Ever since the first experimental investigations of organic field effect transistors (OFETs) the dimensionality of charge transport has alternately been described as two dimensional (2D) and three dimensional (3D). More recently, researchers have turned to an analytical analysis of the temperature-dependent transfer characteristics to classify the dimensionality as either 2D or 3D as well as to determine the disorder of the system, thereby greatly simplifying dimensionality investigations. We applied said analytical analysis to the experimental results of our OFETs comprising molecularly well-defined polymeric layers as the active material as well as to results obtained from kinetic Monte Carlo simulations and found that it was not able to correctly distinguish between 2D and 3D transports or give meaningful values for the disorder and should only be used for quasiquantitative and comparative analysis. We conclude to show that the dimensionality of charge transport in OFETs is a function of the interplay between transistor physics and morphology of the organic material.
The recent upswing in attention for the thermoelectric properties of organic semiconductors (OSCs) adds urgency to the need for a quantitative description of the range and energetics of hopping transport in organic semiconductors under relevant circumstances, i.e., around room temperature (RT). In particular, the degree to which hops beyond the nearest neighbor must be accounted for at RT is still largely unknown. Here, measurements of charge and energy transport in doped OSCs are combined with analytical modeling to reach the univocal conclusion that variable-range hopping is the proper description in a large class of disordered OSC at RT. To obtain quantitative agreement with experiment, one needs to account for the modification of the density of states by ionized dopants. These Coulomb interactions give rise to a deep tail of trap states that is independent of the materials initial energetic disorder. Insertion of this effect into a classical Mott-type variable-range hopping model allows one to give a quantitative description of temperature-dependent conductivity and thermopower measurements on a wide range of disordered OSCs. In particular, the model explains the commonly observed quasiuniversal power-law relation between the Seebeck coefficient and the conductivity.
The Becke-Johnson model potential [A. D. Becke and E. R. Johnson, J. Chem. Phys. 124, 221101 ( 2006)] and the potential of the AK13 functional [R. Armiento and S. Kummel, Phys. Rev. Lett. 111, 036402 ( 2013)] have been shown to mimic features of the exact Kohn-Sham exchange potential, such as step structures that are associated with shell closings and particle-number changes. A key element in the construction of these functionals is that the potential has a limiting value far outside a finite system that is a system-dependent constant rather than zero. We discuss a set of anomalous features in these functionals that are closely connected to the nonvanishing asymptotic potential. The findings constitute a formidable challenge for the future development of semilocal functionals based on the concept of a nonvanishing asymptotic constant.
Nodal surfaces of orbitals, in particular of the highest occupied one, play a special role in Kohn-Sham density-functional theory. The exact Kohn-Sham exchange potential, for example, shows a protruding ridge along such nodal surfaces, leading to the counterintuitive feature of a potential that goes to different asymptotic limits in different directions. We show here that nodal surfaces can heavily affect the potential of semilocal density-functional approximations. For the functional derivatives of the Armiento-Kummel (AK13) [Phys. Rev. Lett. 111, 036402 (2013)] and Becke88 [Phys. Rev. A 38, 3098 (1988)] energy functionals, i.e., the corresponding semilocal exchange potentials, as well as the Becke-Johnson [J. Chem. Phys. 124, 221101 (2006)] and van Leeuwen-Baerends (LB94) [Phys. Rev. A 49, 2421 (1994)] model potentials, we explicitly demonstrate exponential divergences in the vicinity of nodal surfaces. We further point out that many other semilocal potentials have similar features. Such divergences pose a challenge for the convergence of numerical solutions of the Kohn-Sham equations. We prove that for exchange functionals of the generalized gradient approximation (GGA) form, enforcing correct asymptotic behavior of the potential or energy density necessarily leads to irregular behavior on or near orbital nodal surfaces. We formulate constraints on the GGA exchange enhancement factor for avoiding such divergences.
We investigate the migration mechanism of the carbon vacancy (V-C) in silicon carbide (SiC) using a combination of theoretical and experimental methodologies. The V-C, commonly present even in state-of-the-art epitaxial SiC material, is known to be a carrier lifetime killer and therefore strongly detrimental to device performance. The desire for V-C removal has prompted extensive investigations involving its stability and reactivity. Despite suggestions from theory that V(C )migrates exclusively on the C sublattice via vacancy-atom exchange, experimental support for such a picture is still unavailable. Moreover, the existence of two inequivalent locations for the vacancy in 4H-SiC [hexagonal, V-C(h), and pseudocubic, V-C(k)] and their consequences for V-C migration have not been considered so far. The first part of the paper presents a theoretical study of V(C )migration in 3C- and 4H-SiC. We employ a combination of nudged elastic band (NEB) and dimer methods to identify the migration mechanisms, transition state geometries, and respective energy barriers for V(C )migration. In 3C-SiC, V-C is found to migrate with an activation energy of E-A = 4.0 eV. In 4H-SiC, on the other hand, we anticipate that V-C migration is both anisotropic and basal-plane selective. The consequence of these effects is a slower diffusivity along the axial direction, with a predicted activation energy of E-A = 4.2 eV, and a striking preference for basal migration within the h plane with a barrier of E-A = 3.7 eV, to the detriment of the k-basal plane. Both effects are rationalized in terms of coordination and bond angle changes near the transition state. In the second part, we provide experimental data that corroborates the above theoretical picture. Anisotropic migration of V-C in 4H-SiC is demonstrated by deep level transient spectroscopy (DLTS) depth profiling of the Z(1/2) electron trap in annealed samples that were subject to ion implantation. Activation energies of E-A = (4.4 +/- 0.3) eV and E-A = (3.6 +/- 0.3) eV were found for V-C migration along the c and a directions, respectively, in excellent agreement with the analogous theoretical values. The corresponding prefactors of D-0 = 0.54 cm(2)/s and 0.017 cm(2)/s are in line with a simple jump process, as expected for a primary vacancy point defect.
