Order-disorder component in the phase transition mechanism of 18O enriched strontium titanate

Ti and Sr nuclear magnetic resonance spectra of 18O enriched SrTiO3 (STO-18) provide direct evidence for Ti disorder already in the cubic phase and show that the ferroelectric transition at T(C)=24 K occurs in two steps. Below 70 K rhombohedral polar clusters are formed in the tetragonal matrix. These clusters subsequently grow in concentration, freeze out, and percolate, leading to an inhomogeneous ferroelectric state below T(C). This shows that the elusive ferroelectric transition in STO-18 is indeed connected with local symmetry lowering and implies the existence of an order-disorder component in addition to the displacive soft mode one. Rhombohedral clusters, Ti disorder, and a two-component state are found in the so-called quantum paraelectric state of STO-16 as well. The concentration of the rhombohedral clusters is, however, not high enough to allow for percolation.     

NMR evidence for the coexistence of order-disorder and displacive components in barium titanate

A quadrupole coupling induced 47Ti and 49Ti satellite background which transforms into well-defined satellite lines below T(c) in the ferroelectric phase has been observed in the cubic phase of an ultrapure BaTiO3 single crystal. The results demonstrate the coexistence of a displacive and order-disorder component in the phase transition mechanism and tetragonal breaking of the cubic symmetry due to biased Ti motion between off-center sites in the paraelectric phase above T(c).     

(1-x)PMN-xPT铁电致冷陶瓷的研究

概括介绍了铁电致冷基本原理，给出了三种电生热效应，即线性电生热效应、二次电生热效应和电场诱导一级相变型电生热效应的表达式，测量了(1-x)Pb(Mg_1/3 Nb_2/3 )O₃-xPbTiO₃［简记为(1-x)PMN-xPT］，当x=0.08, 0.10和0.25时在室温附近的电生热性能，分析了其电生热效应的起源.研究结果表明，(1-x)PMN-xPT铁电固溶体陶瓷在室温附近具有较大的电生热效应；该效应起源于电场诱导一级相变型电生热效应和线性电生热效应；该系列陶瓷可望用于室温附近多级铁电致冷. 关键词：     

Phase transition at a nanometer scale detected by acoustic emission within the cubic phase Pb(Zn1/3Nb2/3)O3-xPbTiO3 relaxor ferroelectrics

Pb(Zn(1/3)Nb(2/3))O3-xPbTiO(3) (x=4.5%-12%) relaxor ferroelectric crystals have been studied by means of acoustic emission (AE) in the 400-540 K temperature range. An anomalous AE activity independent of the ground state relaxor/morphotropic/ferroelectric crossover has been revealed at around 500 K, and it is associated with the "waterfall" feature related to the existence of polar nanoregions (PNRs). The 500 K AE anomaly is attributed to local martensitelike cubic-to-tetragonal ferroelectric transitions within the PNRs imbedded in a nonpolar (cubic) matrix.     

Synthesis and Raman investigation of sol–gel‐derived relaxor ferroelectric thin films

Pb(Fe_2/3W_1/3)O₃ (PFW) thin films were deposited on platinized silicon substrate by a chemical solution deposition technique. Room‐temperature X‐ray diffraction (XRD) revealed a pure cubic crystal structure of the investigated material. The microstructure indicated good homogeneity and density of the thin films. A Raman spectroscopic study was carried out on PFW to study the polar nano‐regions in the temperature range 85–300 K. The Raman spectra showed a change in the peak intensity and a shift towards the lower wavenumber side with temperature. The Raman spectra also revealed the transition from the relaxor to the paraelectric state of PFW. There was no evidence of a soft mode in the low‐temperature region, in contrast to the normal ferroelectric behavior. The polar nano‐regions tend to grow and join at low temperatures (∼85 K), which become smaller with increase in temperature. The presence of strong Raman spectra in the cubic phase of the material is due to the presence of distributed Fm3m(Z = 2) symmetry nano‐ordered regions in the Pm3m(Z = 1) cubic phase. Copyright © 2007 John Wiley & Sons, Ltd.     

Finite-temperature properties of multiferroic BiFeO3

An effective Hamiltonian scheme is developed to study finite-temperature properties of multiferroic BiFeO3. This approach reproduces very well (i) the symmetry of the ground state, (ii) the Néel and Curie temperatures, and (iii) the intrinsic magnetoelectric coefficients (that are very weak). This scheme also predicts (a) an overlooked phase above Tc approximately 1100 K that is associated with antiferrodistortive motions, as consistent with our additional x-ray diffractions, (b) improperlike dielectric features above Tc, and (c) that the ferroelectric transition is of first order with no group-subgroup relation between the paraelectric and polar phases.     

