Band Structure Research Articles

Band Engineering of Mn-P Alloy Enables HER-suppressed Aqueous Manganese Ion Batteries.

Aqueous manganese ion batteries hold potential for stationary storage applications owing to their merits in cost, energy density, and environmental sustainability. However, the formidable challenge is the instability of metallic manganese (Mn) anodes in aqueous electrolytes due to severe hydrogen evolution reaction (HER), which is more serious than the commonly studied Zn metal anodes. Moreover, the mechanism of HER side reactions has remained unclear. Herein, we design a series of Mn-P alloying anodes by precisely regulating their energy band structures to mitigate the HER issue. It is found that the serious HER primarily originates from the spontaneous Mn-H2O reaction driven by the excessively high HOMO energy level of Mn, rather than electrocatalytic water splitting. Owing to a reduced HOMO energy level and enhanced electron escape work function, the MnP anode achieves an evidently enhanced cycle durability (over 1000 hours at a high current density of 5 mA cm-2). The MnP||AgVO full cell with an N/P ratio of 4 exhibits better rate capability and extended cycle life (7000 cycles) with minimal capacity degradation than the cell using metallic Mn anode (less than 100 cycles). This study provides a practical approach for developing highly durable aqueous Mn ion batteries.

Adsorption and evolution of N2 molecules over ZnO monolayer: a combined DFT and kinetic Monte-Carlo insight

A large surface area, wide band gap, and unique bonding property between Zn and O atoms make the hexagonal ZnO monolayer attractive as a gas sensor. In the present work, the adsorption and evolution of nitrogen (N2) molecules over a ZnO monolayer have been studied using two different theoretical methods: van der Waals density functional theory (vdW-DFT) and kinetic Monte-Carlo (kMC) simulation. The adsorption and diffusion (hopping over the surface) energy of a N2 gas molecule has been calculated considering the different sites over the ZnO substrate using the revPBE-vdW functional. Bader charge, electron localization function analysis, density of states and band structure plotting have been used to understand the adsorption mechanism. Lateral repulsive interaction between two N2 molecules limits the maximum packing number of gas molecules within one hexagonal ring. The output of the vdW-DFT calculation has been fed to the kMC code to predict the rate of adsorption, desorption, and diffusion, along with the overall surface coverage at different temperatures and pressures. Finally, the change in the N2 adsorption energy has been predicted with the increase of the ZnO layer number.

Novel superhard orthorhombic O12 carbon: a first principle study

Abstract In this study, a new orthorhombic carbon structure with Ama2 symmetry, designated as O12 carbon, has been predicted on basis of the first-principles method. The thermal stability and dynamic stability of O12 carbon were evaluated and confirmed by combining ab initio molecular dynamics and phonon spectra analyses. Meanwhile, the mechanical properties of O12 carbon, compared with other superhard carbon allostrope like diamond, M-carbon, Bct-c4 and Cco-C8, have also been systematically investigated. With a bulk modulus of 351 GPa, a shear modulus of 333 GPa, and a Vickers hardness of 53 GPa, O12 carbon is identified as a superhard material of significantly technological and industrial applications. The existence of elastic anisotropy in O12 carbon has also been confirmed. The electronic band structure calculations have revealed that O12 carbon exhibits a semiconductor characteristic with a direct band gap of 2.5 eV, making it promising candidate in electronic applications. Additionally, the XRD spectra of O12 carbon were obtained to offer further insights for potential experimental observations. Our findings enrich the family of carbon structure and are expected to stimulate additional experimental interest.

The first-principles prediction of mechanical, electronic, elastic and thermodynamic properties of Mo2XB2 (X=Nb, Os, Ta)

The mechanical, electronic and elastic properties of Mo2XB2 (X = Nb, Os, Ta) at different pressures (0–50 GPa) were predicted using first-principles calculations. The enthalpy of formation and the elastic constant calculations show that the three transition metal borides are thermodynamically and mechanically stable. The analysis of density of state and band structure reveals that Mo2XB2 (X = Nb, Os, Ta) have metallic and covalent properties. The increase of pressure will increase the elastic modulus of Mo2XB2 (X = Nb, Os, Ta). The elastic modulus of Mo2XB2 (X = Nb, Os, Ta) are anisotropic. Furthermore, the quasi-harmonic Debye model is used to predict thermodynamic parameters at various temperatures (0–1200K) and pressures (0–50 GPa), such as heat capacity at constant pressure, heat capacity at constant volume, coefficient of thermal expansion, Debye temperature, and the Grüneisen parameter.