Recent experimental studies of Zeeman-split one-dimensional subbands in ballistic quantum wires in an in-plane magnetic field show that additional nonquantized conductance structures occur as subbands cross at low electron densities [A. C. Graham et al., Phys. Rev.Lett. 91, 136404 (2003)]. These structures are called 0.7 analogs. We analyze the experimental transconductance data within the Kohn-Sham spin-density-functional method, including exchange and correlation effects for an infinite split-gate quantum wire in a parallel, in-plane magnetic field B∥. Energy levels are found to rearrange abruptly as they cross due to polarization effects driven by exchange and Coulomb interactions. Experimental qualitative features are explained well by this model. ©2005 The American Physical Society.
The phase diagram of iridium is investigated using the Z methodology. The Z methodology is a technique for phase diagram studies that combines the direct Z method for the computation of melting curves and the inverse Z method for the calculation of solid-solid phase boundaries. In the direct Z method, the solid phases along the melting curve are determined by comparing the solid-liquid equilibrium boundaries of candidate crystal structures. The inverse Z method involves quenching the liquid into the most stable solid phase at various temperatures and pressures to locate a solid-solid boundary. Although excellent agreement with the available experimental data (to less than or similar to 65 GPa) is found for the equation of state (EOS) of Ir, it is the third-order Birch-Murnaghan EOS with B-0 = 5 rather than the more widely accepted B-0 = 4 that describes our ab initio data to higher pressure (P). Our results suggest the existence of a random-stacking hexagonal close-packed structure of iridium at high P. We offer an explanation for the 14-layer hexagonal structure observed in experiments by Cerenius and Dubrovinsky.
The electronic properties of monolayer graphene grown epitaxially on SiC(0001) are known to be highly sensitive to the presence of NO2 molecules. The presence of small areas of bilayer graphene, on the other hand, considerably reduces the overall sensitivity of the surface. We investigate how NO2 molecules interact with monolayer and bilayer graphene, both free-standing and on a SiC(0001) substrate. We show that it is necessary to explicitly include the effect of the substrate in order to reproduce the experimental results. When monolayer graphene is present on SiC, there is a large charge transfer from the interface between the buffer layer and the SiC substrate to the molecule. As a result, the surface work function increases by 0.9 eV after molecular adsorption. A graphene bilayer is more effective at screening this interfacial charge, and so the charge transfer and change in work function after NO2 adsorption is much smaller.
An effective two-dimensional real-space model is developed to investigate the nature of charge distribution in nanoribbons of transition metal dichalcogenides. Our description is based on a lattice relaxation endowed tight-binding Hamiltonian with spin-orbit and Hubbard interactions, which is parameterized to describe molybdenum disulfide lattices. As our main finding, we observed that electron-phonon coupling induces the creation of quasiparticles such as polarons in the same fashion as observed in conducting polymers and graphene nanoribbons. These similarities suggest that the charge transport in transition metal dichalcogenides can also be mediated by quasiparticles, which is a fundamental aspect concerning the application of these structures in electronics. We determine a range of possible electron-phonon coupling that correctly describes the system and also the critical value where quasiparticle transport is present. Our findings may have profound consequences on the understanding of the transport mechanism of transition metal dichalcogenides nanoribbons.
Inherently layered magnetic materials, such as magnetic M(n+1)AX(n) (MAX) phases, offer an intriguing perspective for use in spintronics applications and as ideal model systems for fundamental studies of complex magnetic phenomena. The MAX phase composition M(n+1)AX(n) consists of M(n+1)AX(n) blocks separated by atomically thin A-layers where M is a transition metal, A an A-group element, X refers to carbon and/or nitrogen, and n is typically 1, 2, or 3. Here, we show that the recently discovered magnetic Mn2GaC MAX phase displays structural changes linked to the magnetic anisotropy, and a rich magnetic phase diagram which can be manipulated through temperature and magnetic field. Using first-principles calculations and Monte Carlo simulations, an essentially one-dimensional (1D) interlayer plethora of two-dimensioanl (2D) Mn-C-Mn trilayers with robust intralayer ferromagnetic spin coupling was revealed. The complex transitions between them were observed to induce magnetically driven anisotropic structural changes. The magnetic behavior as well as structural changes dependent on the temperature and applied magnetic field are explained by the large number of low energy, i.e., close to degenerate, collinear and noncollinear spin configurations that become accessible to the system with a change in volume. These results indicate that the magnetic state can be directly controlled by an applied pressure or through the introduction of stress and show promise for the use of Mn2GaC MAX phases in future magnetoelectric and magnetocaloric applications.
We study the effect of electronic Coulomb correlations on the vacancy formation energy in paramagnetic alpha-Fe within ab initio dynamical mean-field theory. The calculated value for the formation energy is substantially lower than in standard density-functional calculations and in excellent agreement with experiment. The reduction is caused by an enhancement of electronic correlations at the nearest neighbors of the vacancy. This effect is explained by subtle changes in the corresponding spectral function of the d electrons. The local lattice relaxations around the vacancy are substantially increased by many-body effects.
Density functional theory is a standard model for condensed-matter theory and computational material science. The accuracy of density functional theory is limited by the accuracy of the employed approximation to the exchange-correlation functional. Recently, the so-called strongly constrained appropriately normed (SCAN) [Sun, Ruzsinszky, and Perdew, Phys. Rev. Lett. 115, 036402 (2015)] functional has received a lot of attention due to promising results for covalent, metallic, ionic, as well as hydrogen- and van der Waals-bonded systems alike. In this work, we focus on assessing the performance of the SCAN functional for itinerant magnets by calculating basic structural and magnetic properties of the transition metals Fe, Co, and Ni. We find that although structural properties of bcc-Fe seem to be in good agreement with experiment, SCAN performs worse than standard local and semilocal functionals for fcc-Ni and hcp-Co. In all three cases, the magnetic moment is significantly overestimated by SCAN, and the 3d states are shifted to lower energies, as compared to experiments.
