Tailoring Magnetic Properties of Co-Fe Thin Films by Topographical Modifications Using Thermal Annealing and Swift Heavy Ion Irradiation and Fabrication of Magnetoelectric Multilayers for Device Applications

Magnetism and magnetic materials have been playing a lead role in improving the quality of life. They are increasingly being used in a wide variety of applications ranging from compasses to modern technological devices. Metallic glasses occupy an important position among magnetic materials. They assume importance both from a scientific and an application point of view since they represent an amorphous form of condensed matter with significant deviation from thermodynamic equilibrium. Metallic glasses having good soft magnetic properties are widely used in tape recorder heads, cores of high-power transformers and metallic shields. Superconducting metallic glasses are being used to produce high magnetic fields and magnetic levitation effect. Upon heat treatment, they undergo structural relaxation leading to subtle rearrangements of constituent atoms. This leads to densification of amorphous phase and subsequent nanocrystallisation. The short-range structural relaxation phenomenon gives rise to significant variations in physical, mechanical and magnetic properties. Magnetic amorphous alloys of Co-Fe exhibit excellent soft magnetic properties which make them promising candidates for applications as transformer cores, sensors, and actuators. With the advent of microminiaturization and nanotechnology, thin film forms of these alloys are sought after for soft under layers for perpendicular recording media. The thin film forms of these alloys can also be used for fabrication of magnetic micro electro mechanical systems (magnetic MEMS). In bulk, they are drawn in the form of ribbons, often by melt spinning. The main constituents of these alloys are Co, Fe, Ni, Si, Mo and B. Mo acts as the grain growth inhibitor and Si and B facilitate the amorphous nature in the alloy structure. The ferromagnetic phases such as Co-Fe and Fe-Ni in the alloy composition determine the soft magnetic properties. The grain correlation length, a measure of the grain size, often determines the soft magnetic properties of these alloys. Amorphous alloys could be restructured in to their nanocrystalline counterparts by different techniques. The structure of nanocrystalline material consists of nanosized ferromagnetic crystallites embedded in an amorphous matrix. When the amorphous phase is ferromagnetic, they facilitate exchange coupling between nanocrystallites. This exchange coupling results in the vanishing of magnetocrystalline anisotropy which improves the soft magnetic properties. From a fundamental perspective, exchange correlation length and grain size are the deciding factors that determine the magnetic properties of these nanocrystalline materials. In thin films, surfaces and interfaces predominantly decides the bulk property and hence tailoring the surface roughness and morphology of the film could result in modified magnetic properties. Surface modifications can be achieved by thermal annealing at various temperatures. Ion irradiation is an alternative tool to modify the surface/structural properties. The surface evolution of a thin film under swift heavy ion (SHI) irradiation is an outcome of different competing mechanism. It could be sputtering induced by SHI followed by surface roughening process and the material transport induced smoothening process. The impingement of ions with different fluence on the alloy is bound to produce systematic microstructural changes and this could effectively be used for tailoring magnetic parameters namely coercivity, saturation magnetization, magnetic permeability and remanence of these materials. Swift heavy ion irradiation is a novel and an ingenious tool for surface modification which eventually will lead to changes in the bulk as well as surface magnetic property. SHI has been widely used as a method for the creation of latent tracks in thin films. The bombardment of SHI modifies the surfaces or interfaces or creates defects, which induces strain in the film. These changes will have profound influence on the magnetic anisotropy and the magnetisation of the specimen. Thus inducing structural and morphological changes by thermal annealing and swift heavy ion irradiation, which in turn induce changes in the magnetic properties of these alloys, is one of the motivation of this study. Multiferroic and magneto-electrics is a class of functional materials with wide application potential and are of great interest to material scientists and engineers. Magnetoelectric materials combine both magnetic as well as ferroelectric properties in a single specimen. The dielectric properties of such materials can be controlled by the application of an external magnetic field and the magnetic properties by an electric field. Composites with magnetic and piezo/ferroelectric individual phases are found to have strong magnetoelectric (ME) response at room temperature and hence are preferred to single phasic multiferroic materials. Currently research in this class of materials is towards optimization of the ME coupling by tailoring the piezoelectric and magnetostrictive properties of the two individual components of ME composites. The magnetoelectric coupling constant (MECC) (_ ME) is the parameter that decides the extent of interdependence of magnetic and electric response of the composite structure. Extensive investigates have been carried out in bulk composites possessing on giant ME coupling. These materials are fabricated by either gluing the individual components to each other or mixing the magnetic material to a piezoelectric matrix. The most extensively investigated material combinations are Lead Zirconate Titanate (PZT) or Lead Magnesium Niobate-Lead Titanate (PMNPT) as the piezoelectric, and Terfenol-D as the magnetostrictive phase and the coupling is measured in different configurations like transverse, longitudinal and inplane longitudinal. Fabrication of a lead free multiferroic composite with a strong ME response is the need of the hour from a device application point of view. The multilayer structure is expected to be far superior to bulk composites in terms of ME coupling since the piezoelectric (PE) layer can easily be poled electrically to enhance the piezoelectricity and hence the ME effect. The giant magnetostriction reported in the Co-Fe thin films makes it an ideal candidate for the ferromagnetic component and BaTiO3 which is a well known ferroelectric material with improved piezoelectric properties as the ferroelectric component. The multilayer structure of BaTiO3- CoFe- BaTiO3 is an ideal system to understand the underlying fundamental physics behind the ME coupling mechanism. Giant magnetoelectric coupling coefficient is anticipated for these multilayer structures of BaTiO3-CoFe-BaTiO3. This makes it an ideal candidate for cantilever applications in magnetic MEMS/NEMS devices. SrTiO3 is an incipient ferroelectric material which is paraelectric up to 0K in its pure unstressed form. Recently few studies showed that ferroelectricity can be induced by application of stress or by chemical / isotopic substitution. The search for room temperature magnetoelectric coupling in SrTiO3-CoFe-SrTiO3 multilayer structures is of fundamental interest. Yet another motivation of the present work is to fabricate multilayer structures consisting of CoFe/ BaTiO3 and CoFe/ SrTiO3 for possible giant ME coupling coefficient (MECC) values. These are lead free and hence promising candidates for MEMS applications. The elucidation of mechanism for the giant MECC also will be the part of the objective of this investigation.

