Room temperature electrical manipulation of giant magnetoresistance in spin valves exchange-biased with BiFeO3

Magnetoelectric multiferroics are attractive materials for the development of low-power electrically controlled spintronic devices. Here we report the optimization of the exchange bias as well as the giant magnetoresistance effect (GMR) of spin valves deposited on top of BiFeO(3)-based heterostructures. We show that the exchange bias can be electrically controlled through a change in the relative proportion of 109° domain walls and propose solutions toward a reversible process.     

Ferroelectric behavior in bismuth ferrite thin films of different thickness

The ferroelectric behavior of BiFeO(3) thin films is modified by changing the film thicknesses, where the BiFeO(3) thin films with different thicknesses were grown on SrRuO(3)/Pt/TiO(2)/SiO(2)/Si(100) substrates by radio frequency sputtering. The mixture of (110) and (111) orientations is induced for all BiFeO(3) thin films regardless of their thicknesses, together with the columnar structure and the dense microstructure. Their dielectric behavior is almost independent of the film thickness where all thin films have a low dielectric loss. A giant remanent polarization of 2P(r) ≈ 156.6-188.8 μC/cm(2) is induced for the BiFeO(3) thin films in the thickness range of 190-600 nm. As a result, it is an effective way to improve the ferroelectric behavior of the BiFeO(3) thin film by tailoring the film thickness.     

Effect of top electrodes on photovoltaic properties of polycrystalline BiFeO3 based thin film capacitors

We investigated capacitors based on polycrystalline narrow-band-gap BiFeO(3) (BFO) thin films with different top electrodes. The photovoltaic response for the capacitor with a Sn-doped In(2)O(3) (ITO) top electrode is about 25 times higher than that with a Au top electrode, which indicates that the electrode plays a key role in determining the photovoltaic response of ferroelectric thin film capacitors, as simulated by Qin et al (2009 Appl. Phys. Lett. 95 22912). The light-to-electricity photovoltaic efficiency for the ITO/polycrystalline BFO/Pt capacitor can reach 0.125%. Furthermore, under incident light of 450 μW cm(-2) and zero bias, the corresponding photocurrent varies from 0.2 to 200 pA, that is, almost a 1000-fold photoconductivity enhancement. Our experiments suggest that polycrystalline BFO films are promising materials for application in photo-sensitive and energy-related devices.     

Electromagnetic excitation of ultrasonic oscillations by yttrium iron garnet films on gallium gadolinium garnet substrates

We have studied the phenomenon of contactless excitation of ultrasonic oscillations by thin yttrium iron garnet (YIG) films on gallium gadolinium garnet (GGG) substrates upon application of the superposition of a constant magnetic bias field and alternating magnetic field. Dimensional resonance effects that cannot be explained in the framework of existing theoretical notions have been discovered, in particular, in dependences of the amplitude of excited longitudinal oscillations on the YIG film thickness, frequency of ultrasound, and degree of homogeneity and strength of the magnetic bias field. It is suggested that the observed phenomenon is caused by resonant participation of the intrinsic oscillations of domain walls in the excitation of ultrasound.     

Fatigue-less relaxor ferroelectric thin films with high energy storage density via defect engineer

Thin film capacitors with excellent energy storage performances,thermal stability and fatigue endurance are strongly desired in modern electrical and electronic industry.Herein,we design and prepare lead-free 0.7Sr0.7Bi0.2TiO3-0.3BiFeO3-x％Mn(x=0,0.5,1.5,2,3)thin films via sol-gel method.Mn ions of divalent valence combine with oxygen vacancies,forming defect complex,which results in marked decline in leakage current and obvious enhancement in breakdown strength.A high energy storage density～47.6 J cm-3 and good efficiency～65.68％are simultaneously achieved in 2％Mn doped 0.7Sr0.7Bi0.2TiO3-0.3BiFeO3 thin film capacitor.Moreover,the 2％Mn-doped thin film exhibits excellent thermal stability in wide operating temperature range(35-115℃)and strong fatigue endurance behaviors after 108 cycles.The above results demonstrate that 2％Mn-doped 0.7Sr0.7Bi0.2TiO3-0.3BiFeO3 thin film capacitor with superior energy storage performances is a potential candidate for electrostatic energy storage.     

