arXiv subjects

Oleksandr I. Malyi

Publications and source records attributed to Oleksandr I. Malyi.

At least 37 records · Page 2Linked to original sources

arXiv2020

False metals, real insulators, and degenerate gapped metals

This paper deals with a significant family of compounds predicted by simplistic electronic structure theory to be metals but are, in fact, insulators. This false metallic state has been traditionally attributed in the literature to reflect the absence of proper treatment of electron-electron correlation ("Mott insulators") whereas, in fact, even mean-field like density functional theory describes the insulating phase correctly if the restrictions posed on the simplistic theory are avoided. Such unwarranted restrictions included different forms of disallowing symmetry breaking described in this article. As science and technology of conductors have transitioned from studying simple elemental metals such as Al or Cu to compound conductors such as binary or ternary oxides and pnictides, a special class of degenerate but gapped metals has been noticed. Their presumed electronic configurations show the Fermi level inside the conduction band or valence band, yet there is an "internal band gap" between the principal band edges. The significance of this electronic configuration is that it might be unstable towards the formation of states inside the internal band gap when the formation of such states costs less energy than the energy gained by transferring carriers from the conduction band to these lower energy acceptor states, changing the original (false) metal to an insulator.

cond-mat.mtrl-sci↗

arXiv2020

Understanding doping of quantum materials

Doping mobile carriers into ordinary semiconductors such as Si, GaAs, and ZnO was the enabling step in the electronic and optoelectronic revolutions. The recent emergence of a class of "Quantum Materials", where uniquely quantum interactions between the components produce specific behaviors such as topological insulation, unusual magnetism, superconductivity, spin-orbit-induced and magnetically-induced spin splitting, polaron formation, and transparency of electrical conductors, pointed attention to a range of doping-related phenomena associated with chemical classes that differ from the traditional semiconductors. These include wide-gap oxides, compounds containing open-shell d electrons, and compounds made of heavy elements yet having significant band gaps. The atomistic electronic structure theory of doping that has been developed over the past two decades in the sub-field of semiconductor physics has recently been extended and applied to quantum materials. The present review focuses on explaining the main concepts needed for a basic understanding of the doping phenomenology and indeed peculiarities in quantum materials from the perspective of condensed matter theory, with the hope of forging bridges to the chemists that have enabled the synthesis of some of the most interesting compounds in this field.

cond-mat.mtrl-sci↗

arXiv2020

Mass enhancement in 3d and s-p perovskites from symmetry breaking

In some d-electron oxides the measured effective mass m(exptl) has long been known to be significantly larger than the model effective mass m(model) deduced from mean-field band theory, i.e., m(exptl) = beta * m(model), where beta > 1 is the "mass enhancement", or "mass renormalization" factor. Previous applications of density functional theory (DFT), based on the smallest number of possible magnetic, orbital, and structural degrees of freedom, missed such mass enhancement, a fact that was taken as evidence of strong electronic correlation being the exclusive enabling physics. The current paper reports that known modalities of energy-lowering symmetry-broken spin and structural effects included in mean-field DFT show mass enhancement for both electrons and holes in a range of d-electron perovskites SrVO3, SrTiO3, BaTiO3, and LaMnO3 as well as p-electron perovskites CsPbI3 and SrBiO3, including metals (SrVO3) and insulators (the rest). This is revealed only when enlarged unit cells of the same parent global symmetry, which are large enough to allow for symmetry breaking distortions and concomitant variations in spin order, are explored for their ability to lower the total energy. The paper analyzes the contributions of different symmetry-broken modalities to mass enhancement, finds common effects in the range of d- as well as p-electron perovskites. Thus, symmetry breaking in mean-field theory could describe effects that were previously attributed exclusively to complex correlated treatments. Indeed, broken symmetries are often experimentally observed, e.g., octahedral tilting, Jahn-Teller distortions, or bond disproportionation, and often provide intuitive explanations in terms of degeneracy removal due to lowering of structural symmetry, or as shifting of band energies in explainable directions.

cond-mat.mtrl-sci↗

arXiv2019

First-Principles Mapping of the Electronic Properties of Two-Dimensional Materials for Strain-Tunable Nanoelectronics

Herein, we demonstrate that first-principles calculations can be used for mapping electronic properties of two-dimensional (2d) materials with respect to non-uniform strain. By investigating four representative single-layer 2d compounds with different symmetries and bonding characters, namely 2d-${MoS_2}$, phosphorene, $α$-Te, and $β$-Te, we reveal that such a mapping can be an effective guidance for advanced strain engineering and development of strain-tunable nanoelectronics devices, including transistors, sensors, and photodetectors. Thus, we show that $α$-Te and $β$-Te are considerably more elastic compared to the 2d compounds with strong chemical bonding. In case of $β$-Te, the mapping uncovers an existence of curious regimes where non-uniform deformations allow to achieve unique localization of band edges in momentum space that cannot be realized under either uniform or uniaxial deformations. For all other systems, the strain mapping is shown to provide deeper insight into the known trends of band gap modulation and direct-indirect transitions under strain. Hence, we prove that the standard way of analyzing selected strain directions is insufficient for some 2d systems, and a more general mapping strategy should be employed instead.

