Time-dependent speckle pattern of paraelectric barium titanate observed in a soft x-ray laser pump-probe measurement is theoretically investigated as a correlated optical response to the pump and probe pulses. The scattering probability is calculated based on a model with coupled soft x-ray photon and ferroelectric phonon mode. It is found that the speckle variation is related with the relaxation dynamics of ferroelectric clusters created by the pump pulse. Additionally, critical slowing down of cluster relaxation arises on decreasing temperature towards the paraelectric-ferroelectric transition temperature. Relation between critical slowing down, local dipole fluctuation and crystal structure are revealed by quantum Monte Carlo simulation.
We demonstrate an approach for calculating temperature-dependent quantum and anharmonic effects with beyond density-functional theory accuracy. By combining machine-learned potentials and the stochastic self-consistent harmonic approximation, we investigate the cubic to tetragonal transition in strontium titanate and show that the paraelectric phase is stabilized by anharmonic quantum fluctuations. We find that a quantitative understanding of the quantum paraelectric behavior requires a higher-level treatment of electronic correlation effects via the random phase approximation. This approach e…
A magneto-quantum-paraelectric family is emergent from the shared low-temperature characteristics of representative SrCu3Ti4O12 (SCTO), CaCu3Ti4O12 (CCTO), and Ca0.9Li0.1Cu3Ti4O12 (CLCTO) antiferro-tilted/A1/4A'3/4BO3-structures. Above their magnetic ordering temperatures TN, dielectric permittivity of SCTO and CLCTO follow typical quantum paraelectric Barrett-form unambiguously, whereas in CCTO, this behaviour is masked by the huge ε'-step, born of thermally-activated site-antisite (Ca/Cu) disorder. The hidden quantum paraelectricity in CCTO is revealed with Li-doping at Ca-site, by considera…
We report experimental and theoretical investigation of anisotropy in optical properties and their origin in the ferroelectric and paraelectric phases of bismuth titanate. Room temperature ellipsometric measurements performed on pulsed laser deposited bismuth titanate thin films of different orientations show anisotropy in the dielectric and optical constants, Subsequent first-principles calculations performed on the ground state structures of ferroelectric and high temperature paraelectric phases of bismuth titanate show that the material demonstrates anisotropic optical behavior in both ferr…
The dielectric properties of strontium titanate (SrTiO$_3$) have previously been reported from room temperature to low temperatures with conflicting results. In this work, precision measurement of the permittivity is undertaken by simultaneously measuring transverse electric and transverse magnetic resonant modes within a single crystal. It is unequivocally shown that the permittivity is isotropic at room temperature with a permittivity of order $316.3\pm2.2$ by measuring multiple modes of different electric field polarisations. As the crystal is cooled to 5 K and undergoes well known phase tr…
X-ray photoelectron diffraction is used to directly probe the intra-cell polar atomic distortion and tetragonality associated with ferroelectricity in ultrathin epitaxial PbTiO3 films. Our measurements, combined with ab-initio calculations, unambiguously demonstrate non-centro-symmetry in films a few unit cells thick, imply that films as thin as 3 unit cells still preserve a ferroelectric polar distortion, and also show that there is no thick paraelectric dead layer at the surface.
In this study, we present the results of our first-principles calculations of the band structure, density of states and the Born effective charge tensors for the ferroelectric (ground state B1a1) and paraelectric (I4/mmm) phases of bismuth titanate. The calculations are done using the generalized gradient approximation (GGA) as well as the local density approximation (LDA) of the density functional theory. In contrast to the literature, our calculations on B1a1 structure using GGA and LDA yield smaller indirect band gaps as compared to the direct band gaps, in agreement with the experimental d…
The results of the first investigations of the process of local decomposition of lead-lanthanum zirconate-titanate solid solution in the vicinity of the interphase boundaries separating domains of coexisting ferroelectric and antiferroelectric phases are presented. The solid solution with the composition: 6 at% of La, 73 at% of Zr, and 27 at% of Ti is considered. The kinetics of the local decomposition of this solid solution in the process of aging of samples quenched down to room temperature from the paraelectric phase is studied. The mechanisms that define the kinetics of the process of esta…
We revisit the quantum phase transition from a paraelectric state to a ferroelectric one and in particular the widespread distinction between a longitudinal modes to transverse one. In contrast to transitions at finite temperature, for a quantum phase transition breaking a discrete symmetry the splitting between the modes is irrelevant. We show that an anisotropy in the context of a quantum phase transition leads to a different behavior, compared to a classical transition, and suggest an experiment to observe it. The result is essential for explaining the pairing mechanism in strontium titanat…
Precise specific heat of barium titanate single crystals of different quality has been measured with special attention to the temperature region above the ferroelectric phase transition. It is shown that excess specific heat of the multiaxial barium titanate in the paraelectric phase has a fluctuation nature and its temperature dependence is in accordance with the theoretical predictions of Levanyuk theory for multiaxial ferroelectrics. In this study the first observation of fluctuation contribution to the specific heat is presented.
