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.

Synthesis of L1(0) Fe-Pd films by electrodeposition and thermal annealing

Fe-Pd alloy films have been prepared by electrochemical deposition from an alkaline electrolyte containing Fe sulfate, Pd chloride and 5-sulfosalicylic acid onto polycrystalline titanium substrates. The as-deposited films were nanocrystalline and magnetically soft (coercivity similar to 25 Oe). L1(0) Fe-Pd films with a (111) preferred orientation were obtained by post-deposition thermal annealing of films with composition about 37 at% Fe in an (Ar + 5% H-2) gas flow at 500 degrees C. Such films exhibit hard magnetic properties, with a coercivity up to 1880 Oe, and a slightly anisotropic magnetic response, with a larger in-plane remanence. Preliminary magnetic investigations support magnetization switching through pinning of domain walls. (c) 2008 Elsevier B.V. All rights reserved.

Temperature dependence and magnetocrystalline anisotropy studies of self-assembled L1(0)-Fe55Pt45 ferromagnetic nanocrystals

Temperature dependence and uniaxial magnetocrystalline anisotropy properties of the chemically synthesized 4 nm L1(0)-Fe55Pt45 nanoparticle assembly by a modified polyol route are reported. As-prepared nanoparticles are superparamagnetic presenting fcc structure, and annealing at 550 degrees C converts the assembly into ferromagnetic nanocrystals with large coercivity (H-C>1 T) in an L1(0) phase. Magnetic measurements showed an increasing in the ferromagnetically ordered fraction of the nanoparticles with the annealing temperature increases, and the remanence ratio, S=M-R/M-S congruent to 0.76, suggests an (111) textured film. A monotonic increase of the blocking temperature T-B, the uniaxial magnetocrystalline anisotropy constant K-U, and the coercivity H-C with increasing annealing temperature was observed. Magnetic parameters indicate an enhancement in the magnetic properties due to the improved Fe55Pt45 phase stabilizing, and the room-temperature stability parameter of 67, which indicates that the magnetization should be stable for more than ten years, makes this material suitable for ultrahigh-density magnetic recording application.(c) 2007 American Institute of Physics.

Self-assembled FePt nanocrystals with large coercivity: Reduction of the fcc-to-L1(0) ordering temperature

Herein we report the synthesis and properties of Fe55Pt45 nanoparticles, both monodisperse and self-assembled into hexagonal close-packed and cubic arrays of 4.0 +/- 0.2 nm size in an L1(0) structure, obtained by a modified polyol process. The new synthetic route improved the control over the particle composition, thereby reducing the temperature required to convert from face-centered cubic (fcc) to face-centered tetragonal (fct) phase by some 30-50 degrees C without additives. Annealing at 550 degrees C for 30 min converts the self-assembled nanoparticles into ferromagnetic nanocrystals with large coercivity, H-C = 11.1 kOe. Reducing the fcc-to-fct (L1(0)) ordering temperature avoided particle coalescence and decreased the loss in particle positional order without compromising the magnetic properties, as is generally observed when additives are used.

The influence of residual stress and crystallite size on the magnetic properties of electrodepo sited nanocrystalline Pd-Co alloys

Nanocrystalline Pd-Co alloys were obtained by electrodeposition from an ammoniacal chloride bath. The influence of the crystallite size and the residual stress on the magnetic properties of the alloys was investigated. The residual stress increased as the applied current density was increased. It was associated to the high nucleation rate during electrodeposition and correlated to the lattice strain, estimated from the XRD patterns. Also from the XRD patterns the average crystallite size and the lattice constant were determined by Scherrer's and Rietveld's methods, respectively. Both parameters were directly influenced by the applied current density. Magnetic properties such as coercivity, remanence, saturation magnetization and squareness showed strong dependence on the residual stress and crystallite size. Coercivity higher than 1 kOe was achieved when a high current density was applied. High coercivity was attributed to the presence of residual stress and to the small crystallite size of deposits. (C) 2007 Elsevier B.V. All rights reserved.

Effects of the Compaction Pressure on the Magnetic Properties of a Sintered Fe-Based Alloy

The structural and magnetic properties of a Fe-based alloy before and after sintering have been analyzed. X ray diffraction measurements confirm the deformation of the magnetic particles in the compacted samples. After sintering, hysteresis energy dissipation, remanence and intrinsic coercivity differ by less than 10% as porosity changes from 15 to 7%.

