In this letter we obtain the finite-temperature structure of 180^o domain walls in PbTiO3 using a quasi-harmonic lattice dynamics approach. We obtain the temperature dependence of the atomic structure of domain walls from 0K up to room temperature. We also show that both Pb-centered and Ti-centered 180^o domain walls are thicker at room temperature; domain wall thickness at T=300K is about three times larger than that of T=0K. Our calculations show that Ti-centered domain walls have a lower free energy than Pb-centered domain walls and hence are more likely to be seen at finite temperatures.
We investigate oscillation dynamics of a periodic structure of the $180^\circ$ domain walls in nanometricaly thin substrate-deposited ferroelectric films and superlattices. We calculate dynamic permittivity of such structures and reveal a collective resonance mode, which in the typical ferroelectric compounds, PbTiO3/SrTiO3, lies in the sub- and low THz frequency range of 0.3-3THz. We propose the reflection-absorbtion spectroscopy experiments to observe this mode.
Deterministic polarization reversal in ferroelectric and multiferroic films is critical for their exploitation in nanoelectronic devices. While ferroelectricity has been studied for nearly a century, major discrepancies in the reported values of coercive fields and saturation polarization persist in literature for many materials. This raises questions about the atomic-scale mechanisms behind polarization reversal. Unconventional ferroelectric switching in $ε$-Fe2O3 films, a material that combines ferrimagnetism and ferroelectricity at room temperature, is reported here. High-resolution in-situ…
Flexoelectric effect is the coupling between strain, polarization and their gradients, which are prominent at the nanoscale. Although this effect is important to understand nanostructures, such as domain walls in ferroelectrics, its electronic mechanism is not clear. In this work, we combined phase-field simulations and first-principles calculations to study the 180° domain walls in tetragonal ferroelectric PbTiO3, and found that the ultimate source of Néel components is the gradient of the square of spontaneous polarizations. Electronic structural analysis reveals that there is a redistributi…
Ferroelectric domain walls are attracting broad attention as atomic-scale switches, diodes and mobile wires for next-generation nanoelectronics. Charged domain walls in improper ferroelectrics are particularly interesting as they offer multifunctional properties and an inherent stability not found in proper ferroelectrics. Here we study the energetics and structure of charged walls in improper ferroelectric YMnO$_3$, InMnO$_3$ and YGaO$_3$ by first principles calculations and phenomenological modeling. Positively and negatively charged walls are asymmetric in terms of local structure and width…
The conductive domain wall (CDW) is extensively investigated in ferroelectrics, which can be considered as a quasi-two-dimensional reconfigurable conducting channel embedded into an insulating material. Therefore, it is highly important for the application of ferroelectric nanoelectronics. Hitherto, most CDW investigations are restricted in oxides, and limited work has been reported in non-oxides to the contrary. Here, by successfully synthesizing the non-oxide ferroelectric Sn2P2S6 single crystal, we observed and confirmed the domain wall conductivity by using different scanning probe techniq…
Ferroelectric domain walls are boundaries between regions with different polarization orientations in a ferroelectric material. Using first principles calculations, we characterize all different types of domain walls forming on ($11\bar{1}$), ($111$) and ($1\bar{1}0$) crystallographic planes in thermoelectric GeTe. We find large structural distortions in the vicinity of most of these domain walls, which are driven by polarization variations. We show that such strong strain-order parameter coupling will considerably reduce the lattice thermal conductivity of GeTe samples containing domain walls…
The Interaction of an 180 degree Ferroelectric Domain Wall with a Biased Scanning Probe Microscopy Tip: Effective Wall Geometry and Thermodynamics in Ginzburg-Landau-Devonshire Theory
Domain walls are the topological defects that mediate polarization reversal in ferroelectrics, and they may exhibit quite different geometric and electronic structures compared to the bulk. Therefore, a detailed atomic-scale understanding of the static and dynamic properties of domain walls is of pressing interest. In this work, we use first-principles methods to study the structures of $180^{\circ}$ domain walls, both in their relaxed state and along the ferroelectric reversal pathway, in ferroelectrics belonging to the family of corundum derivatives. Our calculations predict their orientatio…