Electric Field and Nanocontact Effects in Metal-Organic Framework/Li6.4La3Zr1.4Ta0.6O12 Ionic Conductors for Fast Interfacial Lithium-Ion Transport Kinetics.

The slow ion transport kinetics inside or between the nanofillers in composite polymer electrolytes (CPEs) lead to the formation of lithium dendrites for solid-state lithium batteries. To address the critical issues, CPEs (U@UNL) composed of a UIO-66@UIO-66-NH2 (U@UN) core-shell heterostructure and Li6.4La3Zr1.4Ta0.6O12 (LLZTO) filler is designed. Due to the different band structures of the U@UN heterostructure, a built-in electric field is constructed to promote the transfer kinetics of carriers. Besides, the introduction of LLZTO facilitates the formation of a close nanometer contact interface between U@UN and LLZTO, reducing interface impedance and accelerating the lithium-ion transfer rate. As a benefit from the built-in electric field and the nanometer contact interface, U@UNL exhibits a wide electrochemical window of 5.17 V, a large lithium-ion transference number of 0.76, and a high ionic conductivity of 3.50 × 10-3 S cm-1. Consequently, the U@UNL electrolyte possesses excellent interfacial stability against Li metal after 1200 h at 0.1 mA cm-2 and shows a high specific capacity of 160.2 and 152.6 mAh g-1 at 0.5 and 1 C, respectively. This work proposes a complete strategy for building high-performance solid-state lithium batteries by a built-in electric field and nanometer contact interface between U@UN and LLZTO.

Band Engineering of Mn‐P Alloy Enables HER‐suppressed Aqueous Manganese Ion Batteries

Aqueous manganese ion batteries hold potential for stationary storage applications owing to their merits in cost, energy density, and environmental sustainability. However, the formidable challenge is the instability of metallic manganese (Mn) anodes in aqueous electrolytes due to severe hydrogen evolution reaction (HER), which is more serious than the commonly studied Zn metal anodes. Moreover, the mechanism of HER side reactions has remained unclear. Herein, we design a series of Mn‐P alloying anodes by precisely regulating their energy band structures to mitigate the HER issue. It is found that the serious HER primarily originates from the spontaneous Mn‐H2O reaction driven by the excessively high HOMO energy level of Mn, rather than electrocatalytic water splitting. Owing to a reduced HOMO energy level and enhanced electron escape work function, the MnP anode achieves an evidently enhanced cycle durability (over 1000 hours at a high current density of 5 mA cm‐2). The MnP||AgVO full cell with an N/P ratio of 4 exhibits better rate capability and extended cycle life (7000 cycles) with minimal capacity degradation than the cell using metallic Mn anode (less than 100 cycles). This study provides a practical approach for developing highly durable aqueous Mn ion batteries

Unraveling the Oxygen Vacancy-Performance Relationship in Perovskite Oxides at Atomic Precision via Precise Synthesis.

Understanding the fundamental effect of the oxygen vacancy atomic structure in perovskite oxides on catalytic properties remains challenging due to diverse facets, surface sites, defects, etc. in traditional powder catalysts and the inherent structural complexity. Through quantitative synthesis of tetrahedral (LaCoO2.5-T), pyramidal (LaCoO2.5-P), and octahedral (LaCoO3) epitaxial thin films as model catalysts, we demonstrate the reactivity orders of active-site geometrical configurations in oxygen-deficient perovskites during the CO oxidation model reaction: CoO4 tetrahedron > CoO6 octahedron > CoO5 pyramid. Ambient-pressure Co L-edge and O K-edge XAS spectra clarify the dynamic evolutions of active-site electronic structures during realistic catalytic processes and highlight the important roles of defect geometrical structures. In addition, in situ XAS and resonant inelastic X-ray scattering spectra and density functional theory calculations directly reveal the nature of high reactivity for CoO4 sites and that the derived shallow-acceptor defect levels in the band structure facilitate the adsorption and activation of reactive gases, resulting in more than 23-fold enhancement for catalytic reaction rates than CoO5 sites.

