Raman spectral studies of Zr4+‐rich BaZrxTi1−xO3(0.5⩽x⩽1.00) phase diagram

This paper reports a systematic study of the composition and the temperature‐dependent‐Raman spectra of Zr⁴⁺‐rich BaZr_xTi_1−xO₃ (BZT) ceramic compositions (0.50⩽x⩽1.00). On the basis of the dielectric behavior of Zr rich BZT ceramics, the observed relaxor behavior has been hypothesized as a result of increasing long‐range interactions of nanosized, Ti⁴⁺‐rich polar regions in a Zr⁴⁺‐rich nonpolar matrix. Beyond an optimum concentration of BaTiO₃ (BT) in the nonpolar matrix of BaZrO₃ (x⩽0.75), a critical size and density of the polar regions is reached when the polar clusters start showing the relaxor like behavior, which finally show classical relaxor behavior for compositions with x = 0.5 and 0.6. This hypothesis is strongly supported from the Raman data on Zr‐rich BZT presented in this paper. Well‐defined BT Raman spectra for 5% BT in BZT composition were recorded, which followed completely up to the 50% Ti addition in the BZT samples. The temperature‐dependent Raman spectra collected on the BZT ceramics far beyond the dielectric transition temperatures supported the existence of the nano‐polar BT regions, like in typical relaxor samples. The full width at half‐maximum (FWHM), integrated intensity of the peaks in the Raman spectra has been analyzed to further support the conclusions. Copyright © 2008 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.     

A Raman spectroscopic and TEM study on the structural evolution of Na2Ti3O7 during the transition to Na2Ti6O13

The synthesis of sodium hexatitanate from sodium trititanate was characterized by Raman spectroscopy, X‐ray diffraction (XRD) and high‐resolution transmission electron microscopy (HRTEM). The structural evolution from trititanate to hexatitanate was studied using Raman spectra, XRD and HRTEM techniques. It was found that the Raman bands at 279 cm⁻¹ corresponding to very long Ti O bonds and at 883 cm⁻¹ corresponding to the very short Ti O bonds decrease in intensity and finally disappear during the transition from sodium trititanate to sodium hexatitanate. The band at 922 cm⁻¹ corresponding to an intermediate‐length Ti O bond was observed to become stronger with the increase in temperature, indicating that there is no terminal oxygen atom in the crystal structure of Na₂Ti₆O₁₃ and that all the oxygen atoms become linearly coordinated by two titanium atoms. Furthermore, the TiO₆ octahedron in Na₂Ti₆O₁₃ are more regular because the very long (2.2 Å) or very short (1.7 Å) Ti O bonds disappear. It is revealed that the phase transition from trititanate to hexatitanate is a step‐by‐step slipping process of the TiO₆ octahedral slabs with the loss of sodium cations, and a new phase with formula Na_1.5H_0.5Ti₃O₇ has been discovered as an intermediate phase to interlink Na₂Ti₃O₇ and Na₂Ti₆O₁₃. Copyright © 2010 John Wiley & Sons, Ltd.     

氮氢混合气氛退火中氢对Bi4Ti3O12铁电性能的影响

采用基于密度泛函理论的第一性原理研究了在氮氢混合气氛中退火后Bi₄Ti₃O₁₂铁电性的退化机理. 分别计算了无氢、含氢模型中Ti沿c轴位移时体系总能量的变化,电子云密度分布,以及电子结构的总能态密度的变化. 结果表明含氢Bi₄Ti₃O₁₂铁电相Ti-O,Bi-O间的电子云重叠布居分布较无氢情况下变化明显,氢氧之间较强的轨道杂化使它们趋于形成共价键;晶格中氢氧键的 关键词： 氮氢混合气氛退火 铁电性 4Ti₃O₁₂')" href="#">Bi₄Ti₃O₁₂ 第一性原理     

