Band Gap Opening Research Articles

Ab-initio prediction of gigantic anomalous Nernst effect in ferromagnetic monolayer transition metal trihalides

The anomalous Hall conductivity of all transition metal trihalides was explored using first-principles calculations. Employing the Fukui-Hatsugai-Suzuki method, we found that ferromagnetic monolayersXBr3(X= Pd, Pt) possessed the quantized anomalous Hall conductivity (QAHC) with and without carrier doping. Due to unique QAHC, their transverse thermoelectric properties ofXBr3(X= Pd, Pt) were investigated. Employing the semi-classical Boltzmann transport theory, the transverse thermoelectric coefficient of each monolayer was analyzed. Anomalous Nernst coefficients (ANCs) of theXBr3monolayers were prominent both at and near the Fermi level. Under an assumed relaxation time of 10 fs, the maximum ANCs for the PdBr3(PtBr3) monolayer reached -54.1 (-23.3)µV K-1atT=300 K upon doping with 1.21 × 1014(5.64 × 1013) holes cm-2. The large ANCs of theXBr3monolayers were attributed to the opening of a narrow bandgap generated by spin-orbit coupling both at and near the Fermi level, which led to a large Seebeck-induced charge current and large anomalous Nernst conductivity. These results suggest that ferromagneticXBr3monolayers have significant potential for application in thermoelectric devices.

Light-Induced Polaronic Crystals in Single-Layer Transition Metal Dichalcogenides.

Light-induced ordered states can emerge in materials after irradiation with ultrafast laser pulses. However, their prediction is challenging because the inverted band occupation confounds our chemical intuition. Hence, we use a recently developed constrained density functional perturbation theory approach to systematically screen single-layer transition metal dichalcogenides (TMDs) for light-induced ordered states. We demonstrate that all examined single-layer TMDs reveal similar light-induced charge orderings. The corresponding reconstructions are periodic arrangements of polarons (polaronic crystals), characterized by triangular metal clusters and having no equivalent at equilibrium conditions. The polarons are accompanied by localized midgap states in the electronic band structure, detectable by experimental methods. We assess the selenides as the most promising candidates for potential photoexcitation experiments because they transition at low critical fluences, have low transition barriers, and maintain an open band gap under photoexcitation. Our work paves the way for innovative material design approaches targeting light-induced phases.

Minimum Tracking Linear Response Hubbard and Hund Corrected Density Functional Theory in CP2K.

We present the implementation of the Hubbard (U) and Hund (J) corrected Density Functional Theory (DFT + U + J) functionality in the Quickstep program, which is part of the CP2K suite. The tensorial and Löwdin subspace representations are implemented and compared. Full analytical DFT + U + J forces are implemented and benchmarked for the tensorial and Löwdin representations. We also present the implementation of the recently proposed minimum-tracking linear-response method that enables the U and J parameters to be calculated on first-principles basis without reference to the Kohn-Sham eigensystem. These implementations are benchmarked against recent results for different materials properties including DFT + U band gap opening in NiO, the relative stability of various polaron distributions in TiO2, the dependence of the calculated TiO2 band gap on +J corrections, and, finally, the role of the +U and +J corrections for the computed properties of a series of the hexahydrated transition metals. Our implementation provides results consistent with those already reported in the literature from comparable methods. We conclude the contribution with tests on the influence of the Löwdin orthonormalization on the occupancies, calculated parameters, and derived properties.

First Principle Investigations of Structural, Electronic and Thermal Properties of Pristine, Metal and Non-Metal Doped Silicene for Thermoelectric Applications

Silicene, a two-dimensional hexagonal silicon layer, exhibits exceptional electronic and thermoelectric properties. However, its application in semiconductors is hindered by its zeroband gap, which could be overcome by modifying its electronic properties through doping. In this paper, Density Functional Theory (DFT) calculations were performed to investigate the band gap opening in silicene by studying the effect of magnesium and sulphur doping on its electronic, structural and thermal properties. Pristine silicene has a lattice constant of 3.86 Å and a zero-band gap. Upon doping with 12.5% S and Mg atoms, the lattice constant modifies to 3.45 Å and 3.93 Å, respectively, resulting in a direct band gap opening. For 25% Mg and S doping, the result shows that Mg and S effectively alter the band structure and the band gap of silicene monolayer at various configurations. The maximum band gap was 0.98 eV and 1.22 eV for Mg and S doping into the meta position to the reference point R, respectively. The power factor significantly increases with doping, reaching 1.20 x 1011 WK-2m-1 and 1.40 x 1011 WK- 2 m-1 for 12.5% Mg and S doping compared to 7.4 x 1010 WK-2m-1 for pristine silicene. This substantial enhancement indicates improved thermoelectric performance, making silicene a promising candidate for thermoelectric applications. Results demonstrate that tuning the band gap through doping can simultaneously enhance the power factor, highlighting the potential of Mg/S-doped silicene for efficient energy harvesting and conversion.

