Mn4+掺杂对BiFeO3陶瓷微观结构和电学性能的影响研究

利用传统的固相反应法制备了BiFe_1-xMn_xO₃ (x= 0-0.20)陶瓷样品, 研究了不同Mn⁴⁺掺杂量对BiFeO₃陶瓷密度、物相结构、显微形貌、 介电性能和铁电性能的影响.实验结果表明:所制备的BiFe_1-xMn_xO₃ 陶瓷样品的钙钛矿主相均已形成,具有良好的晶体结构, 且在掺杂量x=0.05附近开始出现结构相变.随着Mn⁴⁺添加量的增加, 体系的相结构有从菱方钙钛矿向斜方转变的趋势,且样品电容率大幅度增大, 而介电损耗也略有增加;在测试频率为10⁴ Hz条件下, BiFe_0.85Mn_0.15O₃ (ε_r=1065)的 ε_r是纯BiFeO₃ (ε_r=50.6)的22倍; 掺杂后样品的铁电极化性能均有不同程度的提高,可能是由于Mn⁴⁺稳定性优于 Fe³⁺,高价位Mn⁴⁺进行B位替代改性BiFeO₃陶瓷, 能减少Bi³⁺挥发,抑制Fe³⁺价态波动,从而降低氧空位浓度,减小样品的电导和漏电流.     

Nd掺杂对Bi4Ti3O12铁电薄膜的微结构和铁电性能的影响

利用溶胶-凝胶法在Pt/Ti/SiO₂/Si(100)衬底上制备了Nd掺杂Bi₄Ti₃O₁₂(Bi_4-xNd_xTi₃O₁₂, x=0.00,0.30,0.45,0.75,0.85,1.00,1.50)铁电薄膜样品.研究了Nd掺杂对Bi₄Ti₃O₁₂薄膜的微结构和铁电性能的影响.研究结果表明:Nd掺杂未改变Bi₄Ti₃O₁₂薄膜的基本晶体结构.在掺杂量x<0.45时,Nd³⁺只取代类钙钛矿层中的A位Bi³⁺.当x=0.45时,样品剩余极化强度达最大值,在270kV·cm^-1的电场下为32.7μC·cm^-2.掺杂量进一步增加时,结构无序度开始明显增大,Nd³⁺开始进入(Bi₂O₂)²⁺层,削弱其绝缘层和空间电荷库的作用,导致材料剩余极化逐渐下降.当掺杂量x达到1.50时,掺杂离子最终破坏(Bi₂O₂)²⁺层的结构,材料发生铁电-顺电相变.     

Multiferroic properties of solben gel derived Bi5Fe1-xCoxTi3O15 thin films

Co-doped Bi₅FeTi₃O₁₅ thin films (BFCT-x, Bi₅Fe_1-xCo_xTi₃O₁₅) were prepared using a sol—gel technique. XRD patterns confirm their single phase Aurivillius structure, and the corresponding powder Rietveld analysis indicates the change of space group around x=0.12. The magnetic hysteresis loops are obtained and ferromagnetism is therefore confirmed in BFCT-x thin films. The remanent magnetization (M_r) first increases and reaches the maximum value of 0.42 emu/cm³ at x=0.12 due to the possible Fe³⁺—O—Co³⁺ ferromagnetic coupling. When x = 0.25, the M_r increases again because of the dominant Fe³⁺—O—Co³⁺ ferromagnetic coupling. The remanent polarization (2P_r) of BFCT-0.25 was measured to be as high as 62 μC/cm², a 75% increase when compared with the non-doped BFCT-0 films. The 2P_r remains almost unchanged after being subjected to 5.2 × 10⁹ read/write cycles. Greatly enhanced ferroelectric properties are considered to be associated with decreased leakage current density.     