It has been known for more than a decade that phonons can produce an off-diagonal thermal conductivity in presence of magnetic field. Recent studies of thermal Hall conductivity, $κ_{xy}$, in a variety of contexts, however, have assumed a negligibly small phonon contribution. We present a study of $κ_{xy}$ in quantum paraelectric SrTiO$_3$, which is a non-magnetic insulator and find that its peak value exceeds what has been reported in any other insulator, including those in which the signal has been qualified as 'giant'. Remarkably, $κ_{xy}(T)$ and $κ(T)$ peak at the same temperature and the …
We report on a study of charge transport in EuTiO$_{3-δ}$ single crystals with carrier density tuned across several orders of magnitude. Comparing this system with other quasi-cubic perovskites, in particular strontium titanate, we draw a comprehensive picture of metal-insulator transition and dilute metallicity in this $AB$O$_3$ family. Because of a lower electric permittivity, the metal-insulator transition in EuTiO$_{3-δ}$ occurs at higher carrier densities compared to SrTiO$_3$. At low temperature, a distinct $T^2$ resistivity is visible. Its prefactor $A$ smoothly decreases with increasin…
Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory（斯坦福材料能源科学研究所，SLAC国家加速器实验室）；Stanford PULSE Institute, SLAC National Accelerator Laboratory（斯坦福PULSE研究所，SLAC国家加速器实验室）；Department of Chemistry, Massachusetts Institute of Technology（麻省理工学院化学系）；Elettra-Sincrotrone（埃莱特拉同步辐射中心）；Paul Scherrer Institut（保罗谢尔研究所）
Spatial correlation between atoms can generate a depletion in the energy dispersion of acoustic phonons. Two well known examples are rotons in superfluid helium and the Kohn anomaly in metals. Here we report on the observation of a large softening of the transverse acoustic mode in quantum paraelectric SrTiO$_3$ by means of inelastic neutron scattering. In contrast to other known cases, this softening occurs at a tiny wave vector implying spatial correlation extending over a distance as long as 40 lattice parameters. We attribute this to the formation of mesoscopic fluctuating domains due to t…
First-principles calculations are performed to investigate alloying and ferroelectric effects in lead zirconate titanate (PZT) with high Ti composition. We find that the main effect of alloying in the paraelectric phase of PZT is the existence of two sets of B-O bonds, i.e., shorter Ti-O bonds vs. longer Zr-O bonds. On the other hand, ferroelectricity leads to the formation of very short covalent Ti-O bonds and to the formation of covalent chains of Pb-O bonds. The covalency in the ferroelectric phase is mainly induced by an enhancement of hybridization between Ti 3d and O 2p, and between Pb 6…
We have measured the temperature dependence of the direct band gap, $E_g$, in SrTi$^{16}$O$_3$ and BaTiO$_3$ and related materials with quantum-paraelectric and ferroelectric properties using optical spectroscopy. We show that $E_g$ exhibits an anomalous temperature dependence with pronounced changes in the vicinity of the ferroelectric transition that can be accounted for in terms of the Fröhlich electron-phonon interaction with an optical phonon mode, the so-called soft mode. We demonstrate that these characteristic changes of $E_g$ can be readily detected even in very thin films of SrTi$^{1…
A single crystal of lead-zirconate-titanate (PZT), composition Pb(Zr0.80Ti0.20)O3, was studied by polarized-Raman scattering as a function of temperature. Raman spectra reveal that the local structure deviates from the average structure in both ferroelectric and paraelectric phases. We show that the crystal possesses several, inequivalent complex domain boundaries which show no sign of instability even 200 K above the ferroelectric-to-paraelectric phase transition temperature TC. Two types of boundaries are addressed. The first boundary was formed between ferroelectric domains below TC. This b…
Entanglement of two different quantum orders is of an interest of the modern condensed matter physics. One of the examples is the dynamical multiferroicity, where fluctuations of electric dipoles lead to magnetization. We investigate this effect at finite temperature and demonstrate an elevated magnetic response of a ferroelectric near the ferroelectric quantum critical point (FE QCP). We calculate the magnetic susceptibility of a bulk sample on the paraelectric side of the FE QCP at finite temperature and find enhanced magnetic susceptibility near the FE QCP. We propose quantum paraelectric s…
The dielectric and magnetic polarizations of quantum paraelectrics and paramagnetic materials have in many cases been found to initially increase with increasing thermal disorder and hence exhibit peaks as a function of temperature. A quantitative description of these examples of 'order-by-disorder' phenomenona has remained elusive in nearly ferromagnetic metals and in dielectrics on the border of displacive ferroelectric transitions. Here we present an experimental study of the evolution of the dielectric susceptibility peak as a function of pressure in the nearly ferroelectric material, stro…
Quantum matter hosts a large variety of phases, some coexisting, some competing; when two or more orders occur together, they are often entangled and cannot be separated. Dynamical multiferroicity, where fluctuations of electric dipoles lead to magnetisation, is an example where the two orders are impossible to disentangle. Here we demonstrate elevated magnetic response of a ferroelectric near the ferroelectric quantum critical point (FE QCP) since magnetic fluctuations are entangled with ferroelectric fluctuations. We thus suggest that any ferroelectric quantum critical point is an \textit{in…
Flexoelectric effect impact on the generalized susceptibility and soft phonons dispersion was not studied in the long-range ordered phases of ferroics. The gap in the knowledge motivated us to establish the impact of the flexocoupling on the correlation function of the long-range order parameter fluctuations in ferroelectric phase of ferroics with local disordering sources. Within Landau-Ginzburg-Devonshire approach we obtained analytical expressions for the generalized susceptibility and phonon dispersion relations in the ferroelectric phase. Unexpectedly, the joint action of static and dynam…