Tunable low-frequency broadband band gap in nonlinear locally resonant metamaterial inspired by sarcomere structure

Since traditional locally resonant metamaterials (LRMs) cannot achieve a broadband band gap in the low-frequency band, the suppression and isolation of low-frequency broadband vibration has always been a difficult problem in the field of vibration control. Therefore, in this paper, inspired by the structure of the sarcomere, a novel nonlinear LRM is proposed, aiming to open a wider band gap in the low-frequency band. Firstly, a statics model of the nonlinear local resonator (LR) is established to explore the mechanical nonlinear characteristics of the structure with different geometric parameters. And the inflection point fitting method is used to approximate the nonlinear statics model of nonlinear LR. Then a dynamics model was established, the nonlinear dispersion relationship of the infinite periodic system was obtained by Bloch's theorem and l-P perturbation method. And an analytical investigation of the theoretically calculated band gap is conducted through the band gap ratio and relative band gap width. In addition, according to the influence of different structural parameters on the real and imaginary parts of the wave vector, the regulation rules and mechanisms for nonlinear LRM to open low-frequency broadband band gaps are revealed. Finally, the Runge-Kutta method was used to numerically calculate the vibration transmissibility curve of the nonlinear LRM composed of a limited number of nonlinear LRs. And the correctness of the theoretically calculated band gap was verified. The research results provide theoretical support for the application of nonlinear LRMs in the suppression and isolation of low-frequency broadband vibrations.

Spin-dependent electronic phenomena in heavily-doped monolayer graphene

The controlled manipulation of doping levels in graphene is crucial for advancing next-generation low-power electronics. Owing to its peculiar band structure, graphene's electronic functionalities can be easily tuned by electron doping, resulting in the bandgap openings, orbital hybridization, and induced spin-polarization. Here, we unveil the substantial doping of the graphene layer and the emergence of a significant bandgap by sandwiching a monolayer graphene, supported on ferromagnetic cobalt, between two europium layers. Our angle- and spin-resolved photoemission spectroscopy experiments, accompanied by dedicated density functional theory calculations, demonstrate that single-spin electron pockets form as a result of the hybridization of the topmost europium majority bands with graphene, while hybridization gaps are induced in the graphene π∗ bands by the Eu minority bands. Spin-resolved measurements further emphasize a single-spin dispersionless contribution proximal to the Fermi level, possibly arising from the coupling of single-spin polarized graphene bands to optical phonons. This work provides crucial insights into the phase diagram of heavily doped graphene, with significant potential for the design and development of novel 2D systems.

Semiconducting Heusler Compounds beyond the Slater-Pauling Rule

Heusler compounds with semiconducting properties represent an important class of functional materials. Usually, research on these systems is guided by simple electron-counting rules, such as the Slater-Pauling principle. Here, we report on the discovery of Heusler-type semiconductors, significantly deviating from the Slater-Pauling rule. We theoretically predict the occurrence of nonmagnetic semiconducting ground states in various highly off-stoichiometric full-Heusler alloys, where self-substitution leads to a band-gap opening. This unexpected trend is confirmed experimentally by thermoelectric transport measurements on a multitude of Fe2−2xV1−xAl1+3x samples with up to 20% substitution of Fe and V atoms. The band-gap opening leads to an exceptionally large Seebeck coefficient in p-type Fe2VAl thermoelectrics, previously limited by bipolar conduction and low-density-of-states effective mass. Consequently, our work presents a paradigm to tune the band gap of Heusler compounds by self-substitution and introduces a hitherto unexplored class of semiconductors with exceptional thermoelectric properties, offering significant potential for advancements in energy science and sustainable-energy technologies. Published by the American Physical Society 2024

Interdigitated-comb piezoelectric phononic crystals for innovative SAW devices

In this paper, piezoelectric phononic crystals made up of interdigitated combs in floating potential condition are studied. Calculation of the dispersion curves shows that, in addition to Bragg bandgaps due to the presence of periodic electrodes, supplementary bandgaps are present corresponding to electrical resonance/antiresonance of the comb pairs. Calculation of the reflection coefficient of finite-sized mirrors reveals the presence of high amplitude reflection coefficient lobes near these bandgap frequencies. The electrical response of single port resonators using these interdigitated comb mirrors fabricated with Al metallization on LiTaO3 POI substrate is contrasted with that of a resonator with classical mirrors, providing experimental verification of this mechanism for bandgap opening. Possible applications for SAW device design are finally discussed.