Sr和Ba替代对Eu掺杂Ca2.955Si2O7的结构和发光特性的影响研究

利用固相反应法制备了Sr和Ba替代的Ca_2.955-xM_xSi₂O₇: 0.045Eu²⁺ (M= Sr, Ba, x= 0.1-0.5)系列荧光粉, 利用较大离子半径的Sr和Ba元素替代Eu掺杂Ca_2.955-xM_xSi₂O₇ 中的Ca元素,研究Sr和Ba替代对样品结构和发光特性的影响. X射线衍射测试结果表明,少量Sr和Ba替代不会改变基质的晶体结构, 样品仍然为单斜晶系.未替代前, Ca_2.955Si₂O₇: 0.045Eu²⁺ 样品的发射峰在574 nm左右,随着Sr含量的增加,样品的发射峰发生蓝移; 而Ba含量在x= 0.1-0.4时不会引起发射峰位置的移动, 但x= 0.5样品的发射峰发生蓝移.同等含量的Sr和Ba部分替代样品中的Ca元素, Ba替代样品的光谱强度较强.     

固相反应法制备的CoxZn1-xO磁性能的研究

采用固相反应烧结法制备了Co掺杂ZnO的粉末和压片样品. XRD衍射表明样品中Co²⁺离子取代Zn²⁺离子进入了ZnO晶格中. 在室温下样品均表现为顺磁性, 利用密度泛函理论(DFT+U)方法计算得到的Co₂Zn₁₄O₁₆体系反铁磁基态更稳定, 并通过Co, O原子电子迁移变化, 表明了CoZnO体系中磁性机理更倾向于Co²⁺—O^2-—Co²⁺成键的间接交换作用模型. 改进了安德森模型中的直接交换积分J_pd公式. 提出两个可能的途径来实现具有本征铁磁性氧化物半导体.     

层状钙钛矿La1.3Sr1.7Mn2-xCuxO7的磁性及电特性

通过固相反应烧结法成功制备了层状钙钛矿La_1.3Sr_1.7Mn_2-xCu_xO₇多晶，主要研究了其磁电特性.结果表明，样品为Sr₃Ti₂O₇型钙钛矿结构.随着温度的降低，其磁性经历了一个很复杂的转变过程.当x=0时，在T^*=231K出现二维短程铁磁有序，在<     

Co掺杂对铁磁金属La0.8Sr0.2MnO3磁电阻影响机理

通过对La_0.8Sr_0.2Mn_1-yCo_yO₃(y≤02)饱和磁矩和输运的测量,研究了Co对La_0.8Sr_0.2MnO₃的磁电阻影响机制.结果表明,在La_0.8Sr_0.2Mn_1-yCo_yO₃（y≤02）中Co³⁺离子是低自旋态.由于Mn³⁺—O—Co³⁺—O—Mn³⁺类型的磁交换与Mn³⁺-Mn⁴⁺离子间双交换作用相比较弱,Curie温度T_C附近的磁电阻随着Co掺杂量的增加而降低.与此相反,由于Co²⁺离子与e_g巡游电子的反铁磁交换耦合作用,低温区间的磁电阻随着Co掺杂量的增加而升高.     

锰位铁掺杂La0.67Sr0.33FexMn1-xO3薄膜的光诱导效应

分别采用溶胶-凝胶法和脉冲激光沉积的方法制备了La_067Sr_033Fe_xMn_1-xO₃(x=0, 005, 010, 015)系列块材和薄膜，研究了Fe部分替代对La_067Sr_033Fe_xMn_1-xO₃薄膜     

Tb1－xDyxFe2－y-Fe掺杂BaTiO3多层膜中的磁电耦合

用溶胶-凝胶法制备了Fe掺杂BaTiO₃粉体，在1350℃下烧结成圆片状多晶样品，并与Tb_1-xDy_xFe_2-y胶合成磁电(ME)双层膜或三层膜.实验分析表明Fe：BaTiO₃依然是四方相钙钛矿结构，但是居里温度及相变潜热均略低于纯净BaTiO₃.研究了Tb_1-xDy_xFe_2-y-Fe∶BaTiO₃双层膜和Tb_1-xDy_xFe_2-y-Fe∶BaTiO₃-Tb_1-xDy_xFe_2-y三层膜的ME效应.在2.8×10⁴A/m的磁场下，两者的横向ME电压系数均达其峰值，分别为6.225和26.25mV·(A·m^-1)^-1·cm^-1.并且，用掺杂BaTiO₃制备的双层膜和三层膜的横向ME电压系数均为相同条件下用纯净BaTiO₃制备的双层膜和三层膜的横向ME电压系数的1.5倍.另外由于不含铅，锆等有害物质，符合环保要求，因此采用掺杂BaTiO₃制备的磁电效应器件具有深入研究和应用价值.     