Utilizing armchair and zigzag nanoribbons for improved detection of SO2 Toxicity with graphene biosensor

Graphene nanoribbons (GNRs), with their distinctive structural and electronic characteristics, offer significant potential for use as biosensors in the detection of sulfur dioxide (SO₂) levels. This study employs Density Functional Theory (DFT) to evaluate the sensitivity of armchair graphene nanoribbons (AGNRs) to SO₂ gas. Specifically, we investigate the influence of SO₂ molecules on the electronic and transport characteristics of both pure and Cr-doped zigzag graphene nanoribbons (ZGNRs) and Cr-doped AGNRs. Key electronic properties, including band structure, adsorption energy, and density of states (DOS), were analyzed following SO₂ adsorption. The results indicate that Cr doping leads to significant changes in the electronic properties of AGNRs upon SO₂ exposure, including alterations in the Fermi surface that result in band separation and the formation of a forbidden band. The adsorption energy of Cr-doped AGNR increased from 0.07 eV (pristine AGNR) to 0.55 eV (Cr-doped AGNR), nearly eight times higher, indicating strong chemisorption of SO₂. These findings suggest that Cr-doped AGNRs exhibit high sensitivity to SO₂, making them promising candidates for gas detection. Furthermore, this study reveals that SO₂ adsorption in the armchair direction results in a more pronounced peak-to-valley ratio compared to the zigzag direction, highlighting distinct characteristics in SO₂ adsorption behavior. These findings could facilitate the development of advanced sensors with improved sensitivity and selectivity for environmental monitoring and safety applications.

Mid-Infrared Emission in Ge/Ge1-xSnx/Ge Quantum Well Modeled Within 14-Band k.p Model

Band structure and gain in a Ge/Ge1-xSnx/Ge quantum well are described theoretically using a 14-band k.p model. It has been shown that the quantum well width and the α-Sn concentration considerably modify the conduction and valence subband structure, and, as a result, the optical gain changes with the insertion of a very small concentration of α-Sn. In particular, we have determined the necessary injection carrier density Nj and the critical α-Sn concentration for elevated high gain lasing. It is found that for Nj = 1.5 × 1018 cm−3, we achieved a maximum peak gain for α-Sn concentration of the order 0.155. We can predict that Ge/Ge1-xSnx/Ge QWs should be manufactured with an α-Sn concentration less than 0.155 in devices for optoelectronics applications such as telecommunication and light emitting laser diodes.

Interface-resolved photovoltage generation dynamics and band structure evolution in a PbS quantum dot solar cell.

For directed development of solar cells using nanomaterials such as quantum dots, there is a need to understand the device function in detail. Understanding where photovoltage is generated in a device and where energy losses occur is a key aspect of this, and development of methods which can provide this information is needed. We have previously shown that time-resolved photoelectron spectroscopy of core levels can be used to follow the photovoltage dynamics at a specific interface of a lead sulfide quantum dot solar cell. Here, we use the method's selectivity and sample design to investigate the photovoltage generation in different parts of this solar cell and determine how the different layers (including the absorber layer thickness) contribute to charge separation. We show that all layers contribute to photovoltage generation and that a gold contact deposited on the quantum dots is necessary for full photovoltage generation and slow charge recombination. By combining the information obtained, we are able to experimentally follow the time evolution of the solar cell band structure during the charge separation process. Furthermore, we can identify which specific layers need to be optimized for an overall improvement of quantum dot cells. In the future, this methodology can be applied to other types of devices to provide insights into photovoltage generation mechanisms.

A study of optical properties and electron energy loss spectra of ZnS by linear response theory

The linear response theory has been applied to study the optical properties and electron energy loss spectra of ZnS. The ground state is built using the Full-Potential Linearized Augmented Plane Wave method. Thereafter, the electronic properties such as band structure and density of states are calculated. Calculations of electron energy loss spectra and optical properties are performed on the top of these ground state electronic properties. The calculations are performed using three exchange–correlation kernels namely, adiabatic local density approximation, long range contribution, and the bootstrap. The random phase approximation is also considered. An approach proposed by us to find the material dependent parameter α is used in long range contribution kernel to capture more accurate optical properties. Three values of α viz 0.78, 1.09, and 1.22 are considered. It is observed that the α = 0.78 gives very good results. This proposed scheme is found to work very well for ZnS also. The effect of local field and electron–hole interaction on the spectra is examined. For example after incorporating local field effect the high frequency dielectric constant ε∞ [i.e. ε1E→0eV ], reduces by 9.19, 12.26, 13.51 and 11.02% for random phase approximation, adiabatic local density approximation, long range contribution and bootstrap kernel respectively. In EELS plasmon peak positions are found using the three kernels and random phase approximation. A good accord with experimental results is noted after incorporating local field effects. It is observed that local field effect causes redshift of prominent peak (i.e. plasmon peak) in electron energy loss spectra by 0.61 eV.