Structure of PbTe(SiO(2))/SiO(2) multilayers deposited on Si(111)

The structure of thin films composed of a multilayer of PbTe nanocrystals embedded in SiO(2), named as PbTe(SiO(2)), between homogeneous layers of amorphous SiO(2) deposited on a single-crystal Si( 111) substrate was studied by grazing-incidence small-angle X-ray scattering (GISAXS) as a function of PbTe content. PbTe(SiO(2))/SiO(2) multilayers were produced by alternately applying plasma-enhanced chemical vapour deposition and pulsed laser deposition techniques. From the analysis of the experimental GISAXS patterns, the average radius and radius dispersion of PbTe nanocrystals were determined. With increasing deposition dose the size of the PbTe nanocrystals progressively increases while their number density decreases. Analysis of the GISAXS intensity profiles along the normal to the sample surface allowed the determination of the period parameter of the layers and a structure parameter that characterizes the disorder in the distances between PbTe layers. (C) 2010 International Union of Crystallography Printed in Singapore - all rights reserved

Magnetoelectric effects in an organometallic quantum magnet

Metal-organic materials constitute a new field in which to search for ferroelectricity and coupling between electricity and magnetism. We observe a magnetic field-induced change in the electric polarization, Delta P(H), that reaches 50 mu C/m(2) in single crystals of NiCl(2)-4SC(NH(2))(2) (DTN). DTN forms a tetragonal structure that breaks inversion symmetry with the electrically polar thiourea molecules [SC(NH(2))] all tilted in the same direction along the c axis. The field H induces canted antiferromagnetism of the Ni S = 1 spins between 2 and 12 T and our measurements show that the electric polarization increases monotonically in this range, saturating above 12 T. By modeling the microscopic origin of this magnetoelectric effect, we find that the leading contribution to Delta P comes from the change in the crystal electric field, with a smaller contribution from magnetic exchange striction. The finite value of Delta P induced by magnetostriction results from the polar nature of the thiourea molecules bonded to the Ni atoms, and it is amplified by the softness of these organic molecules.

