Ab initio studies of dielectric,piezoelectric, and elastic properties of BaTiO 3 /SrTiO 3 ferroelectric superlattices

The phonon spectrum; crystal structure of the polar phase; spontaneous polarization; dielectric constant, piezoelectric, and elastic moduli tensors for free_standing and substrate_supported superlattices mBaTiO₃/nSrTiO₃ (with m = n = 1–4) were calculated within the density functional theory. The simulation of properties of the disordered Ba_0.5Sr_0.5TiO₃ solid solution using two special quasirandom SQS-4 structures and their comparison with the properties of the superlattices revealed a tendency of the BaTiO₃-SrTiO₃ system to superstructure ordering and showed that the superlattices are thermodynamically quite stable. The ground state of the free-standing superlattice corresponds to the monoclinic polar phase Cm, which transforms to the tetragonal polar phase P4mm under in-plane compressive strain of the superlattice and to the orthorhombic polar phase Amm2 under in-plane tensile strain. With a change in the in-plane lattice parameter, in the vicinity of boundaries between neighboring polar phases, some optical and acoustic modes soften and some components of the static dielectric constant, piezoelectric, and elastic moduli tensors diverge critically.     

四方相BaTiO3铁电性的第一性原理研究

在广义梯度近似下,利用超软赝势对立方相和四方相BaTiO3晶胞中Ti原子沿c轴位移时体系的能量、原子间电子云重叠布局数和各原子上的净电荷等进行了自洽计算.结果显示,当Ti原子沿c轴位移0.012nm时,四方相BaTiO3体系能量最低,其自发极化强度为0.261C/m2,该结果与实验数据相符合;同时表明,O原子的2p轨道和Ti原子的3d轨道的杂化是BaTiO3晶体出现铁电性的重要原因.     

Size effect on SrRuO3/BaTiO3/SrRuO3 ferroelectric ultrathin film capacitor

We have carried out a detailed investigation on the size effect on SrRuO₃/BaTiO₃/SrRuO₃ ferroelectric ultrathin film capacitors with film thickness fully strained with a SrTiO₃ substrate. We employ the transverse field Ising model, taking into account the incomplete charge compensation of the realistic SrRuO₃ electrode and the misfit strain imposed by the SrTiO₃ substrate in the Hamiltonian, to quantitatively explain the experimental observation in the literature. It is found that BaTiO₃ ultrathin films between two metallic electrodes lose their ferroelectric properties below a critical thickness of about 4.17 nm due to the enhancement of the quantum effect under the influence of the incomplete charge compensation of the electrode.     

Nanosecond dynamics of ferroelectric/dielectric superlattices

The nanosecond response of a PbTiO(3)/SrTiO(3) ferroelectric/dielectric superlattice to applied electric fields is closely linked to the dynamics of striped domains of the remnant polarization. The intensity of domain satellite reflections observed with time-resolved x-ray microdiffraction decays in 5-100 ns depending on the magnitude of the electric field. The piezoelectric response of the superlattice within stripe domains is strongly suppressed due to electromechanical clamping between adjacent regions of opposite polarization. Regions of the superlattice that have been switched into a uniform polarization state by the applied electric field, however, exhibit piezoelectricity during the course of the switching process. We propose a switching model different from previous models of the switching of superlattices, based instead on a spatially heterogeneous transformation between striped and uniform polarization states.     

Unusual behavior of the ferroelectric polarization in PbTiO3/SrTiO3 superlattices

Artificial PbTiO3/SrTiO3 superlattices were constructed using off-axis rf magnetron sputtering. X-ray diffraction and piezoelectric atomic force microscopy were used to study the evolution of the ferroelectric polarization as the ratio of PbTiO3 to SrTiO3 was changed. For PbTiO3 layer thicknesses larger than the 3-unit cell SrTiO3 thickness used in the structure, the polarization is found to be reduced as the thickness is decreased. This observation confirms the primary role of the depolarization field in the polarization reduction in thin films. For the samples with ratios of PbTiO3 to SrTiO3 of less than one, a surprising recovery of ferroelectricity that cannot be explained by electrostatic considerations was observed.     

