Ab initio study of shear strain effects on ferroelectricity at PbTiO3 thin films

Ferroelectric thin film with the perovskite ABO₃ structure have been widely used in technology applications, e.g., actuators in MEMS/NEMS and nonvolatile random access memories (FeRAM). In order to clarify the effect of the shear strain on the ferroelectricity, the PbTiO₃ thin film as a typical one is chosen. The focus of this study is to put on the PbO-terminated (1? × ?1) and c(2? × ?2) surfaces and the TiO₂-terminated (1? × ?1) surface. Based on ab initio density functional theory calculations with the local density approximation, we have found out that in both the PbO and TiO₂-terminated (1? × ?1) models, the ferroelectricity in the PbO layers was enhanced under the positive shear strain while it was suppressed under the negative one. For the TiO₂ layers, the ferroelectricity was slightly enhanced and sharply suppressed under the positive and negative shear strains, respectively. In the PbO-terminated (2? × ?2) model, the AFE phase was suppressed by the FE phase under the positive shear strain while the opposite trend was found under the negative shear strain. For the PbO layers, the ferroelectricity was enhanced under the positive and negative shear strains. For the TiO₂ layers, the influence of the negative shear strain on the ferroelectricity was larger than that of the positive one. In addition, the ideal strength of the PbTiO₃ thin film with the different terminations was investigated as well.     

Local suppression of ferroelectricity at PbTiO3 surface steps: a density functional theory study

Ab initio (first-principles) density functional theory (DFT) calculations are performed within the local density approximations (LDA) to investigate the ferroelectricity at PbTiO(3) surface steps consisting of (001) and (100) surfaces with a spontaneous polarization along [100]. For both the PbO- and TiO(2)-terminated surface steps, the [100] polarization is suppressed and the [001] polarization appears at their upper terraces, which results in a rotation of polarizations at the surface steps. The polarization rotation is induced by the local variation of the covalent Pb-O bond due to the charge redistribution at the surface steps. Furthermore, we investigate the interaction of the surface steps. Although surface steps with the same polarization configuration exhibit little interaction, steps of different types interact with each other strongly, suppressing the ferroelectricity, especially on the upper terrace.     

钛酸钡纳米颗粒铁电性临界尺寸的理论分析

从铁电体的Eular-Lagrange方程出发, 取贝塞尔方程级数解的形式, 得到了钛酸钡陶瓷颗粒的总极化强度表达式, 分析了各系数对总极化强度的影响. 根据总极化强度表达式, 采用MATLAB软件对尺寸在100 nm以下的钛酸钡纳米颗粒的铁电性进行了仿真分析. 结合实际数据探讨了尺寸效应对陶瓷颗粒铁电性的影响, 获得了与实验数据相符的数值解和极小值, 从而预测了钛酸钡纳米颗粒铁电性存在的临界尺寸为6 nm.     

Local ferroelectricity in SrTiO3 thin films

The temperature-dependent polarization of SrTiO3 thin films is investigated using confocal scanning optical microscopy. A homogeneous out-of-plane and an inhomogeneous in-plane ferroelectric phase are identified from images of the linear electro-optic response. Both hysteretic and nonhysteretic behavior are observed under a dc bias field. Unlike classical transitions in bulk ferroelectrics, local ferroelectricity is observed at temperatures far above the dielectric permittivity maximum. The results demonstrate the utility of local probe experiments in understanding inhomogeneous ferroelectrics.     

Incomplete ferroelectricity in SrTi 18O 3

Motivated by recent experiments demonstrating suppression of ferroelectricity with pressure in SrTi¹⁸O₃, the dynamics of the phase transition mechanism are reinvestigated within a nonlinear polarizability model. For temperatures far above the phase transition polar micro domains are formed which increase in size with decreasing temperature to freeze out at T_c without forming long range order. Experimentally, soft mode dynamics are simultaneously observed, evidencing that displacive and order/disorder features coexist. In the ferroelectric phase both components persist whereby an incomplete and inhomogeneous ferroelectric state is formed.     

Dynamical study of phonons in PbTiO3

Lattice dynamical formalism, using rigid ion model, was applied to the crystal of PbTiO₃ in the tetragonal phase. The model includes long range Coulomb forces and short range axially symectric forces. The radial part of the short range force constants was assumed to be of Born-Meyer type. The parameters of the model were determined through a least squares analysis of zone center and a few zone boundary phonons. Dispersion curves for [100] and [001] directions are presented.     