Pb(Zr_(0.4)Ti_(0.6))O_3电子结构的第一性原理研究

采用基于密度泛函理论的赝势平面波方法计算了Pb(Zr0.4Ti0.6)O3五层超晶胞的顺电相和铁电相的电子结构.由态密度、电子密度和能带结构的计算结果发现顺电相下钛氧八面体Ti-O6和锆氧八面体Zr-O6在铁电相中分裂为由1个O1离子和4个O2离子组成的金字塔结构Ti-O5和Zr-O5;与顺电相相比,铁电相中钛离子的3d电子和氧离子的2p电子存在更强的轨道杂化,这种杂化降低了离子间的短程排斥力,使得具有铁电性的四方结构更为稳定,而且钛离子与氧离子的相互作用对于铁电相Pb(Zr0.4Ti0.6)O3沿c轴自发极化的贡献大于锆离子与氧离子的相互作用;由电子密度的分布可推断立方结构的Pb-O键呈现离子键特征,而铁电相下Pb-O键则有较大的共价成分,铅离子与氧离子的这种轨道杂化对Pb(Zr0.4Ti0.6)O3的铁电性起重要作用.所得结果对深入理解Pb(Zr0.4Ti0.6)O3铁电性的微观机理具有参考价值.     

Critical and multicritical behavior in the Ising–Heisenberg universality class

Critical behavior of three-dimensional classical frustrated antiferromagnets with a collinear spin ordering and with an additional twofold degeneracy of the ground state is studied. We consider two lattice models, whose continuous limit describes a single phase transition with a symmetry class differing from the class of non-frustrated magnets as well as from the classes of magnets with non-collinear spin ordering. A symmetry breaking is described by a pair of independent order parameters, which are similar to order parameters of the Ising and O(N) models correspondingly. Using the renormalization group method, it is shown that a transition is of first order for non-Ising spins. For Ising spins, a second order phase transition from the universality class of the O(2) model may be observed. The lattice models are considered by Monte Carlo simulations based on the Wang–Landau algorithm. The models are a ferromagnet on a body-centered cubic lattice with the additional antiferromagnetic exchange interaction between next-nearest-neighbor spins and an antiferromagnet on a simple cubic lattice with the additional interaction in layers. We consider the cases N = 1, 2, 3 and in all of them find a first-order transition. For the N = 1 case we exclude possibilities of the second order or pseudo-first order of a transition. An almost second order transition for large N is also discussed.     

Observation of Ferroelastic and Ferroelectric Domains in AgNbO_3 Single Crystal

Compared to AgNbO_3 based ceramics, the experimental investigations on the single crystalline AgNbO_3, especially the ground state and ferroic domain structures, are not on the same level. Here, based on successfully synthesized AgNbO_3 single crystal using a flux method, we observed the coexistence of ferroelastic and ferroelectric domain structures by a combination study of polarized light microscopy and piezoresponse force microscopy.This finding may provide a new aspect for studying AgNbO_3. The result also suggests a weak electromechanical response from the ferroelectric phase of AgNbO_3, which is also supported by the transmission electron microscope characterization. Our results reveal that the AgNbO_3 single crystal is in a polar ferroelectric phase at room temperature, clarifying its ground state which is controversial from the AgNbO_3 ceramic materials.     

Raman spectra of cadmium titanate

Polarized Raman spectra of CdTiO₃ single crystals are recorded for the first time over the frequency range 5 < ν < 1000 cm^?1 at temperatures of 10 to 1200 K. The emphasis was on the low-frequency range, where an anomalous temperature dependence of a few phonon modes was observed. At high temperatures, four phonon modes exhibiting a behavior typical of soft modes were found to exist. These phonon modes are assumed to restore the cubic symmetry of the lattice. Their extrapolated temperature dependences suggest that there exists a sequence of three hypothetical high-temperature phase transitions analogous to those observed in the genuine perovskite CaTiO₃. At temperatures below 78 K, the Raman spectrum exhibits new lines associated with polar distortions of the unit cell. At low frequencies, three lines are observed whose parameters exhibit an anomalous behavior typical of soft modes in a ferroelectric phase. Several different polar states are assumed to exist at low temperatures.     