We report two series of structures representing two types of $180^\circ$ ferroelectric domain walls in $\mathrm{HfO_2}$ and $\mathrm{ZrO_2}$. We model the domain structures with different width by density functional theory calculations. The results reveal the dependency of domain wall energy and polarization on domain width. We show how the directions of polarization of ferroelectric domains can be determined from experimentally observed Hf atoms, despite the fact that the knowledge about the positions of O atoms is missing. The two series of structures thus provide more thorough interpretatio…
First-principles calculations for pristine neutral ferroelectric domain walls in BiFeO$_3$ reveal that excess electrons are selectively trapped by the domain walls, while holes are only weakly attracted. Such trapped excess electrons may be responsible for the thermally activated electrical conductivity at domain walls observed in experiments. In the case of a periodic array of domain walls, the trapped excess electrons create a zigzag potential, whose amplitude depends on the electron concentration in the material and the domain-wall distance. The potential is asymmetric for 71° and 109° doma…
Ferroelectrics usually adopt a multi-domain state with domain walls separating domains with polarization axes oriented differently. It has long been recognized that domain walls can dramatically impact the properties of ferroelectric materials. The enhancement of low-field susceptibility/permittivity under subswitching conditions is usually attributed to the reversible domain wall vibration. Recent experiments highlight the stationary domain wall contribution to the dielectric susceptibility irrespective of any lateral displacements or deformations of the wall. We study the effects of domain w…
Ferroelectric domain walls exhibit a range of interesting electrical properties and are now widely recognized as functional two-dimensional systems for the development of next-generation nanoelectronics. A major achievement in the field was the development of a fundamental framework that explains the emergence of enhanced electronic direct-current (DC) conduction at the domain walls. In this Review, we discuss the much less explored behavior of ferroelectric domain walls under applied alternating-current (AC) voltages. We provide an overview of the recent advances in the nanoscale characteriza…
Ferroelectric domain walls represent multifunctional 2D-elements with great potential for novel device paradigms at the nanoscale. Improper ferroelectrics display particularly promising types of domain walls, which, due to their unique robustness, are the ideal template for imposing specific electronic behavior. Chemical doping, for instance, induces p- or n-type characteristics and electric fields reversibly switch between resistive and conductive domain-wall states. Here, we demonstrate diode-like conversion of alternating-current (AC) into direct-current (DC) output based on neutral 180$^{\…
Modulating the polarization of a beam of quantum particles is a powerful method to tailor the macroscopic properties of the ensuing energy flux as it directly influences the way in which its quantum constituents interact with other particles, waves or continuum media. Practical polarizers, being well developed for electric and electromagnetic energy, have not been proposed to date for heat fluxes carried by phonons. Here we report on atomistic phonon transport calculations demonstrating that ferroelectric domain walls can operate as phonon polarizers when a heat flux pierces them. Our simulati…
The sensitivity of ferroelectric domain walls to external stimuli makes them functional entities in nanoelectronic devices. Specifically, optically driven domain reconfiguration with in-plane polarization is advantageous and thus highly sought. Here, we show the existence of in-plane polarized sub-domains imitating a single domain state and reversible optical control of its domain wall movement in a single-crystal of ferroelectric BaTiO3. Similar optical control in the domain configuration of non-polar ferroelastic material indicates long-range ferroelectric polarization is not essential for t…
We report a theoretical investigation of a charged 180$^\circ$ domain wall in ferroelectric PbTiO$_3$, compensated by randomly distributed immobile charge defects. For this we utilize atomistic shell-model simulations and continuous phase-field simulations in the framework of the Ginzburg-Landau-Devonshire model. We predict that domain walls form a zig-zag pattern and we discuss its properties in a broad interval of compensation-region widths, ranging from a couple to over a hundred nanometers.