Magnetic ordering of EuTe/PbTe multilayers determined by x-ray resonant diffraction

In this work we use resonant x-ray diffraction combined with polarization analysis of the diffracted beam to study the magnetic ordering in EuTe/PbTe multilayers. The presence of satellites at the (1/2 1/2 1/2) magnetic reflection of a 50 /repetition EuTe/PbTe superlattice demonstrated the existence of magnetic correlations among the alternated EuTe layers. The behavior of the satellites intensity as T increases toward the Neel temperature T(N) indicates that these correlations persist nearly up to T(N) and suggests the preferential decrease of the magnetic order parameter of external monolayers of each EuTe layer within the superlattice. (C) 2008 American Institute of Physics.

Spectroscopic evidence of extended states in the quantized Hall phase of weakly coupled GaAs/AlGaAs multilayers

The influence of interlayer coupling on the formation of the quantized Hall phase at the filling factor nu=2 was studied in multilayer GaAs/AlGaAs heterostructures. The disorder broadened Gaussian photoluminescence line due to localized electrons was found in the quantized Hall phase of the isolated multi-quanturn-well structure. On the other hand, the quantized Hall phase of weakly coupled multilayers emitted an unexpected asymmetrical line similar to that observed in metallic electron systems. We demonstrated that the observed asymmetry is caused by the partial population of extended electron states formed in the insulating quantized Hall phase due to spin-assisted interlayer percolation. A sharp decrease in the single-particle scattering time associated with these extended states was observed for the filling factor nu=2. (C) 2008 American Institute of Physics. [DOI: 10.1063/1.2978194]

Organic-inorganic nanostructured multilayers for calcium phosphate biomineralization

The weak fixation of biomaterials within the bone structure is one of the major reasons of implants failures. Calcium phosphate (CaP) coatings are used in bone tissue engineering to improve implant osseointegration by enhancing cellular adhesion, proliferation and differentiation, leading to a tight and stable junction between implant and host bone. It has also been observed that materials compatible with bone tissue either have a CaP coating or develop such a calcified surface upon implantation. Thus, the development of bioactive coatings becomes essential for further improvement of integration with the surrounding tissue. However, most of current applied CaP coatings methods (e.g. physical vapor deposition), cannot be applied to complex shapes and porous implants, provide poor structural control over the coating and prevent incorporation of bioactive organic compounds (e.g. antibiotics, growth factors) because of the used harsh processing conditions. Layer-by-layer (LbL) is a versatile technology that permits the building-up of multilayered polyelectrolyte films in mild conditions based on the alternate adsorption of cationic and anionic elements that can integrate bioactive compounds. As it is recognized in natureâ s biomineralization process the presence of an organic template to induce mineral deposition, this work investigate a ion based biomimetic method where all the process is based on LbL methodology made of weak natural-origin polyelectrolytes. A nanostructured multilayer component, with 5 or 10 bilayers, was produced initially using chitosan and chondroitin sulphate polyelectrolyte biopolymers, which possess similarities with the extracellular matrix and good biocompatibility. The multilayers are then rinsed with a sequential passing of solutions containing Ca2+ and PO43- ions. The formation of CaP over the polyelectrolyte multilayers was confirmed by QCM-D, SEM and EDX. The outcomes show that 10 polyelectrolyte bilayer condition behaved as a  better site for initiating the formation of CaP as the precipitation occur at earlier stages than in 5 polyelectrolyte bilayers one. This denotes that higher number of bilayers could hold the CaP crystals more efficiently. This work achieved uniform coatings that can be applied to any surface with access to the liquid media in a low-temperature method, which potentiates the manufacture of effective bioactive biomaterials with great potential in orthopedic applications.

Novel hybrid multifunctional magnetoelectric porous composite films

Novel multifunctional porous films have been developed by the integration of magnetic CoFe2O4 (CFO) nanoparticles into poly(vinylidene fluoride)-Trifuoroethylene (P(VDF-TrFE)), taking advantage of the synergies of the magnetostrictive filler and the piezoelectric polymer. The porous films show a piezoelectric response with an effective d33 coefficient of -22 pC/N-1, a maximum magnetization of 12 emu.g-1 and a maximum magnetoelectric coefficient of 9 mV.cm-1.Oe-1. In this way, a multifunctional membrane has been developed suitable for advanced applications ranging from biomedical to water treatment.

