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Structural softness - often characterized by unstable phonon modes and large electromechanical responses - is a hallmark of ferroelectric perovskites like BaTiO3 or Pb(Ti,Zr)O3. Whether HfO2 ferroelectrics present any such structural softness is still a matter of debate. Here, using first principles calculations, we predict that it is possible to induce structural instabilities in hafnia. More specifically, our calculations show that in-plane epitaxial tensile strain causes a mechanical instability of the ferroelectric phase, which transforms discontinuously into an antipolar polymorph. Then, upon release of the tensile strain, the antipolar polymorph transforms back to the ferroelectric state by a soft phonon instability. We show that the softening is accompanied by enhancements in the dielectric and piezoelectric responses. While these transitions occur at high epitaxial strains for pure ferroelectric HfO2, we show that the required deformations are considerably lowered in superlattices with other simple oxides, which may facilitate realizing these effects experimentally., Comment: 15 pages including supplementary information

Ferroelectrics under suitable electric boundary conditions can present a negative capacitance response, whereby the total voltage drop across the ferroelectric opposes the externally applied bias. When the ferroelectric is in a heterostructure, this behavior yields a voltage amplification in the other elements, an effect that could be leveraged in low-power electronic devices. Interestingly, the mentioned voltage amplification should have an accompanying elastic effect. Specifically, in the typical case that the materials in contact with the ferroelectric are non-polar dielectrics, those should present an enhanced electrostrictive response. Here we use atomistic simulations - of model PbTiO$_{3}$/SrTiO$_{3}$ ferroelectric/dielectric superlattices displaying negative capacitance - to show that this is indeed the case: we reveal the enhanced elastic response of the dielectric layer and show that it is clearly linked to the voltage amplification. We argue that this "elastic amplification" could serve as a convenient experimental fingerprint for negative capacitance. Further, we propose that it may have interest on its own, e.g. for the development of low-power electromechanical actuators.

The metastable nature of the ferroelectric phase of HfO$_2$ is a significant impediment to its industrial application as a functional ferroelectric material. In fact, no polar phases exist in the bulk phase diagram of HfO$_2$, which shows a dominant non-polar monoclinic ground state. As a consequence, ferroelectric orthorhombic HfO$_2$ needs to be kinetically stabilized. Here, we propose an alternative approach, demonstrating the feasibility of thermodynamically stabilizing polar HfO$_2$ in superlattices with other simple oxides. Using the composition and stacking direction of the superlattice as design parameters, we obtain heterostructures that can be fully polar, fully antipolar or mixed, with improved thermodynamic stability compared to the orthorhombic polar HfO$_2$ in bulk form. Our results suggest that combining HfO$_2$ with an oxide that does not have a monoclinic ground state generally drives the superlattice away from this non-polar phase, favoring the stability of the ferroelectric structures that minimize the elastic and electrostatic penalties. As such, these diverse and tunable superlattices hold promise for various applications in thin-film ferroelectric devices.

In this work we use a phenomenological theory of ferroelectric switching in BiFeO$_3$ thin films to uncover the mechanism of the two-step process that leads to the reversal of the weak magnetization of these materials. First, we introduce a realistic model of a BiFeO$_3$ film, including the Landau energy of isolated domains as well as the constraints that account for the presence of the substrate and the multidomain configuration found experimentally. We use this model to obtain statistical information about the switching behavior - by running dynamical simulations based on the Landau-Khalatnikov time-evolution equation, including thermal fluctuations - and we thus identify the factors that drive the two-step polarization reversal observed in the experiments. Additionally, we apply our model to test potential strategies for optimizing the switching characteristics., Comment: 16 pages, 9 figures

In this work we introduce the simplest, lowest-order Landau-like potential for BiFeO$_3$ and La-doped BiFeO$_3$ as an expansion around the paraelectric cubic phase in powers of polarization, FeO$_6$ octahedral rotations and strains. We present an analytical approach for computing the model parameters from density functional theory. We illustrate our approach by computing the potentials for BiFeO$_3$ and La$_{0.25}$Bi$_{0.75}$FeO$_3$ and show that, overall, we are able to capture the first-principles results accurately. The computed models allow us to identify and explain the main interactions controlling the relative stability of the competing low-energy phases of these compounds., Comment: 12 pages, 6 figures

The polarization response of antiferroelectrics to electric fields is such that the materials can store large energy densities, which makes them promising candidates for energy storage applications in pulsed-power technologies. However, relatively few materials of this kind are known. Here we consider ferroelectric/paraelectric superlattices as artificial electrostatically-engineered antiferroelectrics. Specifically, using high-throughput second-principles calculations, we engineer PbTiO$_{3}$/SrTiO$_{3}$ superlattices to optimize their energy-storage performance at room temperature (to maximize density and release efficiency) with respect to different design variables (layer thicknesses, epitaxial conditions, stiffness of the dielectric layer). We obtain results competitive with the state-of-the-art antiferroelectric capacitors and reveal the mechanisms responsible for the optimal properties., Comment: 8 pages, 5 figures