CSD法在亲水性的FTO基板上制备BiFeO3薄膜及其电性能的研究

利用化学溶液沉积法在亲水性的FTO基板上制备BiFeO3薄膜。利用XRD、FE-SEM、XPS、Agi-lent E4980A精密LCR仪及TF-Analyzer2000等分析手段对BiFeO3薄膜进行表征。结果表明,薄膜为纯相的结晶良好的多晶BiFeO3薄膜,由100～300nm的BiFeO3晶粒紧密的堆积而成,表面均匀平整。薄膜厚度为450nm。Fe的氧化态为Fe3+,并没有Fe2+出现。在10kHz时,介电常数和损耗分别为134和0.005。薄膜的剩余极化率为0.58μC/cm2,在0～250kV/cm的测试电场下漏导电流步伐保持在10-6 A/cm2以下。     

Electric-field control of local ferromagnetism using a magnetoelectric multiferroic

Multiferroics are of interest for memory and logic device applications, as the coupling between ferroelectric and magnetic properties enables the dynamic interaction between these order parameters. Here, we report an approach to control and switch local ferromagnetism with an electric field using multiferroics. We use two types of electromagnetic coupling phenomenon that are manifested in heterostructures consisting of a ferromagnet in intimate contact with the multiferroic BiFeO(3). The first is an internal, magnetoelectric coupling between antiferromagnetism and ferroelectricity in the BiFeO(3) film that leads to electric-field control of the antiferromagnetic order. The second is based on exchange interactions at the interface between a ferromagnet (Co(0.9)Fe(0.1)) and the antiferromagnet. We have discovered a one-to-one mapping of the ferroelectric and ferromagnetic domains, mediated by the colinear coupling between the magnetization in the ferromagnet and the projection of the antiferromagnetic order in the multiferroic. Our preliminary experiments reveal the possibility to locally control ferromagnetism with an electric field.     

The Influence of Mechanical Stresses on the Magnetic Properties of NiFe2O4 and CoFe2O4 Films

We have studied the influence of mechanical stresses on the magnetic properties of nickel ferrite (NiFev) and cobalt ferrite (CoFe₂O₄) films deposited on sapphire substrates with a- and c-oriented step terrace nanostructures. It is established that compressive stresses favor enhancement of the coercive field in thin ferrite films in the strain direction. Films of magnetically soft nickel ferrite with a room-temperature coercive field of 32.5 mT were obtained.

     

Adsorption-Controlled Growth of BiFeO3 by MBE and Integration with Wide Band Gap Semiconductors

BiFeO3 thin films have been deposited on (001) SrTiO3, (101) DyScO3, (011) DyScO3, (0001) AlGaN/GaN, and (0001) 6H-SiC single crystal substrates by reactive molecular beam epitaxy in an adsorption-controlled growth regime. This is achieved by supplying a bismuth over-pressure and utilizing the differential vapor pressures between bismuth oxides and BiFeO₃ to control stoichiometry in accordance with thermodynamic calculations. Four-circle x-ray diffraction and transmission electron microscopy reveal phase-pure, epitaxial films with rocking curve full width at half maximum values as narrow as 7.2 arc seconds (0.002°). Epitaxial growth of (0001)-oriented BiFeO3 thin films on (0001) GaN, including AlGaN HEMT structures, and (0001) SiC has been realized using intervening epitaxial (111) SrTiO₃ / (100) TiO₂ buffer layers. The epitaxial BiFeO3 thin films have 2 in-plane orientations: [1120] BiFeO>sub>3 || [1120] GaN (SiC) plus a twin variant related by a 180° in-plane rotation. This epitaxial integration of the ferroelectric with the highest known polarization, BiFeO3, with high bandgap semiconductors is an important step toward novel field-effect devices.     

Lead-free (K,Na)NbO3 thin films derived from chemical solution deposition modified with EDTA

Potassium sodium niobate is an important and promising functional material due to its ferroelectric, piezoelectric, and pyro-electric properties, and have received much attention for decades. In this paper, lead-free (K, Na)NbO₃ (KNN)-based ferroelectric thin films were successfully prepared by a chemical solution approach using Nb₂O₅ as niobium resource instead of the expensive niobium ethoxide. The films with a pure perovskite phase were obtained by such an approach modified with ethylenediaminetetraacetic acid (EDTA). EDTA plays a positive role in suppressing the volatilization of alkali metal and facilitates a better film growth rate. EDTA introduction prevents the formation of the pyrochlore phase. The films synthesized with EDTA show large grains and good crystallization, indicating decreased nucleation temperature. The obtained KNN thin films exhibit low leakage current, large saturated polarization, and small coercive field. These results are attributed to the added EDTA, which is effective in inhibiting the formation of vacancies, and to the weakened effect of the defect pinning or clamping of domain walls.     

