磁电复合材料PMN-PT/Terfenol-D/PMN-PT磁电耦合性能的有限元分析

由铁电相和铁磁相组成的磁电复合材料被证明有非常显著的磁电耦合效应,近年来受到越来越多的关注。利用有限元PDE的方法对磁电复合材料PMN-PT/Terfenol-D/PMN-PT的磁电耦合性能进行了分析,主要研究了边界条件、结构尺寸对磁电耦合性能的影响。研究发现,当上下表面y方向固定,其它表面自由时,磁电复合材料长度方向伸缩更加明显,具有更大的磁电耦合系数;铁电相和铁磁相厚度比与磁电耦合系数程非线性关系,当铁电相厚度为1.1mm,铁磁相厚度为1.9mm时,磁电耦合系数具有最大值3.354((V/m)/A/m));当铁电层尺寸保持不变,铁磁层长度超过10mm后,铁磁层长度对磁电耦合系数影响不明显。该理论结果可以用于提高磁电耦合性能同时达到节省材料的目的。     

铁电相BiFeO3对多铁复合薄膜CoFe2O4-BiFeO3铁磁性能的影响

为了研究铁电相BiFeO₃对复合薄膜磁性能的影响,在LaNiO₃ (LNO)缓冲层的Si (100)衬底上旋涂制备了含有0、6、9、10层等不同厚度BiFeO₃的层状CoFe₂O₄-BiFeO₃ (CFO-BFO) 多铁复合薄膜。采用XRD、SEM以及TEM对其结构和形貌进行了表征,采用振动样品磁强计测量磁性,研究了不同厚度BFO对复合薄膜磁性的影响。结果表明: CFO和BFO在异质结构薄膜中共存。缓冲层LNO和铁磁相CFO薄膜具有精细微观结构及明显界面。铁电相BFO的厚度对CFO-BFO复合薄膜的磁性能产生了很大影响。在含有不同层数铁电相BFO的复合薄膜中,含有9层BFO复合薄膜的饱和磁化强度最大,达到了230 emu·cm^-3,相比无铁电相BFO的薄膜,饱和磁化强度提高了18.6%。初步讨论认为: 随着铁电相BFO厚度的增加,CFO与BFO之间的应力传导引起了复合薄膜饱和磁化强度的提高。     

TiO2 /BiFeO3薄膜中增强的磁性和铁电性能

为改善铁酸铋(Bi Fe O3)薄膜的铁电性能,通过溶胶-凝胶和磁控溅射的方法在Au/Pt/Cr/Si基底上制备了Ti O2/Bi Fe O3(Ti O2/BFO)和Bi Fe O3薄膜.采用扫描探针显微镜、扫描电子显微镜、X射线衍射仪、铁电测试仪和物理性能测量仪对薄膜进行了物性表征.实验结果表明:Ti O2阻挡层抑制了BFO薄膜表面缺陷的形成,提高了复合薄膜的绝缘性能,使Ti O2/BFO薄膜中泄漏电流明显降低,且导电机制由欧姆型向空间电荷限制传导型转变.此外,溅射Ti O2阻挡层破坏了BFO表面的螺旋结构,使Ti O2和BFO之间晶格失配而产生界面应力,提高了薄膜的磁电性能.在顶电极和铁电层之间引入阻挡层是提高BFO薄膜磁电性能的一种有效方法.     

流延成型法制备2-2型多层(CoFe_2O_4-Pb(Zr_(0.52)Ti_(0.48))O_3)_n磁电复合薄膜

运用流延成型法制备了具有良好铁电铁磁性能的2-2型多层(CoFe_2O_4-Pb(Zr_(0.52)Ti_(0.48))O_3)_n[(CFOPZT)n]磁电复合薄膜。通过X射线衍射仪、扫描电镜、振动样品磁强计和铁电测试仪测试研究了(CFO-PZT)n复合薄膜的组织结构、铁磁和铁电性能。结果表明,钙钛矿结构的PZT和尖晶石结构的CFO相对均匀地分布在多层复合薄膜各层中,界面平整均匀。随热处理温度的升高,薄膜致密度提高,晶粒长大,但相结构未变,无新相形成。900℃热处理的(CFO-PZT)n复合薄膜结晶更完善,磁电性能好,剩余极化强度为32.63μC/cm~2,饱和磁化强度高达80.56kA/m,在2.29×10~4 A/m偏置磁场处有最大磁电耦合系数17.69kV/(cm·T)。     

