Temperature‐dependent,micro‐Raman spectroscopic study of barium titanate nanoparticles

A comparative, temperature‐dependent (80–500 K at 5 K intervals), micro‐Raman spectroscopic study of 300 and 50 nm diameter ceramic BaTiO₃ nanoparticles was carried out with the purpose of elucidating the nanoparticle size effect on the temperature dependence of the polar and non‐polar phonons. A method for calibrating Raman intensities, along with an iterative spectral fitting algorithm, is proposed for concurrent Raman band position and intensity analysis, increasing the analytical abilities of single temperature point Raman spectroscopy. The 300 nm particles exhibit all three phase transitions, whereas the 50 nm particles do not show evidence of these phase transitions in the same temperature range. The Curie temperature appears to be a phonon converging point, irrespective of the phonon symmetry. An attempt was made to qualitatively relate the temperature‐dependent Raman spectra to complimentary non‐spectroscopic methods, such as heat capacity and X‐ray diffraction studies. The study proves that the temperature‐dependent behavior of the polar phonon, 265 cm⁻¹, can be utilized as a sensitive phase transition probe. Copyright © 2014 John Wiley & Sons, Ltd.     

First-principle study of strain-driven phase transition in incipient ferroelectric SrTiO3

First-principle calculations were carried out to investigate the epitaxial strain dependence of the structural stability and related properties of SrTiO₃. The P4mm-to-P4/mmm-to-Amm2 phase transitions in SrTiO₃ with the epitaxial strain changing from compressive to expansive have been identified by analysis of the soft-mode eigendisplacement. The zero-temperature critical strains for the P4mm-to-P4/mmm and P4/mmm-to-Amm2 phase transitions are −0.72% and 0.83%, respectively, which is consistent with the previous predictions based on the phenomenological thermodynamic model and the parameterized total-energy model. The influences of the epitaxial strain on the dielectric tensor and spontaneous polarization along the phase transition path are discussed in terms of charge transfer. Further investigations on the vibration modes show unusual softening behaviors of the A₁ and B₂ modes in the Amm2 phase, which may be associated with the soft phonon modes away from Γ point and possibly result in other phase transitions unreported by any previous studies.     

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.     

Critical behaviour of Sn2P2S6 and Sn2P2(Se0.28S0.72)6 crystals under high hydrostatic pressures

Basing on the temperature dependences of optical birefringence for Sn₂P₂S₆ and Sn₂P₂(Se_0.28S_0.72)₆ crystals subjected to hydrostatic pressures, we prove unambiguously that Sn₂P₂S₆ reveals a tricritical point on its (p, T)-phase diagram with the coordinates (p, T) = (4.3 kbar, 259 K), so that the second-order phase transition transforms into the first-order one whenever the pressure increases above 4.3 kbar. We also find that increasing hydrostatic pressure applied to Sn₂P₂(Se_0.28S_0.72)₆ leads to the change in the phase transition character from tricritical to first order. Further increase in the pressure up to ~2.5 kbar imposes splitting of the first-order paraelectric-to-ferroelectric phase transition into two phase transitions, a second-order paraelectric-to-incommensurate one and a first-order incommensurate-to-ferroelectric transition.     

Incommensurability induced by intermolecular hydrogen bonding

Non-symmetric dimesogens are composed of two different mesogenic units linked via a flexible spacer. In this study, a new type of non-symmetric dimesogen has been built through the self-assembly via intermolecular hydrogen bonding between appropriately designed H-bond donor (3-cholesteryloxycarbonylpentanoic acid) and acceptor (aromatic mesogen with a pyridyl group) moieties. As for covalently linked dimesogens, several types of smectic periodicities are observed for these H-bonded cholesteryl compounds depending on the length of the terminal chain of the acceptor moiety: a smectic periodicity resulting from associated dimesogens is observed for long terminal chains, while short chain homologues display an intercalated structure corresponding to half the molecular length. The competition between these two incommensurate lengths can induce an incommensurate smectic phase where the two smectic periodicities coexist at long range.     