Influence of coercive force on low-frequency creep in bloch-wall permalloy films

A very high resolution Bitter pattern technique is used to observe the motion of Bloch walls in Permalloy films excited by slowly rising and slowly falling hard-axis fields. For low coercive force films, the basic motion consists of approximately equal and opposite jumps induced by simultaneous wall structure changes at two transition fields. Net motion begins with the application of small easy-axis bias fields. For high coercive force films, although the wall structure changes continue to occur, the wall jumps and a net displacement do net occur until the easy-axis bias field exceeds a certain critical value which is a function of the wall coercive force.     

Growth temperature dependent dielectric properties of BiFeO3 thin films deposited on silica glass substrates

We have studied the dependence of dielectric properties on the deposition temperature of BiFeO₃ thin films grown by the pulsed laser deposition technique. Thin films have been grown onto amorphous silica glass substrates with pre-patterned Au in-plane capacitor structures. It is shown that on the amorphous glass substrate, BiFeO₃ films with a near-bulk permittivity of 26 and coercive field of 80 kV/cm may be grown at a deposition temperature of about 600 °C and 1 Pa oxygen pressure. Low permittivity and higher coercive field of the films grown at the temperatures below and above 600 °C are associated with an increased amount of secondary phases. It is also shown that the deposition of BiFeO₃ at low temperature (i.e. 500 °C) and post deposition ex-situ annealing at elevated temperature (700 °C) increases the permittivity of a film. The applied bias and time dependence of capacitance of the films deposited at 700 °C and ex-situ annealed films are explained by the de-pinning of the ferroelectric domain-walls.     

Influence of coercive force and easy-axis bias on domain wall motion in NiFeCo films excited by hard-axis pulses

Domain wall motion in vacuum-deposited 1200 Å- 2000 Å-thick NiFe and NiFeCo films, excited by a 0.5 ns rise time/200 ns fall time hard-axis pulse field with an easy-axis dc field, is examined with regard to coercive force, easy-axis bias, and low-frequency creep results. Both NiFe and NiFeCo films have the same threshold field characteristics despite large differences in properties. The magnitude of the hard-axis pulse field necessary to cause creep increases with increasing difference between wall coercive force and easy-axis bias. Furthermore, the average creep displacement, for a given hard-axis pulse field magnitude, versus the easy-axis bias field normalized by wall coercive force results in almost identical curves for both NiFe and NiFeCo films except for a shift related to the threshold field. This result is consistent with previous low-frequency creep data and implies that the basic mechanism of low- and high-frequency creep may be closely related. The direction of the basic wall motion depends on the spin polarity in the wall and the durection of the hard-axis pulsed field. Motion in a direction opposite to the basic motion may be produced by an esay-axis bias field of sufficient magnitude but less than then wall coercive force, which is a new and significant result. A theory based on the dynamic torque equation and nonconservative spring coercive force model has been developed to explain the high-frequency creep phenomenon. This theory qualitatively predicts the observed experimental results very well.     

Ferroelectric BiFeO3-PbTiO3 thin films on Pt/Si substrates

In this work we report on the preparation and properties of bismuth ferrite lead titanate films [(1- x)BiFeO(3-x)PbTiO3] with tetragonal compositions (x = 0.8 and 0.7) and compare them with compositions close to the morphotropic phase boundary (MPB; x = 0.4 and 0.3). The films were prepared by pulsed laser deposition on Pt/Si substrates, and exhibited a dense columnar grain growth. X-ray diffraction analysis revealed that the films have a perovskite structure with a preferred (111) texture. The dielectric properties, polarization-field hysteresis, and leakage current behavior of the films is also reported. For MPB compositions, the films exhibited remanent polarizations with 2Pr up to 100 microC cm(-2) and E(c) approximately 185 kV cm(-1) under a maximum applied field of 500 kV cm(-1), while the tetragonal compositions exhibited 2Pr values in the range of 45-52 microC cm(-2) with a coercive field E(c) approximately 118 kV (-1).     

Electrical Tunability of Domain Wall Conductivity in LiNbO3 Thin Films

Domain wall nanoelectronics is a rapidly evolving field, which explores the diverse electronic properties of the ferroelectric domain walls for application in low‐dimensional electronic systems. One of the most prominent features of the ferroelectric domain walls is their electrical conductivity. Here, using a combination of scanning probe and scanning transmission electron microscopy, the mechanism of the tunable conducting behavior of the domain walls in the sub‐micrometer thick films of the technologically important ferroelectric LiNbO₃ is explored. It is found that the electric bias generates stable domains with strongly inclined domain boundaries with the inclination angle reaching 20° with respect to the polar axis. The head‐to‐head domain boundaries exhibit high conductance, which can be modulated by application of the sub‐coercive voltage. Electron microscopy visualization of the electrically written domains and piezoresponse force microscopy imaging of the very same domains reveals that the gradual and reversible transition between the conducting and insulating states of the domain walls results from the electrically induced wall bending near the sample surface. The observed modulation of the wall conductance is corroborated by the phase‐field modeling. The results open a possibility for exploiting the conducting domain walls as the electrically controllable functional elements in the multilevel logic nanoelectronics devices.     

