Ferroelectrics are attractive candidate materials for environmentally friendly solid state refrigeration free of greenhouse gases. Their thermal response upon variations of external electric fields is largest in the vicinity of their phase transitions, which may occur near room temperature. The magnitude of the effect, however, is too small for useful cooling applications even when they are driven close to dielectric breakdown. Insight from microscopic theory is therefore needed to characterize materials and provide guiding principles to search for new ones with enhanced electrocaloric performance. Here, we derive from well-known microscopic models of ferroelectricity meaningful figures of merit which provide insight into the relation between the strength of the effect and the characteristic interactions of ferroelectrics such as dipole forces. We find that the long range nature of these interactions results in a small effect. A strategy is proposed to make it larger by shortening the correlation lengths of fluctuations of polarization.
We study the free energy landscape of a minimal model for relaxor ferroelectrics. Using a variational method which includes leading correlations beyond the mean-field approximation as well as disorder averaging at the level of a simple replica theory, we find metastable paraelectric states with a stability region that extends to zero temperature. The free energy of such states exhibits an essential singularity for weak compositional disorder pointing to their necessary occurrence. Ferroelectric states appear as local minima in the free energy at high temperatures and become stable below a coexistence temperature $T_c$. We calculate the phase diagram in the electric field-temperature plane and find a coexistence line of the polar and non-polar phases which ends at a critical point. First-order phase transitions are induced for fields sufficiently large to cross the region of stability of the metastable paraelectric phase. These polar and non-polar states have distinct structure factors from those of conventional ferroelectrics. We use this theoretical framework to compare and to gain physical understanding of various experimental results in typical relaxors.
Using a Ginzburg--Landau--Devonshire model that includes the coupling of polarization to strain, we calculate the fluctuation spectra of ferroelectric domain walls. The influence of the strain coupling differs between 180 degree and 90 degree walls due to the different strain profiles of the two configurations. The finite speed of acoustic phonons, $v_s$, retards the response of the strain to polarization fluctuations, and the results depend on $v_s$. For $v_s to infty$, the strain mediates an instantaneous electrostrictive interaction, which is long-range in the 90 degree wall case. For finite $v_s$, acoustic phonons damp the wall excitations, producing a continuum in the spectral function. As $v_s to 0$, a gapped mode emerges, which corresponds to the polarization oscillating in a fixed strain potential.
We study zigzag interfaces between insulating compounds that are isostructural to graphene, specifically II-VI, III-V and IV-IV two-dimensional (2D) honeycomb insulators. We show that these one-dimensional interfaces are polar, with a net density of excess charge that can be simply determined by using the ideal (integer) formal valence charges, regardless of the predominant covalent character of the bonding in these materials. We justify this finding on fundamental physical grounds, by analyzing the topology of the formal polarization lattice in the parent bulk materials. First principles calculations elucidate an electronic compensation mechanism not dissimilar to oxide interfaces, which is triggered by a Zener-like charge transfer between interfaces of opposite polarity. In particular, we predict the emergence of one dimensional electron and hole gases (1DEG), which in some cases are ferromagnetic half-metallic.
Solid state quantum condensates can differ from other condensates, such as Helium, ultracold atomic gases, and superconductors, in that the condensing quasiparticles have relatively short lifetimes, and so, as for lasers, external pumping is required to maintain a steady state. In this chapter we present a non-equilibrium path integral approach to condensation in a dissipative environment and apply it to microcavity polaritons, driven out of equilibrium by coupling to multiple baths, describing pumping and decay. Using this, we discuss the relation between non-equilibrium polariton condensation, lasing, and equilibrium condensation.
Atoms, molecules or excitonic quasiparticles, for which excitations are induced by external radiation fields and energy is dissipated through radiative decay, are examples of driven open quantum systems. We explain the use of commutator-free exponential time-propagators for the numerical solution of the associated Schrodinger or master equations with a time-dependent Hamilton operator. These time-propagators are based on the Magnus series but avoid the computation of commutators, which makes them suitable for the efficient propagation of systems with a large number of degrees of freedom. We present an optimized fourth order propagator and demonstrate its efficiency in comparison to the direct Runge-Kutta computation. As an illustrative example we consider the parametrically driven dissipative Dicke model, for which we calculate the periodic steady state and the optical emission spectrum.
We consider performing adiabatic rapid passage (ARP) using frequency-swept driving pulses to excite a collection of interacting two-level systems. Such a model arises in a wide range of many-body quantum systems, such as cavity QED or quantum dots, where a nonlinear component couples to light. We analyze the one-dimensional case using the Jordan-Wigner transformation, as well as the mean field limit where the system is described by a Lipkin-Meshkov-Glick Hamiltonian. These limits provide complementary insights into the behavior of many-body systems under ARP, suggesting our results are generally applicable. We demonstrate that ARP can be used for state preparation in the presence of interactions, and identify the dependence of the required pulse shapes on the interaction strength. In general interactions increase the pulse bandwidth required for successful state transfer, introducing new restrictions on the pulse forms required.
Against expectations, robust switchable ferroelectricity has been recently observed in ultrathin (1 nm) ferroelectric films exposed to air [V. Garcia $et$ $al.$, Nature {bf 460}, 81 (2009)]. Based on first-principles calculations, we show that the system does not polarize unless charged defects or adsorbates form at the surface. We propose electrochemical processes as the most likely origin of this charge. The ferroelectric polarization of the film adapts to the bound charge generated on its surface by redox processes when poling the film. This, in turn, alters the band alignment at the bottom electrode interface, explaining the observed tunneling electroresistance. Our conclusions are supported by energetics calculated for varied electrochemical scenarios.
We study the stability of collective amplitude excitations in non-equilibrium polariton condensates. These excitations correspond to renormalized upper polaritons and to the collective amplitude modes of atomic gases and superconductors. They would be present following a quantum quench or could be created directly by resonant excitation. We show that uniform amplitude excitations are unstable to the production of excitations at finite wavevectors, leading to the formation of density-modulated phases. The physical processes causing the instabilities can be understood by analogy to optical parametric oscillators and the atomic Bose supernova.
The issue of the net charge at insulating oxide interfaces is shortly reviewed with the ambition of dispelling myths of such charges being affected by covalency and related charge density effects. For electrostatic analysis purposes, the net charge at such interfaces is defined by the counting of discrete electrons and core ion charges, and by the definition of the reference polarisation of the separate, unperturbed bulk materials. The arguments are illustrated for the case of a thin film of LaAlO$_3$ over SrTiO$_3$ in the absence of free carriers, for which the net charge is exactly 0.5$e$ per interface formula unit, if the polarisation response in both materials is referred to zero bulk values. Further consequences of the argument are extracted for structural and chemical alterations of such interfaces, in which internal rearrangements are distinguished from extrinsic alterations (changes of stoichiometry, redox processes), only the latter affecting the interfacial net charge. The arguments are reviewed alongside the proposal of Stengel and Vanderbilt [Phys. Rev. B {bf 80}, 241103 (2009)] of using formal polarisation values instead of net interfacial charges, based on the interface theorem of Vanderbilt and King-Smith [Phys. Rev. B {bf 48}, 4442 (1993)]. Implications for non-centrosymmetric materials are discussed, as well as for interfaces for which the charge mismatch is an integer number of polarisation quanta.