Prediction of Intriguing Valley Properties in Two-Dimensional Hf2TeIX (X = I, Br) Monolayers

The valley degree of freedom, as a new information carrier, is important for basic physical research and the development of advanced devices. Herein, using first-principle calculations, we predict that two-dimensional Hf2TeIX (X = I, Br) monolayers harbor intriguing valley properties. Without considering spin–orbit coupling (SOC), the Hf2TeI2 monolayer has a semi-metallic nature, with Dirac cones located at the high-symmetry point K, and feature, with considerable Fermi velocity. When the SOC is taken into account, a band gap opening of 271 meV can be observed at the Dirac cones. More interestingly, the Hf2TeIBr monolayer exhibits intrinsic spatial inversion symmetry breaking, which leads to the emergence of valley-contrasting physics under SOC. This is demonstrated by the presence of spin–valley splitting and opposite Berry curvature at adjacent K points. Besides, the spin–valley splitting, the band gap and magnitude of the Berry curvature of the Hf2TeIBr monolayer can be effectively tuned by strain engineering. These findings contribute significantly to the design of valleytronic devices and extend opportunities for exploring two-dimensional valley materials.

Transfer-free p-type graphene field-effect transistors with high mobility and on/off ratio

Graphene is considered a promising material because of the novel functionalities associated with its outstanding charge transport properties. However, because graphene has no bandgap, its electrical conductivity cannot be controlled as in semiconductors, at present. Although many attempts have been made to achieve a bandgap opening in graphene, a meaningful bandgap opening for p-type field-effect-transistors (FETs) still remains a challenge. In this study, boron-doping in transfer-free monolayer graphene was successfully demonstrated for digital logic devices. Our approach is highly versatile, as it allows the fabrication of p-type single-crystal graphene FETs having a mobility of ∼290 cm2V−1s−1, an on/off ratio of 1.9 × 105, and a subthreshold swing of 70 mVdec−1. The scalability and versatility of this transfer-free approach for the fabrication of p-type graphene FETs pave the way for high-performance p-type graphene-based digital logic circuits.

Mott interactions driven insulating behaviour in ruthenium based double perovskites: A2SmRuO6 (A = Ba & Sr)

Double perovskites (DP’s) are important for understanding the diverse physical properties arising from strongly correlated interactions. According to experimental observations, the DP’s A2SmRuO6 (A = Ba & Sr) are insulators; however, first-principles calculations using GGA approximations show that they are metallic. We observed a band gap (Eg) opening of 1.3 eV for Ba2SmRuO6 (BSRO) and 1.4 eV for Sr2SmRuO6 (SSRO) upon the insertion of Hubbard parameter (U) in the theoretical computations for accounting the electron-electron interactions. Further investigations using core-level spectroscopy reveal Eg of 1.05 eV for BSRO and 0.85 eV for SSRO. Furthermore, the calculations for Δ (charge transfer energy), U (coulomb repulsion energy), and W (bandwidth) from the combined spectra show U < Δ and U/W > 1.15, which confirms these compounds be classified as Mott-Hubbard insulators. These results expand our understanding of the strongly correlated compounds around the Fermi level, which might have applications in optoelectronics.

Harvesting Magneto-Acoustic Waves Using Magnetic 2D Chromium Telluride (CrTe3).

A vast majority of electrical devices have integrated magnetic units, which generate constant magnetic fields with noticeable vibrations. The majority of existing nanogenerators acquire energy through friction/mechanical forces and most of these instances overlook acoustic vibrations and magnetic fields. Magnetic two-dimensional (2D) tellurides present a wide range of possibilities for devising a potential flexible energy harvester. 2D chromium telluride (2D CrTe3) is synthesized, which exhibits ferromagnetic behavior with a higher T c of ≈224 K. The structure exhibits stable high remnant magnetization, making 2D CrTe3 a potential material for harvesting magneto-acoustic waves. A magneto-acoustic nanogenerator (MANG) is fabricated and the basic mechanical stability and sensitivity of the device with change in load conditions are tested. A high surface charge density of 2.919 mC m-2 is obtained for the device. The thermal strain created in the lattice structure is examined using in-situ Raman spectroscopy. The magnetic anisotropy energy (MAE) responsible for long-range FM ordering is calculated by theoretical modelling with insights into opening of electronic bandgap which enhances the flexoelectric effects. The MANG can be a potential NG to synergistically tap into the magneto-acoustic vibrations generated from the frequency changes of a vibrating device such as loudspeakers.