Preparation and structural instability of the 0.1BiFeO3-0.9Bi4Ti3O12 system

The solid solution of 0.1BiFeO₃-0.9Bi₄Ti₃O₁₂ (BF-BT) with bismuth-layered perovskite structure was obtained by conventional solid-state reaction. The lattice instability of BF-BT has been investigated by variable-temperature Raman scattering and X-ray diffraction. The results showed that there was a ferroelectric phase transition in the 450∼550 °C region in terms of the evolution of temperature dependence of Raman scattering frequencies. Some changes at about 530 °C in the XRD lines, the lattice parameters (a, b and c) as well as the orthorhombic distortion b/a have been detected in the high temperature X-ray diffraction, which can be interpreted by a phase transition and it is in good agreement with the results of high temperature Raman scattering. PACS 77.80.Bh; 61.10.Eq; 63.20.Dj     

Temperature dependent Raman scattering in polycrystalline Bi4Ti3O12 thin films

Polycrystalline Bi₄Ti₃O₁₂ thin films were prepared on quartz substrates by pulsed laser deposition. The films were crystallized in the orthorhombic layer perovskite structure confirmed by X-ray diffraction and Raman spectroscopy. The Raman spectra are strongly dependent on temperature. A subtle phase transition in the temperature range 473-573 K exists in polycrystalline BTO thin films, which is evidenced by the disappearance of the Raman band at 116 cm⁻¹ and appearance of a new Raman band at 151 cm⁻¹. The two broad Raman bands centered at the 57 and 93 cm⁻¹ at 300 K break up into clusters of several sharp Raman peaks at 77 K, due to monoclinic distortion of orthorhombic structure at low temperature in the as-prepared Bi₄Ti₃O₁₂ thin films.     

LaxBi2-xTi4O11的合成及相变研究

合成了Ｌａ_xＢｉ_2-xＴｉ₄Ｏ₁₁系列样品，并完成了它们的喇曼光谱和ｘ射线衍射测量；结果表明，该体系在Ｘ＝１．２经历了一次相变，且相变与最低频声子模随Ｘ的变化有关。Ｌａ_0.2Ｂｉ_1.8·Ｔｉ₄Ｏ₁₁的相变温度为２００℃。初步获得Ｌａ₂Ｔｉ₄Ｏ₁₁的结构为正交结构。 关键词：     

Enhanced electrical properties of lead-free Bi4−xSbxTi3O12 ceramics with high Tc

Bi_4?xSb_xTi₃O₁₂ (BST) ceramics were prepared and studied in this work in terms of Sb³⁺-modified microstructure and phase development as well as electrical response. By increasing Sb content, the phase structure of the ceramics changed from orthorhombic (Bi₄Ti₃O₁₂-like) to pyrochlore (Bi₂Ti₂O₇-like) phase. Raman spectroscopy showed that the intensities of the lattice vibration modes at frequencies decrease, whereas all bands and bandwidths in all frequency numbers also demonstrate changes. According to the results processed from SEM, Sb³⁺ into the Bi₄Ti₃O₁₂ (BIT) matrix had the effect of increasing the material grain size. ε_r, ε_m, P_r, d₃₃ and T_c of Bi_3.90Sb_0.10Ti₃O₁₂ ceramics are found to be 307, 3492, 8.09 μC cm^?2, 18 pC/N and 660 °C, respectively. And Bi_4?xSb_xTi₃O₁₂ ceramics have good temperature stability, which is very suitable for the practical high-temperature applications.     

Dielectric properties of Bi4Ti3O12–SrBi4Ti4O15 intergrowth ceramics synthesized by a modified oxalate route

In this study, Bi₄Ti₃O₁₂–SrBi₄Ti₄O₁₅ (BIT–SBTi) intergrowth ferroelectric ceramics was synthesized by a modified oxalate route. The phase formation behaviour, structure, morphology and electrical properties of the intergrowth ceramics were also investigated. The phase formation takes place through intermediate phases like SrBi₂O₄ and Bi₁₂TiO₂₀. The precursor mostly changes to Bi₄Ti₃O₁₂ at 600°C and to BIT–SBTi intergrowth at 800°C. Rietveld analysis of the X-ray diffraction pattern showed that the structure of the intergrowth compound was orthorhombic with lattice parameters a = 5.4408(3), b = 5.4505(1) and c = 74.0851(4) Å. The intergrowth ferroelectrics showed a phase transition at 610°C and a frequency-stable permittivity and dielectric loss behaviour. The intergrowth ferroelectrics also showed a larger 2P_r than their constituents BIT and SBTi.     

