Enhancement in multiferroic properties of Bi0.7−xLaxDy0.3FeO3 system with removal of La

La doping at Bi Site in multiferroic BiFeO₃ (BFO) is known to stabilize the ferroelectric perovskite phase and reduce the leakage current. It has been observed that in Dy modified BFO sample, La is not required for the said reason. In fact, the removal of La from Dy modified BFO system leads to the reduction in leakage current. Moreover, the magnetic properties are enhanced by order of magnitude in the absence of La in the system. Remarkably, a similar trend in properties has been also observed in thin films grown on Pt/TiO₂/SiO₂/Si substrate by using the pulsed laser deposition technique. This significant variation in the properties after removal of La from the system could be attributed to the change in lattice parameters, bond lengths and Fe–O–Fe bond angle as determined by powder x-ray and neutron diffraction study.     

Bi1-xLaxFeO3±δ薄膜的快速制备及铁电性

样品的制备是对影响样品质量的各个工艺参数进行优化的过程. 传统的试错法是对各个参数逐个进行尝试, 需要的周期较长. 与传统的单参数尝试法相比, 高通量样品制备方法可以对参数实现并行筛选, 因而极大地缩短了优化工艺所需的时间. 本工作借助高通量制备方法成功实现系列镧掺杂BiFeO₃薄膜的快速优化, 包括对烧结温度、镧元素含量和高温固态反应气氛等关键工艺参数的快速筛选, 同时分析了不同生长条件下样品的结构并测试了其铁电性. 实验结果表明: 1) 560 ℃ 烧结可得到单相薄膜; 2)测量不同La含量样品的铁电性, 发现当E=75 kV/cm时, La=15%的样品剩余极化值(2Pr)最大, 约为26.7 μC/cm²; 3) 在纯氧气氛下烧结有助于得到结晶性更好的单相Bi_0.75La_0.25FeO_3±δ 薄膜, 并且能够提高薄膜的铁电性.     

Effect of bilayer structure and a SrRuO3 buffer layer on ferroelectric properties of BiFeO3 thin films

Effects of the BiFe_0.95Mn_0.05O₃ thickness and a SrRuO₃ (SRO) buffer layer on the microstructure and electrical properties of BiFeO₃/BiFe_0.95Mn_0.05O₃ (BFO/BFMO) bilayered thin films were investigated, where BFO/BFMO bilayered thin films were fabricated on the SRO/Pt/Ti/SiO₂/Si(100) substrate by a radio frequency sputtering. All thin films are of a pure perovskite structure with a mixture of (110) and (111) orientations regardless of the BFMO layer thickness. Dense microstructure is demonstrated in all thin films because of the introduction of BFMO layers. The SRO buffer layer can also further improve the ferroelectric properties of BFO/BFMO bilayered thin films as compared with those of these thin films without a SRO buffer layer. The BFO/BFMO bilayered thin film with a thickness ratio of 220/120 has an enhanced ferroelectric behavior of 2P _r??165.23???C/cm² and 2E _c??518.56?kV/cm, together with a good fatigue endurance. Therefore, it is an effective way to enhance the ferroelectric and fatigue properties of bismuth ferrite thin films by constructing such a bilayered structure and using a SRO buffer layer.     

Enhanced electrical and ferroelectric properties in a multiferroic (BiFeO3/Bi0.5Na0.5TiO3)3/LaNiO3 superlattices structure

Artificial multiferroic superlattices (SL), consisting of BiFeO₃ (16 nm)/Bi_0.5Na_0.5TiO₃ (5 nm) (BFO/BNT SL), were grown on (001) SrTiO₃ single crystal by pulsed laser deposition method. The cross-sectional, surface morphology, and crystallographic structure of BFO/BNT SL and BFO single layer were investigated. It was found that the electrical, ferroelectric, and magnetic properties of BFO/BNT SL exhibit a remarkably enhancement compared with BFO single layer. The influence of BNT buffering layer, lattice strain, and interfaces interplay of the SL structure are supposed to benefit their ferroelectric and ferromagnetic properties. Our works suggested the BFO/BNT SL with an improved multiferroic characteristics have a promising application for the future informational storage devices.     