Influence of the bias field on dielectric properties of the SmCA* in the vicinity of the SmC*–SmCA* phase transition

In a large class of smectic mixtures prepared at our University, the phase transition between chiral ferroelectric smectic C (SmC*) and chiral antiferroelectric smectic C (SmC_A*) phases can be observed on cooling. Under bias field the temperature of the phase transition SmC*?SmC_A* decreases (ca. 100°C in the investigated mixture). The transition is called: unwound SmC*?twisted SmC_A* phase transition. The Goldstone mode in SmC* phase is reduced by a direct current field while two modes (P_H and P_L) in the SmC_A* phase are amplified. The amplitude of the fast X mode observed in the SmC_A* phase is reduced. The aim of this paper is to show how parameters of the modes in SmC_A* phase (calculated from Cole–Cole model) change with bias voltage—when twisted structure in SmC_A* phase is gradually unwound. The character of the modes observed in SmC_A* is discussed. A new effect is shown: a high value of dielectric loss is detected in the unwound SmC* phase, which is very close to SmC_A*.     

单晶铁电畴反转的简化模型

建立具有钙钛矿结构铁电材料的基本电畴结构类型及电畴反转系的表示方法;将电畴反转类似为晶体塑性理论的位错运动,采用内时理论的类似方法,提出一个较简便的电畴体积分数的演化方程,能综合考虑到反转驱动力、180和90反转的不同形式、电畴体积分数及反转的变形历史等对反转的影响.对不同外加力电载荷条件下单晶材料的响应进行了模拟计算,能较好反映铁电材料的电位移与电场强度、应变与电场强度、应力与应变、应力与电位移等的非线性力电耦合关系.     

层状铁电体Ba_(1-x)Bi_(2+x)Ti_xNb_(2-x)O_9的结构相变研究

本文应用拉曼光谱方法研究了Ba1-xBi2+xTixNb2-xO9的结构相变。与x≠0的情况相比,x=0的情况BaBi2Bn2O9表现出了明确不同的拉曼光谱。前者有与Aurivillius层状铁电体家族的铁电相相似的拉曼光谱。因此认为BaBi2Nb2O9发生了铁电—非铁电相变。此外,用内模方法对层次铁电体Ba1-xBi2+xTixNb2-xO9的拉曼振动模式进行了初步的指认     

Electron irradiation‐induced effects on optical spectra of (NH4)2ZnCl4: x Sr2+ single crystals

The effect of electron‐beam irradiation with different doses on optical constants of (NH₄)₂ZnCl₄: x Sr²⁺ crystals with x=0.000, 0.020, 0.039, 0.087 or 0.144 wt% has been studied. The optical transmission in the energy range 3.4‐6.4 eV was measured hence the absorption coefficient was computed as a frequency function. The absorption coefficient was also calculated as a function of electron‐beam dose. Irradiation with e‐beam did not affect the allowed indirect type of transition responsible for interband transitions of (NH₄)₂ZnCl₄: x Sr²⁺ crystals. Values of the optical energy gap E_g and optical moment E_p for electronic interband transition of unexposed and (NH₄)₂ZnCl₄: x Sr²⁺ crystals after e‐beam exposure were deduced. The area under the absorption band at 5.30 eV was used to evaluate the effect of e‐irradiation on optical parameters of samples with x=0.00, 0.020 or 0.039. A shift in the position and a nonmonotonic change in the intensity of this band with increasing e‐beam dose was observed. Changes in the E_g value were used to evaluate the effect of e‐beam exposure dose on (NH₄)₂ZnCl₄: x Sr²⁺ samples with x=0.087 or 0.144. The obtained results were compared with those obtained for the same crystals after irradiation with different γ‐doses.     

Growth,Ferroelectric Properties,and Phonon Modes of YMnO3 Single Crystal

YMnO₃ single crystals were grown by flux method and plate‐like single crystals with the c‐axis perpendicular to the surfaces were obtained. The maximum size of these crystals was about 2 × 2 × 0.07 mm³. Ferroelectric properties were measured at various frequencies and abnormal behavior at the low frequencies were observed and discussed using non‐linear current‐voltage behavior. Raman and IR spectra were obtained, and those results were compared with previous work.