钛酸铋铁电薄膜的改性及其复合薄膜的磁电耦合效应研究

对铋层状钙钛矿结构钛酸铋无铅铁电薄膜的制备、改性、失效行为,以及钛酸铋-铁酸钴多铁复合材料进行了研究。通过分析A位和B位离子的极化率和半径关系,设计了一系列复合掺杂钛酸铋基无铅铋层状钙钛矿铁电体系,并制备出了一系列性能优良的单掺杂和复合掺杂的钛酸铋基无铅铁电薄膜,结果表明A位La~(3 )、Nd~(3 )、Eu~(3 )掺杂,B位V~(5 )、Zr~(4 )、Mn~(4 )都可以明显提高薄膜的性能,特别是A位Nd~(3 )掺杂可以很好地提高剩余极化强度和抗疲劳性,B位Mn~(4 )掺杂可以降低矫顽场和漏电电流,有望突破无铅铁电薄膜的应用瓶颈;同时,研究了铁电薄膜及其在辐照条件下的疲劳、保持性能损失和印记失效等失效行为,提出了一个能合理解释印记失效的双界面层的理论模型;还利用化学溶液沉积法制备了不同复合结构(颗粒复合和层状复合)的Nd掺杂钛酸铋/铁酸钴多铁薄膜,并研究了不同复合结构中的磁电耦合效应,研究发现在铁电/铁磁多铁复合材料中,铁电/铁磁界面处两种不同材料之间的原子相互耦合对磁电耦合效应具有很大的贡献。     

纳米尺度的磁电复合薄膜

纳米尺度的磁电复合薄膜具有优良的铁电铁磁耦合特性,其在下一代新型多功能器件中具有大的应用潜力,从而引起了广泛关注.介绍了纳米尺度磁电复合薄膜的实验制备和性能,重点论述了磁电复合薄膜中的铁电相和铁磁相材料,最后指出了磁电复合薄膜中尚待进一步研究的问题.     

相扩散阻挡法制备铁酸钴/改性钛酸铋钠0-3复合多铁性陶瓷

通过溶胶-凝胶工艺在CoFe₂O₄(简称CFO)粉体表面包覆二氧化锆陶瓷层来阻挡烧结过程中铁磁相与铁电相之间的离子扩散. 包覆后的CFO与0.92(Bi_0.5Na_0.5)TiO3-0.02(Bi_0.5K_0.5)TO₃-0.06BaTiO₃(简称BNBT) 陶瓷粉体分别按照xCFO/(1-x) BNKLABT (质量分数x = 0.05、0.10、0.15、0.20、0.25、0.30)混合均匀, 并用聚乙烯醇为粘结剂模压成圆片; 再经过1050℃烧结制备了铁磁/铁电0-3型复合材料. XRD分析表明: 二氧化锆在高温烧结过程中对离子扩散具有良好的阻挡作用. 复合陶瓷的耐击穿电压大于75kV/cm. 测量结果表明: 复合陶瓷的压电应变常数、机电耦合系数、介电常数和剩余极化随CFO含量的增加而降低; 磁电耦合系数、介电损耗随CFO含量的增加而有所增大. -35mm×1.5mm的复合陶瓷样品(x=0.05)在谐振频率(90kHz)和199kA/m 偏置磁场下的磁电系数为1.39V/A.     

膜/块体结构氧化物复合磁电材料研究进展

由铁氧体(如: CoFe₂O₄, NiFe₂O₄)和铁电相(如: BaTiO₃, Pb(Zr_xTi_1-x)O₃)组成的复合材料是经典的复合磁电材料, 也是最早在室温下观察到大磁电耦合效应的复合材料。这类复合材料的制备通常是在高于1200℃的高温条件下将铁氧体相和铁电相两相共烧而成。然而, 在高温过程中不可避免的存在原子互扩散及两相界面反应, 甚至出现微裂纹。本文综合介绍了几种通过直接在一种铁性氧化物块体上生长另一种铁性陶瓷膜的方法, 从而实现铁电、铁磁两相之间的低温复合(一般不高于800℃), 避免了高温共烧过程中的固有问题, 并展示了此类膜/块体复合体系的磁电耦合性能常用的表征方法。     

Ba_(0.8)Sr_(0.2)TiO_3/CoFe_2O_4异质结层状多铁复合薄膜的制备与性能

利用射频磁控溅射法在Pt(200)/TiO_2/SiO_2/Si(100)衬底上沉积Ba_(0.8)Sr_(0.2)TiO_3/CoFe_2O_4异质结层状多铁磁电耦合复合薄膜。Ba_(0.8)Sr_(0.2)TiO_3/CoFe_2O_4异质结复合薄膜为多晶,由钙钛矿Ba_(0.8)Sr_(0.2)TiO_3相和尖晶石CoFe_2O_4相组成。复合薄膜表现为良好的铁电性和铁磁性共存。在测量磁场平行于样品表面情况下测得的复合薄膜的饱和磁化强度(M_s)、剩余磁化强度(M_r)值要大于在测量磁场垂直于样品表面时测得的M_s、M_r值。另外,复合薄膜具有直接的磁电耦合效应,磁电电压系数αE先随着偏置磁场H_(dc)的增大而增大,当偏置磁场H_(dc)增加到445.8kA/m后,αE反而随偏置磁场的增加而减少。当偏置磁场H_(dc)=445.8kA/m时,复合薄膜具有最大的磁电电压系数αE=18.8mV/A。     