Enhanced multiferroic properties in La and Ce co-doped BiFeO3 nanoparticles

Room temperature multiferroic properties of BiFeO₃ (BFO), Bi_0.9La_0.1FeO₃ ((La)BFO) and Bi_0.9La_0.075Ce_0.025FeO₃ ((La,Ce)BFO) nanoparticles have been reported in this paper. XRD (X-ray diffraction) analyses of the nanoparticles show a decrease in the lattice constants and cell volume with the substitution of La and Ce. It is evident from the SEM (scanning electron microscope) micrographs that the (La,Ce) co-doped sample possesses dense microstructure made of smaller particles. Raman study accounts for the weakening of the strong hybridization between Bi-O by the substitution of La and Ce ions. This is also accompanied by an increase in the remanent magnetization, dielectric constant, and ferroelectric polarization. BFO nanoparticles show exchange bias effect under an applied magnetic field while the (La)BFO and (La,Ce)BFO samples show no trace of such effect. Ac-conductivity of (La,Ce) co-doped sample is observed to be several orders lesser in magnitude than bulk BFO ceramics. These results are interpreted by means of the subtle change in the structure, suppression of the spin cycloid and reduction of oxygen vacancies in the doped samples.     

Magnetoelectric properties of Mn-substituted BiFeO3 thin films with a TiO2 barrier

Multiferroic thin films with the general formula TiO₂/BiFe_1−xMn_xO₃ (x=0.00, 0.05, 0.10 and 0.15) (TiO₂/BFMO) were synthesized on Au/Ti/SiO₂/Si substrates using a chemical solution deposition (CSD) method assisted with magnetron sputtering. X-ray diffraction analysis shows the thin films contained perovskite structures with random orientations. Compared with BFMO films, the leakage current density of the TiO₂/BFMO thin films was found to be lower by nearly two orders of magnitude, and the remnant polarizations were increased by nearly ten times. The enhanced ferroelectric properties may be attributed to the lower leakage current caused by the introduction of the TiO₂ layer. The J-E characteristics indicated that the main conduction mechanism for the TiO₂/BFMO thin film was trap-free Ohmic conduction over a wide range of electric fields (0-500 kV/cm). In addition, ferromagnetism was observed in the Mn doped BFO thin films at room temperature. The origin of ferromagnetism is related to the competition between distortion of structure and decrease of grain size and decreasing net magnetic moment in films due to Mn doping.     

Direct observation of ferroelectric domain switching in varying electric field regimes using in situ TEM

In situ Transmission Electron Microscopy (TEM) techniques can potentially fill in gaps in the current understanding interfacial phenomena in complex oxides. Select multiferroic oxide materials, such as BiFeO(3) (BFO), exhibit ferroelectric and magnetic order, and the two order parameters are coupled through a quantum-mechanical exchange interaction. The magneto-electric coupling in BFO allows control of the ferroelectric and magnetic domain structures via applied electric fields. Because of these unique properties, BFO and other magneto-electric multiferroics constitute a promising class of materials for incorporation into devices such as high-density ferroelectric and magnetoresistive memories, spin valves, and magnetic field sensors. The magneto-electric coupling in BFO is mediated by volatile ferroelastically switched domains that make it difficult to incorporate this material into devices. To facilitate device integration, an understanding of the microstructural factors that affect ferroelastic relaxation and ferroelectric domain switching must be developed. In this article, a method of viewing ferroelectric (and ferroelastic) domain dynamics using in situ biasing in TEM is presented. The evolution of ferroelastically switched ferroelectric domains in BFO thin films during many switching cycles is investigated. Evidence of partial domain nucleation, propagation, and switching even at applied electric fields below the estimated coercive field is revealed. Our observations indicate that the occurrence of ferroelastic relaxation in switched domains and the stability of these domains is influenced the applied field as well as the BFO microstructure. These biasing experiments provide a real time view of the complex dynamics of domain switching and complement scanning probe techniques. Quantitative information about domain switching under bias in ferroelectric and multiferroic materials can be extracted from in situ TEM to provide a predictive tool for future device development.     

