Magneto-transport in the monolayer MoS2material system for high-performance field-effect transistor applications.

Electronic transport in monolayer MoS2is significantly constrained by several extrinsic factors despite showing good prospects as a transistor channel material. Our paper aims to unveil the underlying mechanisms of the electrical and magneto-transport in monolayer MoS2. In order to quantitatively interpret the magneto-transport behavior of monolayer MoS2on different substrate materials, identify the underlying bottlenecks, and provide guidelines for subsequent improvements, we present a deep analysis of the magneto-transport properties in the diffusive limit. Our calculations are performed on suspended monolayer MoS2and MoS2on different substrate materials taking into account remote impurity and the intrinsic and extrinsic phonon scattering mechanisms. We calculate the crucial transport parameters such as the Hall mobility, the conductivity tensor elements, the Hall factor, and the magnetoresistance over a wide range of temperatures, carrier concentrations, and magnetic fields. The Hall factor being a key quantity for calculating the carrier concentration and drift mobility, we show that for suspended monolayer MoS2at room temperature, the Hall factor value is around 1.43 for magnetic fields ranging from 0.001 to 1 Tesla, which deviates significantly from the usual value of unity. In contrast, the Hall factor for various substrates approaches the ideal value of unity and remains stable in response to the magnetic field and temperature. We also show that the MoS2over an Al2O3substrate is a good choice for the Hall effect detector. Moreover, the magnetoresistance increases with an increase in magnetic field strength for smaller magnetic fields before reaching saturation at higher magnetic fields. The presented theoretical model quantitatively captures the scaling of mobility and various magnetoresistance coefficients with temperature, carrier densities, and magnetic fields.

Unveiling Valence State-Dependent Photocatalytic Water Splitting Activity and Photocathodic Behavior in Visible Light-Active Iridium-Doped BaTiO3.

Despite having favorable energetics and tunable optoelectronic properties, utilization of BaTiO3 (BTO) for photocatalytic reactions is limited by its absorption only in the ultraviolet region. To address this challenge, BTO is doped with iridium (Ir) to induce visible light absorption. The visible light-induced photocatalytic H2 generation efficiency is enhanced by 2 orders of magnitude on selective conversion of the Ir valence state from Ir4+ to Ir3+. To understand such intriguing behavior, valence state-dependent changes in the optoelectronic, structural, and surface properties and electronic band structure are comprehensively investigated. The effect of electron occupancy change between Ir4+ (t2g5 eg0) and Ir3+ (t2g6 eg0) and their energetic positions within the band gap is found to significantly influence H2 generation. Besides this, converting Ir4+ to Ir3+ enhanced the photocathodic current and lowered the onset potential. Results aid in designing photocatalysts to efficiently use low-energy photons for enhancing solar H2 production in these emerging BTO-based photocatalysts. Collectively, the observations made in this work highlight the promising application of Ir3+:BTO in z-scheme photocatalysis.

Insights into Heterogeneous Catalysis on Surfaces with 3d Transition Metals: Spin-Dependent Chemisorption Models and Magnetic Field Effects.

This Perspective provides an overview of recent developments in the field of 3d transition metal (TM) catalysts for different reactions, including oxygen-based reactions such as the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The spin moments of 3d TMs can be exploited to influence chemical reactions, and recent advances in this area, including the theory of chemisorption based on spin-dependent d-band centers and magnetic field effects, are discussed. The Perspective also explores the use of scaling relationships and surface magnetic moments in catalyst design as well as the effect of magnetism on chemisorption and vice versa. In addition, recent studies on the influence of a magnetic field on the ORR and the OER are presented, demonstrating the potential of ferromagnetic catalysts to enhance these reactions through spin polarization.

Combining First-Principles Modeling and Symbolic Regression for Designing Efficient Single-Atom Catalysts in the Oxygen Evolution Reaction on Mo2CO2 MXenes.