Photorefractive detection of antiparallel ferroelectric domains in BaTiO3 and BaTiO3:Co crystals

3 ). Rod-shaped domains with square cross sections are revealed. Received: 11 July 1997/Accepted: 19 November 1997     

Effect of domain wall on the dielectric properties of the BaTiO3/SrTiO3 superlattices

Based on a phenomenological thermodynamical theory, the effect of the domain wall on the dielectric properties of the polydomain BaTiO₃/SrTiO₃ superlattices with 180° electric domains in the BaTiO₃ layer is investigated. Theoretical analysis indicates that complete polarization suppression and the largest dielectric response take place at approximately 72% and 53% of the critical volume fraction of the SrTiO₃ layer for the domain wall energy parameter A=3×10⁷ and 5×10⁷, respectively. The dielectric properties largely depend on both the volume fraction of the SrTiO₃ layer and the domain wall energy parameter. Moreover, the gigantic dielectric response which occurs in single-domain BaTiO₃/SrTiO₃ superlattices cannot appear due to the 180° polydomain state in the BaTiO₃ layer, which is in agreement with the previous prediction. The high domain wall energy parameter results in the stabilization of the paraelectric state in the BaTiO₃ layer, however, the enhancement of the domain wall energy parameter within a certain scale increases the dielectric properties greatly.     

Domain-enhanced interlayer coupling in ferroelectric/paraelectric superlattices

We investigate the ferroelectric phase transition and domain formation in a periodic superlattice consisting of alternate ferroelectric (FE) and paraelectric (PE) layers of nanometric thickness. We find that the polarization domains formed in the different FE layers can interact with each other via the PE layers. By coupling the electrostatic equations with those obtained by minimizing the Ginzburg-Landau functional, we calculate the critical temperature of transition Tc as a function of the FE/PE superlattice wavelength Lambda and quantitatively explain the recent experimental observation of a thickness dependence of the ferroelectric transition temperature in KTaO3/KNbO3 strained-layer superlattices.     

Low frequency electroluminescence in ferroelectric BaTiO3 single crystals

Electroluminescence has been studied in ferroelectric BaTiO₃ single crystals. The variation of EL with potential temperature and d.c. biasing suggests the existence of complex surface charge layer on the surface of these crystals. The mode of growth of EL pulses reveals the nature of these layers.     

Predicted magnetoelectric effect in Fe/BaTiO3 multilayers: ferroelectric control of magnetism

An unexplored physical mechanism which produces a magnetoelectric effect in ferroelectric-ferromagnetic multilayers is studied based on first-principles calculations. Its origin is a change in bonding at the ferroelectric-ferromagnet interface that alters the interface magnetization when the electric polarization reverses. Using Fe/BaTiO3 multilayers as a representative model, we show a sizable difference in magnetic moments of Fe and Ti atoms at the two interfaces dissimilar by the orientation of the local electric dipole moments. The predicted magnetoelectric effect opens a new direction to control magnetic properties of thin-film layered structures by electric fields.     

Stress-induced phase transition in ferroelectric domain walls of BaTiO3

The seminal paper by Zhirnov (1958 Zh. Eksp. Teor. Fiz. 35 1175-80) explained why the structure of domain walls in ferroelectrics and ferromagnets is drastically different. Here we show that the antiparallel ferroelectric walls in rhombohedral ferroelectric BaTiO(3) can be switched between the Ising-like state (typical for ferroelectrics) and a Bloch-like state (unusual for ferroelectric walls but typical for magnetic ones). Phase-field simulations using a Ginzburg-Landau-Devonshire model suggest that this symmetry-breaking transition can be induced by a compressive epitaxial stress. The strain-tunable chiral properties of these domain walls promise a range of novel phenomena in epitaxial ferroelectric thin films.     