Tailored magnetic and magnetoelectric responses of polymer-based composites

The manipulation of electric ordering with applied magnetic fields has been realized on magnetoelectric (ME) materials, however, their ME switching is often accompanied by significant hysteresis and coercivity that represents, for some applications, a severe weakness. To overcome this obstacle, this work focus on the development of a new type of ME polymer nanocomposites that exhibits tailored ME response at room temperature. The multiferroic nanocomposites are based on three different ferrite nanoparticles, Zn0.2Mn0.8Fe2O4 (ZMFO), CoFe2O4 (CFO) and Fe3O4 (FO), dispersed in a piezoelectric co-polymer poly(vinylindene fluoride-trifluoroethylene), P(VDF-TrFE), matrix. No substantial differences were detected on the time-stable piezoelectric response of the composites (≈ -28 pC.N−1) with distinct ferrite fillers and for the same ferrite content of 10wt.%. Magnetic hysteresis loops from pure ferrite nanopowders showed different magnetic responses. ME results of the nanocomposite films with 10wt.% ferrite content revealed that the ME induced voltage increases with increasing DC magnetic field until a maximum of 6.5 mV∙cm−1∙Oe−1, at an optimum magnetic field of 0.26 T, and 0.8 mV∙cm−1∙Oe−1, at an optimum magnetic field of 0.15T, for the CFO/P(VDF-TrFE) and FO/P(VDF-TrFE) composites, respectively. On the contrary, the ME response of the ZMFO/P(VDF-TrFE) exposed no hysteresis and high dependence on the ZMFO filler content. Possible innovative applications such as memories and information storage, signal processing, ME sensors and oscillators have been addressed for such ferrite/PVDF nanocomposites.

Novel anisotropic magnetoelectric effect on δ-FeO(OH)/P(VDF-TrFE) multiferroic composites

The last decade has witnessed an increased research effort on multi-phase magnetoelectric (ME) composites. In this scope, this paper presents the application of novel materials for the development of anisotropic magnetoelectric (ME) sensors based on δ-FeO(OH)/P(VDF-TrFE) composites. The composite is able to precisely determine the amplitude and direction of the magnetic field. A new ME effect is reported in this study, as it emerges from the magnetic rotation of the δ-FeO(OH) nanosheets inside the piezoelectric P(VDF-TrFE) polymer matrix. δ-FeO(OH)/P(VDF-TrFE) composites with 1, 5, 10 and 20 δ-FeO(OH) filler weigh percentage in three δ-FeO(OH) alignment states (random, transversal and longitudinal) have been developed. Results shown that the modulus of the piezoelectric response (10-24 pC.N-1) is stable at least up to three months, the shape and magnetization maximum value (3 emu.g-1) is dependent on δ-FeO(OH) content and the obtained ME voltage coefficient, with a maximum of ≈0.4 mV.cm-1.Oe-1, is dependent on the incident magnetic field direction and intensity. In this way, the produced materials are suitable for innovative anisotropic sensor and actuator applications.

Determination of the magnetostrictive response of nanoparticles via magnetoelectric measurements

It is successfully demonstrated that nanoparticle’s magnetostriction can be accurately determined based on the magnetoelectric effect measured on polymeric-composite materials. This represents a novel, simple and versatile method for the determination of particle’s magnetostriction at their nano-sized and dispersed state, which is, up to date, a difficult and imprecise task.

Dielectric relaxation and ferromagnetic resonance in magnetoelectric (Polyvinylidene-fluoride)/ferrite composites

In this work the dielectric properties and ferromagnetic resonance of Polyvinylidene- uoride embedded with 10 wt. % of NiFe2O4 or Ni0.5Zn0.5Fe2O4 nanoparticles are presented. The mechanisms of the dielectric relaxation in these two composites do not differ from each other. For more precise characterization of the dielectric relaxation, a two dimensional distribution of relaxation times was calculated from the temperature dependencies of the complex dielectric permittivity. The results obtained from the 2D distribution and the mean relaxation time are found to be consistent. The dynamics of the dielectric permittivity is described by the Arrhenius law. The energy and attempt time of the dielectric relaxators lie in a narrow energy and time region thus proving that the single type chains of polymer are responsible for a dispersion. The magnetic properties of the composites were investigated using the fer- romagnetic resonance. A single resonance line was observed for both samples. From the temperature dependence (100 K - 310 K) of the resonance eld and linewidth, the origin of the observed line was attributed to the NiFe2O4 and Ni0.5Zn0.5Fe2O4 superparamagnetic nanoparticles. By measuring lms at dif- ferent orientations with respect to the external magnetic eld, the angular dependence of the resonance was observed, indicating the magnetic dipolar in-plane interactions.