In this study, we address the significant challenge of overcoming limitations in the catalytic efficiency for the oxygen evolution reaction (OER). The current linear scaling relationships hinder the optimization of the electrocatalytic performance. To tackle this issue, we investigate the potential of designing single-atom catalysts (SACs) on Mo2CO2 MXenes for electrochemical OER using first-principles modeling simulations. By employing the Electrochemical Step Symmetry Index (ESSI) method, we assess OER intermediates to fine-tune the activity and identify the optimal SAC for Mo2CO2 MXenes. Our findings reveal that both Ag and Cu exhibit effectiveness as single atoms for enhancing OER activity on Mo2CO2 MXenes. However, among the 21 chosen transition metals (TMs) in this study, Cu stands out as the best catalyst for tweaking the overpotential (ηOER). This is due to Cu's lowest overpotential compared to other TMs, which makes it more favorable for the OER performance. On the other hand, Ag is closely aligned with ESSI = ηOER, making the tuning of its overpotential more challenging. Furthermore, we employ symbolic regression analysis to identify the significant factors that exhibit a correlation with the OER overpotential. By utilizing this approach, we derive mathematical formulas for the overpotential and identify key descriptors that affect the catalytic efficiency in the electrochemical OER on Mo2CO2 MXenes. This comprehensive investigation not only sheds light on the potential of MXenes in advanced electrocatalytic processes but also highlights the prospect of improved activity and selectivity in OER applications.

Spin torques and anomalous velocity in spin textures induced by fast electron injection from topological ferromagnets: The role of gauge fields.

A new method for analyzing magnetization dynamics in spin textures under the influence of fast electron injection from topological ferromagnetic sources such as Dirac half metals has been proposed. These electrons, traveling at a velocityvwith a non-negligible value ofv/c(wherecis the speed of light), generate a non-equilibrium magnetization density in the spin-texture region, which is related to an electric dipole moment via relativistic interactions. When this resulting dipole moment interacts with gauge fields in the spin-texture region, an effective field is created that produces spin torques. These torques, like spin-orbit torques that occur when electrons are injected from a heavy metal into a ferromagnet, can display both damping-like and anti-damping-like properties. Finally, we demonstrate that such an interaction between the dipole moment and the gauge field introduces an anomalous velocity that can contribute to transverse electrical conductivity in the spin texture in a way comparable to the topological Hall effect.

Can magnetotransport properties provide insight into the functional groups in semiconducting MXenes?

Hall scattering factors of Sc2CF2, Sc2CO2 and Sc2C(OH)2 are calculated using Rode's iterative approach by solving the Boltzmann transport equation. This is carried out in conjunction with calculations based on density functional theory. The electrical transport in Sc2CF2, Sc2CO2 and Sc2C(OH)2 is modelled by accounting for both elastic (acoustic and piezoelectric) and inelastic (polar optical phonon) scattering. Polar optical phonon (POP) scattering is the most significant mechanism in these MXenes. We observe that there is a window of carrier concentration where the Hall factor acts dramatically; Sc2CF2 obtains an incredibly high value of 2.49 while Sc2CO2 achieves a very small value of approximately 0.5, and Sc2C(OH)2 achieves the so called ideal value of 1. We propose in this paper that such Hall factor behaviour has significant promise in the field of surface group identification in MXenes, an issue that has long baffled researchers.

Chemical Bonding in Large Systems Using Projected Population Analysis from Real-Space Density Functional Theory Calculations.

We present an efficient and scalable computational approach for conducting projected population analysis from real-space finite-element (FE)-based Kohn-Sham density functional theory calculations (DFT-FE). This work provides an important direction toward extracting chemical bonding information from large-scale DFT calculations on materials systems involving thousands of atoms while accommodating periodic, semiperiodic, or fully nonperiodic boundary conditions. Toward this, we derive the relevant mathematical expressions and develop efficient numerical implementation procedures that are scalable on multinode CPU architectures to compute the projected overlap and Hamilton populations. The population analysis is accomplished by projecting either the self-consistently converged FE discretized Kohn-Sham orbitals or the FE discretized Hamiltonian onto a subspace spanned by a localized atom-centered basis set. The proposed methods are implemented in a unified framework within the DFT-FE code where the ground-state DFT calculations and the population analysis are performed on the same FE grid. We further benchmark the accuracy and performance of this approach on representative material systems involving periodic and nonperiodic DFT calculations with LOBSTER, a widely used projected population analysis code. Finally, we discuss a case study demonstrating the advantages of our scalable approach to extract the quantitative chemical bonding information of hydrogen chemisorbed in large silicon nanoparticles alloyed with carbon, a candidate material for hydrogen storage.