Dielectric and ferroelectric properties of pulsed-laser deposited BaTiO3 films

3 films were produced by KrF excimer-laser ablation. Films deposited on fused silica substrates were polycrystalline without preferential orientation and had cubic rather than tetragonal structure. BaTiO₃/Au/Ti/fused silica films showed a large dielectric constant, which increased with the thickness of the film, but poor ferroelectric properties. This behavior seems to be related to the small size of grains. On (100)MgO substrates oriented films were obtained. BaTiO₃/YBa₂Cu₃O_7-δ/(100)MgO films showed a large dielectric constant also and improved ferroelectric properties. Although this indicates a larger degree of tetragonality, the tetragonal structure of single crystal BaTiO₃ has not yet developed. Localized reduction and metallization of BaTiO₃/(100)MgO films by means of Ar⁺-laser radiation was demonstrated. This technique allows to produce conducting patterns in a single-s tep process. Received: 6 January 1997/Accepted: 21 April 1997     

Singularities of ferroelectric properties of BaTiO3 crystals obtained with different crystallization rates

Ferroelectric properties are investigated of BaTiO₃ particles as a function of their growth rates. This latter was given as the rate of reduction of the temperature = dT/dt of the mother solution BaTiO₃-KF and varied between the limits 3.6–43 K/h. It is established that as a grows the reversible macroscopic polarization P_m diminishes according to the law , where P_m0 = 22·10^–2 C/m² and k = 6·10^–2 h/K. The coercive force E_c increases here while the domain contribution to measured in weak fields diminishes. It is shown that diminution of the growth rate results in improvement of the reverse polarization characteristics of BaTiO₃ crystals, a rise in the efficiency of their mono-domainization that would permit utilization of crystals obtained for = 3.6 K/h for optical purposes.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 76–78, November, 1990.     

Anti-parallel ferroelectric domains in surface space-charge layers of BaTiO3

It is shown on simplified models of a surface space-charge layer of a single crystal of BaTiO ₃ that in the surface region, in which the direction of the electric field is opposite to the direction of spontaneous polarization inside the crystal, anti-parallel domains can exist. The dimensions of these domains are determined. The use of the results obtained is proposed for interpreting the microrelief of the etch figures and for explaining the different phases of the polarization reversal process of a single-domain single crystal of BaTiO ₃.

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BatiO₃

BaTiO₃ , , , . . BaTiO₃.

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The author would like to thank J. Kaczer, Z. Málek and V. Dvoák of the Institute of Physics, Czechoslovak Academy of Sciences, for valuable remarks on this paper and H. Havlíková for carefully carrying out the numerical calculations.     

Enhancement of dielectric and ferroelectric properties in ferroelectric superlattices

I studied theoretically the enhancement of remanent polarization and dielectric permittivity of interfacial-coupled ferroelectric superlattices based on the Landau–Ginzburg theory. Our model adopts the Landau–Khalatnikov equation to describe hysteresis behavior and takes the time-dependent space-charge-limited conductivity into account to investigate the ferroelectric and dielectric properties of ferroelectric superlattices. The results are in good agreement with recent experimental observations on the enhancement of remanent polarization and permittivity of BaTiO₃/SrTiO₃ superlattices and heterolayered Pb(Zr,Ti)O₃ thin films.     

Raman spectroscopy of BaTiO3/(Ba,Sr)TiO3 superlattices

A series of BaTiO₃/Ba_{1 ? x} Sr _x TiO₃ (BT/BST) superlattices were prepared by pulsed laser deposition on MgO substrates with a constant period of 80 Å (40 Å BT and 40 Å BST) and varying compositions of the BST layer so that the Ba/Sr concentration ratios were 0/100, 30/70, 40/60, 50/50, 60/40, 70/30, 100/0. The soft mode E(1TO) of the polarized Raman spectra transformed depending on the Ba/Sr ratio in the BST layer. As the Sr concentration in the BST layers increased from 0 to 100%, the E(1TO) soft mode half-width varied from 171 to 103 cm^?1 and its frequency increased from 31 to 109 cm^?1 due to the interaction between the epitaxial layers forming the superlattices.     

In-plane and out-of-plane ferroelectric instabilities in epitaxial SrTiO3 films

The in-plane and out-of-plane ferroelectric instabilities in compressed (100)-epitaxial SrTiO3 films were examined by infrared reflection spectroscopy. The strongly stiffened in-plane soft mode frequency softened very slowly on cooling. On the other hand, the silent mode appeared at around 150 K, indicating an out-of-plane ferroelectric transition. This behavior points to a split of in-plane and out-of-plane ferroelectric instability temperatures due to the lowered symmetry of the SrTiO3 lattice caused by mechanical misfit strain. Infrared spectroscopy provides a possibility to detect such an effect in the strained epitaxial ferroelectric films.