The phase stability of icosahedral boron subselenide B-12(B1-xSex)(2), where 0.5 amp;lt;= x amp;lt;= 1, is explored using a first-principles cluster expansion. The results shows that, instead of a continuous solid solution, B-12(B1-xSex)(2) is thermodynamically stable as an individual line compound at the composition of B9.5Se. The ground-state configuration of B9.5Se is represented by a mixture of B-12(Se-Se), B-12(B-Se), and B-12(Se-B) with a ratio of 1: 1: 1, where they form a periodic ABCABC... stacking sequence of B-12(Se-Se), B-12(B-Se), and B-12(Se-B) layers along the c axis of the hexagonal conventional unit cell. The structural and electronic properties of the ground-state B9.5Se are also derived and discussed. By comparing the derived ground-state properties of B9.5Se to the existing experimental data of boron subselenide B similar to 13Se, I proposed that the as-synthesized boron subselenide B similar to 13Se, as reported in the literature, has the actual composition of B9.5Se.
We examine the thermodynamic stability of compounds and alloys in the ternary B-As-P system theoretically using first-principles calculations. We demonstrate that the icosahedral B12As2 is the only stable compound in the binary B-As system, while the zinc-blende BAs is thermodynamically unstable with respect to B12As2 and the pure arsenic phase at 0 K, and increasingly so at higher temperature, suggesting that BAs may merely exist as a metastable phase. On the contrary, in the binary B-P system, both zinc-blende BP and icosahedral B12P2 are predicted to be stable. As for the binary As-P system, As1-xPx disordered alloys are predicted at elevated temperature-for example, a disordered solid solution of up to similar to 75 at.% As in black phosphorus as well as a small solubility of similar to 1 at.% P in gray arsenic at T = 750 K, together with the presence of miscibility gaps. The calculated large solubility of As in black phosphorus explains the experimental syntheses of black-phosphorus-type As1-xPx alloys with tunable compositions, recently reported in the literature. We investigate the phase stabilities in the ternary B-As-P system and demonstrate a high tendency for a formation of alloys in the icosahedral B-12(As1-xPx)(2) structure by intermixing of As and P atoms at the diatomic chain sites. The phase diagram displays noticeable mutual solubility of the icosahedral subpnictides in each other even at room temperature as well as a closure of a pseudobinary miscibility gap around 900 K. As for pseudobinary BAs1-xPx alloys, only a tiny amount of BAs is predicted to be able to dissolve in BP to form the BAs1-xPx disordered alloys at elevated temperature. For example, less than 5% of BAs can dissolve in BP at T = 1000 K. The small solubility limit of BAs in BP is attributed to the thermodynamic instability of BAs with respect to B12As2 and As.
We perform first-principles calculations to investigate the phase stability of boron carbide, concentrating on the recently proposed alternative structural models composed not only of the regularly studied B11Cp(CBC) and B-12(CBC), but also of B-12(CBCB) and B-12(B-4). We find that a combination of the four structural motifs can result in low-energy electron precise configurations of boron carbide. Among several considered configurations within the composition range of B10.5C and B4C, we identify in addition to the regularly studied B11Cp(CBC) at the composition of B4C two low-energy configurations, resulting in a new view of the B-C convex hull. Those are [B-12(CBC)](0.67)[B-12(B-4)](0.33) and [B-12(CBC)](0.67)[B-12(CBCB)](0.33), corresponding to compositions of B10.5C and B6.67C, respectively. As a consequence, B-12(CBC) at the composition of B6.5C, previously suggested in the literature as a stable configuration of boron carbide, is no longer part of the B-C convex hull. By inspecting the electronic density of states as well as the elastic moduli, we find that the alternative models of boron carbide can provide a reasonably good description for electronic and elastic properties of the material in comparison with the experiments, highlighting the importance of considering B-12(CBCB) and B-12(B-4), together with the previously proposed B11Cp(CBC) and B-12(CBC), as the crucial ingredients for modeling boron carbide with compositions throughout the single-phase region.
We use the first-principles approach to clarify the thermodynamic stability as a function of pressure and temperature of three different alpha-rhombohedral-boron-like boron subnitrides, with the compositions of B6N, B13N2, and B38N6, proposed in the literature. We find that, out of these subnitrides with the structural units of B-12(N-N), B-12(NBN), and [B-12(N-N)](0.33)[B-12(NBN)](0.67), respectively, only B38N6, represented by [B-12(N-N)](0.33)[B-12(NBN)](0.67), is thermodynamically stable. Beyond a pressure of about 7.5 GPa depending on the temperature, also B38N6 becomes unstable, and decomposes into cubic boron nitride and a-tetragonalboron- like boron subnitride B50N2. The thermodynamic stability of boron subnitrides and relevant competing phases is determined by the Gibbs free energy, in which the contributions from the lattice vibrations and the configurational disorder are obtained within the quasiharmonic and the mean-field approximations, respectively. We calculate lattice parameters, elastic constants, phonon and electronic density of states, and demonstrate that [B-12(N-N)](0.33)[B-12(NBN)](0.67) is bothmechanically and dynamically stable, and is an electrical semiconductor. The simulated x-ray powder-diffraction pattern as well as the calculated lattice parameters of [B-12(N-N)](0.33)[B-12(NBN)](0.67) are found to be in good agreement with those of the experimentally synthesized boron subnitrides reported in the literature, verifying that B38N6 is the stable composition of a-rhombohedral-boron-like boron subnitride.
Reversible martensitic transformations (MTs) are the origin of many fascinating phenomena, including the famous shape memory effect. In this work, we present a fully ab initio procedure to characterize MTs in alloys and to assess their reversibility. Specifically, we employ ab initio molecular dynamics data to parametrize a Landau expansion for the free energy of the MT. This analytical expansion makes it possible to determine the stability of the high- and low-temperature phases, to obtain the Ehrenfest order of the MT, and to quantify its free energy barrier and latent heat. We apply our model to the high-temperature shape memory alloy Ti-Ta, for which we observe remarkably small values for the metastability region (the interval of temperatures in which the high-and low-temperature phases are metastable) and for the barrier: these small values are necessary conditions for the reversibility of MTs and distinguish shape memory alloys from other materials.
