Band Structure Research Articles

Achieving Tunable Band Structure and Photocarrier Dynamics by Regulating 2D Atomic Layer Stacking Toward High‐Performance Self‐Powered Broadband and Deep‐UV Photodetection

Abstract2D materials with unique layer‐dependent electronic structure can bring precise control to their photocarrier dynamics for optimizing and expanding optoelectronic applications, while the challenge of controlling layer stacking makes the layer dependency law still underexplored in emerging 2D ternary metal chalcogenides. Herein, 2D rhombohedral‐phase ZnIn2S4 (R‐ZIS) with controllable layer thickness is achieved by confined‐growth strategy in high yield, exhibiting continuously tunable direct bandgap (2.39–2.77 eV) with evident upshift of conduction band minimum (CBM) and Fermi level (EF), demonstrated arising from the synergistic effect of reduced interlayer interaction with inevitably increasing Zn defects. Remarkably, the carrier dynamics of R‐ZIS in photoelectrochemical (PEC) device is successfully regulated by adjusted CBM and EF, resulting in continuously tunable optical absorption band, photocarrier separation efficiency, self‐powered capability, and dark current noise. Beneficial from tailored band structure and carrier dynamics, self‐powered PEC‐type photodetector with broadband photoresponse (254–765 nm), is achieved fast response speed (12.3/5.3 ms) and high responsivity (90.29 mA W−1) in multilayer R‐ZIS, while deep‐UV photodetector with ultra‐high specific detectivity (1.62 × 1012 Jones) at 254 nm in monolayer R‐ZIS, exhibiting the record performance in both fields. This work motivates the development of tailored band structure for 2D‐materials‐based optoelectronic devices in strategy and mechanism.

Origin of the vibrational structure of the first absorption band of cis/trans isomeric 1,6-diphenylhexatrienes by (TD)DFT calculations

We present a detailed spectroscopic analysis of the first absorption band of the six possible conformers of 1,6-diphenyl-1,3,5-hexatriene, obtained by changing the configuration of trans double bonds to cis. To this end, we computed the absorption spectra using FCclasses 3.0 code. First, we assessed the performance of PBE0 and CAM-B3LYP density functional theory functionals with different basis sets to reproduce the experimental spectra. Additionally, we considered different models to compute the spectra. PBE0/def2tZVP with an adiabatic hessian model with internal coordinates yields results in very good agreement with experimental data. Subsequently, we analyzed the different contributions of vibronic transition to the spectral structure, correlating ground state conformation with spectral shape, and studied the effect of temperature on the absorption first band.

On the use of complex band structure to study valley photovoltaics: toward efficient hot carrier extraction

On the use of complex band structure to study valley photovoltaics: toward efficient hot carrier extraction

Synergistic interaction of S-type heterojunction and sulfur vacancies in g-C3N5@Sv-ZnIn2S4 composites: Simultaneous promotion of complete 2,4-dichlorophenol mineralization and Cr(VI) reduction

Constructing efficient heterojunction photocatalysts is an effective measure for degrading pesticides and reducing heavy metals. In this study, g-C3N5@Sv-ZnIn2S4 (g-C3N5@Sv-ZIS) composite with large specific surface area has been successfully prepared by a simple low-temperature water bath method. The g-C3N5@Sv-ZIS composite showed complete mineralization of 2,4-dichlorophenol (2,4-DCP) and reduction of Cr(VI) within 60 min. The results of electron spin resonance spectroscopy, photoelectrochemical characterization, and energy band structure calculations indicated the formation of an S-type heterojunction at the interface of g-C3N5 and Sv-ZIS. In situ XPS analysis showed the transfer of photogenerated charges from g-C3N5 to Sv-ZIS. The molecular structure of 2,4-DCP was analyzed using frontier molecular orbital and electrostatic potential calculations. The possible degradation pathways of 2,4-DCP were proposed based on liquid chromatography– mass spectrometry results. Biotoxicity simulations of the intermediates revealed decreased toxicities. Furthermore, The kinetic rate constant of CZSv-200 for degrading 2,4-DCP and Cr(Ⅵ) in deionized water was approximately 2.20, 3.10 and 2.46, 4.03 times higher than that in lake and sewage plant water, respectively. The composites designed in this study provide reliable theoretical support for the removal of composite pollutants.

