Raman and IR studies of BaBi2Ta2O9 prepared by a sol–gel process

The formation of ferroelectric BaBi₂Ta₂O₉ (BBT) by a sol–gel process was studied by X‐ray, Raman and infrared (IR) spectroscopy. Our results show that the formation of a Bi‐layered phase proceeds via an intermediate fluorite‐type phase. This method allows obtaining a BBT phase already at 750 °C. This temperature is about 150–200 °C lower than that required in the conventional solid‐state reaction. Therefore, a material with smaller particle size can be obtained. Raman and IR studies of the obtained Bi‐layered phase show that phonon properties of the synthesized particles are slightly different from those of the bulk material due to the size effect, defects and weak changes in local order. Temperature dependence of Raman and IR wavenumbers is consistent with the orthorhombic distortion of the BBT structure. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and phonon properties of nanosized Aurivillius phase of Bi2MoO6

Nanosized crystallites Bi₂MoO₆ of a platelet shape were synthesized by a mild hydrothermal crystallization process. The effect of particle size on the structure and properties of Bi₂MoO₆ was studied by X‐ray diffraction, transmission electron microscopy, as well as Raman and infrared (IR) spectroscopies. Moreover, temperature‐dependent Raman spectra were collected for bulk and nanocrystalline Bi₂MoO₆. These studies showed that the thickness of the smallest crystallites is about 8–11 nm. Raman and IR studies have revealed that the damping and the intensity of Raman and IR bands are significantly modified with decreasing particle size and temperature. Moreover, some bands experience significant shifts both towards lower and higher wavenumbers. The obtained results indicate that, similar to the isostructural Bi₂WO₆, the orthorhombic distortion decreases with decreasing particle size. However, the structure of nanocrystalline Bi₂MoO₆ remains orthorhombic and noncentrosymmetric, and the structural changes are not the same as those observed in Bi₂WO₆. Copyright © 2010 John Wiley & Sons, Ltd.     

Phonon properties of nanosized bismuth layered ferroelectric material—Bi2WO6

Nanosized Bi₂WO₆ was synthesized by a mild hydrothermal crystallization process. This method allowed obtaining plate‐like crystallites of very small thickness (down to 3 nm). The effect of particle size on the structure and properties of Bi₂WO₆ was studied by X‐ray diffraction (XRD), transmission electron microscopy, and Raman and infrared spectroscopies. It has been shown that the orthorhombic distortion decreases with decreasing particle size, but the structure of the smallest crystallites is still orthorhombic. Raman studies have also revealed a very strong intensity decrease for those modes that appear mainly for incident and scattered light polarized perpendicular to the layers. This behavior has been attributed to a decrease in the orthorhombic distortion and a plate‐like shape of the nanocrystallites. Copyright © 2009 John Wiley & Sons, Ltd.     

Micro‐Raman study of Zr‐substituted Bi4Ti3O12 ceramics

We have studied the lattice vibrational modes of Zr‐substituted Bi₄Ti₃O₁₂ ceramics using micro‐Raman spectroscopy. Replacement of Zr at the Ti site in the perovskite block is found from the increase in the lattice parameters as a function of Zr contents. Combined X‐ray diffraction patterns and Raman analysis suggested less than 40 mole% Zr solubility in Bi₄Ti₃O₁₂. At 40 mole% of Zr substitution or above, the unreacted monoclinic‐phase ZrO₂ is observed in the X‐ray diffraction patterns and the Raman spectra. The incorporation of Zr in Bi₄Ti₃O₁₂ reduces the soft mode wavenumber and the transition temperature. Moreover, temperature dependent studies confirmed the ferroelectric to paraelectric transition in Bi₄Ti₃O₁₂ at about 675 °C. On increasing the Zr content up to 40% on the Ti sites of Bi₄Ti₃O₁₂, a systematic decrease in the phase transition temperature from 675 to 630 °C was observed. Copyright © 2007 John Wiley & Sons, Ltd.     