Nonlinear pendulum metamaterial to realize an ultra-low-frequency field effect bandgap

A field effect transistor (FET) is an extensively employed component in large-scale integrated circuits to regulate circuit on or off by modulating its gate voltage. The mechanical counterpart of a FET is of great significance for advanced regulations of acoustic or elastic waves. Recently proposed active metamaterials are promising scenarios of FET based on the opening and closing of frequency bandgaps through active elements, but hindered by the structural complexity in practice. In this study, we propose and experimentally realize a nonlinear pendulum metamaterial (NPMM) as a mechanical ultra-low-frequency FET. By employing the perturbation method to investigate its dispersion relationship, we show that the NPMM possess a field effect bandgap. Namely, the bandgap can be opened or closed by controlling the excitation amplitude of the impinging wave, which is largely affected by the relative mass of the inner pendulum unit. As a verification, the transmission behavior of the NPMM is numerically studied and experimentally tested. It shows that, once the amplitude of the impinging wave exceeds a certain threshold, the disappearance of a bandgap will be observed with a sudden amplification of the output wave. The central frequency of the field effect bandgap is as low as 4 Hz, whereas the characteristic size of the unit cell is only 4 cm. We expect that the present work opens a new avenue for low-frequency wave regulation.

A theoretical analysis of the effect of hydrostatic pressure on cerium oxide for renewable energy applications

The characteristics of cubic cerium oxide (CeO2) have been investigated using density functional theory (DFT) using the PBE-GGA exchange–correlation functional. This study mainly focused on the structural, elastic, and optoelectronic properties of the CeO2 under the application of external hydrostatic pressure. It is observed that lattice constants and volume tend to decrease with increasing pressure. Based on the observed trends in lattice constants variations, CeO2 exhibits compressibility at high-pressure conditions, although it remains structurally unchanged throughout the pressure range of 0 to 100 GPa. Applying pressure within the range of 0 to 100 GPa reveals a distinct characteristic associated with the emergence of electronic bandgap opening. The material displays an indirect energy bandgap, with its magnitude increasing from 2.659 eV to 4.055 eV under rising pressure. To deeply understand the impact of external pressure on the optical behaviour of CeO2, extensive investigation has been conducted on several optical parameters such as the dielectric function, refractive index, optical reflectivity, absorption coefficient, optical conductivity, and loss function throughout the energy range up to 50 eV. However, there is a tendency for optical parameters to show sharpening peaks that shift somewhat towards higher energies. Furthermore, we have also tested the impact of bandgap modulation induced in CeO2 by proposing a CsSnBr3-based solar cell with the One-Dimensional Solar Cell Capacitance Simulator software. Based on our findings, the use of cubic cerium oxide may find its potential to enhance the performance of optoelectronic and renewable energy devices.

Band gap opening in Bernal bilayer graphene under applied electric field calculated by DFT

This paper proposes the induction and further analysis of band gap opening in Bernal bilayer graphene based on Density Functional Theory (DFT). By simulating a sawtooth-like potential configured so that the electric field (the slope) ranges from 1 V/nm to 10 V/nm, it was found that the band gap reached approximately 325 meV, where it saturated. Although the band gap was consistently direct, it was observed that as the applied electric field increased, the band gap shifted from the high-symmetry K point to other points.

Topological photonic band gaps in honeycomb atomic arrays

lattice of two-level atoms coupled by the in-plane electromagnetic field may exhibit band gaps that can be opened either by applying an external magnetic field or by breaking the symmetry between the two triangular sublattices of which the honeycomb one is a superposition. We establish the conditions of band gap opening, compute the width of the gap, and characterize its topological property by a topological index (Chern number). The topological nature of the band gap leads to inversion of the population imbalance between the two triangular sublattices for modes with frequencies near band edges. It also prohibits a transition to the trivial limit of infinitely spaced, noninteracting atoms without closing the spectral gap. Surrounding the lattice by a Fabry-Pérot cavity with small intermirror spacing d &lt; \pi/k_0d&lt;π/k0, where k_0k0 is the free-space wave number at the atomic resonance frequency, renders the system Hermitian by suppressing the leakage of energy out of the atomic plane without modifying its topological properties. In contrast, a larger dd allows for propagating optical modes that are built up due to reflections at the cavity mirrors and have frequencies inside the band gap of the free-standing lattice, thus closing the latter.