Hydrostatic Pressure‐Tuning of Opto‐Electronic and Thermoelectric Properties Half‐Heusler Alloy RhTiP With DFT Analysis

ABSTRACTUtilizing DFT along with Boltzmann transport theory, the structural, elastic, electrical, optical, and thermoelectric properties of half‐Heusler compound RhTiP have been calculated in principle to examine the pressure effect in the range of 0–40 GPa. As pressure increases, the volume and normalized lattice parameter decreased. In addition to satisfying the Born stability criterion, which ensured the compound RhTiP “natural stability,” the zero pressure elastic constants and the pressure‐dependent elastic constants are positive up to 40 GPa. The band structure computations guarantee the semiconductor nature of RhTiP, as demonstrated by the presence of electronic band gap of 1.035 eV at zero pressure. Using the Voigt‐Reuss‐Hill (VRH) averaging scheme under pressure, we have determined the values of this compound's bulk modulus , shear modulus , Young's modulus , Pugh ratio , Poisson's ratio , and anisotropy factor . Because the bulk modulus responds linearly to pressure, the material's hardness increases as pressure rises. Additionally, under pressures up to 40 GPa, the optical characteristics of RhTiP, including their reflectivity, absorptivity, conductivity, dielectric constant, refractive index, and loss function, were assessed and discussed. Furthermore, the thermoelectric properties are also studied for the materials and supports the tunning of pressure. This study provides a gateway to how the optoelectronic and transport properties of cubic RhTiP could be tuned by employing external pressure.

A Novel Cross Tetrachiral Honeycomb Metamaterial with Designable Static and Dynamic Performances.

A novel cross tetrachiral honeycomb metamaterial is proposed, which not only possesses the negative Poisson's ratio property, but also has a wide-frequency bandgap. The effective elastic parameters of the cross tetrachiral honeycomb are first theoretically analyzed; then, its designable performances for negative Poisson's ratio and elastic modulus are studied by varying geometric parameters. The dynamic properties of the cross tetrachiral honeycomb metamaterial are investigated by analyzing the band structure. It is shown that without the addition of external mass to the structure, a designable wide bandgap can be generated to isolate the in-plane waves effectively by selecting the ligament angles and the radius of central cylinder. In addition, an effective approach is proposed for tuning the bandwidth without changing the geometric parameters of the structure. Compared to classical negative Poisson's ratio metamaterials, the proposed cross tetrachiral honeycomb metamaterial is designable and tunable for achieving a specific static or dynamic performance, and has potential applications in engineering practice.

Analysis of semiconductor properties of fabricated graphene materials

Introducing dopant elements into graphene is a crucial process for creating bandgaps, which will have significant importance in developing nanoelectronic devices in the future. In this study, we provide an analysis of the electrical and carrier mobility properties of graphene doped with BN in ratios of 1 %, 3 %, and 5 %, graphene 95 %, ZnO-3 %, and BN2 %, graphene-95 %, Al2O3-3 % and BN-2 %, graphene-95 %, TiO2-3 % and BN-2 % by using a sintering process. Upon analyzing the band structure, it was determined that the mentioned materials demonstrate a bandgap in graphene. The resistivity values for fabricated graphene materials doped with different nanoparticles are estimated using the Source-meter Unit (SMU) at room temperature (25°C), 100°C and 200°C. The conductivity of graphene is 8.93E+07 Ω−1cm−1 and reduced gradually with the doping percentages. The resistivity of graphene is measured at 1.12 E-08 Ω.cmand increases with the doping percentages, and carrier mobility is measured to be 9239 cm2V−1s−1 and gradually reduced with the doping percentages. The temperature-dependent conductivity is determined using electrical conductivity under the constant relaxation time approximation.