Environmental control on the occurrence of high-coercivity magnetic minerals and formation of iron sulfides in a 640 ka sediment sequence from Lake Ohrid (Balkans)

The bulk magnetic mineral record from Lake Ohrid, spanning the past 637 kyr, reflects large-scale shifts in hydrological conditions, and, superimposed, a strong signal of environmental conditions on glacial–interglacial and millennial timescales. A shift in the formation of early diagenetic ferrimagnetic iron sulfides to siderites is observed around 320 ka. This change is probably associated with variable availability of sulfide in the pore water. We propose that sulfate concentrations were significantly higher before  ∼  320 ka, due to either a higher sulfate flux or lower dilution of lake sulfate due to a smaller water volume. Diagenetic iron minerals appear more abundant during glacials, which are generally characterized by higher Fe / Ca ratios in the sediments. While in the lower part of the core the ferrimagnetic sulfide signal overprints the primary detrital magnetic signal, the upper part of the core is dominated by variable proportions of high- to low-coercivity iron oxides. Glacial sediments are characterized by high concentration of high-coercivity magnetic minerals (hematite, goethite), which relate to enhanced erosion of soils that had formed during preceding interglacials. Superimposed on the glacial–interglacial behavior are millennial-scale oscillations in the magnetic mineral composition that parallel variations in summer insolation. Like the processes on glacial–interglacial timescales, low summer insolation and a retreat in vegetation resulted in enhanced erosion of soil material. Our study highlights that rock-magnetic studies, in concert with geochemical and sedimentological investigations, provide a multi-level contribution to environmental reconstructions, since the magnetic properties can mirror both environmental conditions on land and intra-lake processes.

(Table 1) Remanence properties of samples from ODP Core 126-792A-7H

A combination of high sedimentation rates and high concentrations of magnetic grains in cores from Ocean Drilling Program Leg 126 resulted in the recovery of detailed direction and intensity records of the Brunhes/Matuyama geomagnetic polarity reversal. Virtual geomagnetic poles (VGPs) computed from azimuthally oriented samples taken from the cores of Hole 792A in the western Izu-Bonin forearc basin reveal that the geomagnetic pole persisted at moderate to high southern latitudes for several thousand years before a rapid migration to northern latitudes. Alternating-field demagnetization behavior, as well as NRM, NRM/ARM, and NRM/IRM intensities for samples from this same interval, and the NRM/IRM intensities derived from unoriented core samples from Holes 790C and 791B, drilled in the ~100-km distant Sumisu Rift, all suggest that the dipole field oscillated widely in intensity before the reversal. The fast polarity change occurred at the low point of an ~1100-yr field intensity cycle. This "reversal cycle" immediately followed earlier intensity cycles whose peaks rivaled or surpassed the normalized intensities of discrete samples from well above and below the reversal interval; furthermore, the troughs indicate a much diminished dipole field at their nadir.

Magnetic petrology of ODP Leg 121 holes

Given the importance of the inversion of seamount magnetic anomalies, particularly to the motion of the Pacific plate, it is important to gain a better understanding of the nature of the magnetic source of these features. Although different in detail, Ninetyeast Ridge is composed of submarine and subaerial igneous rocks that are similar to those found at many seamounts, making it a suitable proxy. We report here on the magnetic petrology of a collection of samples from Ninetyeast Ridge in the Indian Ocean. Our purpose is to determine the relationship between primary petrology, subsequent alteration, and magnetic properties of the recovered rocks. Such information will eventually lead to a more complete understanding of the magnetization of seamounts and presumably improvements in the accuracy of anomaly inversions. Three basement sites were drilled on Ninetyeast Ridge, with recovery of subaerial basalt flows at the first two (Sites 756 and 757) and submarine massive and pillow flows at the final one (Site 758). The three sites were distinctly different. Site 756 was dominated by ilmenite. What titanomagnetite was present had undergone deuteric alteration and secondary hematite was present in many samples. The magnetization was moderate and stable although it yielded a paleolatitude somewhat lower than expected. Site 757 was highly oxidized, presumably while above sea level. It was dominated by primary titanomagnetite, which was deuterically altered. Secondary hematite was common. Magnetization was relatively weak but quite stable. The paleolatitude for all but the lowermost flows was approximately 40° lower than expected. Site 758 was also dominated by primary titanomagnetite. There was relatively little oxidation with most primary titanomagnetite showing no evidence of high-temperature alteration. No secondary hematite was in evidence. This site had the highest magnetization of the three (although somewhat low relative to other seamounts) but was relatively unstable with significant viscous remanence in many samples. Paleolatitude was close to the expected value. It is not possible, at present, to confidently associate these rocks with specific locations in a seamount structure. A possible and highly speculative model would place rocks similar to Site 757 near the top of the edifice, Site 756 lower down but still erupted above sea level, and Site 758 underlying these units, erupted while the seamount was still below sea level.

Magnetic properties of basalts from DSDP Hole 69-504B

The NRM intensity, AF demagnetization characteristics, hysteresis parameters, initial susceptibility, and thermomagnetic characteristics of 18 basalt specimens from Deep Sea Drilling Project Hole 504B were determined. In six samples, the grain size was large enough to allow microprobe analysis. We conclude (1) that the dominant magnetic mineral is titanomagnetite/titanomaghemite; (2) that, except for the upper few meters of the core where the grains are in the stable monodomain state, the grain size of the magnetic mineral lies in the pseudo-single-domain range (< 10 µm); (3) that maghemitization (i.e., low-temperature (< 350°C) oxidation) has taken place. We discuss possible geological histories.