Energy harvesting device based on a metallic glass/PVDF magnetoelectric laminated composite

A flexible and low cost energy harvester device based on the magnetoelectric (ME) effect has been designed using Fe64Co17Si7B12 as amorphous magnetostrictive ribbons and PVDF as the piezoelectric element. Sandwich-type laminated composite of 3 cm long has been fabricated by gluing these ribbons to the PVDF with the Devcon 5 minute epoxy. Good power output and power density of 6.4 μW and 1.5 mW/cm3, respectively, have been obtained through a multiplier circuit. All values have been measured at the magnetomechanical resonance of the laminate. The effect of the length of the ME laminate on the power output has been also studied, exhibiting a decay as the length of the ME laminate does. Nevertheless, good performance of such device has been obtained for a 0.5 cm long device, working already at 337 KHz, within the low radio frequency (LRF) range.

Size effects on the magnetoelectric response on PVDF/Vitrovac 4040 laminate composites

Tri-layered and bi-layered magnetoelectric (ME) flexible composite structures of varying geometries and sizes consisting on magnetostrictive Vitrovac and piezoelectric poly(vinylidene fluoride) (PVDF) layers were fabricated by direct bonding. From the ME measurements it was determined that tri-layered composites structures (magnetostrictive-piezoelectric-magnetostrictive type), show a higher ME response (75 V.cm-1.Oe-1) than the bi-layer structure (66 V.cm 1.Oe-1). The ME voltage coefficient decreased with increasing longitudinal size aspect ratio between PVDF and Vitrovac layers (from 1.1 to 4.3), being observed a maximum ME voltage coefficient of 66 V.cm-1.Oe-1. It was also observed that the composite with the lowest transversal aspect ratio between PVDF and Vitrovac layers resulted in better ME performance than the structures with higher transversal size aspect ratios. It was further determined an intimate relation between the Vitrovac PVDF Area Area ratio and the ME response of the composites. When such ratio values approach 1, the ME response is the largest. Additionally the ME output value and magnetic field response was controlled by changing the number of Vitrovac layers, which allows the development of magnetic sensors and energy harvesting devices.

Development of magnetoelectric CoFe2O4/poly(vinylidene fluoride) microspheres

Magnetoelectric microspheres based on piezoelectric poly(vinylidene fluoride) (PVDF) and magnetrostrictive CoFe2O4 (CFO), a novel morphology for polymer-based ME material, have been developed by an electrospray process. The CFO nanoparticles content in the (3-7 μm diameter) microspheres reaches values up to 27 wt.%, despite their concentration in the starting solution reaching values up to 70 wt.%. Additionally, the inclusion of magnetostrictive nanoparticles into the polymer spheres has no relevant effect on the piezoelectric β-phase content (≈60%), crystallinity (40%) and the onset degradation temperature (460º-465ºC) of the polymer matrix. The multiferroic microspeheres show a maximum piezoelectric reponse |d33|≈30 pC.N-1, leading to a magnetoelectric response of Δ|d33|≈5 pC.N-1 obtained when a 220 mT DC magnetic field was applied. It is also shown that the interface between CFO nanoparticles and PVDF (from 0 to 55%) has a strong influence on the ME response of the microspheres. The simplicity and the scalability of the processing method suggest a large application potential of this novel magnetoelectric geometry in areas such as tissue engineering, sensors and actuators.

Induced magnetoelectric effect driven by magnetization in BaFe12O19 -/P(VDF-TrFE) composites

Films of BaFe12O19/P(VDF-TrFE) composites with 5, 10 and 20 %wt Barium ferrite content have been fabricated. BaFe12O19 microparticles have the shape of thin hexagonal platelets, the easy direction of magnetization remaining along the c axis, which is perpendicular to the plates. This fact allows for ferrite particles orientation in-plane and out-of-plane within the composite films, as confirmed by measured hysteresis loops. While the in-plane induced magnetoelectric effect (ME) is practically zero, these composite films show a good out-of-plane magnetoelectric effect. with maximum ME coupling coefficient changes of 3, 17 and 2 mV/cm.Oe for the 5, 10 and 20%wt Barium ferrite content films, respectively. We infer that this ME behavior appears as driven by the magnetization process arising when we applied the external magnetic field. We have also measured linear and reversible magnetoelectric effect for low applied bias field, when magnetization process is still reversible.