Defect-Dipole Formation in Copper-Doped PbTiO3 Ferroelectrics

The defect structure of hard copper-modified polycrystalline PbTiO3 ferroelectrics is investigated by means of electron paramagnetic resonance and hyperfine sublevel correlation spectroscopy, as well as density functional theory calculations. Special emphasis is put on the 207Pb-hyperfine couplings, which are resolved up to the third coordination sphere. The results prove that copper is incorporated at the octahedrally coordinated Ti site, acting as an acceptor. Because of charge compensation the formation of Cu impurity-oxygen vacancy pairs is energetically very favorable. The corresponding (CuTi'-VO)x defect dipole is found to be orientated along the [001] axis.     

Size effect in isometric PbTiO3 crystals

The phase transitions Pm3m⇄P4mm and domain-structure formation in 5–500 μm isometric PbTiO₃ crystals were investigated. The phase transition is characterized by a high rate and by the formation of a single flat interphase boundary {023}. A size effect was observed: In crystals smaller than a critical size (about 20 μm), formation of 90° domains stops and, in agreement with a phenomenological theory, the temperature hysteresis of the phase transition doubles. Fiz. Tverd. Tela (St. Petersburg) 40, 1546–1547 (August 1998)     

First principles study of improper ferroelectricity in TbMnO3

We carry out a first-principles theoretical study of the magnetically induced polarization in orthorhombic TbMnO3, a prototypical material in which a cycloidal-spin structure generates an electric polarization via the spin-orbit interaction. We compute both the electronic and the lattice-mediated contributions to the polarization and find that the latter is strongly dominant. We analyze the spin-orbit induced forces and lattice displacements from both atomic and mode-decomposition viewpoints, and show that a simple model based on nearest Mn-Mn neighbor Dzyaloshinskii-Moriya interactions is not able to account fully for the results. The direction and magnitude of our computed polarization are in good agreement with experiment.     

Toroidal dipole‐induced transparency in core–shell nanoparticles

The scattering of nanoparticles plays a profound role in the recently flourishing fields of plasmonics and metamaterials. However, current investigations into nanoparticle scattering are based on the electric and magnetic resonances only, where their toroidal counterparts are usually not considered. The inclusion of toroidal terms can render new explanations for some fundamental scattering properties and thus may stimulate further breakthroughs in both scattering‐related basic researches and applications. Here we revisit the most fundamental problem of Mie scattering by individual spherical nanoparticles and show that compared to conventional interpretations in terms of electric and magnetic responses, the roles played by their toroidal counterparts are indispensable. Based on the demonstration of efficient toroidal dipole excitation in homogeneous dielectric particles, we reveal that the extensively studied scattering transparencies of core–shell nanoparticles can actually be classified into two categories: (i) the trivial transparency with no effective multipole excitations and (ii) the non‐trivial transparency induced by the destructive interferences of excited electric and toroidal multipoles. The incorporation of toroidal multipoles offers new insights into the study of nanoparticle scattering in both near and far fields, which may shed new light on many applications, such as biosensing, imaging, nanoantennas, photovoltaic devices, and so on.

     

Magnetic inversion symmetry breaking and ferroelectricity in TbMnO3

TbMnO3 is an orthorhombic insulator where incommensurate spin order for temperature T(N)<41 K is accompanied by ferroelectric order for T<28 K. To understand this, we establish the magnetic structure above and below the ferroelectric transition using neutron diffraction. In the paraelectric phase, the spin structure is incommensurate and longitudinally modulated. In the ferroelectric phase, however, there is a transverse incommensurate spiral. We show that the spiral breaks spatial inversion symmetry and can account for magnetoelectricity in TbMnO3.     

Ferroelectricity and tetragonality in ultrathin PbTiO3 films

The evolution of tetragonality with thickness has been probed in epitaxial c-axis oriented PbTiO3 films with thicknesses ranging from 500 down to 24 A. High resolution x ray pointed out a systematic decrease of the c-axis lattice parameter with decreasing film thickness below 200 A. Using a first-principles model Hamiltonian approach, the decrease in tetragonality is related to a reduction of the polarization attributed to the presence of a residual unscreened depolarizing field. It is shown that films below 50 A display a significantly reduced polarization but still remain ferroelectric.     

Frustration of tilts and A-site driven ferroelectricity in KNbO3-LiNbO3 alloys

Density functional calculations for K(0.5)Li(0.5)NbO(3) show strong A-site driven ferroelectricity, even though the average tolerance factor is significantly smaller than unity and there is no stereochemically active A-site ion. This is due to the frustration of tilt instabilities by A-site disorder. There are very large off centerings of the Li ions, which contribute strongly to the anisotropy between the tetragonal and rhombohedral ferroelectric states, yielding a tetragonal ground state even without strain coupling.     

Stabilization of monodomain polarization in ultrathin PbTiO3 films

Using in situ high-resolution synchrotron x-ray scattering, the Curie temperature TC has been determined for ultrathin c-axis epitaxial PbTiO3 films on conducting substrates (SrRuO3 on SrTiO3), with surfaces exposed to a controlled vapor environment. The suppression of TC was relatively small, even for the thinnest film (1.2 nm). We observe that 180 degrees stripe domains do not form, indicating that the depolarizing field is compensated by free charge at both interfaces. This is confirmed by ab initio calculations that find polar ground states in the presence of ionic adsorbates.     

