arXiv subjects

Umesh V. Waghmare

Publications and source records attributed to Umesh V. Waghmare.

At least 37 records · Page 2Linked to original sources

arXiv2016

NH3 adsorption on PtM (Fe, Co, Ni) surfaces: cooperating effects of charge transfer, magnetic ordering and lattice strain

Adsorption of a molecule or group with an atom which is less electronegative than oxygen (O) and directly interacting with the surface is very relevant to development of PtM (M=3d-transition metal) catalysts with high activity. Here, we present theoretical analysis of the adsorption of NH3 molecule (N being less electronegative than O) on (111) surfaces of PtM(Fe,Co,Ni) alloys using the first principles density functional approach. We find that, while NH3-Pt interaction is stronger than that of NH3 with the elemental M-surfaces, it is weaker than the strength of interaction of NH3 with M-site on the surface of PtM alloy.

cond-mat.mtrl-sci↗

arXiv2015

Controlled confinement of half-metallic two-dimensional electron gas in BaTiO3/Ba2FeReO6/BaTiO3 heterostructures: A first-principles study

Using density functional theory calculations, we establish that the half-metallicity of bulk Ba2FeReO6 survives down to 1 nm thickness in BaTiO3/Ba2FeReO6/BaTiO3 heterostructures grown along the (001) and (111) directions. The confinement of the two-dimensional (2D) electron gas in this quantum well structure arises from the suppressed hybridization between Re/Fe d states and unoccupied Ti d states, and it is further strengthened by polar fields for the (111) direction. This mechanism, distinct from the polar catastrophe, leads to an order of magnitude stronger confinement of the 2D electron gas than that at the LaAlO3/SrTiO3 interface. We further show low-energy bands of (111) heterostructure display nontrivial topological character. Our work opens up the possibility of realizing ultrathin spintronic devices.

cond-mat.mtrl-sci↗

arXiv2015

Engineering the electronic bandgaps and band edge positions in carbon-substituted 2D boron nitride: a first-principles investigation

Modification of graphene to open a robust gap in its electronic spectrum is essential for its use in field effect transistors and photochemistry applications. Inspired by recent experimental success in the preparation of homogeneous alloys of graphene and boron nitride (BN), we consider here engineering the electronic structure and bandgap of C$_{2x}$B$_{1-x}$N$_{1-x}$ alloys via both compositional and configurational modification. We start from the BN end-member, which already has a large bandgap, and then show that (a) the bandgap can in principle be reduced to about 2 eV with moderate substitution of C $(x<0.25)$; and (b) the electronic structure of C$_{2x}$B$_{1-x}$N$_{1-x}$ can be further tuned not only with composition $x$, but also with the configuration adopted by C substituents in the BN matrix. Our analysis, based on accurate screened hybrid functional calculations, provides a clear understanding of the correlation found between the bandgap and the level of aggregation of C atoms: the bandgap decreases most when the C atoms are maximally isolated, and increases with aggregation of C atoms due to the formation of bonding and anti-bonding bands associated with hybridization of occupied and empty defect states. We determine the location of valence and conduction band edges relative to vacuum and discuss the implications on the potential use of 2D C$_{2x}$B$_{1-x}$N$_{1-x}$ alloys in photocatalytic applications. Finally, we assess the thermodynamic limitations on the formation of these alloys using a cluster expansion model derived from first-principles.

cond-mat.mtrl-sci↗

arXiv2015

Electron-Phonon Coupling and Thermal Conductance at a Metal-Semiconductor Interface: First-principles Analysis

The mechanism of heat transfer and the contribution of electron-phonon coupling to thermal conductance of a metal-semiconductor interface remains unclear in the present literature. We report ab initio simulations of a technologically important titanium silicide (metal) - silicon (semiconductor) interface to estimate the Schottky barrier height (SBH), and the strength of electron-phonon and phonon-phonon heat transfer across the interface. The electron and phonon dispersion relations of TiSi$_2$ with C49 structure and the TiSi$_2$-Si interface are obtained using first-principles calculations within the density functional theory (DFT) framework. These are used to estimate electron-phonon linewidths and the associated Eliashberg function that quantifies coupling. We show that the coupling strength of electrons with interfacial phonon modes is of the same order of magnitude as coupling of electrons to phonon modes in the bulk metal, and its contribution to electron-phonon interfacial conductance is comparable to the harmonic phonon-phonon conductance across the interface.

cond-mat.mtrl-sci↗

arXiv2015

A combined experimental and theoretical study of the electronic and vibrational properties of bulk and few-layer Td-WTe2

