The role of chemical and microstructural inhomogeneities on interface magnetism.

The study of interfacing effects arising when different magnetic phases are in close contact has led to the discovery of novel physical properties and the development of innovative technological applications of nanostructured magnetic materials. Chemical and microstructural inhomogeneities at the interfacial region, driven by interdiffusion processes, chemical reactions and interface roughness may significantly affect the final properties of a material and, if suitably controlled, may represent an additional tool to finely tune the overall physical properties. The activity at the Nanostructured Magnetic Materials Laboratory (nM2-Lab) at CNR-ISM of Italy is aimed at designing and investigating nanoscale-engineered magnetic materials, where the overall magnetic properties are dominated by the interface exchange coupling. In this review, some examples of recent studies where the chemical and microstructural properties are critical in determining the overall magnetic properties in core/shell nanoparticles, nanocomposites and multilayer heterostructures are presented.

Perpendicularly magnetized Co/Pd-based magneto-resistive heterostructures on flexible substrates.

Flexible magneto-resistive heterostructures have received a great deal of attention over the past few years as they allow for new product paradigms that are not possible with conventional rigid substrates. While the progress and development of systems with longitudinal magnetic anisotropy on non-planar substrates has been remarkable, flexible magneto-resistive heterostructures with perpendicular magnetic anisotropy (PMA) have never been studied despite the possibility to obtain additional functionality and improved performance. To fill this gap, flexible PMA Co/Pd-based giant magneto-resistive (GMR) spin-valve stacks were prepared by using an innovative transfer-and-bonding strategy exploiting the low adhesion of a gold underlayer to SiO x /Si(100) substrates. The approach allows overcoming the limits of the direct deposition on commonly used polymer substrates, whose high surface roughness and low melting temperature could hinder the growth of complex heterostructures with perpendicular magnetic anisotropy. The obtained PMA flexible spin-valves show a sizeable GMR ratio (∼1.5%), which is not affected by the transfer process, and a high robustness against bending as indicated by the slight change of the magneto-resistive properties upon bending, thus allowing for their integration on curved surfaces and the development of a novel class of advanced devices based on flexible magneto-resistive structures with perpendicular magnetic anisotropy. Besides endowing the family of flexible electronics with PMA magneto-resistive heterostructures, the exploitation of the results might apply to high temperature growth processes and to the fabrication of other functional and flexible multilayer materials engineered at the nanoscale.

Symbiotic, low-temperature, and scalable synthesis of bi-magnetic complex oxide nanocomposites.

Functional oxide nanocomposites, where the individual components belong to the family of strongly correlated electron oxides, are an important class of materials, with potential applications in several areas such as spintronics and energy devices. For these materials to be technologically relevant, it is essential to design low-cost and scalable synthesis techniques. In this work, we report a low-temperature and scalable synthesis of prototypical bi-magnetic LaFeO3-CoFe2O4 nanocomposites using a unique sol-based synthesis route, where both the phases of the nanocomposite are formed during the same time. In this bottom-up approach, the heat of formation of one phase (CoFe2O4) allows the crystallization of the second phase (LaFeO3), and completely eliminates the need for conventional high-temperature annealing. A symbiotic effect is observed, as the second phase reduces grain growth of the first phase, thus yielding samples with lower particle sizes. Through thermogravimetric, structural, and morphological studies, we have confirmed the reaction mechanism. The magnetic properties of the bi-magnetic nanocomposites are studied, and reveal a distinct effect of the synthesis conditions on the coercivity of the particles. Our work presents a basic concept of significantly reducing the synthesis temperature of bi-phasic nanocomposites (and thus also the synthesis cost) by using one phase as nucleation sites for the second one, as well as using the heat of formation of one phase to crystallize the other.

Co/Pd-Based synthetic antiferromagnetic thin films on Au/resist underlayers: towards biomedical applications.

Thin film stacks consisting of multiple repeats M of synthetic antiferromagnetic (SAF) [Co/Pd]N/Ru/[Co/Pd]N units with perpendicular magnetic anisotropy were explored as potential starting materials to fabricate free-standing micro/nanodisks, which represent a promising candidate system for theranostic applications. The films were directly grown on a sacrificial resist layer spin-coated on SiOx/Si(100) substrates, required for the preparation of free-standing disks after its dissolution. Furthermore, the film stack was sandwiched between two Au layers to allow further bio-functionalization. For M ≤ 5, the samples fulfill all the key criteria mandatory for biomedical applications, i.e., zero remanence, zero field susceptibility at small fields and sharp switching to saturation, together with the ability to vary the total magnetic moment at saturation by changing the number of repetitions of the multi-stack. Moreover, the samples show strong perpendicular magnetic anisotropy, which is required for applications relying on the transduction of a mechanical force through the micro/nano-disks under a magnetic field, such as the mechanical cell disruption, which is nowadays considered a promising alternative to the more investigated magnetic hyperthermia approach for cancer treatment. In a further step, SAF microdisks were prepared from the continuous multi-stacks by combining electron beam lithography and Ar ion milling, revealing similar magnetic properties as compared to the continuous films.

