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, strontium titanate, which reveals that the peak position collapses towards absolute zero as the ferroelectric quantum critical point is approached. We show that this behaviour can be described in detail without the use of adjustable parameters in terms of the Larkin-Khmelnitskii-Shneerson-Rechester (LKSR) theory, first introduced nearly 50 years ago, of the hybridization of polar and acoustic modes in quantum paraelectrics, in contrast to alternative models that have been proposed. Our study allows us to construct for the first time a detailed temperature-pressure phase diagram of a material on the border of a ferroelectric quantum critical point comprising ferroelectric, quantum critical paraelectric and hybridized polar-acoustic regimes. Furthermore, at the lowest temperatures, below the susceptibility maximum, we observe a new regime characterized by a linear temperature dependence of the inverse susceptibility that differs sharply from the quartic temperature dependence predicted by the LKSR theory. We find that this non-LKSR low temperature regime cannot be accounted for in terms of any detailed model reported in the literature, and its interpretation poses a new empirical and conceptual challenge.
We present a simple theory for structural transitions in displacive ferroelectrics of the perovskite type. In our theory, the competition between the elastic energy cost for the displacement of the homopolar ion from the centrosymmetric position, and the energy gain due to a ferroelectric ordering of the dipoles formed by the ionic displacements, leads naturally to a first-order transition from a paraelectric to a ferroelectric phase. This transition takes place at a certain temperature $T_c(L)$ as the temperature is decreased and, at a certain size $L_c (T)$ as the size of the system is incre…
Experimental investigations of the phase transition in GeTe provide contradictory conclusions regarding the nature of the phase transition. Considering growing interest in technological applications of GeTe, settling these disputes is of great importance. To that end, we present a molecular dynamics study of the structural phase transition in GeTe using a machine-learned interatomic potential with ab-initio accuracy. First, we calculate the asymmetric shape of the radial distribution function of the nearest-neighbor bonds above the critical temperature, in agreement with previous studies. Howe…
Perovskite oxide ferroelectrics show classical soft mode behaviour typical for the onset of a homogeneous long-range polar state and a displacive phase transition. Besides these long wave length properties, local effects are observed by different probes which reveal that dynamical symmetry breaking already takes place already far above the actual instability. It is shown here that displacive mean-field type dynamics can indeed coexist with local dynamical symmetry breaking.
A dielectric nonlinear response in model two-phase composites, prepared from a displacive ferroelectric material with a dominant dielectric response due to a single oscillator ferroelectric mode and a dielectric material, is characterized by the existence of new modes due to geometric resonances below the percolation threshold in the ferroelectric matrix. The geometric nature of oscilations depends on composition and geometric properties of the mixture. Generation of higher frequency modes is studied within our model and discussed for displacive ferroelectric materials of the $BaTiO_{3}$ type.…
Terahertz Control of Optical Second-Harmonic Generation in Displacive Ferroelectrics: Electronic Bloch-State Reconstruction
School of Information Science and Technology, University of Science and Technology of China（中国科学技术大学信息科学与技术学院）；Guilin Julian Technology Co., Ltd.（桂林朱利安科技有限公司）；School of Electronic Engineering and Automation, Guilin University of Electronic Technology（桂林电子科技大学电子工程与自动化学院）；School of Chemistry and Chemical Engineering, Shaanxi University of Science and Technology（陕西科技大学化学与化工学院）；Laboratory of Quantum Information, University of Science and Technology of China（中国科学技术大学量子信息实验室）
SrTiO3 is an incipient ferroelectric that is believed to exhibit a prototype displacive, soft mode ferroelectric transition when subjected to mechanical stress or alloying. We use high-angle annular dark-field imaging in scanning transmission electron microscopy to reveal local polar regions in the room-temperature, paraelectric phase of strained SrTiO3 films, which undergo a ferroelectric transition at low temperatures. These films contain nanometer-sized domains in which the Ti columns are displaced. In contrast, these nanodomains are absent in unstrained films, which do not become ferroelec…
The interactions between the dielectric polarization and the fluctuations of the strain (stress) tensor in relaxor ferroelectrics are shown to give rise to the anisotropy of the anharmonic P4-term in the Landau-type free energy, however, the harmonic P2-term is still properly described by the rigid spherical random bond--random field model. These are the essential features of the compressible spherical dipolar glass model, which is used to calculate the singularities of the specific heat near field-induced critical points. The results agree with recent high-resolution calorimetric experiments …
We analyze theoretically the finite-temperature polarization dynamic in displacive-type ferroelectrics. In particular we consider the thermally-activated switching time of a single-domain ferroelectric polarization studied by means of the Landau-Khalatnikov equation, extended as to capture thermal fluctuations. The results are compared with the switching time formula that follows from the analytical solution of Pauli master equations. In a second step we focus on the phase diagram of a prototypical ferroelectric as described by the temperature-dependent Landau-Devonshire model including therma…