The recent discovery of non-saturating giant positive magnetoresistance in Td-WTe2 has aroused great interest in this material. We have studied the structural, electronic and vibrational properties of bulk and few-layer Td-WTe2 experimentally and theoretically. Spin-orbit coupling is found to govern the semi-metallic character of Td-WTe2. Its structural link with the metallic 1T form provides an understanding of its structural stability. We observe a metal to insulator transition and a change in the sign of the Seebeck coefficient around 373 K. Lattice vibrations in Td-WTe2 have been analyzed by first principle calculations. Out of the 33 possible zone-center Raman active modes, five distinct Raman bands are observed around 112, 118, 134, 165 and 212 cm-1 in bulk Td-WTe2. Based on symmetry analysis and the calculated Raman tensors, we assign the intense bands at 165 cm-1 and 212 cm-1 to the A_1^' and A_1^" modes respectively. We have examined the effect of temperature and the number of layers on the Raman spectrum. Most of the bands of Td-WTe2 stiffen, and the ratio of the integrated intensities of the A_1^" to A_1^' bands decreases in the few-layer sample, while all the bands soften in both bulk and few-layer samples with increasing temperature.

cond-mat.mtrl-sci↗

arXiv2014

Strain induced $\mathbb{Z}_2$ topological insulating state of $β$-As$_2$Te$_3$

Topological insulators are non-trivial quantum states of matter which exhibit a gap in the electronic structure of their bulk form, but a gapless metallic electronic spectrum at the surface. Here, we predict a uniaxial strain induced electronic topological transition (ETT) from a band to topological insulating state in the rhombohedral phase (space group: R$\bar{3}$m) of As$_2$Te$_3$ ($β$-As$_2$Te$_3$) through \textit{first-principles} calculations including spin-orbit coupling within density functional theory. The ETT in $β$-As$_2$Te$_3$ is shown to occur at the uniaxial strain $ε_{zz}$ = -0.05 ($σ_{zz}$=1.77 GPa), passing through a Weyl metallic state with a single Dirac cone in its electronic structure at the $Γ$ point. We demonstrate the ETT through band inversion and reversal of parity of the top of the valence and bottom of the conduction bands leading to change in the $\mathbb{Z}_2$ topological invariant $ν_0$ from 0 to 1 across the transition. Based on its electronic structure and phonon dispersion, we propose ultra-thin films of As$_2$Te$_3$ to be promising for use in ultra-thin stress sensors, charge pumps and thermoelectrics.

cond-mat.mtrl-sci↗

arXiv2012

Multiferroic and magnetoelectric nature of GaFeO3, AlFeO3 and related oxides

GaFeO3, AlFeO3 and related oxides are ferrimagnetic exhibiting magnetodielectric effect. There has been no evidence to date for ferroelectricity and hence multiferroicity in these oxides. We have investigated these oxides as well as oxides of the composition Al1-x-yGaxFe1+yO3 (x = 0.2, y = 0.2) for possible ferroelectricity by carrying out pyroelectric measurements. These measurements establish the occurrence of ferroelectricity at low temperatures below the Nèel temperature in these oxides. They also exhibit significant magnetoelectric effect. We have tried to understand the origin of ferroelectricity based on non-centrosymmetric magnetic ordering and disorder by carrying out first-principles calculations.

cond-mat.mtrl-sci↗

arXiv2012

90-degree Ferroelectric Domains in PbTiO3: Experimental Observation and Molecular Dynamics Simulations

We report observation of 90-degree ferroelectric domain structures in transmission electron microscopy (TEM) of epitaxially-grown films of PbTiO3. Using molecular dynamics (MD) simulations based on first-principles effective Hamiltonian of bulk PbTiO3, we corroborate the occurance of such domains showing that it arises as metastable states only in cooling simulations (as the temperature is lowered) and establish characteristic stability of 90-degree domain structures in PbTiO3. In contrast, such domains do not manifest in similar simulations of BaTiO3. Through a detailed analysis based on energetics and comparison between PbTiO3 and BaTiO3, we find that 90-degree domain structures are energetically favorable only in the former, and the origin of their stability lies in the polarization-strain coupling. Our analysis suggests that they may form in BaTiO3 due to special boundary condition and/or defect-related inhomogeneities.

cond-mat.mtrl-sci↗

arXiv2010

Phase separation and surface segregation in ceria-zirconia solid solutions

Using a combination of density functional theory calculations and statistical mechanics, we show that a wide range of intermediate compositions of ceria - zirconia solid solutions are thermodynamically metastable with respect to phase separation into Ce-rich and Zr-rich oxides. We estimate that the maximum equilibrium concentration of Zr in CeO2 at 1373 K is ~2%, and therefore equilibrated samples with higher Zr content are expected to exhibit heterogeneity at the atomic scale. We also demonstrate that in the vicinity of the (111) surface, cation redistribution at high temperatures will occur with significant Ce enrichment of the surface, which we attribute to the more covalent character of Zr-O bonds compared to Ce-O bonds. Although the kinetic barriers for cation diffusion normally prevent the decomposition/segregation of ceria-zirconia solid solutions in typical catalytic applications, the separation behaviour described here can be expected to occur in modern three-way catalytic converters, where very high temperatures are reached.