激发态电荷转移有机体的多铁性研究

随着人们对多铁性的深入了解,越来越多不同类型的有机多铁材料被合成出来.激发态电荷转移有机体的电荷转移网络是由一个提供电子的分子(给体donor,D~+)和一个接受电子的分子(受体acceptor,A~-)有序排列后构成的.D~+A~-长程有序排列,其激发态(激子)具有较长寿命和±1/2自旋,这是产生室温铁电性和铁磁性的根本原因.激发态容易受外场刺激,因此光照、磁场、电场、应力等能够很好地调控这类材料的铁电极化、磁矩和相应的磁电耦合系数.激发态电荷转移有机体不仅大大丰富了室温多铁材料体系,而且可以为开发新型多功能电子器件提供材料基础和技术储备.     

High optical performance and practicality of active plasmonic devices based on rhombohedral BiFeO3

First principles calculations of electronic and optical properties of multiferroic oxide BiFeO₃ are used in combination with a plasmonic device model of optical switch to show that a BiFeO₃ based device can have much better performance than devices based on existing materials. This arises from the combination of octahedral tilts, ferroelectricity and G‐type antiferromagnetism in BiFeO₃ leading to a strong dependence of the optical refractive indices on the orientation with respect to the polarization. A prototype of a plasmonic resonator with an R‐BFO thin film layer is used as an example and shows excellent switch and modulation responses. The proposed approach provides potential opportunities to develop high performance nanophotonic devices for optical communication.     

Surface enhanced strong visible photoluminescence from one-dimensional multiferroic BiFeO3 nanostructures

The surface defect dominated visible emission from one-dimensional multiferroic BiFeO₃ (BFO) nanowires (NWs) is characterized by photoluminescence (PL) spectroscopy. The PL spectra of BFO NWs exhibit a weak near band emission (NBE) along with a strong defect-level emission (DLE). It is suggested that excess surface defects exist in BFO NWs which are responsible for strong visible green emission. Passivation of BFO NW surface with H₂ significantly improves the NBE emission while suppressing surface recombination. Such a surface enhanced emission promises many potential applications of BFO NWs not only in photonic devices such as LEDs but also in fluorescence-based chemical sensing.     

Structural,electrical and magneto-electric characteristics of double perovskite: BiCaFeCeO6

A double perovskite sample of (Ca, Ce) modified bismuth ferrite (i.e., BiCaFeCeO₆) has been synthesized by a solid state reaction method. A single-phase characteristic of the material was carried out by analyzing basic X-ray crystal structure. The micrograph of the sintered sample was recorded at room temperature by using scanning electron microscope. The image of the micrograph shows the homogeneous distribution of with different grain size and shape. It shows that a high-density sample can be fabricated in the above experimental condition. This prepared complex electronic system (BiCaFeCeO₆) exhibits multiferroic characteristics that has experimentally been supported by detailed analysis of capacitive, impedance, magnetic and other related behavior of the material Attempts have been made to study the (a) effect of microstructures containing grains, grain boundaries and electrodes in impedance and capacitive characteristics, (b) relationship between properties and crystal structure and (c) nature of relaxation mechanism of the prepared samples. Detailed impedance analysis with experimental data, collected at different frequency (10³–10⁶ Hz) and temperatures, has provided many important characteristics of the material. The variation of conductivity in alternating current of the material at different temperatures follows Jonsher's universal power law. Some multiferroic characteristics (dielectric constant, tangent loss, conductivity, magneto-electric) of bismuth ferrite have been tailored (decrease/increase) by multiple doping of (Ca, Ce) which will be useful to explore the possibility for applications.     

Synthesis, microstructures, and magnetoelectric couplings of electrospun multiferroic nanofibers

Multiferroic materials with two or more types of ferroic orders have attracted a great deal of attention in the last decade for their magnetoelectric coupling, and new ideas and concepts have been explored recently to develop multiferroic materials at nano-scale. Motivated by theoretical analysis, we synthesized single-phase BiFeO₃ (BFO) nanofibers, Pb(Zr_0.52Ti_0.48)O₃-CoFe₂O₄ (PZT-CFO) and Pb(Zr_0.52Ti_0.48)O₃-NiFe₂O₄ (PZT-NFO) composite nanofibers, and CoFe₂O₄-Pb(Zr_0.52Ti_0.48)O₃ (CFO-PZT) core-shell nanofibers using sol-gel based electrospinning. These nanofibers typically have diameters in the range of a few hundred nanometers and grain size in the range of 10s nanometers, and exhibits both ferroelectric and ferromagnetic properties. Piezoresponse force microscopy (PFM) based techniques have also been developed to examine the magnetoelectric coupling of the nanofibers, which is estimated to be two orders of magnitude higher than that of thin films, consistent with our theoretical analysis. These nanofibers are promising for a variety of multiferroic applications.     