cond-mat.mtrl-sci↗

arXiv2019

Realization of predicted exotic materials: The burden of proof

Trove of exotic topoloid structures has recently been predicted by searching for compounds whose calculated band structure crossing points fulfill specific symmetry requirements. Discovery of exciting physical phenomena by experimental studies of such predicted compounds is just around the corner. Yet, the examination of some of these assumed high-symmetry structures suggests that not always will assembly of atoms in a configuration that yields exotic topological properties be protected against energy-lowering symmetry breaking modes. Indeed, although bulk topological characteristics lead to protected surface/edge states, nothing protects bulk states from structural instability. The burden of proof for theoretical predictions of exciting physical phenomena should include some compelling hints that such phenomena can live in thermodynamically stable (or near stable) compounds. Herein, we illustrate how the use of the calculated total (electron + ion) energies of candidate structures can remove false-positive predicted topoloids from the list of likely realizable compounds, to the benefit of the much-cherished iterative process of theory-experiment materials discovery.

cond-mat.mtrl-sci↗

arXiv2019

Noble gas as a functional dopant in ZnO

Owing to fully occupied orbitals, noble gases are considered to be chemically inert and to have limited effect on materials properties under standard conditions. However, using first-principles calculations, we demonstrate herein that the insertion of noble gas (i.e., He, Ne, or Ar) in ZnO results in local destabilization of electron density of the material driven by minimization of an unfavorable overlap of atomic orbitals of the noble gas and its surrounding atoms. Specifically, the noble gas defect (interstitial or substitutional) in ZnO pushes the electron density of its surrounding atoms away from the defect. Simultaneously, the host material confines the electron density of the noble gas. As a consequence, the interaction of He, Ne, or Ar with O vacancies of ZnO in different charge states q (ZnO:VOq) affects the vacancy stability and their electronic structures. Remarkably, we find that the noble gas is a functional dopant that can delocalize the deep in-gap VOq states and lift electrons associated with the vacancy to the conduction band.

cond-mat.mtrl-sci↗

arXiv2019

Energy, phonon, and dynamic stability criteria of 2d materials

First-principles calculations have become a powerful tool to exclude the Edisonian approach in search of novel 2d materials. However, no universal first-principles criteria to examine the realizability of hypothetical 2d materials have been established in the literature yet. Because of this, and since the calculations are always performed in an artificial simulation environment, one can unintentionally study compounds that do not exist in the experiments. Although investigations of physics and chemistry of unrealizable materials can provide some fundamental knowledge, the discussion of their applications can mislead experimentalists for years and increase the gap between experimental and theoretical research. By analyzing energy convex hull, phonon spectra, and structure evolution during ab initio molecular dynamics simulations for a range of synthesized and recently proposed 2d materials, we construct energy, phonon, and dynamic stability filters which need to be satisfied before proposing novel 2d compounds. We demonstrate the power of the suggested filters for several selected 2d systems, revealing that some of them cannot be ever realized experimentally.

cond-mat.mtrl-sci↗

arXiv2019

Spontaneous non-stoichiometry and ordering of metal vacancies in degenerate insulators

We point to a class of materials representing an exception to the Daltonian view that compounds maintain integer stoichiometry at low temperatures, because forming stoichiometry-violating defects cost energy. We show that carriers in the conduction band (CB) of degenerate insulators in Ca-Al-O, Ag-Al-O, or Ba-Nb-O systems can cause a self-regulating instability, whereby cation vacancies form exothermically because a fraction of the free carriers in the CB decay into the hole states formed by such vacancies, and this negative electron-hole recombination energy offsets the positive energy associated with vacancy bond breaking. This Fermi level-induced spontaneous non-stoichiometry can lead to the formation of crystallographically ordered vacancy compounds (OVCs), explaining the previously peculiar occurrence of unusual atomic sequences such as BalNbmOn with l:m:n ratios of 1:2:6, 3:5:15, or 9:10:30. This work has general ramifications as the degenerate insulators have found growing interests in many fields ranging from transparent conductors to electrides that are electron donating promotors for catalyst.

cond-mat.mtrl-sci↗

arXiv2018

Suppression of Surfaces States at Cubic Perovskite (001) Surfaces by CO${_2}$ Adsorption