Polarized Raman and IR spectra of non‐centrosymmetric PbB4O7 single crystal

Polarized Raman and IR spectra of a PbB₄O₇ single crystal were measured. The obtained spectra are discussed within the factor group approach for the orthorhombic P2₁nm(C_2v⁷) space group with Z = 2 assuming that the crystal structure is built up of the (B₄O₇)_∞²⁻ framework and Pb²⁺ ions. It has been shown that vibrations of borate and Pb²⁺ units are observed above 240 and below 160 cm⁻¹, respectively. The results obtained for the spontaneous Raman scattering have also been used in the discussion of the stimulated Raman spectra of the material studied—a new Raman‐laser crystal. The obtained results revealed that mainly translational motions of Pb²⁺ ions participate efficiently in the SRS effect. Copyright © 2008 John Wiley & Sons, Ltd.     

γ射线辐照与O2退火对Bi∶CdWO4单晶体光谱性能的影响

用500和800℃,在氧气下,对掺Bi钨酸镉晶体进行热退火处理,测定了处理后晶体的吸收光谱与发射光谱。随退火处理温度的升高晶体的吸收强度降低,吸收边带发生蓝移。在373与980nm的光激发下,分别观察到发光中心为528nm的CdWO4晶体本征发光与发光中心为1 078nm的Bi 5+发光。晶体样品通过高温氧气处理,发光中心为528nm的荧光带强度增强,但发光中心为1 078nm的荧光带强度变弱。这可能是由于氧退火使Bi 5+转化成Bi 3+所致。经退火处理后,晶体的颜色逐渐变浅,透光率明显提高,这是由于晶体中氧空位减少所致。经γ射线辐照处理后,528nm处的发光增强,而1 078nm处的发光减弱,这可能是由于γ射线辐照后导致Bi 5+变成Bi 3+。     

Raman and IR spectra of noncentrosymmetric Bi0.21La0.91Sc2.88(BO3)4 single crystal with the huntite‐type structure

Single crystals of optical nonlinear borate, Bi_0.21La_0.91Sc_2.88(BO₃)₄, were grown and polarized Raman and IR spectra were recorded for this material at room temperature. The spectra have been discussed on the factor group approach for the trigonal R32 (D₃⁷) space group with Z = 3. The assignment of the observed bands to the respective internal and lattice modes is proposed. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman and IR spectra of K4Nb6O17and K4Nb6O17·3H2O single crystals

Polarised Raman and IR spectra of K₄Nb₆O₁₇ and K₄Nb₆O₁₇· 3H₂O single crystals were measured. The obtained spectra are discussed using the factor group approach for the orthorhombic P2₁nb space group and assignment of bands to the respective motions of atoms is proposed. In particular, we have shown that the bands above 770 cm⁻¹ can be attributed to the stretching modes of short niobium–oxygen bonds, which are present in this material due to the pronounced layered structure, whereas the potassium atoms contribute to the bands observed below 180 cm⁻¹. Our studies have revealed that intercalation of water molecules leads to shifts, broadening and changes in intensity of some bands. These changes have been attributed to slight changes in the bond lengths and angles, interactions of the water molecules with K atoms and structural disorder introduced by the intercalated water molecules. However, the main structural framework was preserved. Copyright © 2010 John Wiley & Sons, Ltd.     

静电纺丝法制备Bi2Fe4O9及其磁学性能的研究

采用静电纺丝法合成了纤维状的Bi₂Fe₄O₉前驱体,再对前驱体进行热处理得到了棒状的Bi₂Fe₄O₉.通过X射线衍射、扫描电子显微镜及透射电子显微镜表征了合成样品的物相及形貌特征.结果表明合成的样品为Bi₂Fe₄O₉单相,属于正交晶系;退火处理导致纤维状的前驱体转变为棒状的Bi₂Fe₄O₉.紫外-可见吸收光谱表明制备的Bi₂Fe₄O₉对光的吸收范围广,不仅对紫外光具有较强吸收,而且对可见光也有一定的吸收.通过振动样品磁强计测定Bi₂Fe₄O₉磁滞回线研究其磁学特性,相应的矫顽力H_C≈82 Oe（1 Oe=79.5775 A/m）,剥离顺磁信号后的剩磁M_r≈0.25 emu/g,研究发现Bi₂Fe₄O₉样品具有弱铁磁性,并且软磁性能有所提高.     