Ba0.85Ca0.15Zr0.1Ti0.9O3/CoFe2O4叠层复合陶瓷的制备与磁电耦合效应研究

以CoFe2O4压磁体、掺CuO和CeO2助烧剂的压电体Ba0.85Ca0.15Zr0.1Ti0.9O3为基本叠层材料,采用界面固相熔融渗透法制备了掺助烧剂Ba0.85Ca0.15Zr0.1Ti0.9O3-CoFe2O4叠层复合陶瓷。叠层复合陶瓷的压电压磁相叠层界面结合良好。随着压磁相与压电相厚度比比率的增加,叠层复合陶瓷的饱和磁致伸缩系数–λ从67×10-6增加到134×10-6、压电系数d33从340 pC/N逐渐减小到205 pC/N;磁电耦合系数先增大后减小,在厚度比为2、外磁场为100 mT时得到最大值3200 mV/(cm.mT)。     

Magnetic field induced ferroelectric and dielectric properties in Pb(Zr0.5Ti0.5)O3 films containing Fe3O4 nanoparticles

About 1.05 µm-thick Pb(Zr_0.5Ti_0.5)O₃ (PZT) films containing Fe₃O₄ nanoparticles were deposited on LaNiO₃-coated silicon substrates through a sol-gel technique. Fe₃O₄ nanoparticles were effectively dispersed into PZT solution under the involvement of polyvinylpyrrolidone. X-ray diffraction confirmed the coexistence of PZT and Fe₃O₄ phases without other impurity phases. Scanning electron microscope revealed that the thick composite films possess well-defined and crack-free microstructure. The composite films exhibit good ferroelectric and ferromagnetic properties at room temperature. An obvious magnetodielectric effect has been demonstrated in the Pb(Zr_0.5Ti_0.5)O₃/Fe₃O₄ composite films. Magnetic field induced change in ferroelectric polarization loop may support the possible magnetoelectric coupling between PZT and Fe₃O₄ phases.     

Multiferroic Bi0.7Dy0.3FeO3 thin films directly integrated on Si for integrated circuit compatible devices

Magnetoelectric multiferroic Bi_0.7Dy_0.3FeO₃ (BDFO) thin films deposited on p-type Si (100) substrate using pulsed laser deposition technique demonstrated a saturated ferroelectric and ferromagnetic hysteresis loop at room temperature. More interestingly, the observed change in electric polarization with applied magnetic field in these films indicated the presence of room temperature magnetoelectric coupling behavior. Using high-frequency capacitance-voltage measurements, the fixed oxide charge density, interface trap density and dielectric constant were estimated on Au/BDFO/Si capacitors. These results suggest the integrated circuit compatible application potential of BDFO films in the field of micro-electro-mechanical systems and non-volatile memories.     

Fine-grained multiferroic BaTiO3/(Ni0.5Zn0.5)Fe2O4 composite ceramics synthesized by novel powder-in-sol precursor hybrid processing route

Dense, homogeneous, and fine-grained multiferroic BaTiO₃/(Ni_0.5Zn_0.5)Fe₂O₄ composite ceramics are synthesized by a novel powder-in-sol precursor hybrid processing route. This route includes the dispersion of nanosized BaTiO₃ ferroelectric powders prepared via conventional sold-state ceramic process into (Ni_0.5Zn_0.5)Fe₂O₄ ferromagnetic sol-gel precursor prepared via sol-gel wet chemistry process. Uniformly distributed slurry is obtained after ball milling and used in the fabrication of the ceramics with low sintering temperatures. The ceramics show coexistence of ferromagnetic and ferroelectric phases with obvious ferromagnetic and ferroelectric hysteresis loops at room temperature, besides exhibiting excellent magnetic and dielectric properties in a wide range of frequency. The combination of high permeability and permittivity with low losses in the ceramics enables significant miniaturization of electronic devices based on the ceramics.     