Computational design of novel MAX phase alloys as potential hydrogen storage media combining first principles and cluster expansion methods.

Finding a suitable material for hydrogen storage under ambient atmospheric conditions is challenging for material scientists and chemists. In this work, using a first principles based cluster expansion approach, the hydrogen storage capacity of the Ti2AC (A = Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, and Zn) MAX phase and its alloys was studied. We found that hydrogen is energetically stable in Ti-A layers in which the tetrahedral site consisting of one A atom and three Ti atoms is energetically more favorable for hydrogen adsorption than other sites in the Ti-A layer. Ti2CuC has the highest hydrogen adsorption energy than other Ti2AC phases. We find that the 83.33% Cu doped Ti2AlxCu1-xC alloy structure is both energetically and dynamically stable and can store 3.66 wt% hydrogen under ambient atmospheric conditions, which is higher than that stored by both Ti2AlC and Ti2CuC phases. These findings indicate that the hydrogen capacity of the MAX phase can be significantly improved by doping an appropriate atom species.

Identifying the Critical Surface Descriptors for the Negative Slopes in the Adsorption Energy Scaling Relationships via Density Functional Theory and Compressed Sensing.

Adsorption energy scaling relationships have progressed beyond their original form, which was primarily focused on optimizing catalytic sites and lowering computational costs in simulations. The recent rise in interest in adsorption energy scaling relations is to investigate surfaces other than transition metals (TMs) as well as interactions involving complex compounds. In this work, we report our extensive study on the scaling relation (SR) between oxygen (O), with elements of neighboring groups such as boron (B), aluminum (Al), carbon (C), silicon (Si), nitrogen (N), phosphorus (P), and fluorine (F) on magnetic bimetallic surfaces. We observed that only O versus N and F seems to have a positive slope; the other slopes are negative. We present new theoretical model in terms of multiple surface descriptors using density functional theory and compressed sensing, whereas the original scaling theory was based on a single adsorbate descriptor: adsorbate valency.

Population analysis with Wannier orbitals.

We formulate Wannier orbital overlap population and Wannier orbital Hamilton population to describe the contribution of different orbitals to electron distribution and their interactions. These methods, which are analogous to the well-known crystal orbital overlap population and crystal orbital Hamilton population, provide insight into the distribution of electrons at various atom centers and their contributions to bonding. We apply this formalism in the context of a plane-wave density functional theory calculation. This method provides a means to connect the non-local plane-wave basis to a localized basis by projecting the wave functions from a plane-wave density functional theory calculation to a localized Wannier orbital basis. The main advantage of this formulation is that the spilling factor is strictly zero for insulators and can systematically be made small for metals. We use our proposed method to study and obtain bonding and electron localization insights in five different materials.

Cooperation and competition between magnetism and chemisorption.

Chemisorption on ferromagnetic and non-magnetic surfaces is discussed within the Newns-Anderson-Grimley model along with the Stoner model of ferromagnetism. In the case of ferromagnetic surfaces, the adsorption energy is formulated in terms of the change in surface magnetic moments. Using such a formulation, we address the issue of how an adsorbate's binding strength depends on the magnetic moments of the surface and how the adsorption process reduces/enhances the magnetic moments of the surface. Our results indicate a possible scaling relationship of adsorption energy in terms of surface magnetic moments. In the case of non-magnetic surfaces, we formulate a modified Stoner criterion and discuss the condition for the appearance of magnetism due to chemisorption on an otherwise non-magnetic surface.

Adsorption energy scaling relation on bimetallic magnetic surfaces: role of surface magnetic moments.