The first-principles calculation of many material properties, in particular related to defects and disorder, starts with the relaxation of the atomic positions of the system under investigation. This procedure is routine for nonmagnetic and magnetically ordered materials. However, when it comes to magnetically disordered systems, in particular the paramagnetic phase of magnetic materials, it is not clear how the relaxation procedure should be performed or which geometry should be used. Here we propose a method for the structural relaxation of magnetic materials in the paramagnetic regime, in an adiabatic fast-magnetism approximation within the disordered local moment (DLM) picture in the framework of density functional theory. The method is straightforward to implement using any ab initio code that allows for structural relaxations. We illustrate the importance of considering the disordered magnetic state during lattice relaxations by calculating formation energies and geometries for an Fe vacancy and C insterstitial atom in body-centered cubic (bcc) Fe as well as bcc Fe1-xCrx random alloys in the paramagnetic state. In the vacancy case, the nearest neighbors to the vacancy relax toward the vacancy of 0.14 angstrom (-5% of the ideal bcc nearest-neighbor distance), which is twice as large as the relaxation in the ferromagnetic case. The vacancy formation energy calculated in the DLM state on these positions is 1.60 eV, which corresponds to a reduction of about 0.1 eV compared to the formation energy calculated using DLM but on ferromagnetic-relaxed positions. The carbon interstitial formation energy is found to be 0.41 eV when the DLM relaxed positions are used, as compared to 0.59 eV when the FM-relaxed positions are employed. For bcc Fe0.5Cr0.5 alloys, the mixing enthalpy is reduced by 5 meV/atom, or about 10%, when the DLM state relaxation is considered, as compared to positions relaxed in the ferromagnetic state.
We use the color diffusion (CD) algorithm in nonequilibrium (accelerated) ab initio molecular dynamics simulations to determine Ti monovacancy jump frequencies in NaCl-structure titanium nitride (TiN), at temperatures ranging from 2200 to 3000 K. Our results showthat theCDmethod extended beyond the linear-fitting rate-versus-force regime [Sangiovanni et al., Phys. Rev. B 93, 094305 (2016)] can efficiently determine metal vacancy migration rates in TiN, despite the low mobilities of lattice defects in this type of ceramic compound. We propose a computational method based on gamma-distribution statistics, which provides unambiguous definition of nonequilibrium and equilibrium (extrapolated) vacancy jump rates with corresponding statistical uncertainties. The acceleration-factor achieved in our implementation of nonequilibrium molecular dynamics increases dramatically for decreasing temperatures from 500 for T close to the melting point T-m, up to 33 000 for T approximate to 0.7 T-m
The structural and magnetic properties of siderite FeCO3 have been studied by means of neutron powder diffraction at pressures up to 7.5 GPa and first-principles theoretical calculations. The lattice compression in the rhombohedral calcite-type structure is dominated by the reduction of the Fe-O bonds, while the changes of the C-O bonds are much less pronounced. The Neel temperature of the antiferromagnetic ( AFM) ground state increases substantially under pressure with a coefficient dT(N)/dP = 1.8K/GPa, which is about 1.5 times larger in comparison with those predicted by the empirical Bloch rule. The ab initio calculations were performed in the framework of the density functional theory including Hubbard-U correction. The calculated structural parameters and Neel temperature as functions of pressure provide a reasonable agreement with the experimental results. The analysis of the density of electronic states points toward increased covalent bonding between the Fe and O atoms upon pressure, giving rise to unexpectedly large pressure coefficient of the Neel temperature and reduced ordered magnetic moments of Fe atoms.
Low thermal polarization of nuclear spins is a primary sensitivity limitation for nuclear magnetic resonance. Here we demonstrate optically pumped (microwave-free) nuclear spin polarization of C-13 and N-15 in N-15-doped diamond. (15)Npolarization enhancements up to- 2000 above thermal equilibrium are observed in the paramagnetic system Ns(0). Nuclear spin polarization is shown to diffuse to bulk C-13 with NMR enhancements of -200 at room temperature and -500 at 240 K, enabling a route to microwave-free high-sensitivity NMR study of biological samples in ambient conditions.
The magnetotransport of freestanding, vacuum filtered, thin films of Mo2CTz, Mo1.33CTz, Mo2TiC2Tz, and Mo2Ti2C3Tz was measured in the 10-300-K temperature (T) range. Some of the films were annealed before measuring their transport properties. Analysis of the results suggest that-with the exception of the heavily defective Mo1.33CTz composition-in the 10- to 200-K temperature regime, variable range hopping between individual MXene sheets is the operative conduction mechanism. For Mo1.33CTz it is more likely that variable range hopping within individual flakes is rate limiting. At higher temperatures, a thermally activated process emerges in all cases. It follows that improved fabrication processes should lead to considerable improvements in the electrical transport of Mo-based MXenes.
We present a first-principles theoretical approach to calculate temperature dependent phonon dispersions in bcc Fe, which captures finite temperature spin-lattice coupling by treating thermal disorder in both the spin and lattice systems simultaneously. With increasing temperature, thermal atomic displacements are found to induce increasingly large fluctuations in local magnetic moment magnitudes. The calculated phonon dispersions of bcc Fe show excellent agreement with measured data over a wide range of temperatures both above and below the magnetic and structural transition temperatures, suggesting the applicability of the developed approach to other magnetic materials.
The effects of temperature and pressure on the phonons of GaN were calculated for both the wurtzite and zinc-blende structures. The quasiharmonic approximation (QHA) gave reasonable results for the temperature dependence of the phonon DOS at zero pressure but unreliably predicted the combined effects of temperature and pressure. Pressure was found to change the explicit anharmonicity, altering the thermal shifts of phonons and more notably qualitatively changing the evolution of phonon lifetimes with increasing temperature. These effects were largest for the optical modes, and phonon frequencies below approximately 5 THz were adequately predicted with the QHA. The elastic anisotropies of GaN in both wurtzite and zinc-blende structures were calculated from the elastic constants as a function of pressure at 0 K. The elastic anisotropy increased with pressure until reaching elastic instabilities at 40 GPa (zinc blende) and 65 GPa (wurtzite). The calculated instabilities are consistent with proposed transformation pathways to rocksalt GaN and place upper bounds on the pressures at which wurtzite and zinc-blende GaN can be metastable.