Pressure-induced band gap enhancement and temperature-dependent thermoelectric characterization of semiconducting Transition Metal Chalcogenides LiMS (M = Cu, Ag)

The first principles study of Transition Metal Chalcogenides LiMS (M = Cu, Ag) has been conducted utilizing the concepts of Density Functional Theory (DFT). Both the compounds possess a cubic structure with space group F-43m. The mechanical stability of LiCuS and LiAgS has been predicted based on the values of elastic tensor. These Chalcogenides possess an interesting electronic band structure which reveals their semiconducting nature with a direct band gap. The electronic structure is further subjected to high pressure and the changes in band gap are deeply observed. For these materials, the changes in band gap in response to applied pressure suggest the possibility of their use in band gap engineering. The phonon curves are investigated over the Brillouin zone's high symmetry directions which reveal the lattice dynamical stability of the presently studied compounds. Moreover, the atoms present at different positions inside a crystal lattice exhibit vibrations of different intensities and in different directions which have been studied through the Eigenvector representations. The thermoelectric properties of LiCuS and LiAgS have been characterized using Boltzmann's theory over the range of temperature between 100 K and 1600 K. The calculated thermoelectric parameters reveal the high thermoelectric efficiency of these materials with excellent values of the figure of merit. The interesting properties of ternary Chalcogenides LiMS (M = Cu, Ag) make them promising candidates for thermoelectric applications.

Tunable Ambipolar Transport in a 2D Kagome Semiconductor

AbstractThe interference of electronic wavefunctions within a Kagome lattice can result in a flat band structure, where low‐energy electrons exhibit highly correlated behavior, facilitating exploration of interactions among intriguing electronic states. However, the inherent high carrier density in most known Kagome materials often hampers the manipulation of these quantum phenomena through conventional means, such as gate voltage. In this work, a unique tunability in the electrical and optoelectronic properties of exfoliated Nb3I8, a 2D semiconductor featuring a “breathing” Kagome lattice is uncovered. Characterization via temperature‐dependent ARPES confirms its semiconducting nature with a flat band structure. Experimental results from bias and gate voltage dependent transport measurements on thin film Nb3I8 transistor devices demonstrate ambipolar conductance. Notably, these findings reveal a broadband photoresponse in the device, spanning from visible to near infrared wavelengths (532 −1100 nm), with the photocurrent showing gate‐dependent characteristics that mirror the dark current's ambipolar nature. This observation marks the first instance of ambipolar transport in a Kagome semiconductor, opening up exciting new avenues for electronic and optoelectronic device development.

Ultra-broadband emission from Mg7Ga2GeO12:Ni2+,Cr3+ phosphor spanning the NIR I–III regions for spectroscopy applications

Ultra-broadband near-infrared (NIR) lighting sources covering NIR Ⅰ to III regions are pivotal components for NIR spectroscopy devices. However, achieving ultra-broadband and efficient emission covering the entire NIR Ⅰ to III regions remains a significant challenge. To address this, we selected Mg7Ga2GeO12 as host material to realize ultra-broadband NIR emission. Density functional theory calculations on formation energies confirmed the feasibility of doping both Ni2+ and Cr3+ within Mg7Ga2GeO12. Band structure calculations reveal a significantly reduced band gap upon the doping of Ni2+. Following that, we synthesized Mg7Ga2GeO12:Ni2+ through conventional solid-state-reaction method. This phosphor exhibits broadband NIR emission with a full-width-at-half-maximum of 377 nm in the range of NIR II ∼ III (1100–2100 nm). To further enhance the emission efficiency, we co-doped Mg7Ga2GeO12:Ni2+ phosphor with Cr3+. This co-doping strategy not only dramatically enhances the Ni2+ emission intensity, but also extends the lower limit of emission band to 600 nm. However, a spectral gap around 1150 nm remains between Cr3+ and Ni2+ emission centers. To bridge this spectral gap, we employed LiScSiO4:Cr3+ phosphor alongside Mg7Ga2GeO12:Ni2+,Cr3+ phosphor to fabricate a phosphor converted LED (pc-LED) with ultra-broadband NIR emission covering entire NIR Ⅰ to III regions. By utilizing this pc-LED as the lighting source for NIR spectral detection, multiple organic functional group signals can be identified simultaneously in NIR II and III bands from 1000 to 2100 nm. The performance of such an NIR pc-LED not only confirms the application potential of Mg7Ga2GeO12:Ni2+,Cr3+ phosphor in non-destructive spectral analysis but also underscores the feasibility of combining two phosphors to achieve ultra-broadband NIR pc-LEDs, rendering them suitable to be lighting sources for portable spectrometers.