Understanding the electrical and thermal transport properties of materials is critical to the design of electronics, sensors and energy conversion devices. Computational modeling can accurately predict materials properties but, in order to be reliable, require accurate descriptions of electron and phonon states and their interactions. While first-principles methods are capable of describing the energy spectrum of each carrier, using them to compute transport properties is still a formidable task, both computationally demanding and memory intensive, requiring integration of fine microscopic scattering details for estimation of macroscopic transport properties. To address this challenge, we present Phoebe - a newly developed software package that includes the effects of electron-phonon, phonon-phonon, boundary, and isotope scattering in computations of electrical and thermal transport properties of materials with a variety of available methods and approximations. This open source C++ code combines MPI-OpenMP hybrid parallelization with GPU acceleration and distributed memory structures to manage computational cost, allowing Phoebe to effectively take advantage of contemporary computing infrastructures. We demonstrate that Phoebe accurately and efficiently predicts a wide range of transport properties, opening avenues for accelerated computational analysis of complex crystals.

The Seebeck coefficient and electrical conductivity are two critical quantities to optimize simultaneously in designing thermoelectric materials, and they are determined by the dynamics of carrier scattering. We uncover a new regime where the co-existence at the Fermi level of multiple bands with different effective masses leads to strongly energy-dependent carrier lifetimes due to intrinsic electron-phonon scattering. In this anomalous regime, electrical conductivity decreases with carrier concentration, Seebeck coefficient reverses sign even at high doping, and power factor exhibits an unusual second peak. We discuss the origin and magnitude of this effect using first-principles Boltzmann transport calculations and simplified models. We also identify general design rules for using this paradigm to engineer enhanced performance in thermoelectric materials., Comment: 11 pages, 7 figures

Here, we report on the observation of a random to chaotic temperature transition in the spacing of Fano-Feshbach resonances in the ultracold polarized gas of thulium atoms. This transition is due to the appearance of so-called d-resonances, which are not accessible at low temperatures, in the spectra at high temperatures, which drastically changes thulium's overall resonance statistic. In addition to this statistical change, it has been observed that s- and d-resonances experience quite different temperature shifts: s-resonances experience almost no shift with the temperature, while d-resonances experience an obvious positive shift. In addition, careful analysis of the broad Fano-Feshbach resonances enabled the determination of the sign of thulium's background scattering length. A rethermalization experiment made it possible to estimate a length value of a=144+-38a.u.. This proves that thulium atoms are suitable for achieving Bose-Einstein Condensation.

We use resonant and non-resonant X-ray diffraction measurements in combination with first-principles electronic structure calculations and Monte Carlo simulations to study the relationship between crystal structure and multiferroic orders in the orthorhombic perovskite manganites, o-$R$MnO$_3$ ($R$ is a rare-earth cation or Y). In particular, we focus on how the internal lattice parameters (Mn-O bond lengths and Mn-O-Mn bond angles) evolve under chemical pressure and epitaxial strain, and the effect of these structural variations on the microscopic exchange interactions and long-range magnetic order. We show that chemical pressure and epitaxial strain are accommodated differently by the crystal lattice of o-$R$MnO$_3$, which is key for understanding the difference in magnetic properties between bulk samples and strained films. Finally, we discuss the effects of these differences in the magnetism on the electric polarization in o-$R$MnO$_3$., Comment: 16 pages, 10 figures

We use ab initio electronic structure calculations in combination with Monte Carlo simulations to investigate the magnetic and ferroelectric properties of bulk orthorhombic HoMnO$_3$ and ErMnO$_3$. Our goals are to explain the inconsistencies in the measured magnetic properties of the orthorhombic perovskite manganites (o-$R$MnO$_3$) with small rare-earth ($R$) cations or Y, as well as the contradictions between the directions and amplitudes of the electric polarizations reported by different experimental groups. Our computations stabilize several exotic magnetic orders (so-called w-spiral, H-AFM and I-AFM), whose presence resolve the contradictions in the measured magnetic and ferroelectric properties of o-$R$MnO$_3$. We show that these orders emerge due to strong four-spin ring exchange interactions., Comment: 19 pages, 13 figures

We use ab initio electronic structure calculations within the generalized gradient approximation (GGA+U) to density functional theory (DFT) to determine the microscopic exchange interactions in the series of orthorhombic rare-earth manganites, o-$R$MnO$_3$. Our motivation is to construct a model Hamiltonian (excluding effects due to spin-orbit coupling), which can provide an accurate description of the magnetism in these materials. First, we consider TbMnO$_3$, which exhibits a spiral magnetic order at low temperatures. We map the exchange couplings in this compound onto a Heisenberg Hamiltonian and observe a clear deviation from the Heisenberg-like behavior. We consider first the coupling between magnetic and orbital degrees of freedom as a potential source of non-Heisenberg behavior in TbMnO$_3$, but conclude that it does not explain the observed deviation. We find that higher order magnetic interactions (biquadratic and four-spin ring couplings) should be taken into account for a proper treatment of the magnetism in TbMnO$_3$ as well as in the other representatives of the o-$R$MnO$_3$ series with small radii of the $R$ cation., Comment: 13 pages, 12 figures