The scaling relationships between the adsorption energies of different reaction intermediates have a tremendous effect in the field of surface science, particularly in predicting new catalytic materials. In the last few decades, these scaling laws have been extensively studied and interpreted by a number of research groups which makes them almost universally accepted. In this work, we report the breakdown of the standard scaling law in magnetic bimetallic transition metal (TM) surfaces for hydrogenated species of oxygen (O), carbon (C), and nitrogen (N), where the adsorption energies are estimated using density functional theory (DFT). We propose that the scaling relationships do not necessarily rely solely on the adsorbates, they can also be strongly dependent on the surface properties. For magnetic bimetallic TM surfaces, the magnetic moment plays a vital role in the estimation of adsorption energy, and therefore towards the linear scaling relation.

Transition metal substituted Fe2P: potential candidate for MRAM application.

We propose transition metal substituted Fe2P as a new promising material for spin-transfer torque magnetic random-access memory (STT-MRAM) application. Using first-principles calculations based on density functional theory and Monte Carlo simulations, we demonstrate that this material can be used as a ferromagnetic electrode in the magnetic tunnel junction (MTJ) of STT-MRAM due to its moderate perpendicular magnetic anisotropy, high ferromagnetic transition temperature, and large tunnel magnetoresistance. This work is expected to provide a basis for the development of a new class of Fe2P-based electrode materials for STT-MRAM devices.

Machine Learning and Scaling Laws for Prediction of Accurate Adsorption Energy.

Finding an "ideal" catalyst is a matter of great interest in the communities of chemists and material scientists, partly because of its wide spectrum of industrial applications. Information regarding a physical parameter termed "adsorption energy", which dictates the degrees of adhesion of an adsorbate on a substrate, is a primary requirement in selecting the catalyst for catalytic reactions. Both experiments and in silico modeling are extensively being used in estimating the adsorption energies, both of which are an Edisonian approach, demand plenty of resources, and are time-consuming. In this paper, employing a data-mining approach, we predict the adsorption energies of monoatomic and diatomic gases on the surfaces of many transition metals (TMs) in no time. With less than a set of 10 simple atomic features, our predictions of the adsorption energies are within a root-mean-squared error (RMSE) of 0.4 eV with the quantum many-body perturbation theory estimates, a computationally expensive method with a good experimental agreement. Based on the important features obtained from machine learning models, we construct a set of mathematical equations using the compressed sensing technique to calculate adsorption energy. We also show that the RMSE can be further minimized up to 0.10 eV using the precomputed adsorption energies obtained with the conventional exchange and correlation (XC) functional by a new set of scaling relations.

Semi-classical electronic transport properties of ternary compound AlGaAs2: role of different scattering mechanisms.

Using Rode's iterative method, we have investigated the semi-classical transport properties of the n-type ternary compound AlGaAs2. Four scattering mechanisms have been included in our transport calculation, namely, ionized impurity, piezoelectric, acoustic deformation and polar optical phonon (POP). The scattering rates have been calculated in terms of ab initio parameters. We consider AlGaAs2 to have two distinct crystal geometries, one in tetragonal phase (space group: [Formula: see text]), while the other one having body centered tetragonal crystal structure (space group: [Formula: see text]). Higher electron mobility has been observed in the body centered tetragonal phase, thereby making it more suitable for high mobility device application, over the tetragonal phase. In order to understand the differences in electron mobility for these two phases, curvatures of the E-k dispersion of the conduction bands for these phases have been compared. At room temperature, the dominant contribution in electron mobility was found to be provided by inelastic POP scattering. We have also noted that mobility is underestimated in relaxation time approximation compared with the Rode's iterative approach.

First-principles study of the complex magnetism in Fe16N2.