Paleomagnetic of ODP Hole 133-823A

Hole 823A covers the upper 120 m (Subunits IA and IB) of Site 823 at the bottom of the Queensland Trough. This hole contains an abundance of gravity-flow deposits, but is thought to have a monotonic age sequence. Above 32 mbsf, a strong, stable (normal) magnetic remanence having a relatively small viscous remanent magnetization (VRM) is seen. Below 32 mbsf, the sediments are subject to widespread VRM, which appears to obliterate the primary magnetization and precludes identification of the Brunhes/Matuyama boundary. Progressive alternating field (AF) demagnetization is limited to low fields (typically <400 Oe) by the weak magnetization in these sediments. As a consequence, the possibility of a high-coercivity component of primary magnetization cannot be ruled out. Lowrie-Fuller tests indicate that this VRM overprinting does not have a multidomain origin. An approximately linear relationship exists between median destructive field (MDF) and the logarithm of the natural remanent magnetization (NRM). Carbonate dilution does not appear to be a dominant factor in controlling variations in concentration-dependent magnetic parameters, such as magnetic susceptibility. The sedimentological distinction between Subunits IA and IB does not show up in the magnetic record. However, a sharp change in magnetic properties does occur at 32 mbsf, with low background magnetizations below this level and high background magnetizations above it. The boundary coincides with a change from thick (>10 cm thick) to thin (<10 cm thick) turbidite deposition, and is also near the boundary separating the sulfate-reduction zone in the upper part of the sequence from the sulfate-free zone beneath. The abrupt nature of the magnetic boundary is evidence that nannofossil subzone CN14b is not condensed, but is missing in a hiatus at 32 mbsf. Nine peaks have been identified in the susceptibility (K) record that are superimposed on ôbackgroundö signals. ARM/K ratios are uniformly low for the background sediments below 32 mbsf, intermediate for strong susceptibility peaks, and high for background sediments above 32 mbsf and weak susceptibility peaks. Comparisons with results from Site 820 suggest that (1) the background sediments above 32 mbsf and the weak susceptibility peaks carry a stable single-domain magnetization, and (2) the high susceptibility peaks are caused by the addition of a superparamagnetic contribution. Expectations are that the distinctive features of the Hole 823A magnetic record are linked to major environmental changes.

Magnetic properties and paleomagnetism of basalts from ODP Leg 107 basalts

The basalts recovered at Holes 651A and 655B appear to carry a single component remanent magnetization, which is generally of reversed polarity. These magnetizations are consistent with eruption during the Matuyama (651A) and Gilbert (655B) polarity epochs. The blocking temperature spectra and the Js/T curves indicate that titanomaghemite is the principal remanence carrier. The lower mean destructive field (MDF) and higher susceptibility at 651A probably indicates a lower mean oxidation state at this hole relative to 655B, which may simply reflect the age difference between the two basalt sequences. At both holes, a decreasing downcore trend both in natural remanent magnetization (NRM) and susceptibility probably indicates that maghemitization (from primary titanomagnetite) increases downcore. An interval of high coercivity at hole 655B (119.80-151.45 mbsf) appears to define a magnetically distinct unit within the basalt sequence.

Paleomagneitc of early Cretaceous sediments from the western Central Atlantic

Drilling at Sites 534 and 603 of the Deep Sea Drilling Project recovered thick sections of Berriasian through Aptian white limestones to dark gray marls, interbedded with claystone and clastic turbidites. Progressive thermal demagnetization removed a normal-polarity overprint carried by goethite and/or pyrrhotite. The resulting characteristic magnetization is carried predominantly by magnetite. Directions and reliability of characteristic magnetization of each sample were computed by using least squares line-fits of magnetization vectors. The corrected true mean inclinations of the sites suggest that the western North Atlantic underwent approximately 6° of steady southward motion between the Berriasian and Aptian stages. The patterns of magnetic polarity of the two sites, when plotted on stratigraphic columns of the pelagic sediments without turbidite beds, display a fairly consistent magnetostratigraphy through most of the Hauterivian-Barremian interval, using dinoflagellate and nannofossil events and facies changes in pelagic sediment as controls on the correlations. The composite magnetostratigraphy appears to include most of the features of the M-sequence block model of magnetic anomalies from Ml to Ml ON (Barremian-Hauterivian) and from M16 to M23 (Berriasian-Tithonian). The Valanginian magnetostratigraphy of the sites does not exhibit reversed polarity intervals corresponding to Ml 1 to M13 of the M-sequence model; this may be the result of poor magnetization, of a major unrecognized hiatus in the early to middle Valanginian in the western North Atlantic, or of an error in the standard block model. Based on these tentative polarity-zone correlations, the Hauterivian/Barremian boundary occurs in or near the reversed-polarity Chron M7 or M5, depending upon whether the dinoflagellate or nannofossil zonation, respectively, is used; the Valanginian/Hauterivian boundary, as defined by the dinoflagellate zonation, is near reversed-polarity Chron M10N.