By using first-principles approach, the interaction of CO${_2}$ with (001) surfaces of six cubic ABO${_3}$ perovskites (A = Ba, Sr and B = Ti, Zr, Hf) is studied in detail. We show that CO${_2}$ adsorption results in the formation of highly stable CO${_3}$-like complexes with similar geometries for all investigated compounds. This reaction leads to the suppression of the surfaces states, opening the band gaps of the slab systems up to the corresponding bulk energy limits. For most AO-terminated ABO${_3}$(001) perovskite surfaces, a CO${_2}$ coverage of 0.25 was found to be sufficient to fully suppress the surface states, whereas the same effect can only be achieved at 0.50 CO${_2}$ coverage for the BO${_2}$ terminations. The largest band gap modulation among the AO-terminated surfaces was found for SrHfO${_3}$(001) and BaHfO${_3}$(001), whereas the most profound effect among the BO${_2}$ terminations was identified for SrTiO${_3}$(001) and BaTiO${_3}$(001). Based on these results and considering practical difficulties associated with measuring conductivity of highly resistive materials, TiO${_2}$-terminated SrTiO${_3}$(001) and BaTiO${_3}$(001) were identified as the most prospective candidates for chemiresistive CO${_2}$ sensing applications.

cond-mat.mtrl-sci↗

arXiv2018

Fluid sensitive nanoscale switching with quantum levitation controlled by $α$-Sn/$β$-Sn phase transition

We analyse the Lifshitz pressure between silica and tin separated by a liquid mixture of bromobenzene and chlorobenzene. We show that the phase transition from semimetallic $α$-Sn to metallic $β$-Sn can switch Lifshitz forces from repulsive to attractive. This effect is caused by the difference in dielectric functions of $α$-Sn and $β$-Sn, giving both attractive and repulsive contributions to the total Lifshitz pressure at different frequency regions controlled by the composition of the intervening liquid mixture. In this way, one may be able to produce phase transition-controlled quantum levitation in liquid medium.

cond-mat.other↗

arXiv2018

Distance-dependent sign-reversal in the Casimir-Lifshitz torque

The Casimir-Lifshitz torque between two biaxially polarizable anisotropic planar slabs is shown to exhibit a non-trivial sign-reversal in its rotational sense. The critical distance $a_c$ between the slabs that marks this reversal is characterized by the frequency $ω_c\!\sim \!c/2a_c$ at which the in-planar polarizabilities along the two principal axes are equal. The two materials seek to align their principal axes of polarizabilities in one direction below $a_c$, while above $a_c$ their axes try to align rotated perpendicular relative to their previous minimum energy orientation. The sign-reversal disappears in the nonretarded limit. Our perturbative result, derived for the case when the differences in the relative polarizabilities are small, matches excellently with the exact theory for uniaxial materials. We illustrate our results for black phosphorus and phosphorene.

cond-mat.mes-hall↗

arXiv2017

Tailoring electronic properties of multilayer phosphorene by siliconization

Controlling a thickness dependence of electronic properties for two-dimensional (2d) materials is among primary goals for their large-scale applications. Herein, employing a first-principles computational approach, we predict that Si interaction with multilayer phosphorene (2d-P) can result in the formation of highly stable 2d-SiP and 2d-SiP$_2$ compounds with a weak interlayer interaction. Our analysis demonstrates that these systems are semiconductors with band gap energies that can be governed by varying the thickness and stacking order. Specifically, siliconization of phosphorene allows to design 2d-SiP$_x$ materials with significantly weaker thickness dependence of electronic properties than that in 2d-P and to develop ways for their tailoring. We also reveal the spatial dependence of electronic properties for 2d-SiP$_x$ highlighting difference in effective band gaps for different layers. Particularly, our results show that central layers in the multilayer 2d systems determine overall electronic properties, while the role of the outermost layers is noticeably smaller.

cond-mat.mtrl-sci↗

arXiv2017

Band Gap Modulation of SrTiO3 upon CO2 Adsorption

CO2 chemisorption on SrTiO3(001) surfaces is studied using ab initio calculations in order to establish new chemical sensing mechanisms. We find that CO2 adsorption opens the material band gap, however, while the adsorption on the TiO2-terminated surface neutralizes surface states at the valence band (VB) maximum, CO2 on the SrO-terminated surfaces suppresses the conduction band (CB) minimum. For the TiO2-terminated surface, the effect is explained by the passivation of dangling bonds, whereas for the SrO-terminated surface, the suppression is caused by the surface relaxation. Modulation of the VB states implies a more direct change in charge distribution, and thus the induced change in band gap is more prominent at the TiO2 termination. Further, we show that both CO2 adsorption energy and surface band gap are strongly dependent on CO2 coverage, suggesting that the observed effect can be utilized for sensing application in a wide range of CO2 concentrations.