Type-II multiferroics, where spin interactions induce a ferroelectric polarization, are interesting for new device functionalities due to large magnetoelectric coupling. We report on a new type of multiferroicity in the quadruple-perovskite $\text{BiMn}_{\text{3}}\text{Cr}_{\text{4}}\text{O}_{\text{12}}$, where an antiferromagnetic phase is induced by the structural change at the ferroelectric phase transition. The displacive nature of the ferroelectric phase transition at 125 K, with a crossover to an order-disorder mechanism, is evidenced by a polar soft phonon in the THz range and a central…
Dielectric response as a function of frequency for high-permittivity dielectric and ferroelectric materials is discussed emphasizing the dynamic behaviour in the microwave and infrared range. After introducing the usual modelling of the polar phonon response and anharmonic hopping in locally dynamically disordered solids, including discussion of displacive and order-disorder ferroelectric phase transitions, we summarised the experimental data for selected ferroelectric, incipient ferroelectric and antiferroelectric perovskite ceramics (STO, BTO, BST, PZO), discussing the dielectric grain size …
Understanding the polarization switching mechanisms at play in ferroelectric materials is crucial for their exploitation in electronic devices. The conventional centrosymmetric reference structure-based mechanism which accounts for ferroelectricity in most of the usual displacive ferroelectric materials is too energy-demanding for some newly diagnosed ferroelectric materials such as the Ga2-xFexO3 (0.8 < x < 1.4) compounds. Some alternative theoretical propositions have been made and need experimental confirmation. A dual-scale electron microscopy study is performed on thin films of the Ga0.6F…
Historically, the soft mode theory of ferroelectric phase transitions has been developed for the high-temperature (paraelectric) phase, where the phonon mode softens upon decreasing the temperature. In the low-temperature ferroelectric phase, a similar phonon softening occurs, also leading to a bosonic condensation of the frozen-in mode at the transition, but in this case the phonon softening occurs upon increasing the temperature. Here we present a soft mode theory of ferroelectric and displacive phase transitions by describing what happens in the low-temperature phase in terms of phonon soft…
Experiments reveal that PbK2LiNb5O15 which belongs to the tetragonal tungsten bronze family presents paraelectric and ferroelectric phases and a complex structural change between them. High and low temperature phases are of symmetry P4/mbm and Pba2 respectively, so that this change is also of ferroelastic type. As presented here, crystallographic results hint at a displacive character of the ferroelectric ordering but show a more complex behaviour, with a clear order-disorder mechanism which accompanies the appearance of ferroelasticity. To complete our knowledge of this material, we have perf…
By analyzing the dielectric non-linearity with the Landau thermodynamic expansion, we find a simple and direct way to assess the importance of the eighth order term. Following this approach, it is demonstrated that the eighth order term is essential for the adequate description of the para/ferroelectric phase transition of BaTiO_3. The temperature dependence of the quartic coefficient βis accordingly reconsidered and is strongly evidenced by the change of its sign above 165 C. All these findings attest to the strong polarization anharmonicity of this material, which is unexpected for classical…
Sr_(9-x)PbxCe2Ti12O36 system is derived from the perovskite SrTiO3 and its chemical formula can be written as (Sr_(1-y)Pby)0.75Ce0.167TiO3. We investigated dielectric response of Sr_(9-x)PbxCe2Ti12O36 ceramics (x = 0-9) between 100 Hz and 100 THz at temperatures from 10 to 700 K using low- and high-frequency dielectric, microwave (MW), THz and infrared spectroscopy. We revealed that Sr9Ce2Ti12O36 is an incipient ferroelectric with the R-3c trigonal structure whose relative permittivity e' increases from 167 at 300 K and saturates near 240 below 30 K. The subsequent substitution of Sr by Pb enh…
Strontium titanate (SrTiO3) is regarded as an essential material for oxide electronics. One of its many remarkable features is subtle structural phase transition, driven by antiferrodistortive lattice mode, from a high-temperature cubic phase to a low-temperature tetragonal phase. Classical molecular dynamics (MD) simulation is an efficient technique to reveal atomistic features of phase transition, but its application is often limited by the accuracy of empirical interatomic potentials. Here, we develop an accurate deep potential (DP) model of SrTiO3 based on a machine learning method using d…
Dielectric and magnetic properties of Eu0.5Ba0.25Sr0.25TiO3 are investigated between 10 K and 300 K in the frequency range from 10 Hz to 100 THz. A peak in permittivity revealed near 130 K and observed ferroelectric hysteresis loops prove the ferroelectric order below thistemperature. The peak in permittivity is given mainly by softening of the lowest frequency polar phonon (soft mode revealed in THz and IR spectra) that demonstrates displacive character of the phase transition. Room-temperature X-ray diffraction analysis reveals cubic structure, but the IR reflectivity spectra give evidence o…
Dielectric response e*(f,T) and polar phonon spectra of coarse grain (grain size ~ 4 mkm) and fine grain (grain size ~ 150 nm) ceramics of PbMg_(1/3)Nb_(2/3)O3-35%PbTiO3 were investigated at temperatures 10 - 900 K. e*(f,T) in coarse-grain ceramics exhibits relaxor behavior at high temperatures and a sharp anomaly at the ferroelectric phase transition. The fine-grain ceramics exhibit mainly relaxor ferroelectric behavior with a smaller dielectric constant. The difference is explained by different relaxational dynamics of polar nanoclusters, which appear to be more stabilized at high temperatur…