Assessing the sensing performance of Janus transition metal dichalcogenides (ScSSe, TiSSe and ZrSSe) for oxygencontaining toxic gas molecules such as CO, NO, NO2 and SO2

In this study, the adsorption behavior and sensing capabilities of oxygen-containing gas molecules (CO, NO, NO2, SO2) on Janus ScSSe, TiSSe, and ZrSSe nanosheets have been investigated by using Density Functional Theory (DFT). In order to find the most stable site, two sites (S site and Se site) of the nanosheets have been chosen for gas adsorption. The adsorption energy, charge transfer, work function, and electronic properties have been examined to understand the adsorption behavior. The results show chemisorption for CO, NO, and NO2 gas molecules on ScSSe, at the Sc site with energy −1.52, −1.61 and −1.41 eV respectively. Unlike ScSSe, both TiSSe and ZrSSe show weak physisorption with energy ranges from −0.09 to −0.29 eV, and −0.07 to −0.22 eV respectively. Band structures and Density of States (DOS) indicate the metallic behavior of the nanosheets. Furthermore, the recovery times for CO, NO, and NO2 gas molecules on ScSSe have also been calculated and found that in second range. In the work function calculation, the reduction of work function has been observed after adsorption of CO, NO and NO2 on the ScSSe. Therefore, Janus ScSSe stands out as a promising candidate for detecting CO, NO, and NO2 gas molecules.

When van der Waals Met Kagome: A 2D Antimonide with a Vanadium-Kagome Network.

2D materials showcase unconventional properties emerging from quantum confinement effects. In this work, a "soft chemical" route allows for the deintercalation of K+ from the layered antimonide KV6Sb6, resulting in the discovery of a new metastable 2D-Kagome antimonide K0.1(1)V6Sb6 with a van der Waals gap of 3.2 Å. The structure of K0.1(1)V6Sb6 was determined via the synergistic techniques, including X-ray pair distribution function analysis, advanced transmission electron microscopy, and density functional theory calculations. The K0.1(1)V6Sb6 compound crystallizes in the monoclinic space group C2/m (a = 9.57(2) Å, b = 5.502(8) Å, c = 10.23(2) Å, β = 97.6(2)°, Z = 2). The [V6Sb6] layers in K0.1(1)V6Sb6 are retained upon deintercalation and closely resemble the layers in the parent compound, yet deintercalation results in a relative shift of the adjacent [V6Sb6] layers. The magnetic properties of the K0.1(1)V6Sb6 phase in the 2-300 K range are comparable to those of KV6Sb6 and another Kagome antimonide KV3Sb5, consistent with nearly temperature-independent paramagnetism. Electronic band structure calculation suggests a nontrivial band topology with flat bands and opening of band crossing afforded by deintercalation. Transport property measurements reveal a metallic nature for K0.1(1)V6Sb6 and a low thermal conductivity of 0.6 W K-1 m-1 at 300 K. Additionally, ion exchange in KV6Sb6 via a solvothermal route leads to a successful partial exchange of K+ with A+ (A = Na, Rb, and Cs). This study highlights the tunability of the layered structure of the KV6Sb6 compound, providing a rich playground for the realization of new 2D materials.

Nitrogen-oxygen defect engineering enhanced intrinsic electric field in CoFe2O4/g-C3N4 heterojunctions for photocatalytic tetracycline degradation and H2 evolution

A range of efficient g-C3N4/CoFe2O4 heterojunction with nitrogen deficiencies (NDs) and oxygen deficiencies (ODs) were successfully synthesized through doping-melting and hydrothermal methods. Nitrogen-oxygen defect engineering effectively enhanced the active sites on the catalyst surface and regulated the optical bandgap, band structure, and work function (Φ) of g-C3N4 and CoFe2O4, regulating the strength of the intrinsic electric field (IEF) and promoting the separation of photo-generated carriers at the heterojunction interface. Among the series of samples, CH-H2@CFO-A5 (properly oxalate-doped g-C3N4/CoFe2O4 heterojunctions treated with prolonged annealing) demonstrated remarkable optical properties due to its narrowest optical band gap, while the strongest IEF and redox potential make it has strong carrier dynamics and photocatalytic efficiency. Under visible light, the mineralization rate of tetracycline (TC) on CH-H2@CFO-A5 and the photocatalytic hydrogen production rate were 4.51 times and 2.72 times higher than that of unmodified CN-H0@CFO-A1, respectively. This study aimed to provide an efficient strategy for regulating the IEF within the heterojunction, by altering the Fermi level through multi-element defect engineering.