cond-mat.mtrl-sci↗

arXiv2010

Dopant-vacancy binding effects in Li-doped magnesium hydride

We use a combination of ab initio calculations and statistical mechanics to investigate the substitution of Li+ for Mg2+ in magnesium hydride (MgH2) accompanied by the formation of hydrogen vacancies with positive charge (with respect to the original ion at the site). We show here that the binding energy between dopants and vacancy defects leads to a significant fraction of trapped vacancies and therefore a dramatic reduction of the number of free vacancies available for diffusion. The concentration of free vacancies initially increases with dopant concentration, but reaches a maximum at around 1 mol% Li doping and slowly decreases with further doping. At the optimal level of doping, the corresponding concentration of free vacancies is much higher than the equilibrium concentrations of charged and neutral vacancies in pure MgH2 at typical hydrogen storage conditions. We also show that Li-doped MgH2 is thermodynamically metastable with respect to phase separation into pure magnesium and lithium hydrides at any significant Li concentration, even after considering the stabilization provided by dopant-vacancy interactions and configurational entropic effects. Our results suggest that lithium doping may enhance hydrogen diffusion hydride, but only to a limited extent determined by an optimal dopant concentration and conditioned to the stability of the doped phase.

cond-mat.mtrl-sci↗

arXiv2010

Electric and magnetic polarizabilities of hexagonal Ln2CuTiO6 (Ln=Y, Dy, Ho, Er and Yb)

We investigated the rare-earth transition metal oxide series, Ln2CuTiO6 (Ln=Y, Dy, Ho, Er and Yb), crystallizing in the hexagonal structure with non-centrosymmetric P63cm space group for possible occurrences of multiferroic properties. Our results show that while these compounds, except Ln=Y, exhibit a low temperature antiferromagnetic transition due to the ordering of the rare-earth moments, the expected ferroelectric transition is frustrated by the large size difference between Cu and Ti at the B-site. Interestingly, this leads these compounds to attain a rare and unique combination of desirable paraelectric properties with high dielectric constants, low losses and weak temperature and frequency dependencies. First-principles calculations establish these exceptional properties result from a combination of two effects. A significant difference in the MO5 polyhedral sizes for M = Cu and M = Ti suppress the expected co-operative tilt pattern of these polyhedra, required for the ferroelectric transition, leading to relatively large values of the dielectric constant for every compound investigated in this series. Additionally, it is shown that the majority contribution to the dielectric constant arises from intermediate-frequency polar vibrational modes, making it relatively stable against any temperature variation. Changes in the temperature stability of the dielectric constant amongst different members of this series are shown to arise from changes in relative contributions from soft polar modes.

cond-mat.mtrl-sci↗

arXiv2010

First-principles accurate total-energy surfaces for polar structural distortions of BaTiO3, PbTiO3, and SrTiO3: consequences to structural transition temperatures

Specific forms of the exchange correlation energy functionals in first-principles density functional theory-based calculations, such as the local density approximation (LDA) and generalized-gradient approximations (GGA), give rise to structural lattice parameters with typical errors of -2% and 2%. Due to a strong coupling between structure and polarization, the order parameter of ferroelectric transitions, they result in large errors in estimation of temperature dependent ferroelectric structural transition properties. Here, we employ a recently developed GGA functional of Wu and Cohen [Phys. Rev. B 73, 235116 (2006)] and determine total-energy surfaces for zone-center distortions of BaTiO3, PbTiO3, and SrTiO3, and compare them with the ones obtained with calculations based on standard LDA and GGA. Confirming that the Wu and Cohen functional allows better estimation of structural properties at 0 K, we determine a new set of parameters defining the effective Hamiltonian for ferroelectric transition in BaTiO3. Using the new set of parameters, we perform molecular-dynamics (MD) simulations under effective pressures p=0.0 GPa, p=-2.0 GPa, and p=-0.005T GPa. The simulations under p=-0.005T GPa, which is for simulating thermal expansion, show a clear improvement in the cubic to tetragonal transition temperature and c/a parameter of its ferroelectric tetragonal phase, while the description of transitions at lower temperatures to orthorhombic and rhombohedral phases is marginally improved. Our findings augur well for use of Wu-Cohen functional in studies of ferroelectrics at nano-scale, particularly in the form of epitaxial films where the properties depend crucially on the lattice mismatch.