模拟核素固化体Gd2Zr2-xCexO7(0≤ x≤ 2.0)的物相及化学稳定性研究

为研究钆锆烧绿石固化Pu(Ⅳ)的相变化情况及化学稳定性, 以Gd₂O₃, ZrO₂为原料, Ce(Ⅳ)作为Pu(Ⅳ)的模拟替代物质, 采用冷压热烧结的方法制备出Gd₂Zr_2-xCe_xO₇(0≤ x≤ 2.0)系列样品. 分别在40 °C和70 °C的合成海水中, 对固化体的长期浸出性能进行研究. 借助粉末X射线衍射仪对所制备样品的物相信息进行收集, 利用等离子体质谱仪对固化体的浸出浓度数据进行分析. 研究结果表明: 当x ≤0.08时, 固化体保持为烧绿石相; 当x>0.08时, 固化体转变为具有缺陷的萤石型结构相. 固化体中Gd³⁺, Zr⁴⁺和Ce⁴⁺在合成海水中, 随着浸泡时间的延长浸出浓度逐渐上升, 70 °C下的浸出浓度高于40 °C下的浸出浓度. 在42 d时, 固化体中Gd³⁺的最大浸出浓度在0.032 μg·ml^-1以下, Zr⁴⁺的最大浸出浓度在0.003 μg·ml^-1以下; Ce⁴⁺的最大浸出浓度在0.032 μg·ml^-1以下.     

Effect of Sm,Co codoping on the dielectric and magnetoelectric properties of BiFeO3 polycrystalline ceramics

Multiferroic Bi_0.95Sm_0.05Fe_1−xCo_xO₃ (x=0−0.1) ceramics were prepared by the rapid liquid phase sintering method. For all the samples studied, the dielectric constant and dielectric loss decrease with increasing frequency in the range from 1 kHz to 1 MHz. It shows that the dielectric constant of Bi_0.95Sm_0.05FeO₃ at 10 kHz is about forty times larger than that of pure BiFeO₃. This dramatic change in the dielectric properties of Bi_0.95Sm_0.05Fe_1−xCo_xO₃ (x=0−0.1) samples can be understood in terms of the space charge limited conduction associated with crystal defects, which was indicated by the increase of magnetoelectric effect with doping Co³⁺ under applied magnetic field from 1 to 8 kOe. It was believed that the ferroelectric polarization enhancement comes from the exchange interaction between the Sm³⁺ and Fe³⁺ or Co³⁺ ions for Bi_0.95Sm_0.05Fe_0.95Co_0.05O₃ at room temperature.     

Single or both site doped BiFeO3—Which is better candidate for profound electronic device applications?

Magnesium (Mg) and Zirconium (Zr) doped bismuth ferrite (BiFeO₃; BFO) such as Bi_1?xMg_xFeO₃ (Mg doped BFO; BMO), BiFe_1?xZr_xO₃ (Zr doped BFO; BZO) and Bi_1?xMg_xFe_1?xZr_xO₃ (both Mg and Zr doped BFO; BMZO) were synthesized by solid-state reaction techniques with dopant concentrations x?=?0 and 0.1, respectively. The distorted rhombohedral structures of doped BFO were confirmed by X-ray diffraction analysis. The microstructural analysis revealed that there were uniform dispersions and homogeneous distributions of ceramics in BMZO as compared to BMO, BZO and pure BFO. The presence of both grain and grain boundary in BMZO indicated its good electrical response than others as evidenced from impedance analysis and in agreement with AC conductivity study. The dielectric and ferroelectric measurement signified that BMZO possessed enhanced dielectric constant and high remanent polarization thus could be a better prominent candidate than others to be used in electronic devices.     