Oxygen vacancy dominant strong visible photoluminescence from BiFeO3 nanotubes

In this Letter, we report oxygen vacancy dominant strong visible photoluminescence (PL) from multiferroic BiFeO₃(BFO) nanotubes (NTs) prepared by sol–gel template method. Abundant oxygen vacancies present in BFO NTs provide alternate paths for the photo‐induced carrier generation and recombination thus affecting the PL and photoabsorption characteristics. This study not only assists in understanding the optoelectronic characteristics of BFO NTs at nanoscale but also suggests BFO nanostructures as potential candidates for future photonic and sensing applications. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study of the structural, dielectric and magnetic properties of Bi2O3 and PbO addition on BiFeO3 ceramic matrix

In this paper we studied the effects of Bi₂O₃ and PbO addition on BiFeO₃ (BFO) ceramic matrix. The structural, dielectric and magnetic properties of fifteen BFO samples were discussed in view of possible applications in RF and microwave devices. The present work also reports the preparation of the samples. Polyvinyl alcohol (PVA) and tetraethyl orthosilicate (TEOS) were also added as a binder in the fabrication procedure. The samples have been studied by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and magnetic hysteresis measurements. Further, a study based on impedance spectroscopy also has been done. Dielectric permittivity (ε′) and dielectric loss (tan δ) were measured at room temperature in the frequency range 100 Hz-10 MHz, as well as a.c. conductivity. The -Im[Z(f)] versus Re[Z(f)] plot has been obtained. The samples were investigated in view of possible applications like miniaturized filters, diplexers and dielectric resonator antennas (DRA). In the RF and MW frequency region, the application of magneto-dielectric and multiferroic perovskite composite materials is desirable for the miniaturization of components.     

Modification in structure of La and Nd co‐doped epitaxial BiFeO3 thin films probed by micro Raman spectroscopy

The influence of La and Nd co‐substitution on structure, electric and magnetic properties of epitaxial thin films of BiFeO₃ (BFO) was examined. We demonstrate structural phase transition in co‐doped La and Nd BFO thin films using Raman spectroscopy. Based on group theoretical analysis of the number and symmetry of Raman lines, we provide strong experimental evidence that the structure has been changed from rhombohedral to monoclinic due to co‐doping in BFO. The change in structure was also reflected in morphology of these films. Room temperature magnetic hysteresis curves showed that doped films exhibit enhanced ferromagnetic properties with remnant magnetization of ~10 emu/cm³ and coercive field of 1.2 kOe. The enhanced magnetic properties highlight the potential applications of doped BLNFO thin film for smart devices. Copyright © 2015 John Wiley & Sons, Ltd.     

Structural,dielectric, electrical and magnetic properties of chemicothermally synthesized material: BiCaFeCeO6

In this communication, detailed studies of structural, micro-structural, dielectric, electrical (impedance, modulus and conductivity) and magneto-electric characteristics of a chemico-thermally synthesized sample of a double perovskite bismuth calcium iron cerate (BiCaFeCeO₆) have been reported. Preliminary structural analysis of room temperature X-ray diffraction data shows orthorhombic structure of the material. The homogeneous distribution of the grains of different dimensions (shape, size, etc) with a small number of voids observed in the scanning electron micrograph suggests the formation of high-density sample. Detailed analysis of dielectric and impedance experimental data, collected at different frequency and temperatures, have provided many important characteristics of the material, such as (a) grains, grain boundaries, and electrode dependent capacitive and impedance parameters, (b) co-relation between the structure, micro-structure and physical properties and (c) the relaxation characteristics of the tested samples. The nature of frequency dependence of AC conductivity of the material obeys the Jonscher's universal power law. The temperature dependence of conductivity provides the conduction mechanism in the material. Detailed studies of field dependence of electric polarization, magnetization and magneto-electric coefficient at room temperature exhibit the multiferroic characteristics of the material.     