The electronic and magnetic properties of Cr-doped ZnO monolayer at higher percentage by first principles calculations

The crystal structure, structural stability, electronic band structures and magnetization of Cr-doped ZnO monolayer (ML) have been investigated by GGA+U method using first principles calculations in this work. The stability of these systems is confirmed by the negative formation energies at different Cr concentrations. The calculated band gaps with and without the Hubbard U correction aligned well with other computational results. With the increase of Cr concentration, the band gap of Cr-doped ZnO monolayer decreases for the spin-up configuration. However, in the spin-down configuration, the band gap increases first and then decreases and the maximum band gap is obtained at 22.22% Cr concentrations. At 33.33% Cr concentration, the ZnO ML exhibits metallic behavior. The density of states (DOS) analysis reveals an asymmetric nature, indicating ferromagnetism in Cr-doped ZnO MLs at various concentrations, with a magnetic moment per Cr atom of approximately 3.99 μB. The total magnetic moment rises with increasing Cr concentration. Charge density difference analysis shows increased magnetization with higher Cr concentration. At 22.22% Cr concentration, the ZnO ML exhibits ferromagnetism and semiconducting properties, suggesting significant potential for spintronic applications as a diluted magnetic semiconductor.

Electric Structure and Thermoelectric Performance in Cs2O Crystal

In this work, first principles DFT calculations has been employed with anharmonic phonon scatter theory and Boltzmann transport method to perform a exhaustive study on the thermoelectric properties as electronic and phonon transport of layered Cs2O crystal. The results indicate that Cs2O crystal represents a flat-and-dispersive type band structure, which returns a high power factor. In the other hand, low lattice thermal conductivity is discovered in Cs2O semiconductor, combined with its high power factor, the Cs2O crystal is considered a promising thermoelectric material. It is demonstrated that p-type Cs2O could be optimized to exhibit outstanding thermoelectric performance with a maximum ZT value of 0.71 at 500K. Explored by density functional theory calculations, the high ZT value is due to its high Seebeck coefficient S, high electrical conductivity , and low lattice thermal conductivity .

Two-dimensional BiSbTeX2 (X = S, Se, Te) and their Janus monolayers as efficient thermoelectric materials.

Today, there is a huge need for highly efficient and sustainable energy resources to tackle environmental degradation and energy crisis. We have analyzed the electronic, mechanical and thermoelectric (TE) characteristics of two-dimensional (2D) BiSbTeX2 (X = S, Se and Te) and Janus BiSbTeXY (X/Y = S, Se and Te) monolayers by implementing first principles simulations. These monolayers' dynamic stability and thermal stability have been demonstrated through phonon dispersion spectra and ab initio molecular dynamics (AIMD) simulations, respectively. The band structure of these monolayers can be tuned by applying uniaxial and biaxial strains. The investigated lattice thermal conductivity (κl) for these monolayers lies between 0.23 and 0.37 W m-1 K-1 at 300 K. For a more precise calculation of the scattering rate, we implemented electron-phonon coupling (EPC) and spin-orbit coupling effects to calculate the transport properties. For p(n)-type carriers, the power factor of these monolayers is predicted to be as high as 2.08 × 10-3 W m-1 K-2 and (0.47 × 10-3 W m-1 K-2) at 300 K. The higher thermoelectric figure of merit (ZT) of p-type carriers at 300 K is obtained because of their very low value of κl and high power factor. Our theoretical investigation predicts that these monolayers can be potential candidates for fabricating highly efficient thermoelectric power generators.