Selective Generation of Reactive Oxygen Species in Photocatalytic Oxidation by Tuning Porphyrin-Based COFs' Dimensionality.

Regulating the selective generation of reactive oxygen species (ROS) is a significant challenge in the field of photocatalytic oxidation, with successful approaches still being limited. Herein, we present a strategy to selectively generate singlet oxygen (1O2) and superoxide radicals (O2•-) by tuning the dimensionality of porphyrin-based covalent organic frameworks (COFs). The transformation of COFs from three-dimensional (3D) solids to two-dimensional (2D) sheets was achieved through the reversible protonation of the imine bond. Upon irradiation, both bulk and thin-layer COF-367 can transfer energy to O2 to generate 1O2. However, thin-layer COF-367 exhibited a superior performance compared to its bulk counterpart in activating O2 to form the O2•- radicals via electron transfer. After excluding the influences of the band structure, O2 adsorption energy, and frontier orbital composition attributed to the dimensionality of the COFs, it is reasonably speculated that the variance in ROS generation arises from the differential exposure ratios of the active surfaces, leading to distinct reaction pathways between the carrier and O2. This study is the first to explore the modulation mechanism of COF dimensionality on the activation of the O2 pathway, underscoring the importance of considering COF dimensionality in photocatalytic reactions.

Edge functionalized with benzenesulfonyl groups of g-C3N4 nanosheets as a highly efficient photocatalyst for water purification

Photocatalytic water purification is a promising method for environmental remediation, but it is greatly hindered by the rapid charge carrier recombination behavior of the photocatalysts. Herein, a simple wet-chemical method is developed for grafting electron-withdrawing benzenesulfonyl groups at the edges of g-C3N4 nanosheets. These exhibited a superior and versatile photocatalytic performance on the degradation of organic contaminant, as well as disinfected Escherichia coli (E. coli) bacteria under visible light illumination. Systematic studies reveal that the grafting of benzenesulfonyl groups led to the synergic effect in ultrathin g-C3N4 nanosheets of enhancing the photogenerated charge carrier separation on surface, improving light absorption, changing electronic band structure, and causing surface charge redistribution, all of which are beneficial for enhancing the photocatalytic performance. Notably, these edge-activated g-C3N4 photocatalysts also demonstrate remarkable photocatalytic activity in the real tap water and urban wastewater, indicating their promising potential for application in real wastewater treatment.

Porous-suspended graphite carbon doped TiO2 improves the band structure of photocatalysts to enhance photocatalytic degradation of tetracycline in water

ABSTRACT In order to improve visible light utilization efficiency and enrich low-concentration antibiotics in water systems, a new type of floating TiO2 graphite carbon (FTDGC) photocatalyst was prepared by the one-pot method. These floating materials have good adsorption properties and sufficient mechanical strength, which makes them easy to recycle and reuse in processing. Its photocatalytic performance was evaluated by photocatalytic degradation of tetracycline (TC) in water. The results showed that FTDGC had a high adsorption degradation capacity for TC and the photocatalytic degradation process was accorded with a first-order kinetic equation. The Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy indicated the generation of Ti–C–Ti valence bonds and Ti–C–O bonds on the TiO2 surface with the modification of graphite carbon materials. Optimization of preparation conditions revealed that as the amount of activator phosphoric acid increased and the porosity of the solid surface increased, the external exposure of TiO2 made the effect of the composite catalyst more pronounced. The recycling experiment showed that FTDGC still had good degradation ability for TC after five times reuse. The catalysts developed in this research can provide a new idea and reference for the pretreatment of refractory organic wastewater, as well as for the reuse of medium water.