Selected growth of cubic and hexagonal GaN epitaxial films on polar MgO(111)

Selected molecular beam epitaxy of zinc blende (111) or wurtzite (0001) GaN films on polar MgO(111) is achieved depending on whether N or Ga is deposited first. The cubic stacking is enabled by nitrogen-induced polar surface stabilization, which yields a metallic MgO(111)-(1 x 1)-ON surface. High-resolution transmission electron microscopy and density functional theory studies indicate that the atomically abrupt semiconducting GaN(111)/MgO(111) interface has a Mg-O-N-Ga stacking, where the N atom is bonded to O at a top site. This specific atomic arrangement at the interface allows the cubic stacking to more effectively screen the substrate and film electric dipole moment than the hexagonal stacking, thus stabilizing the zinc blende phase even though the wurtzite phase is the ground state in the bulk.     

Perfect softening of the ferroelectric mode in the isotope-exchanged strontium titanate of SrTi18O3 studied by light scattering

The mode of the isotope-induced ferroelectric strontium titanate shows a perfect softening at the ferroelectric phase transition temperature , where the frequency of the underdamped mode approaches completely to zero within the instrumental resolution. The spectra of the Raman inactive soft mode have been successfully observed owing to local symmetry breaking and by long-term accumulation of the spectral intensity with a high resolution technique. The mechanism of the phase transition is concluded to be an ideal displacive-type accompanied with perfect softening of the Slater-type polar mode. The difference between the soft mode behavior of and indicates that the origin of the quantum paraelectric state of lies in the quantum fluctuation of the oxide octahedron in the perovskite structure.     

Ferroelectricity, nonlinear dynamics, and relaxation effects in monoclinic Sn2P2S6

An ab initio-based model of the temperature-induced ferroelectric phase transition in Sn2P2S6 (SPS) as a prototype of an unconventional ferroelectric is developed. The order parameter in SPS is found as the valley line on a total-energy surface of the zone-center fully symmetrical Ag and polar Bu distortions. Significant nonlinear coupling between order parameter and strain is observed. Monte Carlo simulations describe the additional low-temperature rearrangement in polar structure, which appears in domain boundaries, and describe the relaxation phenomena near the ferroelectric phase transition.     

Absence of relaxor-like ferroelectric phase transition in (Pb,Sr)TiO3 thin films

We have performed dielectric and micro-Raman spectroscopy measurements in the 298–673 K temperature range in polycrystalline Pb_0.50Sr_0.50TiO₃ thin films prepared by a soft chemical method. The phase transition have been investigated by dielectric measurements at various frequencies during the heating cycle. It was found that the temperature corresponding to the peak value of the dielectric constant is frequency-independent, indicating a non-relaxor ferroelectric behavior. However, the dielectric constant versus temperature curves associated with the ferroelectric to paraelectric phase transition showed a broad maximum peak at around 433 K. The observed behavior is explained in terms of a diffuse phase transition. The obtained Raman spectra indicate the presence of a local symmetry disorder, due to a higher strontium concentration in the host lattice. The monitoring of some modes, conducted in the Pb_0.50Sr_0.50TiO₃ thin films, showed that the ferroelectric tetragonal phase undergoes a transition to the paraelectric cubic phase at around 423 K. However, the Raman activity did not disappear, as would be expected from a transition to the cubic paraelectric phase. The strong Raman spectrum observed for this cubic phase is indicative that a diffuse-type phase transition is taking place. This behavior is attributed to distortions of the perovskite structure, allowing the persistence of low-symmetry phase features in cubic phase high above the transition temperature. This result is in contrast to the forbidden first-order Raman spectrum, which would be expected from a cubic paraelectric phase, such as the one observed at high temperature in pure PbTiO₃ perovskite. PACS 78.30.-j; 77.80.Bh; 64.70.Kb; 68.55.-a; 77.22.-a; 77.55.+f     

Layered perovskites with giant spontaneous polarizations for nonvolatile memories

A series of titanate-based layered perovskites having large values of the spontaneous polarization P(s) were developed for their applcations to nonvolatile ferroelectric random access memories. Among these, the Nd-modified bismuth titanate [Bi(4-x)Nd(x)Ti(3)O(12) (BNdT)] system exhibited the most remarkable ferroelectric properties. The c-axis oriented BNdT capacitor was characterized by a switchable remanent polarization 2P(r) of over 100 microC/cm(2) and imprinting and fatigue-free behavior. The active Ti site responsible for the giant P(s) was identified with the help of Rietveld analysis, x-ray absorption near-edge structure study, and ab initio quantum computations.     