Magnetic exchange interactions in pure and vanadium (V)-doped Fe16N2 are studied within the framework of density functional theory (DFT). The Curie temperatures were obtained via both mean field approximation (MFA) and Monte Carlo (MC) calculations based on interactions that were obtained through DFT. The Curie temperature (TC) for pure Fe16N2 that was obtained under MFA is substantially larger than the experimental value, suggesting the importance of thermal fluctuations. At zero field, the calculated magnetic susceptibility shows a sharp peak at T = TC that corresponds to the presence of localized d-states. From the nature of the exchange interactions, we have determined the reason for the occurrence of the giant magnetic moment in this material, which remained a mystery for decades. Finally, we posit that Fe16N2 can also act as a satisfactory spin injector for III-V semiconductors, in addition to its application as a permanent magnet, since it has very high spin polarization (compared to elemental ferromagnets) and smaller lattice mismatch (compared to half-metallic Heusler alloys) with conventional III-V semiconductors such as GaAs and InGaAs. We demonstrate this application in the case of Fe16N2(001)/InGaAs(001) hetero-structures, which exhibit substantial spin polarization in the semiconductor (InGaAs) region. PACS number: 82.65.My, 82.20.Pm, 82.30.Lp, 82.65.Jv.

Ab initio semi-classical electronic transport in ZnSe: the role of inelastic scattering mechanisms.

We present a detailed ab initio study of semi-classical transport in n-ZnSe using Rode's iterative method. Inclusion of ionized impurity, piezoelectric, acoustic deformation and polar optical phonon scattering and their relative importance at low and room temperature for various n-ZnSe samples are discussed in depth. We have clearly noted that inelastic polar optical phonon scattering is the most dominant scattering mechanism over most of the temperature region. Our results are in good agreement with the experimental data for the mobility and conductivity obtained at different doping concentrations over a wider range of temperatures. Also we compare these results with the ones obtained with relaxation time approximation (RTA) which clearly demonstrate the superiority of the iterative method over RTA.

Inducing half metallicity with alloying in Heusler Compound CoFeMnSb.

First principles studies were performed in order to find out the possibility of inducing half-metallicity in Heusler Compound CoFeMnSb, by means of alloying it with 3d-transition metal elements. Proper alloying element is selected through the calculations of formation energies. These calculations were tested with different concentrations of alloying elements at different atomic sites. Among the selected transition metal elements Sc and Ti are proposed to be excellent alloying elements, particularly at Mn site. By using these alloying elements complete half metallic behaviour is obtained in [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text] and CoFeTiSb alloys. Shifting of Co-Fe d-states towards lower energy region leads to zero density of states at Fermi level for the spin minority channel. Alloying effects on the electronic structure and magnetization are discussed in details. Thermodynamical stability of these new alloys is a major part of this study. The Curie temperatures of [Formula: see text] and [Formula: see text] were found to be 324.5 K and 682 K; respectively, showing good candidature for spintronics applications. For understanding the bonding nature of the constituent atom of CoFeMnSb, crystal orbital Hamiltonian populations have been analysed.

Role of zero-point effects in stabilizing the ground state structure of bulk Fe2P.

Structural stability of Fe2P is investigated in detail using first-principles calculations based on density functional theory. While the orthorhombic C23 phase is found to be energetically more stable, the experiments suggest it to be hexagonal C22 phase. In the present study, we show that in order to obtain the correct ground state structure of Fe2P from the first-principles based methods it is utmost necessary to consider the zero-point effects such as zero-point vibrations and spin fluctuations. This study demonstrates an exceptional case where a bulk material is stabilized by quantum effects, which are usually important in low-dimensional materials. Our results also indicate the possibility of magnetic field induced structural quantum phase transition in Fe2P, which should form the basis for further theoretical and experimental efforts.

An improved d-band model of the catalytic activity of magnetic transition metal surfaces.

The d-band center model of Hammer and Nørskov is widely used in understanding and predicting catalytic activity on transition metal (TM) surfaces. Here, we demonstrate that this model is inadequate for capturing the complete catalytic activity of the magnetically polarized TM surfaces and propose its generalization. We validate the generalized model through comparison of adsorption energies of the NH3 molecule on the surfaces of 3d TMs (V, Cr, Mn, Fe, Co, Ni, Cu and Zn) determined with spin-polarized density functional theory (DFT)-based methods with the predictions of our model. Compared to the conventional d-band model, where the nature of the metal-adsorbate interaction is entirely determined through the energy and the occupation of the d-band center, we emphasize that for the surfaces with high spin polarization, the metal-adsorbate system can be stabilized through a competition of the spin-dependent metal-adsorbate interactions.