Atomistic spin dynamics simulations of magnonic spin Seebeck and spin Nernst effects in altermagnets

Magnon band structures in altermagnets are characterized by an energy splitting of modes with opposite chirality, even in the absence of applied external fields and relativistic effects, because of an anisotropy in the Heisenberg exchange interactions. We perform quantitative atomistic spin dynamics simulations based on electronic structure calculations on rutile RuO2, a prototypical “d-wave” altermagnet, to study magnon currents generated by thermal gradients. We report substantial spin Seebeck and spin Nernst effects, i.e., longitudinal or transverse spin currents, depending on the propagation direction of the magnons with respect to the crystal, together with a finite spin accumulation associated with nonlinearities in the temperature profile. Our findings are consistent with the altermagnetic spin-group symmetry, as well as predictions from linear spin-wave theory and semiclassical Boltzmann transport theory. Published by the American Physical Society 2024

Designer spin-orbit superlattices: symmetry-protected Dirac cones and spin Berry curvature in two-dimensional van der Waals metamaterials

The emergence of strong relativistic spin-orbit effects in low-dimensional systems provides a rich opportunity for exploring unconventional states of matter. Here, we present a route to realise tunable relativistic band structures based on the lateral patterning of proximity-induced spin-orbit coupling. The concept is illustrated on a patterned graphene–transition metal dichalcogenide heterostructure, where the spatially periodic spin-orbit coupling induces a rich mini-band structure featuring massless and massive Dirac bands carrying large spin Berry curvature. The envisaged systems support robust and gate-tunable spin Hall responses driven by the quantum geometry of mini-bands, which can be tailored through metasurface fabrication methods and twisting effects. These findings open pathways to two-dimensional quantum material design and low-power spintronic applications.

New semiconducting lead-free halide double perovskite Ag2LiGaF6 for optoelectronic and thermoelectric applications

A comprehensive study of lead-free halide double perovskite using density functional theory (DFT) including structural, electronic, dynamical, mechanical, optical, and thermoelectric properties has been carried out. The tolerance factor and the octahedral factor confirm that the compound belongs to face-centred-cubic structure with Fm-3m space group. The predicted band structure and DOS exhibit that the material is an indirect bandgap semiconductor. Our calculation reveals that material is dynamically stable because of no negative frequency found in phonon-dispersion curve. The material also possesses mechanical stability. The optical spectra of material show good absorbance and low reflectivity in ultraviolet region. The thermoelectric part discusses the Seebeck coefficient, thermal conductivity, electrical conductivity, power factor, and figure of merit (zT) at different chemical potential into temperature range 400–1200 K. The purpose of this investigation is to stimulate researchers to develop this kind of material and assess their potential for the advancement of contemporary thermoelectric and optoelectronic devices.

Unraveling the origin of Kondo-like behavior in the 3d-electron heavy-fermion compound YFe2Ge2

The heavy fermion (HF) state of [Formula: see text]-electron systems is of great current interest since it exhibits various exotic phases and phenomena that are reminiscent of the Kondo effect in [Formula: see text]-electron HF systems. Here, we present a combined infrared spectroscopy and first-principles band structure calculation study of the [Formula: see text]-electron HF compound YFe[Formula: see text]Ge[Formula: see text]. The infrared response exhibits several charge-dynamical hallmarks of HF and a corresponding scaling behavior that resemble those of the [Formula: see text]-electron HF systems. In particular, the low-temperature spectra reveal a dramatic narrowing of the Drude response along with the appearance of a hybridization gap ([Formula: see text] 50 meV) and a strongly enhanced quasiparticle effective mass. Moreover, the temperature dependence of the infrared response indicates a crossover around [Formula: see text] 100 K from a coherent state at low temperature to a quasi-incoherent one at high temperature. Despite of these striking similarities, our band structure calculations suggest that the mechanism underlying the HF behavior in YFe[Formula: see text]Ge[Formula: see text] is distinct from the Kondo scenario of the [Formula: see text]-electron HF compounds and even from that of the [Formula: see text]-electron iron-arsenide superconductor KFe[Formula: see text]As[Formula: see text]. For the latter, the HF state is driven by orbital-selective correlations due to a strong Hund's coupling. Instead, for YFe[Formula: see text]Ge[Formula: see text] the HF behavior originates from the band flatness near the Fermi level induced by the combined effects of kinetic frustration from a destructive interference between the direct Fe-Fe and indirect Fe-Ge-Fe hoppings, band hybridization involving Fe [Formula: see text] and Y [Formula: see text] electrons, and electron correlations. This highlights that rather different mechanisms can be at the heart of the HF state in [Formula: see text]-electron systems.