White-light driven sterilization based on chlorine-doped cuprous oxide for antibacterial food packaging

Microbial spoilage and pathogen contamination present significant challenges to food quality and safety. Incorporating photodynamic sterilization (PDT) into active packaging films, especially using white light-driven methods, is recognized as one of the most effective strategies to combat microbial contamination and extend shelf-life. Cuprous oxide (Cu2O) shows promise due to its suitable band gap for absorbing visible light, although its photocatalytic effectiveness is hindered by electron-hole recombination. In this study, a chlorine (Cl) doping strategy was investigated to enhance Cu2O’s PDT capabilities under visible light. This approach aimed to improve Cu2O’s band structure for generating reactive oxygen species (ROS) and to enhance charge carrier separation efficiency, thereby inhibiting recombination. The resulting Cl-doped Cu2O (Cl-Cu2O) exhibited enhanced antibacterial activity, which was integrated into a gelatin (Gel) and carboxymethylcellulose (CMC)-based food packaging film, referred to as the GC/Cl-Cu2O film. This innovative film provides a white light-driven active packaging solution designed to extend the shelf life of fruits by suppressing microbial growth. This approach not only addresses food safety concerns but also mitigates economic losses associated with food waste, offering a sustainable solution to enhance the quality and safety of perishable goods.

Probing the structural, mechanical, electro-magnetic, thermodynamic and thermoelectric properties of inner-transition based RaXO3 (X: Pr and U) cubic perovskites via first principle calculations

Here, we present ab-initio calculations of the structural, mechanical, electronic, magnetic, thermodynamic and thermoelectric properties of two radium-based perovskites by using density functional theory. These compounds are cubic in nature. Computation of tolerance factor, structural optimization by using the equation of state assures the stability of the materials. Further, we have checked the mechanical stability of the materials by computing the different mechanical parameters. The observed data of B/G and Cauchy pressure for the present materials reveals the ductile nature. The spin polarized band structures and density of states illustrate the half-metallic nature of these materials with the band gap of (3.74 and 4.80) eV in spin down channel for RaPrO3 and RaUO3 alloys respectively. The total magnetic moments calculated via GGA and mBJ approximations were found to be integral in nature (1 and 2) μB, for RaPrO3 and RaUO3 alloys respectively which also is an indication of the half-metallic character of these materials. The effect of temperature and pressure on the different thermodynamic properties like the specific heat capacity, thermal expansion and Gruneisen parameter were studied using the quasi-harmonic Debye model. Finally, we have speculated the temperature dependent thermoelectric properties in terms of Seebeck coefficient, electrical conductivity, thermal conductivity and power factor. The summed -up properties suggest the applications of these materials in thermoelectrics, spintronics and thermoelectric generators outlooks.

The Impact of Hydrostatic Pressure on the Structural, Mechanical, Thermal, and Optoelectronic Characteristics of the RbV3Sb5 Kagome Compound: Ab initio Approach.

We studied the RbV3Sb5 kagome compound's structural, mechanical, thermal, and optoelectronic properties. Mulliken and Hirshfeld population analysis found ionic and covalent connections in RbV3Sb5. The Born stability criterion shows that pure RbV3Sb5 is mechanically stable. The precise measurement of 3.96 indicates that our sample has higher machinability at 20 GPa. Low anticipated hardness of RbV3Sb5 suggests it can be used as a soft solid lubricant. Hardness ratings rise with pressure, however there are exceptions. Pressure causes large nonmonotonic changes in RbV3Sb5's anisotropic characteristics. A comparable 20 GPa Zener anisotropic value, RbV3Sb5 has the highest. The structure's projected Debye temperature at 0 GPa is 284.39 K, indicating softness. Dispersion curves with negative frequencies suggest ground state structural dynamical instability. The structure has no negative-energy phonon branches under 10 GPa stress. From band structure and density of state analysis, the structure behaves metallically under hydrostatic pressure. Also, the structure has maximal ultra-violet conductivity and absorption. The absorption coefficient, conductivity, and loss function plots show uniform patterns at all pressures. As pressure rises, these graphs' peaks blue shift.