Electrical behavior of high resistivity Ce-doped BiFeO3 multiferroic

Bi_1+xCe_xFeO₃ (Ce–BFO) for x=0, 0.05, 0.1, and 0.15 monophasic ceramic samples were successfully synthesized by conventional solid-state reaction routes. The influences of Ce doping on structural, dielectric, ferroelectric, leakage current and capacitive properties of BiFeO₃ ceramics were investigated intensively. At higher concentrations of x (x=0.1 and 0.15) the samples showed good crystallinity with almost impurity free phases. No structural phase transformation took place after partial doping of Ce ions and all ceramic bulk samples remain in their rhombohedral structure with space group R3c. The dielectric behavior of the samples improved significantly and the ferroelectric hysteresis loops changed their shape from rounded to a strongly nonlinear typical ferroelectric feature mainly originating from the domain switching and became enhanced with increase in doping concentration of cerium (Ce). Experimental results also suggested that partial doping of higher valence, smaller ionic radius Ce ions in BiFeO₃ forces the reduction of oxygen vacancies, resulting in a great suppression of leakage current. It is found that the sharp capacitance peak/discontinuity present in the C–V characteristics of Ce–BFO for different Ce doping concentrations is directly associated with the polarization reversal. Incorporation of excess bismuth in the presence of Ce in BiFeO₃ is expected to compensate Bi loss during high temperature sintering and caused structural distortion which also favors enhancement of ferroelectric properties in Ce-doped BFO.     

The structural and multiferroic properties of (Bi1−xLax)(Fe0.95Co0.05)O3 ceramics

La and Co co-doped BiFeO₃ ((Bi_1−xLa_x)(Fe_0.95Co_0.05)O₃ (x=0, 0.10, 0.20, 0.30)) ceramics were prepared by tartaric acid modified sol–gel method. The X-ray diffraction patterns indicate a transition from rhombohedral structure to tetragonal structure at x=0.20, which has been confirmed by the Raman measurements. The band gap increases with increasing x to 0.20, and then decreases with further increasing x to 0.30. The structural transition has significant effects on the multiferroic properties. The remnant magnetization and saturate ferromagnetic magnetization decrease abruptly with increasing x to 0.10, and then gradually increase with further increasing x up to 0.30. The coercivity is significantly reduced with increasing La doping concentration. The ferroelectricity has been improved by La doping, and the polarization increases with increasing x to 0.10, then decreases with further increasing x up to 0.30. The simultaneous coexistence of soft ferromagnetism and ferroelectricity at room temperature in tetragonal Bi_0.70La_0.30Fe_0.95Co_0.05O₃ indicates the potential multiferroic applications.     

Improved multiferroic properties of La-doped 0.6BiFeO3—0.4SrTiO3 solid solution ceramics

The 0.6（Bi1-xLax）FeO 3-0.4SrTiO 3（x = 0,0.1） multiferroic ceramics are prepared by a modified Pechini method to study the effect of substitution of SrTiO3 and La in BiFeO3.The X-ray diffraction patterns confirm the single phase characteristics of all the compositions each with a rhombohedral structure.The magnetic properties of the ceramics are significantly improved by a solid solution with SrTiO3 and substitution of La.The values of the dielectric constant ε r and loss tangent tan δ of all the samples decrease with increasing frequency and become constant at room temperature.The La-doped 0.6BiFeO3-0.4SrTiO3 ceramics exhibit improved dielectric and ferroelectric properties,with higher dielectric constant enhanced remnant polarization（Pr） and lower leakage current at room temperature.Compared with a anti-ferromagnetic BiFeO3 compound,the 0.6（Bi0.9La0.1）FeO3-0.4SrTiO3 sample shows the optimal ferromagnetism with remnant magnetization M r ～ 0.135 emμ/g and ferroelectricity with Pr ～ 5.94 μC/cm 2 at room temperature.     

Effect of La substitution on conductivity and dielectric properties of Bi1−xLaxFeO3 ceramics: An impedance spectroscopy analysis

Bismuth ferrite (BFO) and La-substituted BFO with composition Bi_1−xLa_xFeO₃ (x=0.05, 0.1 and 0.15) (BLFO_x=0.05-0.15) ceramics were prepared using the solid state reaction route. A structural phase transition from rhombohedral phase to triclinic phase was observed for BLFO_x=0.05-0.15 ceramics. Modulus spectroscopy reveals the deviation of dielectric behavior from ideal Debye characteristics and the dependence of conductivity on ion hopping in BFO and BLFO_x=0.05-0.15 ceramics. The conductivity of the BFO ceramics decreases for La content of 5 mol%, followed by a subsequent increase with 10 and 15 mol% of lanthanum doping. The typical values of the activation energies at high temperature reveal the contribution of short range movement of doubly ionized oxygen vacancies to the conduction process in BFO and BLFO_x=0.05 ceramics. Both short range and long range motion of oxygen vacancies are responsible for large conductivity in BLFO_{x=0.1 and 0.15} ceramics.     