Ag/Bi4Ti3O12栅n沟道铁电场效应晶体管制备及存储特性

在溶胶-凝胶工艺获得高质量Bi₄Ti₃O₁₂薄膜的基础上 ，制备了Ag/Bi₄Ti₃O₁₂栅n沟道铁电场效应晶体管. 研 究了Si基Bi₄Ti₃O₁₂薄膜的生长特性及其对铁电薄膜/ 硅的界面状态和铁电场效应晶体管存储特性的影响. 研究表明，在合理的工艺条件下可以获 得具有较高c-轴择优取向的纯钙钛矿相Si基Bi₄Ti₃O₁₂ 铁电薄膜并有利于改善Bi₄Ti₃O₁₂/Si之间的界面特性; 顺时针回滞的C-V特性曲线和C-T曲线表明Ag/Bi₄Ti₃O_{12栅n沟道铁电场效应晶体管具有极化存储效应和一定的极化电荷保持能力; 器件的转移(I< sub>sd}-V_G)特性曲线显示Ag/Bi₄Ti₃O_{12栅n沟道铁电场效应晶体管具有明显的栅极化调制效应. 关键词： 铁电场效应晶体管 4}Ti₃O₁₂')" href="#">Bi₄Ti₃O₁₂ 存储 特性 溶胶-凝胶工艺     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

Controlled synthesis of photoluminescent Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> nanoparticles from metal-organic polymeric precursor

Bi₄Ti₃O₁₂ (BIT) nanoparticles with a narrow average particle size distribution in the range of 11–46 nm was synthesized via a metal-organic polymeric precursor process. The crystallite size and lattice parameter of BIT were determined by XRD analysis. At annealing temperatures >550 °C, the orthorhombic BIT compound with lattice parameters a = 5.4489 Å, b = 5.4147 Å, and c = 32.8362 Å was formed while at lower annealing temperatures orthorhombicity was absent. Reaction proceeded via the formation of an intermediate phase at 500 °C with a stoichiometry close to Bi₂Ti₂O₇. The particle size and the agglomerates of the primary particles have been confirmed by FESEM and TEM. The decomposition of the polymeric gel was ascertained in order to evaluate the crystallization process from TG-DSC analysis. Raman spectroscopy was used to investigate the lattice dynamics in BIT nanoparticles. In addition, investigation of the dependence of the visible emission band around the blue–green color emission on annealing temperatures and grain sizes showed that the effect of grain size plays important roles, and that oxygen vacancies may act as the radiative centers responsible for the observed visible emission band.     

Pr-modified Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> nanofibers as an anode material for lithium-ion batteries with outstanding cycling performance and rate performance