Polarised IR and Raman spectra of non‐centrosymmetric Na3Li(MoO4)2· 6H2O crystal—a new Raman laser material

Polarised IR and Raman spectra of Na₃Li(MoO₄)₂· 6H₂O single crystal were measured. Discussion of the results is based on the factor group approach for the trigonal R 3c(C_3v⁶) space group with Z = 2. The assignment of the observed bands was performed on the basis of their polarisation behaviour and literature data. The obtained results for the spontaneous Raman scattering were used in the analysis of the stimulated Raman spectra of the material studied—a new Raman laser crystal. The promoting modes of the stimulated effect were identified. Copyright © 2009 John Wiley & Sons, Ltd.     

Doping effect on the phase transition temperature in ferroelectric SrBi2−xNdxNb2O9 layer‐structured ceramics: a micro‐Raman scattering study

The temperature dependence of Raman spectra for SrBi_2−xNd_xNb₂O₉ ceramics (x from 0 to 0.2) has been studied in a wide temperature range from 80 to 873 K. It is found that the peak position of the A_1g[Nb] phonon mode at 207 cm^–1, which is directly associated with the distortion of NbO₆ octahedron, decreases with increasing Nd composition, while the A_1g[O] phonon mode at 835 cm^–1 increases. Moreover, both the peak position and intensity of the A_1g[Nb] phonon mode reveal strong anomalies around the ferroelectric to paraelectric phase transition temperature. It indicates that the phase transition temperature decreases from about 710 to 550 K with increasing Nd composition, which is due to the fact that the introduction of Nd ions in the Bi₂O₂ layers reduces the distortion extent of NbO₆ octahedron. Copyright © 2011 John Wiley & Sons, Ltd.     

SrBi2Ta2O9/Bi4Ti3O12复合铁电薄膜的制备与特性研究

采用溶胶凝胶工艺在p-Si衬底上制备了SrBi2Ta2O9/Bi4Ti3O12复合铁电薄膜. 研究了SrBi2Ta2O9/Bi4Ti3O12复合薄膜的微观结构与生长行为、铁电性能和疲劳特性. 研究表明: Si衬底Bi4Ti3O12薄膜易于沿c轴择优生长,并有利于SrBi2Ta2O9/Bi4Ti3O12复合薄膜的生长.合理的SrBi2Ta2O9/Bi4Ti3O12厚度配比能获得较好的铁电性能和优良的抗疲劳特性,SrBi2Ta2O9/Bi4Ti3O12厚度配比为1∶3的复合薄膜的剩余极化强度和矫顽电场分别为8.1 μC/cm2 和 130 kV/cm,其无疲劳极化开关次数达1011以上.     

Bi2ZnOB2O6单晶偏振拉曼光谱

本文通过分析不同几何配置下的偏振拉曼光谱对非线性光学晶体的晶格振动模式进行了研究. 首先根据因子群分析,将晶体的振动模按晶体对称群的不可约表示进行分类,其次测量了晶体在10–1600 cm^-1范围内,不同几何配置下的偏振拉曼光谱,并在此基础上指认了晶体的晶格振动模式. 300 cm^-1以下的振动峰,归结为晶体的外振动,来自[BiO₆],[ZnO₄],[BO₄]和[BO₃]原子基团的平动和转动;300cm^-1以上为晶体的内振动,主要与Bi-O,和Zn-O键振动有关. 晶体拉曼光谱中最高振动频率达到1407 cm^-1,被指认为[BO₃]三角形中B-O键的伸缩振动,体现了[BO₃]基团中高的电子非局域化程度. 关键词： 2ZnOB₂O₆单晶')" href="#">Bi₂ZnOB₂O₆单晶 偏振拉曼光谱 振动模式     

低温拉曼光谱研究钛酸铋尺寸驱动的相变

本文对粒径为25~75 nm的钛酸铋纳米晶在-190℃温度的低温拉曼光谱进行了研究,结果表明,在钛酸铋纳米晶中,除了存在已知的尺寸驱动的铁电正交-顺电四方的结构相变外,还存在尺寸驱动的细微的单斜-正交的结构相变。     

Temperature-dependent Raman scattering study of cation-deficient Aurivillius phases: Bi2WO6 and Bi2W2O9