cond-mat.mtrl-sci↗

arXiv2010

Piezoelectrics by Design: A Route through Short-period Perovskite Superlattices

Using first-principles density functional theory, we study piezoelectricity in short-period superlattices made with combination of ferroelectric and paraelectric components and exhibiting polar discontinuities. We show that piezoelectric response of such a superlattice can be tuned both in terms of sign and magnitude with a choice of its components. As these superlattices with nonswitchable polarization do not undergo ferroelectric transitions, we predict them to exhibit a robust piezoelectric response with weaker temperature dependence compared to their bulk counterparts.

physics.comp-ph↗

arXiv2010

Chemical control of polar behavior in bicomponent short-period superlattices

Using first-principles density functional calculations, we study the interplay of ferroelectricity and polar discontinuities in a range of 1-1 oxide superlattices, built out of ferroelectric and paraelectric components. Studies have been carried out for a varied choice of chemical composition of the components. We find that, when polar interfaces are present, the polar discontinuities induce off- centric movements in the ferroelectric layers, even though the ferroelectric is only one unit cell thick. The distortions yield non-switchable polarizations, with magnitudes comparable to those of the corresponding bulk ferroelectrics. In contrast, in superlattices with no polar discontinuity at the interfaces, the off-centric movements in the ferroelectric layer are usually suppressed. The details of the behavior and functional properties are, however, found to be sensitive to epitaxial strain, rotational instabilities and second-order Jahn-Teller activity, and are therefore strongly in uenced by the chemical composition of the paraelectric layer.

physics.comp-ph↗

arXiv2010

Elastic and structural instability of cubic Sn3N4 and C3N4 under pressure

We use in-situ high pressure angle dispersive x-ray diffraction measurements to determine the equation of state of cubic tin nitride Sn3N4 under pressure up to about 26 GPa. While we find no evidence for any structural phase transition, our estimate of the bulk modulus (B) is 145 GPa, much lower than the earlier theoretical estimates and that of other group IV-nitrides. We corroborate and understand these results with complementary first-principles analysis of structural, elastic and vibrational properties of group IV-nitrides, and predict a structural transition of Sn3N4 at a higher pressure of 88 GPa compared to earlier predictions of 40 GPa. Our comparative analysis of cubic nitrides shows that bulk modulus of cubic C3N4 is the highest (379 GPa) while it is structurally unstable and should not exist at ambient conditions.

cond-mat.mtrl-sci↗

arXiv2008

Polarization Rotation, Switching and E-T phase diagrams of BaTiO$_3$: A Molecular Dynamics Study

We use molecular dynamics simulations to understand the mechanisms of polarization switching in ferroelectric BaTiO$_3$ achieved with external electric field. For tetragonal and orthorhombic ferroelectric phases, we determine the switching paths, and show that polarization rotation through intermediate monoclinic phases (a) facilitates switching at low fields (b) is responsible for a sharp anisotropy in polarization switching. We develop understanding of this through determination of detailed electric field-temperature phase diagrams, that are fundamental to technological applications based on electromechanical and switching response of ferroelectrics.

cond-mat.mtrl-sci↗

arXiv2008

Multiferroic Properties of Nanocrystalline BaTiO3

Some of the Multiferroics [1] form a rare class of materials that exhibit magnetoelectric coupling arising from the coexistence of ferromagnetism and ferroelectricity, with potential for many technological applications.[2,3] Over the last decade, an active research on multiferroics has resulted in the identification of a few routes that lead to multiferroicity in bulk materials.[4-6] While ferroelectricity in a classic ferroelectric such as BaTiO3 is expected to diminish with the reducing particle size,[7,8] ferromagnetism cannot occur in its bulk form.[9] Here, we use a combination of experiment and first-principles simulations to demonstrate that multiferroic nature emerges in intermediate size nanocrystalline BaTiO3, ferromagnetism arising from the oxygen vacancies at the surface and ferroelectricity from the core. A strong coupling between a surface polar phonon and spin is shown to result in a magnetocapacitance effect observed at room temperature, which can open up possibilities of new electro-magneto-mechanical devices at the nano-scale.

cond-mat.mtrl-sci↗

arXiv2008

Fast Molecular-Dynamics Simulation for Ferroelectric Thin-Film Capacitors Using a First-Principles Effective Hamiltonian

A newly developed fast molecular-dynamics method is applied to BaTiO3 ferroelectric thin-film capacitors with short-circuited electrodes or under applied voltage. The molecular-dynamics simulations based on a first-principles effective Hamiltonian clarify that dead layers (or passive layers) between ferroelectrics and electrodes markedly affect the properties of capacitors, and predict that the system is unable to hop between a uniformly polarized ferroelectric structure and a striped ferroelectric domain structure at low temperatures. Simulations of hysteresis loops of thin-film capacitors are also performed, and their dependence on film thickness, epitaxial constraints, and electrodes are discussed.

cond-mat.mtrl-sci↗