cond-mat.mtrl-sci↗

arXiv2017

Lifshitz interaction can promote ice growth at water-silica interfaces

At air-water interfaces, the Lifshitz interaction by itself does not promote ice growth. On the contrary, we find that the Lifshitz force promotes the growth of an ice film, up to 1-8 nm thickness, near silica-water interfaces at the triple point of water. This is achieved in a system where the combined effect of the retardation and the zero frequency mode influences the short-range interactions at low temperatures, contrary to common understanding. Cancellation between the positive and negative contributions in the Lifshitz spectral function is reversed in silica with high porosity. Our results provide a model for how water freezes on glass and other surfaces.

cond-mat.other↗

arXiv2015

Comparison of alpha- and beta- tin for lithium, sodium, and magnesium storage: an ab initio study including phonon contributions

We present a comparative ab initio study of Li, Na, and Mg storage in tin, including phononic effects and phase competition between alpha and beta Sn. Mg doping at low concentration is found to stabilize the beta phase. On the contrary, Li and Na doping is shown to reverse the stability of the phases at room temperature: Li/Na-doped alpha-Sn is more stable than Li/Na-doped beta-Sn up to a temperature of around 380/400 K. This may rationalize the formation of alpha-Sn upon lithiation and delithiation of beta-Sn anodes reported in experimental studies. The changes in phase stability with Li/Na/Mg doping are directly related to the intercalation energies of Li/Na/Mg in one phase versus the other: at 300 K, Li/Na is easier intercalated in alpha-Sn (-0.37/-0.08 eV) than in beta-Sn (0.06/0.49 eV), while Mg intercalation energy is, although positive (i.e. unfavored intercalation), lower in beta-Sn (0.53 eV) than in alpha-Sn (0.66 eV). The temperature effect is found to affect significantly the intercalation energy, by up to 0.13 eV at 300 K. Analysis of diffusion barriers shows that Li, Na, and Mg diffusion in beta-Sn is anisotropic with migration barriers along the (001) direction (respectively 0.01, 0.22, and 0.07 eV) significantly lower than those in alpha-Sn (respectively 0.20, 0.52, and 0.40 eV).

cond-mat.mtrl-sci↗

arXiv2015

Anisotropic contribution to the van der Waals and the Casimir-Polder energies for CO$_2$ and CH$_4$ molecules near surfaces and thin films

In order to understand why carbon dioxide (CO$_2$) and methane (CH$_4$) molecules interact differently with surfaces, we investigate the Casimir-Polder energy of a linearly polarizable CO$_2$ molecule and an isotropically polarizable CH$_4$ molecule in front of an atomically thin gold film and an amorphous silica slab. We quantitatively analyze how the anisotropy in the polarizability of the molecule influences the van der Waals contribution to the binding energy of the molecule.

cond-mat.mes-hall↗

arXiv2015

Evaluation of Phosphorene as Anode Material for Na-ion Batteries from First Principles

We systematically evaluate the prospects of a novel 2D nanomaterial, phosphorene, as anode for Na-ion batteries. Using first-principles calculations, we determine the Na adsorption energy, specific capacity and Na diffusion barriers on monolayer phosphorene. We examine the main trends in electronic structure and mechanical properties as a function of Na concentration. We find favorable Na-phosphorene interaction with theoretical capacity, exceeding those of alternative monolayer anodes for Na-ion batteries. We find that Na-phosphorene undergoes semiconductor-metal transition at high Na concentration. Our results show that Na diffusion on phosphorene is fast and anisotropic with the energy barrier of only 0.04 eV. Owing to the high capacity, good stability, excellent electrical conductivity and high Na mobility, monolayer phosphorene is a very promising anode material for Na-ion batteries. The calculated performance in terms of specific capacity and diffusion barrier is compared to other layered 2D electrode materials, such as graphene, MoS2, polysilane, etc.

cond-mat.mtrl-sci↗

arXiv2014

Comparative Computational Study of the Energetics of Li, Na, and Mg Storage in Amorphous and Crystalline Silicon

To assess the potential of amorphous Si (a-Si) as an anode for Li, Na, and Mg-ion batteries, the energetics of Li, Na, and Mg atoms in a-Si are computed from first-principles and compared to those in crystalline Si (c-Si). It is shown that Si preamorphization increases the average anode voltage and reduces the volume expansion of the anode during the insertion of the metal atoms. Analysis of computed formation energies of Li, Na, and Mg defects in a-Si and c-Si suggests that the energetics of the single atoms into a-Si are thermodynamically more favorable. For instance, defect formation energies of Li, Na, and Mg defects in a-Si are respectively 0.71, 1.72, and 1.82 eV lower compared to those in c-Si. Moreover, the defect formation energies of Li, Na, and Mg defects (vs. vacuum reference states) in a-Si are comparable with the metal cohesive energies and consequently the insertion of the metal atoms might be possible with appropriate control of charging process. This is in contrast to c-Si, where the storage of Na and Mg atoms is limited due to high energy cost of Na and Mg insertion into c-Si.

cond-mat.mtrl-sci↗