Temperature-dependent Raman scattering experiments were performed on Bi(2)WO(6) and Bi(2)W(2)O(9). Significant changes in the phonon properties of Bi(2)WO(6) were observed as the temperature was increased due to decreased distortion from the B2cb structure. It was shown that instability of the 57 cm(-1) mode that behaved as a soft mode under pressure is not responsible for the Pca2(1) to B2cb phase transition taking place in Bi(2)WO(6) at 933 K. This result confirmed that this mode is not related to the [Formula: see text] tilt mode, which disappears upon change in symmetry from Pca2(1) to B2cb. Bi(2)W(2)O(9) does not exhibit any structural phase transition in the 298-800 K range. However, the temperature dependence of Raman bands indicated that the Bi(2)W(2)O(9) structure evolves with decreasing temperature from 800 to 298 K towards a more symmetric structure that was reported above 2.8 GPa at room temperature. This structural change is driven by displacement of the W atoms and is different from that exhibited by Bi(2)WO(6) and other members of the Aurivillius family but similar to that exhibited by WO(3). Our results also show that Bi(2)W(2)O(9) belongs to the small group of compounds that show the presence of low wavenumber modes characterized by unusually small linewidths.     

FT‐IR,FT‐Raman and SERS spectra of anilinium sulfate

The FT‐IR and FT‐Raman spectra of anilinium sulfate were recorded and analyzed. The surface‐enhanced Raman scattering (SERS) was recorded from a silver electrode. The vibrational wavenumbers of the compound have been computed using the Hartree‐Fock/6‐31G* basis and compared with the experimental values. The molecule is adsorbed on the silver surface with the benzene ring in a tilted orientation. The presence of amino and sulfate group vibrations in the SERS spectrum reveal the interaction between amino and sulfate groups with the silver surface. The direction of the charge transfer contribution to SERS has been discussed from the frontier orbital theory. Copyright © 2009 John Wiley & Sons, Ltd.     

Temperature‐dependent Raman scattering in ferroelectric Bi4−xNdxTi3O12(x = 0, 0.5, 0.85) single crystals

The temperature‐dependent Raman spectra of ferroelectric Bi_4−xNd_xTi₃O₁₂(x = 0, 0.5, 0.85) single crystals were recorded from 100 to 800 K. It was found that there is a critical Nd content x₀ between 0.5 and 0.85. The Nd³⁺ ions prefer to replace Bi³⁺ ions in pseudo‐perovskite layers when x < x₀, while they might begin to incorporate into (Bi₂O₂)²⁺ layers when x ≥ x₀. Nd substitution leads to a decrease in the ferroelectric–paraelectric transition temperature (T_c). A monoclinic distortion of orthorhombic structure occurs in Bi₄Ti₃O₁₂ crystals at temperatures below 200 K. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectrum of U4O9: a new interpretation of damage lines in UO2

Characterisation of uranium oxides in different conditions is a challenge both in nuclear and environment sciences. We focus here on U₄O₉, which is a superstructure of UO₂. Homogeneous U₄O₉ powder was fabricated and characterised by Raman spectroscopy. The Raman spectrum of a pure‐phase U₄O₉ is, for the first time, completely described and interpreted. U₄O₉ Raman spectrum derives from the well characterised one of UO₂. Besides reminiscent modes of UO₂, a band at 630 cm^‐1, which has a specific response to polarised light, was interpreted as characteristic of clusters of interstitial oxygen atoms. These experimental data will help to rationalise the interpretation of UO₂ damaged samples. Copyright © 2011 John Wiley & Sons, Ltd.     

DFT,FT‐Raman,FT‐IR and NMR studies of 2‐fluorophenylboronic acid

The experimental and theoretical vibrational spectra of 2‐fluorophenylboronic acid (2fpba) were studied. The Fourier transform Raman and Fourier transform infrared spectra of the 2fpba molecule were recorded in the solid phase. The structural and spectroscopic analysis of the molecule was carried out by using Hartree‐Fock and density functional harmonic calculations. For the title molecule, only one form was found to be the most stable structure, by using B3LYP level with the 6‐31++G(d,p) basis set. Selected experimental bands were assigned and characterized on the basis of the scaled theoretical wavenumbers by their total energy distribution (TED). The ¹H and ¹³C nuclear magnetic resonance (NMR) chemical shifts of the 2fpba molecule were calculated using the Gauge‐Invariant‐ atomic orbital (GIAO) method in DMSO solution using IEF‐PCM model and compared with the experimental data. Finally, geometric parameters, vibrational wavenumbers and chemical shifts were compared with available experimental data of the molecule. Copyright © 2009 John Wiley & Sons, Ltd.