Using Landau-Ginzburg-Devonshire approach, we predict the intrinsic instability of the ferroelectric-ferroelastic domain walls in the multiferroic BiFeO3 emerging from the interplay between the gradient terms of the antiferrodistortive and ferroelectric order parameters at the walls. These instabilities are the interface analogue of the structural instabilities in the vicinity of phase coexistence in the bulk; and so they do not steam from incomplete polarization screening in thin films or its spatial confinement, electrostrictive or flexoelectric coupling. The effect of BiFeO3 material parame…
Domains and domain walls are among the key factors that determine the performance of ferroelectric materials. In recent years, a unique type of domain walls, i.e., the sawtooth-shaped domain walls, has been observed in BiFeO$_{3}$ and PbTiO$_{3}$. Here, we build a minimal model to reveal the origin of these sawtooth-shaped domain walls. Incorporating this model into Monte-Carlo simulations shows that (i) the competition between the long-range Coulomb interaction (due to bound charges) and short-range interaction (due to opposite dipoles) is responsible for the formation of these peculiar domai…
The recently proposed dynamical multiferroic effect describes the generation of magnetization from temporally varying electric polarization. Here, we show that the effect can lead to a magnetic field at moving ferroelectric domain walls, where the rearrangement of ions corresponds to a rotation of ferroelectric polarization in time. We develop an expression for the dynamical magnetic field, and calculate the relevant parameters for the example of 90$^\circ$ and 180$^\circ$ domain walls in BaTiO$_3$ using a combination of density functional theory and phenomenological modeling. We find that the…
Hafnium dioxide (HfO2) is a promising ferroelectric (FE) material for achieving high-density nonvolatile memory and neuromorphic computing, due to its compatibility with the mainstream integrated circuit technology and the surprisingly enhanced ferroelectricity by reduced thickness. The FE switching dynamics is essential to the device performance, but the complexity of HfO2 atomic structure causes unknown of various FE switching paths and domain wall configurations. Here, we demonstrate that its low-barrier paths and domain walls can be comprehensively found and understood from a perspective o…
Domain Walls Stabilized by Intrinsic Phonon Modes and Engineered Defects Enable Robust Ferroelectricity in HfO2
School of Integrated Circuits, Peking University（北京大学集成电路学院）；Advanced Instrumental Analysis Center, School of Chemical Engineering and Technology, Tianjin University（天津大学化学工程与技术学院先进仪器分析中心）
Domain wall fluctuations in ferroelectrics coupled to strain
利用包含极化与应变耦合的Ginzburg-Landau-Devonshire模型，计算了铁电畴壁的涨落谱。由于180度和90度壁的应变分布不同，应变耦合的影响在这两种构造之间不同。声子的有限速度$v_s$延迟了应变对极化涨落的响应，结果依赖于$v_s$。对于$v_s \to \infty$，应变介导瞬时电致伸缩相互作用，这在90度壁的情况下是长程的。对于有限的$v_s$，声学声子阻尼壁激发，产生连续谱函数。作为$v_s\ to 0$，出现带隙模式，其对应于在固定应变势中振荡的极化。
Motion of ferroelectric domain walls greatly contributes to the macroscopic dielectric and piezoelectric response of ferroelectric materials. The domain wall motion through the ferroelectric material is however hindered by pinning on crystal defects which substantially reduces these contributions. Here, using thermodynamic models based on the Landau-Ginzburg-Devonshire theory, we find a relation between microscopic reversible motion of non-ferroelastic 180-degree domain walls interacting with a periodic array of pinning centers and the nonlinear macroscopic permittivity. We show, that the reve…
We report the nanoscale electrical imaging results in hexagonal $Lu_{0.6}Sc_{0.4}FeO_3$ single crystals using conductive atomic force microscopy (C-AFM) and scanning microwave impedance microscopy (MIM). While the dc and ac response of the ferroelectric domains can be explained by the surface band bending, the drastic enhancement of domain wall (DW) ac conductivity is clearly dominated by the dielectric loss due to DW vibration rather than mobile-carrier conduction. Our work provides a unified physical picture to describe the local conductivity of ferroelectric domains and domain walls, which …
The domain structure of uniaxial ferroelectric lithium niobate single crystals is investigated using Raman spectroscopy mapping. The influence of doping with magnesium and poling at room temperature is studied by analysing frequency shifts at domain walls and their variations with dopant concentration and annealing conditions. It is shown that defects are stabilized at domain walls and that changes in the defect structures with Mg concentration can be probed by the shift of Raman modes. We show that the signatures of polar defects in the bulk and at the domain walls differ.