Effects of Co doping on electronic structure and electric/magnetic properties of La0.1Bi0.9FeO3 ceramics

In this work,we report the influence of Co-doping on the electronic band structure,dielectric and magnetic properties of La0.1Bi0.9Fe1-xCoxO3 ceramics.X-ray photoelectron spectroscopy investigation shows that Co dopant can shift the valence band spectrum and core-level lines of constituent elements towards higher bind energy regions simultaneously increase the concentration of oxygen vacancies in ceramics.The effects of dopant are discussed with focus given to the Co-doping induced enhancement of electrical conductivity and resistive switching phenomena.     

Study of glasses and glass ceramics in Bi2O3-GeO2-Fe2O3 and Bi2O3-GeO2-Cr2O3 systems by optical spectroscopy

The ferroelectric Bi₂GeO₅ crystalline phase is synthesized by heat treatment of 1Bi₂O₃-1GeO₂-xFe₂O₃ and 1Bi₂O₃-1GeO₂-yCr₂O₃ glasses. The obtained glass ceramics and initial glasses are studied using X-ray diffraction analysis and optical spectroscopy. The dielectric characteristics are measured, and the Curie temperature is determined. The effect of chromium and iron ions on the absorption spectra and dielectric properties of glasses and glass ceramics is determined.     

Effect of KNbO<Subscript>3</Subscript> modification on structural,electrical and magnetic properties of BiFeO<Subscript>3</Subscript>

The polycrystalline samples of (Bi_1?x K _x ) (Fe_1?x Nb _x ) O₃ (BKFN) for x = 0.0, 0.1, 0.2 and 0.3 were synthesized by a solid-state reaction method. The X-ray diffraction patterns of BKFN exhibit that the addition of KNbO₃ in BiFeO₃ gradually changes its structure from rhombohedral to pseudocubic. The analysis of scanning electron micrograph clearly showed that the sintered samples have well-defined and uniformly distributed grains. Addition of KNbO₃ to BiFeO₃ enhances the dielectric, ferroelectric and ferromagnetic properties of BiFeO₃. Detailed studies of impedance and related parameters of BKFN using the complex impedance spectroscopic technique exhibit the significant contributions of grain and grain boundaries in the resistive and transport properties of the materials. Some oxygen vacancies created in the ceramic samples during high-temperature processing play an important role in the conduction mechanism. The leakage current or tangent loss of BiFeO₃ is greatly reduced on addition of KNbO₃ to the parent compound BiFeO₃. Preliminary studies of ferroelectric and magnetic characteristics of the samples reveal the existence of ferroelectric, and weak ferromagnetic ordered ceramics.     

Effect of Gd doping on structural, electrical and magnetic properties of BiFeO3 electroceramic

Room temperature multiferroic electroceramics of Gd doped BiFeO₃ monophasic materials have been synthesized adopting a slow step sintering schedule. Incorporation of Gd nucleates the development of orthorhombic grain growth habit without the appearance of any significant impurity phases with respect to original rhombohedral (R3c) phase of un-doped BiFeO₃. It is observed that, the materials showed room temperature enhanced electric polarization as well as ferromagnetism when rare earth ions like Gd doping is critically optimized (x=0.15) in the composition formula of Bi_1+2xGd_2x/2Fe_1−2xO₃. We believe that magnetic moment of Gd⁺³ ions in Gd doped BiFeO₃ tends to align in the same direction with respect to ferromagnetic component associated with the iron sub lattice. The dielectric constant as well as loss factor shows strong dispersion at lower frequencies and the value of leakage current is greatly suppressed with the increase in concentration of x in the above composition. Addition of excess bismuth and Gd (x=0.1 and 0.15) caused structural transformation as well as compensated bismuth loss during high temperature sintering. Doping of Gd in BiFeO₃ also suppresses spiral spin modulation structure, which can change Fe-O-Fe bond angle or spin order resulting in enhanced ferromagnetic property.