Dielectric characteristics of La-modified PbTiO3 nanoceramics

The nanoceramics of lanthanum (La³⁺)-modified lead titanate (PbTiO₃) with a general formula Pb_1?yLa_yTi_(1?y/4)O₃ (y = 0.00, 0.06, 0.08, 0.10, 0.12 Lead Lanthanum Titanate (PLT)) were synthesized by a mechanothermal method. Thermal analysis of the PLT samples exhibits their nature of the reaction and thermal stability. The incorporation of La at the Pb site of lead titanate (PT) not only changes the ratios of its unit cell parameters but also reduces the grain and particle size to nanoscale. The dielectric constant of PLT is dependent on La concentration. The La concentration-dependent phase transition temperature of PbTiO₃ is one of the main characteristics of the material.     

Summary data on ferroelectric PbTiO3 structure

The original data and the data available in literature on PbTiO₃ structure are considered and discussed. From the results of an X-ray diffraction study carried out at room temperature it is concluded that the displacive model is more relevant than the order-disorder one. At the same time it is stressed that the Debye-Waller factors of the atoms are very unusual in the region of the phase transition: B(Pb) > B(O) > B(Ti). This may be evidence of order—disorder phenomena taking place in this temperature region.     

Spin-canting-induced improper ferroelectricity and spontaneous magnetization reversal in SmFeO3

SmFeO3, a family of centrosymmetric rare-earth orthoferrites, is known to be nonferroelectric. However, we have found that SmFeO3 is surprisingly ferroelectric at room temperature with a small polarization along the b axis of Pbnm. First-principles calculations indicate that the canted antiferromagnetic ordering with two nonequivalent spin pairs is responsible for this extraordinary polarization and that the reverse Dzyaloshinskii-Moriya interaction dominates over the exchange-striction mechanism in the manifestation of the improper ferroelectricity. SmFeO3 further exhibits an interesting phenomenon of spontaneous magnetization reversal at cryogenic temperatures. This reversal is attributed to the activation of the Sm-spin moment which is antiparallel to the Fe-spin moment below ～5 K.     

PbTiO3/PbZr0.3Ti0.7O3/PbTiO3夹心结构铁电薄膜子晶层的优化

用Sol-Gel法制备了Pb(1 x)TiO3/PbZr0.3Ti0.7O3/Pb(1 x)TiO3(PT/PZT/PT)夹心结构及PZT铁电薄膜,为了获得高质量的PT/PZT/PT夹心结构铁电薄膜,使用不同过量Pb配比(x)的PbTiO3 (PT)层进行制备,以获得优化的PT子晶层.X射线衍射和原子力显微镜分析结果表明PT层中过量Pb配比(x)对薄膜的微结构影响很大,只有PT层中Pb过量配比x＝0.10-0.15的薄膜为表面晶粒大小均匀致密的纯钙钛矿结构.X射线电子能谱对薄膜微区进行元素成分分析表明,对x=0.00的薄膜,在表面和界面处Pb明显的缺乏;而x=0.20时的薄膜,Pb则明显的过量.薄膜的铁电性能、疲劳特性和漏电流特性等电学性能与PT层中过量Pb配比(x)没有明显的变化趋势,但与薄膜的结晶性能密切相关.结晶性能较好的薄膜,其电学性能也较好.说明PT层中过量Pb配比(x)是通过影响PT子晶层自身的结晶,而影响整个薄膜的结晶行为,并进一步影响到整个薄膜的电学性能.因此,在其他工艺参数都相同时,PT层中合适的过量Pb配比应为x=0.10-0.15.优化的子晶层不仅能获得结晶性能较好的薄膜,而且薄膜的电学性能也好.     

Room temperature ferroelectricity in multiferroic HoMnO3 ceramics

We have observed good ferroelectric loops at room temperature in hexagonal HoMnO₃ (HMO) bulk ceramics sintered at 1250 °C. Microstructure and ferroelectric hysteresis loops are observed to be dependent on sintering temperature. It is observed that with an increase of sintering temperature, hexagonal a-axis is compressed and c-axis is marginally dilated with overall contraction of the hexagonal unit-cell volume. We explain the origin of ferroelectricity through relative movement of Ho ion and Mn ion within its unit-cell volume, resulting in the distortion of unit-cell volume. We argue that ferroelectric origin of hexagonal HMO at room temperature may be due to the marginal displacement of Ho ion along a-axis, that influences the exchange interaction among the Mn³⁺ and Ho³⁺ ions, causing magnetically induced ferroelectricity at room temperature.