Heteroatom‐Doped Graphene Nanoribbons: Precision Synthesis and Emerging Properties†

Comprehensive SummaryGraphene nanoribbons (GNRs), which can be considered as a special type of conjugated polymers, are quasi‐one‐dimensional graphene cutouts with an opened band gap, revealing great potential as functional materials in optoelectronic, spintronic, and energy‐related applications. An effective strategy to modulate the properties of GNRs is doping heteroatoms into the π‐skeleton. Thanks to the bottom‐up synthetic approach, a number of heteroatom‐doped GNRs with precise structures have been reported, exhibiting intriguing properties. Nevertheless, a comprehensive summary of the progress of this field has remained elusive. In this review, we summarize the history and advances in bottom‐up synthesized heteroatom‐doped GNRs, including their synthetic routes, electronic properties, and promising applications. We hope to establish the reliable structure–property relationship, and provide guidance for the molecular design of heteroatom‐doped GNRs in the future.

Design of Locally Resonant Acoustic Metamaterials with Specified Band Gaps Using Multi-Material Topology Optimization.

Locally Resonant Acoustic Metamaterials (LRAMs) have significant application potential because they can form subwavelength band gaps. However, most current research does not involve obtaining LRAMs with specified band gaps, even though such LRAMs are significant for practical applications. To address this, we propose a parameterized level-set-based topology optimization method that can use multiple materials to design LRAMs that meet specified frequency constraints. In this method, a simplified band-gap calculation approach based on the homogenization framework is introduced, establishing a restricted subsystem and an unrestricted subsystem to determine band gaps without relying on the Brillouin zone. These subsystems are specifically tailored to model the phenomena involved in band gaps in LRAMs, facilitating the opening of band gaps during optimization. In the multi-material representation model used in this method, each material, except for the matrix material, is depicted using a similar combinatorial formulation of level-set functions. This model reduces direct conversion between materials other than the matrix material, thereby enhancing the band-gap optimization of LRAMs. Two problems are investigated to test the method's ability to use multiple materials to solve band-gap optimization problems with specified frequency constraints. The first involves maximizing the band-gap width while ensuring it encompasses a specified frequency range, and the second focuses on obtaining light LRAMs with a specified band gap. LRAMs with specified band gaps obtained in three-material or four-material numerical examples demonstrate the effectiveness of the proposed method. The method shows great promise for designing metamaterials to attenuate specified frequency spectra as required, such as mechanical vibrations or environmental noise.

Topological design of soft substrate acoustic metamaterial for mechanical tuning of sound propagation

The design of tunable acoustic waves is crucial in phononic crystals (PnCs), as acoustic waves exhibit continuous variation across diverse frequency ranges in practical applications. While there have been research efforts on tunable PnCs, existing design strategies predominantly rely on predetermined topology and scatterer shapes based on empirical experience. This reliance poses challenges in ensuring customized and reversible tuning of the bandgap. In this work, we present a customized tunable PnC design model and solution strategy based on soft substrates, which enables reversible tuning of a specific frequency/order bandgap. The designed structure consists of a soft substrate and crystalline columns dispersed in the soft substrate and air. The relative positions of the scatterers in the air are changed by stretching the substrate, thereby realizing the modulation of sound propagation. Since soft materials have both material nonlinearities and complex geometrical variations that are difficult to obtain design sensitivity information, the material-field series expansion topology optimization approach is employed to achieve custom tunable design of the bandgap. The paper presents simulation-based analyses and experimental verification of the customized bandgap opening and closing. The results demonstrate a close alignment between theoretical predictions of propagation curves and experimental findings. This concurrence serves as evidence that the soft-substrate PnC, derived through topology optimization, effectively facilitates the adjustment of bandgaps of arbitrary orders and enables switching between various acoustic functions.

Large dynamic scissoring mode displacements coupled to band gap opening in the cubic phase of the methylammonium lead halide perovskites

Hybrid perovskites are a rapidly growing research area, having reached photovoltaic power conversion efficiencies of over 25%. There is a increasing consensus that the structures of these materials, and hence their electronic structures, cannot be understood purely from the time and space averaged crystal structures observable by conventional methods. We apply a symmetry-motivated analysis method to analyse x-ray pair distribution function data of the cubic phases of the hybrid perovskites MAPbX 3 (X = I, Br, Cl). We demonstrate that, even in the cubic phase, the local structure of the inorganic components of MAPbX 3 (X = I, Br, Cl), are dominated by scissoring type deformations of the PbX 6 octahedra. We find these modes to have a larger amplitude than equivalent distortions in the A-site deficient perovskite ScF3 and demonstrate that they show a significant departure from the harmonic approximation. Calculations performed on an inorganic perovskite analogue, FrPbBr3, show that the large amplitudes of the scissoring modes are coupled to a dynamic opening of the electronic band gap. Finally, we use density functional theory calculations to show that the organic MA cations reorientate to accommodate the large amplitude scissoring modes.