In situ X-ray diffraction studies of phase transition in Pb1− x La x Zr0.40Ti0.60O3 ferroelectric ceramics

The temperature dependence of the crystalline structure and the lattice parameters of Pb_{1? x} La _x Zr_0.40Ti_0.60O₃ ferroelectric ceramic system with 0.00 ≤ x ≤ 0.21 was determined. The samples with x ≤ 0.11 show a cubic-to-tetragonal phase transition at the maximum dielectric permittivity, T _max. Above this amount and especially for the x = 0.12 sample, a spontaneous phase transition from a relaxor ferroelectric state (cubic phase) to a ferroelectric state (tetragonal phase) is observed upon cooling below the T _max. Unlike what has been reported in other studies, the x = 0.13, 0.14, and 0.15 samples, which present a more pronounced relaxor behavior, also presents a spontaneous normal-to-relaxor transition, indicated by a cubic to tetragonal symmetry below the T _max. The origin of this anomaly has been associated with an increase in the degree of tetragonality, confirmed by the measurements of the X-ray diffraction patterns. The differential thermal analysis (DSC) measurements also confirm the existence of these phase transitions.     

Phase diagram of pb(Zr,Ti)O3 solid solutions from first principles

A first-principles-derived scheme that incorporates ferroelectric and antiferrodistortive degrees of freedom is developed to study finite-temperature properties of Pb(Zr1-xTix)O3 solid solution near its morphotropic phase boundary. The use of this numerical technique (i) resolves controversies about the monoclinic ground state for some Ti compositions, (ii) leads to the discovery of an overlooked phase, and (iii) yields three multiphase points that are each associated with four phases. Additional neutron diffraction measurements strongly support some of these predictions.     

Pb(Zr,Sn,Ti)O3反铁电陶瓷的低温相变扩散与极化弛豫

用弱场介电温谱、热释电流谱、强场电滞回线和变温X射线衍射谱研究了微量La掺杂Pb(Zr,Sn,Ti)O₃(PZST)反铁电(AFEt)陶瓷在-100—180℃温区内的结构与电学特性.弱场介电温谱显示,AFEt陶瓷在低温段(-100—50℃)呈现介电频率弥散(0.1—100kHz)和扩散型相变的特征,而变温X射线衍射谱却表明材料在这一温区内保持四方相结构;低温下经强场作用后,AFEt被诱导为亚稳三方铁电态,介电频率弥散消失.基于多元复杂化合物的组分起伏理论,讨论了PZST AFEt陶瓷 关键词： Pb(Zr Sn 3反铁电陶瓷')" href="#">Ti)O₃反铁电陶瓷 反铁电弛豫 相变 变温X射线衍射     

Anomalous Optical and Electronic Properties of CaTiO3 Perovskites

With the help of the first-principles full potential linearized augmented plane wave method, absorption coefficients, reflectivity, dielectric behavior and electronic properties, including electronic energy bands, density of states and charge density distributions, are studied for the tetragonal and cubic CaTiO3. By considering the thermal expansion effects, an approximate method is proposed for the study of the stability of ground state and a tendency of phase transition, based on the minimum free energy principle. Subsequently, numerical calculations are carried out by using the first-principles perturbation method. We demonstrate that the high-temperature phase is cubic. It is shown that optical spectra in tetragonal phase exhibit single-peak feature and differ from multi-peak character in cubic. We find that strong orbital hybridization results in the co-valent bonds between Ti 3d and O 2p electrons and forms two-type dipoles (Ti-O1 and Ti-O2) in tetragonal, while the Ti-O dipoles are identical in cubic. It is argued that crystal structure determines the dipole distributions and leads to some electron states among which the dipole-dipole transition forbidden is a key, causing such anomalous optical phenomena with the insulator characteristics. The predicted charge density distribution and the tendency of phase transition from tetragonal to cubic are in good agreement with experimental observations.     

Anomalous Optical and Electronic Properties of CaTiO3 Perovskites

With the help of the first-prlnciples full potential linearized augmented plane wave method, absorption coefficients, reflect/vity, dielectric behavior and electronic properties, including electronic energy bands, density of states and charge density distributions, are studied for the tetragonal and cubic CaTiO3. By considering the thermal expansion effects, an approximate method is proposed for the study of the stability of ground state and a tendency of phase transition, based on the minimum free energy principle. Subsequently, numerical calculations are carried out by using the first-principles perturbation method. We demonstrate that the high-temperature phase is cubic. It is shown that optical spectra in tetragonal phase exhibit single-peak feature and differ from multi-peak character in cubic. We find that strong orbital hybridization results in the co-valent bonds between Ti 3d and O 2p electrons and forms two-type dipoles （Ti-Ol and Ti-02） in tetragonal, while the Ti-O dipoles are identical in cubic. It is argued that crystal structure determines the dipole distributions and leads to some electron states among which the dipole-dipole transit/on forbidden is a key, causing such anomalous optical phenomena with the insulator characteristics. The predicted charge density distribution and the tendency of phase transition from tetragonal to cubic are in good agreement with experimental observations.