Defect driven multiferroicity in Gd doped BiFeO3 at room temperature

This paper reports that defect driven magnetism can be obtained at room temperature by optimizing metal ion concentration in bismuth ferrite (BFO) following our novel slow step solid state sintering route. We observed a clean signature of enhanced multiferroic behavior in Gd doped bismuth ferrite (Gd-BFO) bulk ceramics at room temperature (RT). Bismuth rich iron deficient Gd-BFO ceramics were prepared by solid state route through slow step sintering schedule at 850 °C. At particular composition, (Bi_1.2Gd_0.1Fe_0.8O₃), this materials completely transform from rhombohedral R3c to orthorhombic Pn2₁a space group. We emphasized that excess bismuth is expected to act as point defects and occupy interstitials positions, which in turn interact by oxygen vacancies. These defects are likely to promote defect driven ferromagnetism in BFO system. Incorporation of Gd in presence of excess bismuth in BFO enhanced both spin and electric polarization at room temperature. We also infer that Gd substitution in BFO is likely to suppress spiral spin modulation, which also favors ferromagnetism in Gd-BFO.     

Surface State‐Induced Anomalous Negative Thermal Quenching of Multiferroic BiFeO3 Nanowires

Wide‐bandgap semiconductor nanowires with surface defect emission centers have the potential to be used as sensitive thermometers and optical probes. Here, we show that the green luminescence of multiferroic BiFeO₃ (BFO) nanowires shows an anomalous negative thermal quenching (NTQ) with increasing temperatures. The release of trapped carriers from localized surface defect states is suggested as the possible mechanism for the increased green luminescence which was experimentally observed at elevated temperatures. A reasonable interpretation of the photoluminescence (PL) processes in BFO nanowires is achieved, and the activation energies of the PL quenching and thermal hopping are deduced. Negative thermal quenching of BFO nanowires provides a new strategy for optical thermometry at higher temperatures.     

Fundamentals of Multiferroic Materials and Their Possible Applications

Materials science is recognized as one of the main factors driving development and economic growth. Since the silicon industrial revolution of the 1950s, research and developments in materials and solid state science have radically impacted and transformed our society by enabling the emergence of the computer technologies, wireless communications, Internet, digital data storage, and widespread consumer electronics. Today's emergent topics in solid state physics, such as nano-materials, graphene and carbon nano-tubes, smart and advanced functional materials, spintronic materials, bio-materials, and multiferroic materials, promise to deliver a new wave of technological advances and economic impact, comparable to the silicon industrial revolution of the 1950s.

The surge of interest in multiferroic materials over the past 15 years has been driven by their fascinating physical properties and huge potential for technological applications. This article addresses some of the fundamental aspects of solid-state multiferroic materials, followed by the detailed presentation of the latest and most interesting proposed applications of these multifunctional solid-state compounds. The applications presented here are critically discussed in the context of the state-of-the-art and current scientific challenges. They are highly interdisciplinary covering a wide range of topics and technologies including sensors, microwave devices, energy harvesting, photo-voltaic technologies, solid-state refrigeration, data storage recording technologies, and random access multi-state memories. According to their potential and expected impact, it is estimated that multiferroic technologies could soon reach multibillion US dollar market value.     

Structural,optical, and multiferroic properties of single phased BiFeO3

A soft chemical coprecipitation method has been proposed for synthesis of nano-sized multiferroic BiFeO₃ (BFO) powders. The X-ray diffraction pattern confirms the perovskite structure of BFO and Rietveld refinement reveals the existence of rhombohedral R3c symmetry. Crystallite size and strain value are studied from Williamson–Hall (W–H) analysis. The transmission electron microscope (TEM) image shows that the particle size of BFO powders lies between 50–100 nm. 4A₁ and 7E Raman modes have been observed in the range 100–650 cm^?1 and a prominent band centered around 1150–1450 cm^?1 have also been observed corresponding to the two-phonon scattering. Differential Thermal Analysis (DTA) shows the existence of two prominent peaks at 330 ^°C and 837 ^°C corresponding to the magnetic and ferroelectric ordering, respectively. From the temperature dependent dielectric studies, an anomaly in the dielectric constant is observed at the vicinity of Neel temperature (T _N ) indicating a magnetic ordering. Also, BFO shows antiferromagnetic behavior measured from the magnetic studies.