Tuning exchange bias in epitaxial Ni/MgO/TiN heterostructures integrated on Si(1 0 0)

Epitaxial Ni thin films are integrated with tunneling barrier MgO on Si(1 0 0) substrate. During pulsed laser deposition, early island-like structure transformed into uniform thin film with increasing number of laser pulses. This led to transitions in exchange bias from positive to negative and back to positive, which is ascribed to morphology associated residual strain. The Ni island structure has a coercive field as high as 3 times of that of the continuous film. The current work holds a tremendous promise in the realization of magnetic devices integrated with the Si-platform.     

Dynamic properties of spin cluster glass and the exchange bias effect in BiFeO3 nanocrystals

A spin cluster glass behavior and a complicated exchange bias effect are observed in high quality BiFeO(3) nanocrystals grown by a hydrothermal method. The dynamic properties of the spin clusters investigated by measuring the frequency dependences of ac susceptibility show that the relaxation process can be described using a power law with the glass transition temperature T(g) = 57 K, relaxation time constant τ(0) = 4.4 × 10(-10) s, and critical exponent zv = 10.3 ± 1.9, consistent with a three-dimensional Ising spin glass. The exchange bias field (H(EB)) varies non-monotonically with temperature and achieves a minimum at T(g). The abnormal shift of hysteresis loops above T(g) may be interpreted in terms of a Malozemoff's random-field model with a framework of antiferromagnetic core/spin-cluster shell structure and a two-dimensional diluted antiferromagnet in a field (2D-DAFF) model, respectively. The exchange anisotropy of the BiFeO(3) nanocrystals will shed light on a possible application for magnetism related nanosized devices.     

Domain structure and leakage mechanism of BiFeO3 thin films deposited at different temperatures

Pulsed laser deposition method was carried out to fabricate BiFeO₃ (BFO) thin films at different temperatures. Different deposition temperatures resulted in different crystal and domain structures, which affected the leakage mechanism and ferroelectric properties. Attributed to the screen effect of conductive domain walls, the films deposited at high temperature exhibited low leakage. For BFO films, an Ohmic conduction was the main conduction type at low electric field, and a Space-Charge-Limited Current type dominated at higher electric field.     

Dynamic conductivity of ferroelectric domain walls in BiFeO₃

Topological walls separating domains of continuous polarization, magnetization, and strain in ferroic materials hold promise of novel electronic properties, that are intrinsically localized on the nanoscale and that can be patterned on demand without change of material volume or elemental composition. We have revealed that ferroelectric domain walls in multiferroic BiFeO(3) are inherently dynamic electronic conductors, closely mimicking memristive behavior and contrary to the usual assumption of rigid conductivity. Applied electric field can cause a localized transition between insulating and conducting domain walls, tune domain wall conductance by over an order of magnitude, and create a quasicontinuous spectrum of metastable conductance states. Our measurements identified that subtle and microscopically reversible distortion of the polarization structure at the domain wall is at the origin of the dynamic conductivity. The latter is therefore likely to be a universal property of topological defects in ferroelectric semiconductors.     

Ferroelectric and magnetic properties of multiferroic BiFeO(3)-based composite films

BiFeO(3)-based composite films were fabricated onto the Pt/Ti/SiO(2)/Si(100) substrates by a chemical solution deposition (CSD) method using the precursor solutions with various excess iron composition followed by annealing at 923 K for 30 minutes under oxygen gas flow. Coexistence of spontaneous magnetization and remanent polarization could be obtained in the BiFeO(3)-based composite films with high excess iron composition. The remanent magnetization of almost 20 emu/cm(3) and the magnetic coercive field of 1.5 kOe were obtained at the iron composition ratio of Fe/Bi = 1.25. In this specimen, the remanent polarization at 90 K was approximately 10 microC/cm(2) at the electric field of 1500 kV/cm. Structural analysis suggested that the remanent polarization has a possibility to increase by suppressing the formation of the secondary phases of Bi(2)Fe(4)O(9) and alpha-Fe(2)O(3), these are the nonferroelectric material as well as antiferromagnetic phase.