Numerical calculations of anisotropic hopping transport based on the resistor network model are presented. Conductivity is shown to follow the stretched exponential dependence on temperature with exponents increasing from 1/4 to 1 as the wave functions become anisotropic and their localization length in the direction of charge transport decreases. For sufficiently strong anisotropy, this results in nearest- neighbor hopping at lowtemperatures due to the formation of a single conduction path, which adjusts in the planes where the wave functions overlap strongly. In the perpendicular direction, charge transport follows variable- range hopping, a behavior that agrees with experimental data on organic semiconductors.
The identification of a microscopic configuration of point defects acting as quantum bits is a key step in the advance of quantum information processing and sensing. Among the numerous candidates, silicon-vacancy related centers in silicon carbide (SiC) have shown remarkable properties owing to their particular spin-3/2 ground and excited states. Although, these centers were observed decades ago, two competing models, the isolated negatively charged silicon vacancy and the complex of negatively charged silicon vacancy and neutral carbon vacancy [Phys. Rev. Lett. 115, 247602 (2015)], are still argued as an origin. By means of high-precision first-principles calculations and high-resolution electron spin resonance measurements, we here unambiguously identify the Si-vacancy related qubits in hexagonal SiC as isolated negatively charged silicon vacancies. Moreover, we identify the Si-vacancy qubit configurations that provide room-temperature optical readout.
TiPO4 shows interesting structural and magnetic properties as temperature and pressure are varied, such as a spin-Peierls phase transition and the development of incommensurate modulations of the lattice. Recently, high-pressure experiments for TiPO4 reported two structural phases appearing at high pressures, the so-called phases IV and V [M. Bykov et al., Angew. Chem. Int. Ed. 55, 15053 (2016).]. The latter was shown to include the first example of fivefold O-coordinated P atoms in an inorganic phosphate compound. In this work, we characterize the electronic structure and other physical properties of these phases by means of ab initio calculations and investigate the structural transition. We find that the appearance of phases IV and V coincides with a collapse of the Mott insulating gap and quenching of magnetism in phase III as pressure is applied. Remarkably, our calculations show that in the high-pressure phase V, these features reappear, leading to an antiferromagnetic Mott insulating phase, with robust local moments.
The knowledge of lattice thermal conductivity of materials under realistic conditions is vitally important since many modern technologies require either high or low thermal conductivity. Here, we propose a theoretical model for determining lattice thermal conductivity, which takes into account the effect of microstructure. It is based on ab initio description that includes the temperature dependence of the interatomic force constants and treats anharmonic lattice vibrations. We choose ScN as a model system, comparing the computational predictions to the experimental data by time-domain thermoreflectance. Our experimental results show a trend of reduction in lattice thermal conductivity with decreasing domain size predicted by the theoretical model. These results suggest a possibility to control thermal conductivity by microstructural tailoring and provide a predictive tool for the effect of the microstructure on the lattice thermal conductivity of materials based on ab initio calculations.
Instabilities relating to cooperative octahedral tilting is common in materials with perovskite structures, in particular in the subclass of halide perovskites. In this work the energetics of octahedral tilting in the inorganic metal halide perovskites CsPbI3 and CsSnI3 are investigated using first-principles density functional theory calculations. Several low-energy paths between symmetry equivalent variants of the stable orthorhombic (Pnma) perovskite variant are identified and investigated. The results are in favor of the presence of dynamic disorder in the octahedral tilting phase transitions of inorganic halide perovskites. In particular, one specific type of path, corresponding to an out-of-phase "tilt switch," is found to have significantly lower energy barrier than the others, which indicates the existence of a temperature range where the dynamic fluctuations of the octahedra follow only this type of path. This could produce a time averaged structure corresponding to the intermediate tetragonal (P4/mbm) structure observed in experiments. Deficiencies of the commonly employed simple one-dimensional "double-well" potentials in describing the dynamics of the octahedra are pointed out and discussed.
The temperature-induced antiferrodistortive (AFD) structural phase transitions in CaMnO3, a typical perovskite oxide, are studied using first-principles density functional theory calculations. These transitions are caused by tilting of the MnO6 octahedra that are related to unstable phonon modes in the high-symmetry cubic perovskite phase. Transitions due to octahedral tilting in perovskites normally are believed to fit into the standard soft-mode picture of displacive phase transitions. We calculate phonon-dispersion relations and potential-energy landscapes as functions of the unstable phonon modes and argue based on the results that the phase transitions are better described as being of order-disorder type. This means that the cubic phase emerges as a dynamical average when the system hops between local minima on the potential-energy surface. We then perform ab initio molecular dynamics simulations and find explicit evidence of the order-disorder dynamics in the system. Our conclusions are expected to be valid for other perovskite oxides, and we finally suggest how to predict the nature (displacive or order-disorder) of the AFD phase transitions in any perovskite system.
Ab initio molecular dynamics (AIMD) in combination with the temperature dependent effective potential (TDEP) method has been used to go beyond the quasiharmonic approximation and study the lattice dynamics in ceria, CeO2, at finite temperature. The results indicate that the previously proposed connection between the B-1u phonon mode turning imaginary and the transition to the superionic phase in fluorite structured materials is an artifact of the failure of the quasiharmonic approximation in describing the lattice dynamics at elevated temperatures. We instead show that, in the TDEP picture, a phonon mode coupling to the E-u mode prevents the B-1u mode from becoming imaginary. We directly observe the superionic transition at high temperatures in our AIMD simulations and find that it is initiated by the formation of oxygen Frenkel pairs (FP). These FP are found to form in a collective process involving simultaneous motion of two oxygen ions.