Pr-doped Li₄Ti₅O₁₂ in the form of Li_4?x/3Ti_5?2x/3Pr_xO₁₂ (x = 0, 0.01, 0.03, 0.05, and 0.07) was synthesized successfully by an electrospinning technique. ICP shows that the doped samples are closed to the targeted samples. XRD analysis demonstrates that traces of Pr³⁺ can enlarge the lattice parameter of Li₄Ti₅O₁₂ from 8.3403 to 8.3765 Å without changing the spinel structure. The increase of lattice parameter is beneficial to the intercalation and de-intercalation of lithium-ion. XPS results identify the existence form of Ti is mainly Ti⁴⁺ and Ti³⁺ in minor quantity in Li_4?x/3Ti_5?2x/3Pr_xO₁₂ (x = 0.05) samples due to the small amount of Pr³⁺. The transition from Ti⁴⁺ to Ti³⁺ is conducive to the electronic conductivity of Li₄Ti₅O₁₂. FESEM images show that all the nanofibers are well crystallized with a diameter of about 200 nm and distributed uniformly. The results of electrochemical measurement reveal that the 1D Li_4?x/3Ti_5?2x/3Pr_xO₁₂ (x = 0.05) nanofibers display enhanced high-rate capability and cycling stability compared with that of undoped nanofibers. The high-rate discharge capacity of the Li_4?x/3Ti_5?2x/3Pr_xO₁₂ (x = 0.05) samples is excellent (101.6 mAh g^?1 at 50 °C), which is about 58.48 % of the discharge capacity at 0.2 °C and 4.3 times than that of the bare Li₄Ti₅O₁₂ (23.5 mA g^?1). Even at 10 °C (1750 mA g^?1), the specific discharge capacity is still 112.8 mAh g^?1 after 1000 cycles (87.9 % of the initial discharge capacity). The results of cyclic voltammograms (CV) and electrochemical impedance spectroscopy (EIS) illustrate that the Pr-doped Li₄Ti₅O₁₂ electrodes possess better dynamic performance than the pure Li₄Ti₅O₁₂, further confirming the excellent electrochemical properties above.     

Anomalous temperature dependence of phonon modes in Bi2Ti4O11 and modified Bi2Ti4O11

We have observed the anomalous temperature dependence of the phonon modes in the Raman spectra of Bi₂Ti₄O₁₁ and the modified Bi₂Ti₄O₁₁ with the dopant of PbO. The square of the lowest mode frequency in both substances decreases linearly with increasing temperature, while the damping constant increases reaching a peak value at the transition temperature. The mode frequency, however, does not tend to zero but stays finite and the damping constant decreases above the transition temperature. The mode is Raman-active both above and below the transition temperature.     

Si基Bi4Ti3O12铁电薄膜的制备与特性研究

采用sol-gel工艺, 在分层快速退火的工艺条件下成功地制备了高质量Si基Bi_{4Ti3O12铁电薄膜. 研究了Si基Bi4Ti3O12薄膜的生长行为、铁电性能、C-V特性和疲劳特性. 研究表明: Si基Bi4Ti3O12薄膜具有随退火温度升高沿c轴择优生长的趋势; 退火温度通过影响薄膜的晶粒尺寸、生长取向和薄膜中载流子的浓度来改变Si基Bi关键词： sol-gel法 铁电薄膜 4Ti3O12')" href="#">Bi4Ti3O12 C-V特性}     

La掺杂对Bi4Ti3O12薄膜铁电性能的影响

利用Sol-Gel法在Pt/Ti/SiO₂/Si衬底上制备出Bi₄Ti₃O₁₂和Bi_3.25La_0.75Ti₃O₁₂薄膜，研究了La掺杂对Bi₄Ti₃O₁₂薄膜的晶体结构、铁电性能和疲劳特性的影响，发现La掺杂没有改变Bi₄Ti₃O₁₂薄膜的基本晶体结构，并且提高了Bi₄Ti₃O₁₂铁电薄膜的剩余极化值和抗疲劳性能，对La掺杂改善Bi₄Ti₃O₁₂铁电薄膜性能的机理进行了讨论. 关键词： 铁电性能 4Ti₃O₁₂薄膜')" href="#">Bi₄Ti₃O₁₂薄膜 3.25La_0.75Ti₃O₁₂薄膜')" href="#">Bi_3.25La_0.75Ti₃O₁₂薄膜 sol-gel法 La掺杂     