Crystallization behavior and domain structure in textured Pb(Zr0.52Ti0.48)O3 thin films by different annealing processes

Amorphous Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films were prepared on the Pt/Ti/SiO₂/Si substrates by radio-frequency magnetron sputtering at room temperature. After rapid thermal annealing (RTA) and conventional furnace annealing (CFA) at different temperatures, the films were transformed into polycrystalline PZT thin films with (111) and (100) orientation, respectively. The phase formation and ferroelectric domains correlated with different orientation were systematically investigated by X-ray diffraction and piezoresponse force microscopy. The results showed that the perovskite PZT crystal with [111] orientation hetero-nucleated preferentially on top of the PtPb intermetallic phase at the PZT/Pt interface during RTA process. It is of interest to find that the domain self-organized into a structure with rounded shape at the early stage of crystallization. While the nucleation of the films treated by CFA dominantly homo-nucleated, thus the (100) orientation grains with minimum surface energy were easy to grow. The texture effects on ferroelectric properties of PZT films were also discussed in relation to the domain structure.     

Magnetoelectric effect in Pb(Zr0.95Ti0.05)O3 and CoFe2O4 heteroepitaxial thin film composite

Multiferroic epitaxial films, include SrRuO₃/Pb(Zr_0.95Ti_0.05)O₃/CoFe₂O₄ has been successfully deposited on SrTiO₃ substrate by pulsed-laser deposition technique. The results show that the prepared films exhibit a single phase. The Pb(Zr_0.95Ti_0.05)O₃ (PZT) film was highly textured with (1 0 0) orientation and gives good ferroelectric properties with saturated polarization of 15 μC/cm². The magnetic coercivity of CoFe₂O₄ film on Pb(Zr_0.95Ti_0.05)O₃ has been dampened to 0.9 kOe. The anisotropic magnetically behavior of CoFe₂O₄ film was changed to isotropic by using high Zr concentrated PZT as underneath layer. Heterostructure films show a good ferromagnetic and ferroelectric coupling that lead to the large magnetoelectricity of 287 mV/cm Oe.     

Properties of multilayer composite thin films based on morphotropic phase boundary Pb(Mg1/3Nb2/3)O3-PbTiO3

It has been reported that ferroelectric and piezoelectric properties of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMNT) thin films, with compositions close to the morphotropic phase boundary (MPB), show lower values than those reported for bulk ceramics with the same composition, which has been attributed to a reduction of the remnant polarization caused by the small size of the grains in the films. An alternative has been proposed to take full advantage of the excellent piezoelectric properties of polycrystalline PMNT in thin film form: a multilayer configuration that uses ferroelectric layers with large remnant polarization, in this case PbTiO₃, to generate an internal electric bias within the PMNT layers and, thus, anchor an induced polarization on them, resulting in a consequent large piezoelectric behavior. The detailed study of the properties of these multilayer composite films reveals the complex correlations that arise in these heterostructures, which are key for the design of optimized piezoelectric films based on MPB PMNT.     

The study of the electric and magnetic properties of PbZr0.2Ti0.8O3-BiFeO3 multilayers

The results of the electric and magnetic measurements performed on PbZr_0.2Ti_0.8O₃-BiFeO₃ symmetric structures, deposited on Pt/Si wafers, were compared for different number of layers in order to analyse the effect of interfaces over the macroscopic properties. It was found that the shape and magnitude of the capacitance-voltage characteristic, as well as the shape and parameters of the ferroelectric and magnetic hysteresis, depend on the number of interfaces in the intended multilayer structure. A temperature induced gradual transition from a magnetically disordered spin glass like phase of low temperature to an uncompensated antiferromagnetic phase at room temperature takes place in the BiFeO₃ films, under low applied magnetic fields. A partial ferromagnetic like order can be obtained at low temperatures by increasing the field. The observed changes in the electric and magnetic behaviour of the systems were related to an increased degree of disorder for electric dipoles and magnetic moments, due to the increased number of layers and crystallization treatments.     

Comparative analysis for the crystalline and ferroelectric properties of Pb(Zr,Ti)O3 thin films deposited on metallic LaNiO3 and Pt electrodes

The crystalline quality and ferroelectricity of the Pb(Zr,Ti)O₃ (PZT) films deposited on the metallic LaNiO₃ (LNO) and Pt electrodes were comparatively analyzed to investigate the possibility for their application to non-volatile memory devices. LNO thin films were successfully deposited on various substrates by using r.f. magnetron sputtering even at a low temperature ranging from 250 to 500 °C, and the ferroelectric PZT thin films were spin-coated onto the LNO and Pt bottom electrodes. Metallic LNO thin films exhibited [100] orientation irrespective of the substrate species and PZT films coated onto LNO films had highly a- and c-axis orientations, while those with Pt bottom electrode were polycrystalline. PZT films with LNO bottom electrode had smaller grain size and larger dielectric constant compared to those grown on the Pt electrode. The ferroelectric thin films fabricated on LNO bottom electrode displayed an asymmetric D–E hysteresis loop, which was explained by the defect effects formed at the interface. Especially, the LNO/PZT/LNO capacitor was found to significantly improve the polarization fatigue and the effects of the LNO electrodes to the fatigue were discussed.