Spins bound to point defects are increasingly viewed as an important resource for solid-state implementations of quantum information and spintronic technologies. In particular, there is a growing interest in the identification of new classes of defect spin that can be controlled optically. Here, we demonstrate ensemble optical spin polarization and optically detected magnetic resonance (ODMR) of the S = 1 electronic ground state of chromium (Cr4+) impurities in silicon carbide (SiC) and gallium nitride (GaN). Spin polarization is made possible by the narrow optical linewidths of these ensembles (amp;lt;8.5 GHz), which are similar in magnitude to the ground state zero-field spin splitting energies of the ions at liquid helium temperatures. This allows us to optically resolve individual spin sublevels within the ensembles at low magnetic fields using resonant excitation from a cavity-stabilized, narrow-line width laser. Additionally, these near-infrared emitters possess exceptionally weak phonon sidebands, ensuring that amp;gt;73% of the overall optical emission is contained with the defects zero-phonon lines. These characteristics make this semiconductor-based, transition metal impurity system a promising target for further study in the ongoing effort to integrate optically active quantum states within common optoelectronic materials.
Description of elasticity of iron at the ultrahigh pressures is a challenging task for physics, with a potential strong impact on other branches of science. In the present work, we calculate the elastic properties of hcp iron in the pressure range of 50-340 GPa beyond the linear elasticity approximation, conventionally assumed in theoretical studies. We define the higher order elastic constants and present expressions for the long-wave acoustic modes Gruneisen parameters of a compressed hcp crystal. We obtain the second and third order elastic constants of the hcp Fe in the considered pressure interval, as well as its Gruneisen parameters for the high-symmetry directions. The latter are directly compared with the Gruneisen parameters derived from the volume dependences of the vibrational frequencies calculated in the quasiharmonic approximation. The obtained results are used for the stability analysis of the hcp phase of iron at high pressures.
We present a detailed theoretical study of the electronic, magnetic, and structural properties of magnesiowustite Fe-1 Mg-x(x) O with x in the range between 0 and 0.875 using a fully charge self-consistent implementation of the density functional theory plus dynamical mean-field theory method. In particular, we compute the electronic structure and phase stability of the rocksalt B1-structured (Fe,Mg) O at high pressures relevant for the Earths lower mantle. We find that upon compression paramagnetic (Fe,Mg) O exhibits a spin-state transition of Fe2+ ions from a high-spin to low-spin (HS-LS) state which is accompanied by a collapse of local magnetic moments. The HS-LS transition results in a substantial drop in the lattice volume by about 4%-8%, implying a complex interplay between electronic and lattice degrees of freedom. Our results reveal a strong sensitivity of the calculated transition pressure P-tr. upon addition of Mg. While, for Fe-rich magnesiowustite with Mg x amp;lt; 0.5, Ptr. is about 80 GPa, for Mg x = 0.75 it drops to 52 GPa, i. e., by 35%. This behavior is accompanied by a substantial change in the spin transition range from 50 to 140 GPa in FeO to 30 to 90 GPa for x = 0.75. In addition, the calculated bulk modulus (in the HS state) is found to increase by similar to 12% from 142 GPa in FeO to 159 GPa in (Fe,Mg) O with Mg x = 0.875. We find that the pressure-induced HS-LS transition has different consequences for the electronic properties of the Fe-rich and -poor (Fe,Mg) O. For the Fe-rich (Fe,Mg) O, the transition is found to be accompanied by a Mott insulator to a (semi) metal phase transition. In contrast to that, for x amp;gt; 0.25, (Fe,Mg) O remains insulating up to the highest studied pressures, implying a Mott-insulator to band-insulator phase transition at the HS-LS transformation.
We report a detail theoretical study of the electronic structure and phase stability of transition metal oxides MnO, FeO, CoO, and NiO in their paramagnetic cubic B1 structure by employing dynamical mean-field theory of correlated electrons combined with ab initio band-structure methods. Our calculations reveal that under pressure these materials exhibit a Mott insulator-metal transition (IMT) which is accompanied by a simultaneous collapse of local magnetic moments and lattice volume, implying a complex interplay between chemical bonding and electronic correlations. Moreover, our results for the transition pressure show a monotonous decrease from similar to 145 to 40 GPa, upon moving from MnO to CoO. In contrast to that, in NiO, magnetic collapse is found to occur at a remarkably higher pressure of similar to 429 GPa. We provide a unified picture of such a behavior and suggest that it is primarily a localized to itinerant moment behavior transition at the IMT that gives rise to magnetic collapse in transition metal oxides.
The recent nonempirical semilocal exchange functional of Armiento and Kummel [Phys. Rev. Lett. 111, 036402 (2013)], AK13, incorporates a number of features reproduced by higher-order theory. The AK13 potential behaves analogously with the discontinuous jump associated with the derivative discontinuity at integer particle numbers. Recent works have established that AK13 gives a qualitatively improved orbital description compared to other semilocal methods, and reproduces a band structure closer to higher-order theory. However, its energies and energetics are inaccurate. The present work further investigates the deficiency in energetics. In addition to AK13 results, we find that applying the local-density approximation (LDA) non-self-consistently on the converged AK13 density gives very reasonable energetics with equilibrium lattice constants and bulk moduli well described across 13 systems. We also confirm that the attractive orbital features of AK13 are retained even after full structural relaxation. Hence, the deficient energetics cannot be a result of the AK13 orbitals having adversely affected the quality of the electron density compared to that of usual semilocal functionals; an improved orbital description and good energetics are not in opposition. This is also confirmed by direct calculation of the principal component of the electric field gradient. In addition, we prove that the non-self-consistent scheme is equivalent to using a single external-potential-dependent functional in an otherwise consistent, nonvariational Kohn-Sham density-functional theory (KS DFT) scheme. Furthermore, our results also demonstrate that, while an internally consistent KS functional is presently missing, non-self-consistent LDA on AK13 orbitals works as a practical nonempirical computational scheme to predict geometries, bulk moduli, while retaining the band structure features of AK13 at the computational cost of semi-local DFT.
