moment in the absence of external field and reproduces well hysteretic behavior of the AHE. Using analysis of Néel-vector-dependent Berry curvature, we show that the intrinsic AHE in hexagonal MnTe can be nonzero even when the magnetization vanishes and, also, that it changes sign depending on the Fermi energy position. Published by the American Physical Society 2024

Selective Control of Electric Charge of Weyl Fermions in Pyrochlore Iridates.

Weyl fermions can exhibit exotic phenomena due to their magnetic charge in momentum space, while Weyl nodes are usually located away from Fermi energy, which forms electron or hole pockets as the electric charges. Previous studies have mostly focused on the magnetic charge, however, the electric charges are rarely explored. Here, the intriguing Hall responses arising from the interplay between magnetic and electric charges of Weyl fermions in pyrochlore iridates are reported. Explicitly, unexpected linear scaling is observed between the anomalous Hall conductivity and Hall carrier density in strained Nd2Ir2O7 thin films, and its slope shows a sign change approaching the Néel temperature of Nd. Theoretical calculations unveil that the cluster magnetic multipoles induce local energy inversion of Weyl nodes, which alters the electric charge of Weyl fermions and accounts for the observed nontrivial Hall responses. Moreover, the correlation between the magnetic and electric charges is further probed by voltage-controlled hydrogenation, which leads to the suppression of the anomalous Hall effect through electron filling. This work not only reveals the essential role of the both magnetic and electric charges of Weyl fermions, but also demonstrates the hydrogenation as an effective tuning knob in exploring correlated topological properties.

A broadband tunable THz sensor based on graphene metasurface

In this paper, we design a polarization-independent and angle-insensitive wideband THz graphene metamaterial sensor. The proposed metasurface sensor consists of six layers, which are silicon dioxide substrate, metal reflector, air layer, graphene metasurface with microstructure, ion-gel layer and silicon dioxide dielectric layer from bottom to top. The sensor was simulated by using CST Microwave Studio software, and the absorption and sensing performance were analyzed. The results show that the absorption rate is more than 95 % in the range of 1.05–4.07 THz. In addition, when the Fermi energy level of graphene is changed, the absorption rate can be adjusted from 20 % to more than 95 %. At the same time, the absorptivity of the device can be maintained above 80 % before 60° when the TE and TM waves are incident, and it is insensitive to the polarization angle due to the central symmetry of the graphene surface microstructure. By changing the thickness of the air layer, the device can achieve maximum absorption at h2=30μm, where the maximum frequency shift sensitivity is 2.179 THz/RIU. The influence of structure parameters and incident angle on the absorption spectrum shows that the proposed structure has good stability. The proposed metasurface sensor has potential application prospects in biological detection and medical monitoring, broadening the application range of THz functional devices.

New Polymorphic Varieties of Boron Nitride with Diamond-Like TA-Type Phases

In this work, a theoretical study of new polymorphic varieties of boron nitride, which have diamond-like structures with boron and nitrogen atoms in equivalent structural positions, was carried out. The model construction of new phases of boron nitride was performed in the process of crosslinking precursor nanostructures. Single-walled boron nitride nanotubes with chirality indices (3;0), (4;0), and (6;0) were chosen as precursors for the model construction of diamond-like phases. Using the density functional theory method in the generalized gradient approximation, the possibility of stable existence of three new structural varieties of boron nitride with a diamond-like structure was established: BN-TA4, BN-TA5, BN-TA6. The structure of the BN-TA7 diamond-like phase turned out to be unstable and, in the process of geometric optimization, was transformed into the initial structure, a boron nitride nanotube (6;0). As a structural characteristic, the bulk density of the new polymorphs was determined, which is in the range from 2.613 to 3.0836 g/cm3. The sublimation energy of new polymorphic varieties ranges from 17.16 to 17.63 eV/(BN). The value of the band gap near the Fermi energy varies from 5.37 to 5.74 eV.

In Situ Single-phase Formation of LaCl(CN2) Mixed-Anion Compound Via Controlled Pyrolysis of La3+ Modified Melamine Precursor.

Nitride (N3-) or cyanamide (CN22-) based mixed-anion compounds stand as attractive materials due to their unique properties derived from the binary or multiple anions, although their synthesis remains challenging in incorporating the N3- or CN22- anions safely. This work highlights the first demonstration of in situ single phase formation of a LaCl(CN2) mixed-anion compound from a stable single source precursor, melamine modified with LaCl3 preparable under aqueous conditions. The in situ formation of LaCl(CN2) involves the chemical modification of melamine with LaCl3 to form a complex. Upon heating of the precursor under N2 flowing, this complex generates cyanamide species around 400 °C, which react with LaCl3 and nonsublimated melamine to afford a binary LaCl(CN2)/g-C3N4 composite. Further pyrolysis at 800 °C decomposes the g-C3N4 counterpart, resulting in the LaCl(CN2) single-phase formation. The electronic properties of the precursor-derived single phase LaCl(CN2) were studied by the density functional theory calculation and UV-vis spectroscopy combined with X-ray photoelectron spectroscopy analyses and characterized by measuring 4.7, 1.8, and -2.9 eV for the band gap energy, the valence band maximum, and the conduction band minimum relative to Fermi energy, respectively. This study paves the way for exploring various cyanamide-based mixed anion compounds, advancing their potential applications in various fields.