Ferroelectric and dielectric properties of La/Mn co-doped Bi4Ti3O12 ceramics

La/Mn co-doped Bi4Ti3O12 ceramics,Bi3.25La0.75Ti3-xMnxO12(x=0.02,0.04,0.06,0.08),were prepared by the solid-state reaction method.The influence of manganese substitution for the titanium part in Bi 3.25 La 0.75 Ti 3 O 12 on the sintering behaviour,microstructure,Raman spectra and electrical properties was investigated.The experimental results show that the phase composition of all samples with and without manganese doping,sintered at 1000 ℃,consists of a single phase with a bismuth-layered structure belonging to the crystalline phase Bi4Ti3O12.There is no evidence of any impurity phase,but a small change in crystallographic orientation is observed.The Curie temperature of Bi3.25La0.75Ti3-xMnxO12 ceramics is steadily shifted to lower temperature with increasing Mn-doping content.Moreover,the remnant polarisation(Pr) of Bi3.25La0.75Ti2.92Mn0.08O12 samples increases with Mn-doping content,and the Bi3.25La0.75Ti2.92Mn0.08O12 sample exhibits the largest P r of 16.6 μC/cm 2.     

Enhanced multiferroic characteristics in Fe-doped Bi4Ti3O12 ceramics

Modification of Bi₄Ti₃O₁₂ multiferroic ceramics prepared by a conventional solid state reaction method were investigated by substituting Ti partly with Fe. The introduction of Fe does not change the layered perovskite structure of Bi₄Ti₃O₁₂. Upon increasing Fe content, the remnant polarization of the samples is enhanced. The magnetism of the ceramics at room temperature develops from diamagnetism to weak ferromagnetism with increasing Fe doping. The largest variations of 15% and 6% in remnant polarization and magnetization, achieved in a Bi₄Ti₁Fe₂O_12?δ sample after poling it in a magnetic field at 1 T and a DC electric field at 30 kV/cm for 10 min, are evidence of magnetoelectric coupling between the electric dipoles and magnetic dipoles at room temperature. The present results suggest a new candidate for a room temperature multiferroic material with enhanced properties.     

Ferroelectric properties of Pr6O11-doped Bi4Ti3O12

Praseodymium doped Bi₄Ti₃O₁₂ (BIT) ceramics with composition Bi_2.9Pr_0.9Ti₃O₁₂ (BPT) were prepared by solid state reaction. These samples have polycrystalline Bi-layered perovskite structure without preferred orientation, and consist of well-developed plate-like grains with random orientation. Pr doping into BIT causes a large shift of the Curie temperature (T_C) of the BIT from 675 to 398 °C. At an electric field of 87 kV/cm, the remanent polarization and the coercive field of the BPT ceramics are 30 μC/cm² and 52 kV/cm, respectively. Furthermore, the dielectric permittivity and the dissipation factor of the BPT ceramics are 300 and 0.003 at 1 MHz, 1 V, and room temperature. Ferroelectric properties of the BPT ceramics are superior to V-doped Bi₄Ti₃O₁₂ (∼20 μC/cm² and 80 kV/cm) and (Sr, Ta)-doped Bi₄Ti₃O₁₂ (∼12 μC/cm² and 71 kV/cm) ceramics. In addition, the dense ceramics of praseodymium-doped B₄Ti₃O₁₂ were obtained by sintering at 1100 °C, about 100-200 °C lower than those of the SrBi₂Ta₂O₉ system.     

Raman spectral probe on increased local vibrational modes and phonon lifetimes in Ho3+‐doped Bi2O3 micro‐rods

We report the appearance and enhancement in intensity of impurity related local vibrational modes in Bi₂O₃ : Ho micro‐rods along with normal modes. Pure and Ho‐doped Bi₂O₃ micro‐rods were synthesized by conventional co‐precipitation method at 60 °C. The structural and morphological studies were carried out using powder X‐ray diffraction technique and scanning electron microscopy, respectively. Raman spectroscopic studies reveal the existence of local phonon vibrational modes (LVM) due to the incorporation of Ho³⁺. Harmonic approximation method was employed to find the dopant‐related peak in the Raman spectra. Variation in full width at half maximum for LVM with increase in Ho³⁺ was also investigated. This increase in FWHM indicates the decrease in crystallinity of the doped samples. The phonon lifetime calculation carried out for each samples and the decrease in phonon lifetime with doping concentration make this material a potential candidate for optical and electronic applications. Copyright © 2016 John Wiley & Sons, Ltd.