Polarized neutron reflectometry is used to determine the sequence of magnetic switching in interlayer exchange coupled Fe/MgO(001) superlattices in an applied magnetic field. For 19.6 angstrom thick MgO layers we obtain a 90 degrees periodic magnetic alignment between adjacent Fe layers at remanence. In an increasing applied field the top layer switches first followed by its second-nearest neighbor. For 16.4 angstrom MgO layers, a 180 degrees periodic alignment is obtained at remanence and with increasing applied field the layer switching starts from the two outermost layers and proceeds inwards. This sequential tuneable switching opens up the possibility of designing three-dimensional magnetic structures with a predefined discrete switching sequence.
We investigate the quenching of the photoluminescence (PL) from the divacancy defect in 4H-SiC consisting of a nearest-neighbor silicon and carbon vacancies. The quenching occurs only when the PL is excited below certain photon energies (thresholds), which differ for the four different inequivalent divacancy configurations in 4H-SiC. An accurate theoretical ab initio calculation for the charge-transfer levels of the divacancy shows very good agreement between the position of the (0/-) level with respect to the conduction band for each divacancy configuration and the corresponding experimentally observed threshold, allowing us to associate the PL decay with conversion of the divacancy from neutral to negative charge state due to capture of electrons photoionized from other defects (traps) by the excitation. Electron paramagnetic resonance measurements are conducted in the dark and under excitation similar to that used in the PL experiments and shed light on the possible origin of traps in the different samples. A simple model built on this concept agrees well with the experimentally observed decay curves.
We determine the frequency dependence of the four independent Cartesian tensor elements of the dielectric function for monoclinic symmetry Y2SiO5 using generalized spectroscopic ellipsometry from 40-1200 cm(-1). Three different crystal cuts, each perpendicular to a principle axis, are investigated. We apply our recently described augmentation of lattice anharmonicity onto the eigendielectric displacement vector summation approach [A. Mock et al., Phys. Rev. B 95, 165202 (2017)], and we present and demonstrate the application of an eigendielectric displacement loss vector summation approach with anharmonic broadening. We obtain an excellent match between all measured and model-calculated dielectric function tensor elements and all dielectric loss function tensor elements. We obtain 23 A(u) and 22 B-u symmetry long-wavelength active transverse and longitudinal optical mode parameters including their eigenvector orientation within the monoclinic lattice. We perform density functional theory calculations and obtain 23 A(u) symmetry and 22 B-u transverse and longitudinal optical mode parameters and their orientation within the monoclinic lattice. We compare our results from ellipsometry and density functional theory and find excellent agreement. We also determine the static and above reststrahlen spectral range dielectric tensor values and find a recently derived generalization of the Lyddane-Sachs-Teller relation for polar phonons in monoclinic symmetry materials satisfied.
We determine the frequency dependence of four independent Cartesian tensor elements of the dielectric function for CdWO4 using generalized spectroscopic ellipsometry within mid-infrared and far-infrared spectral regions. Different single crystal cuts, (010) and (001), are investigated. From the spectral dependencies of the dielectric function tensor and its inverse we determine all long-wavelength active transverse and longitudinal optic phonon modes with A(u) and B-u symmetry as well as their eigenvectors within the monoclinic lattice. We thereby demonstrate that such information can be obtained completely without physical model line-shape analysis in materials with monoclinic symmetry. We then augment the effect of lattice anharmonicity onto our recently described dielectric function tensor model approach formaterials with monoclinic and triclinic crystal symmetries [ M. Schubert et al., Phys. Rev. B 93, 125209 (2016)], and we obtain an excellent match between all measured and modeled dielectric function tensor elements. All phonon mode frequency and broadening parameters are determined in our model approach. We also perform density functional theory phonon mode calculations, and we compare our results obtained from theory, from direct dielectric function tensor analysis, and from model line- shape analysis, and we find excellent agreement between all approaches. We also discuss and present static and above reststrahlen spectral range dielectric constants. Our data for CdWO4 are in excellent agreement with a recently proposed generalization of the Lyddane-Sachs-Teller relation for materials with low crystal symmetry [ M. Schubert, Phys. Rev. Lett. 117, 215502 (2016)].
A complete set of infrared-active and Raman-active lattice modes is obtained from density functional theory calculations for single-crystalline centrosymmetric orthorhombic neodymium gallate. The results for infrared-active modes are compared with an analysis of the anisotropic long-wavelength properties using generalized spectroscopic ellipsometry. The frequency-dependent dielectric function tensor and dielectric loss function tensor of orthorhombic neodymium gallium oxide are reported in the spectral range of 80-1200 cm(-1). A combined eigendielectric displacement vector summation and dielectric displacement loss vector summation approach augmented by considerations of lattice anharmonicity is utilized to describe the experimentally determined tensor elements. All infrared-active transverse and longitudinal optical mode pairs obtained from density functional theory calculations are identified by our generalized spectroscopic ellipsometry investigation. The results for Raman-active modes are compared to previously published experimental observations. Static and high-frequency dielectric constants from theory as well as experiment are presented and discussed in comparison with values reported previously in the literature.
We employ an eigenpolarization model including the description of direction dependent excitonic effects for rendering critical point structures within the dielectric function tensor of monoclinic beta-Ga2O3 yielding a comprehensive analysis of generalized ellipsometry data obtained from 0.75-9 eV. The eigenpolarization model permits complete description of the dielectric response. We obtain, for single-electron and excitonic band-to-band transitions, anisotropic critical point model parameters including their polarization vectors within the monoclinic lattice. We compare our experimental analysis with results from density functional theory calculations performed using the Gaussian-attenuation-Perdew-Burke-Ernzerhof hybrid density functional. We present and discuss the order of the fundamental direct band-to-band transitions and their polarization selection rules, the electron and hole effective mass parameters for the three lowest band-to-band transitions, and their excitonic contributions. We find that the effective masses for holes are highly anisotropic and correlate with the selection rules for the fundamental band-to-band transitions. The observed transitions are polarized close to the direction of the lowest hole effective mass for the valence band participating in the transition.