Electronic structure and thermoelectric properties of epitaxial Sc1−xVxNy thin films grown on MgO(001)

The electronic structure of Sc1−xVxNy epitaxial films with different alloying concentrations of V are investigated with respect to effects on thermoelectric properties. Band structure calculations on Sc0.75V0.25N indicate that V 3d states lie in the band gap of the parent ScN compound in the vicinity of the Fermi level. Thus, theoretically, the presence of light (dispersive) bands at the Γ point with band multiplicity is expected to lead to lower electrical resistivity, while flat (heavy) bands at X−W−K symmetry points are associated with higher Seebeck coefficients than that of ScN. Hence, to probe the thermoelectric properties experimentally, epitaxial Sc1−xVxNy thin film samples were deposited on MgO(001) substrates. All the samples showed N substoichiometry and pseudocubic crystal structure. The N-vacancy-induced states were visible in the Sc 2p x-ray absorption spectroscopy spectra. The reference ScN and Sc1−xVxNy samples up to x=0.12 were n type, exhibiting carrier concentration of 1021 cm−3, typical for degenerate semiconductors. For the highest V alloying of x=0.15, holes became the majority charge carriers, as indicated by the positive Seebeck coefficient. The underlying electronic structure and bonding mechanisms in Sc1−xVxNy influence the electrical resistivity, Seebeck coefficient, and Hall effect. Thus, this paper contributes to the fundamental understanding to correlate defects and thermoelectric properties to the electronic structure in the Sc-N system with V alloying. Published by the American Physical Society 2024

An intriguing way to synthesize a TiO2–ZnO hybrid nanostructure for the pragmatic application as a photocatalyst

In an attempt to counter the problem of treating wastewater more efficiently, we report the study on photocatalytic properties of metal oxide nanostructures under different light sources. A novel sonication-assisted refluxing method was employed to synthesize a binary heterostructure consisting of TiO2 and ZnO. XRD and EDS analysis of synthesized materials confirm the presence of both TiO2 and ZnO. Also, the change in the intensity of XRD peaks and elemental composition are well observed with a change in molar concentration of Ti and Zn. HR-TEM micrographs show nanostructures having hybrid Janus and Core-shell type structures. The XPS spectra were probed to identify the surface chemical species associated with the prepared heterostructures. Raman spectra confirm the smaller ZnO particles attached over agglomerated TiO2 as a shell layer as depicted in TEM results. Optical studies exhibit the modification in the band structure of the materials due to the formation of the heterostructure. The synthesized hybrid catalyst shows impressive results in photocatalytic performance. The catalytic potency of the prepared heterostructures under UV light is reminiscent of Anatase while it gets convalescent with an increment of Zn content under visible light. The photocatalytic performance of synthesized materials under sunlight shows their potential to be utilized as commercial catalysts for direct application in wastewater treatment. The kinetic study of the degradation data reveals interesting facets of the catalysis. It suggests that the photo-corrosion of the catalyst inordinately changes the rate of photocatalytic reaction which ultimately affects the photocatalytic efficiency of the catalyst. The study also discusses the role of kinetic and validation parameters in the selection of the best-fitted kinetic model with realistic arguments.

Evaporated Copper‐Based Perovskite Dynamic Memristors for Reservoir Computing Systems

AbstractDynamic memristors are considered as the optimal hardware devices for reservoir computing (RC) enabled by their nonlinear conductance variations. This significantly reduces the extensive training workload typically required by traditional neural networks. Lead halide perovskites, with their tunable band structure and active ion migration properties, have emerged as highly promising materials for developing dynamic memristors. However, large‐scale and consistently stable production remains a challenge for perovskite functional films, while lead elements' toxicity and environmental impact also partly restrict their practical device utilization. In this work, lead‐free copper‐based perovskite (i.e., CsCu2I3) films are prepared by thermal evaporation for constructing dynamic memristors. The effective conductivity modulation of CsCu2I3‐based memristor can be utilized in artificial neural networks, achieving a high handwritten digit recognition accuracy of 91.2%. In addition, the RC system is also constructed based on the dynamic behavior of the devices, by which a letter recognition accuracy of 98.2% with simple training is achieved. This technology provides a feasible pathway to construct copper‐based perovskite dynamic memristors for future neural network information processing.