Rippling is an inherent quality of two-dimensional materials playing an important role in determining their properties. Here, we study the effect of structural corrugations on the electronic and transport properties of monolayer black phosphorus (phosphorene) in the presence of tilted magnetic field. We follow a perturbative approach to obtain analytical corrections to the spectrum of Landau levels induced by a long-wavelength corrugation potential. We show that surface corrugations have a non-negligible effect on the electronic spectrum of phosphorene in tilted magnetic field. Particularly, the Landau levels are shown to exhibit deviations from the linear field dependence. The observed effect become especially pronounced at large tilt angles and corrugation amplitudes. Magnetotransport properties are further examined in the low temperature regime taking into account impurity scattering. We calculate magnetic field dependence of the longitudinal and Hall resistivities and find that the nonlinear effects reflecting the corrugation might be observed even in moderate fields (B amp;lt; 10 T).
There are several approaches to the description of van der Waals (vdW) forces within density functional theory. While they are generally found to improve the structural and energetic properties of those materials dominated by weak dispersion forces, it is not known how they behave when the material is subject to an external pressure. This could be an issue when considering the pressure-induced structural phase transitions, which are currently attracting great attention following the discovery of an ultrahard phase formed by the compression of graphite at room temperature. In order to model this transition, the functional must be capable of simultaneously describing both strong covalent bonds and weak dispersion interactions as an isotropic pressure is applied. Here, we report on the ability of several dispersion-correction functionals to describe the energetic, structural, and elastic properties of graphite and diamond, when subjected to an isotropic pressure. Almost all of the tested vdW corrections provide an improved description of both graphite and diamond compared to the local density approximation. The relative error does not change significantly as pressure is applied, and in some cases even decreases. We therefore conclude that the use of dispersion-corrected exchange-correlation functionals, which have been neglected to date, will improve the accuracy and reliability of theoretical investigations into the pressure-induced phase transition of graphite.
Using the disordered local moments approach in combination with the ab initio molecular dynamics method, we simulate the behavior of a paramagnetic phase of NiO at finite temperatures to investigate the effect of magnetic disorder, thermal expansion, and lattice vibrations on its electronic structure. In addition, we study its lattice dynamics. We verify the reliability of our theoretical scheme via comparison of our results with available experiment and earlier theoretical studies carried out within static approximations. We present the phonon dispersion relations for the paramagnetic rock-salt (B1) phase of NiO and demonstrate that it is dynamically stable. We observe that including the magnetic disorder to simulate the paramagnetic phase has a small yet visible effect on the band gap. The amplitude of the local magnetic moment of Ni ions from our calculations for both antiferromagnetic and paramagnetic phases agree well with other theoretical and experimental values. We demonstrate that the increase of temperature up to 1000 K does not affect the electronic structure strongly. Taking into account the lattice vibrations and thermal expansion at higher temperatures have amajor impact on the electronic structure, reducing the band gap from similar to 3.5 eV at 600 K to similar to 2.5 eV at 2000 K. We conclude that static lattice approximations can be safely employed in simulations of the paramagnetic state of NiO up to relatively high temperatures (similar to 1000 K), but as we get closer to the melting temperature vibrational effects become quite large and therefore should be included in the calculations.
We report a multiscale modeling of electronic structure of a conducting polymer poly(3,4-ethylenedioxythiopehene) (PEDOT) based on a realistic model of its morphology. We show that when the charge carrier concentration increases, the character of the density of states (DOS) gradually evolves from the insulating to the semimetallic, exhibiting a collapse of the gap between the bipolaron and valence bands with the drastic increase of the DOS between the bands. The origin of the observed behavior is attributed to the effect of randomly located counterions giving rise to the states in the gap. These results are discussed in light of recent experiments. The method developed in this work is general and can be applied to study the electronic structure of other conducting polymers.
We have investigated the disorder of epitaxial graphene close to the charge neutrality point (CNP) by various methods: (i) at room temperature, by analyzing the dependence of the resistivity on the Hall coefficient; (ii) by fitting the temperature dependence of the Hall coefficient down to liquid helium temperature; (iii) by fitting the magnetoresistances at low temperature. All methods converge to give a disorder amplitude of (20 +/- 10) meV. Because of this relatively low disorder, close to the CNP, at low temperature, the sample resistivity does not exhibit the standard value similar or equal to h/4e(2) but diverges. Moreover, themagnetoresistance curves have a unique ambipolar behavior, which has been systematically observed for all studied samples. This is a signature of both asymmetry in the density of states and in-plane charge transfer. Themicroscopic origin of this behavior cannot be unambiguously determined. However, we propose a model in which the SiC substrate steps qualitatively explain the ambipolar behavior.
We report on nonlocal transport in large-scale epitaxial graphene on silicon carbide under an applied external magnetic field. The nonlocality is related to the emergence of the quantum Hall regime and persists up to the millimeter scale. The nonlocal resistance reaches values comparable to the local (Hall and longitudinal) resistances. At moderate magnetic fields, it is almost independent on the in-plane component of the magnetic field, which suggests that spin currents are not at play. The nonlocality cannot be explained by thermoelectric effects without assuming extraordinary large Nernst and Ettingshausen coefficients. A model based on counterpropagating edge states backscattered by the bulk reproduces quite well the experimental data.
Simulations of diffusion in solids often produce poor statistics of diffusion events. We present an analytical expression for the statistical error in ion conductivity obtained in such simulations. The error expression is not restricted to any computational method in particular, but valid in the context of simulation of Poisson processes in general. This analytical error expression is verified numerically for the case of Gd-doped ceria by running a large number of kinetic Monte Carlo calculations.
A first-principles nonequilibrium molecular dynamics (NEMD) study employing the color-diffusion algorithm has been conducted to obtain the bulk ionic conductivity and the diffusion constant of gadolinium-doped cerium oxide (GDC) in the 850-1150 K temperature range. Being a slow process, ionic diffusion in solids usually requires simulation times that are prohibitively long for ab initio equilibrium molecular dynamics. The use of the color-diffusion algorithm allowed us to substantially speed up the oxygen-ion diffusion. The key parameters of the method, such as field direction and strength as well as color-charge distribution, have been investigated and their optimized values for the considered system have been determined. The calculated ionic conductivity and diffusion constants are in good agreement with available experimental data.