Controlling magnetic coupling in bi-magnetic nanocomposites.

Magnetic nanocomposites constitute a vital class of technologically relevant materials, in particular for next-generation applications ranging from biomedicine, catalysis, and energy devices. Key to designing such materials is determining and controlling the extent of magnetic coupling in them. In this work, we show how the magnetic coupling in bi-magnetic nanocomposites can be controlled by the growth technique. Using four different synthesis strategies to prepare prototypical LaFeO3-CoFe2O4 and LaFeO3-Co0.5Zn0.5Fe2O4 nanocomposite systems, and by performing comprehensive magnetic measurements, we demonstrate that the final material exhibits striking differences in their magnetic coupling that is distinct to the growth method. Through structural and morphological studies, we confirm the link between the magnetic coupling and growth methods due to distinct levels of particle agglomeration at the very microscopic scale. Our studies reveal an inverse relationship between the strength of magnetic coupling and the degree of particle agglomeration in the nanocomposites. Our work presents a basic concept of controlling the particle agglomeration to tune magnetic coupling, relevant for designing advanced bi-magnetic nanocomposites for novel applications.

Tunable single-phase magnetic behavior in chemically synthesized AFeO3-MFe2O4 (A = Bi or La, M = Co or Ni) nanocomposites.

The properties of magnetic nanocomposites rely strongly on the interplay between those of the constituent components. When the individual components themselves are complex systems belonging to the family of correlated electron oxide systems which typically exhibit exotic physical properties, it becomes nontrivial to customize the properties of the nanocomposite. In this paper, we demonstrate an easy, but effective method to synthesize and tune the magnetic properties of nanocomposites consisting of correlated electron oxide systems as the individual components. Our method is based on a novel synthesis technique by which the two components of the nanocomposite can be directly integrated with each other, yielding homogeneous samples on the nanoscale with magnetic behavior reminiscent of a single phase. We illustrate our method using multiferroic BiFeO3 (BFO) and LaFeO3 (LFO) as the major phase (i.e., matrix), and MFe2O4 (M = Co2+ or Ni2+) as the embedded magnetic phase. Furthermore, we show that by a proper selection of the second phase in the nanocomposite, it is possible to customize the magnetic properties of the matrix. We illustrate this by choosing CoFe2O4 and NiFe2O4, two oxides with widely differing magnetic anisotropies, as the embedded phase, and demonstrate that the coercivity of BFO and LFO can be increased or decreased depending on the choice of the embedded phase in the nanocomposite.

L10-FeNi films on Au-Cu-Ni buffer-layer: a high-throughput combinatorial study.

The fct L10-FeNi alloy is a promising candidate for the development of high performance critical-elements-free magnetic materials. Among the different materials, the Au-Cu-Ni alloy has resulted very promising; however, a detailed investigation of the effect of the buffer-layer composition on the formation of the hard FeNi phase is still missing. To accelerate the search of the best Au-Cu-Ni composition, a combinatorial approach based on High-Throughput (HT) experimental methods has been exploited in this paper. HT magnetic characterization methods revealed the presence of a hard magnetic phase with an out-of-plane easy-axis, whose coercivity increases from 0.49 kOe up to 1.30 kOe as the Au content of the Cu-Au-Ni buffer-layer decreases. Similarly, the out-of-plane magneto-crystalline anisotropy energy density increases from 0.12 to 0.35 MJ/m3. This anisotropy is attributed to the partial formation of the L10 FeNi phase induced by the buffer-layer. In the range of compositions we investigated, the buffer-layer structure does not change significantly and the modulation of the magnetic properties with the Au content in the combinatorial layer is mainly related to the different nature and extent of interlayer diffusion processes, which have a great impact on the formation and order degree of the L10 FeNi phase.

Studying nanoparticles' 3D shape by aspect maps: Determination of the morphology of bacterial magnetic nanoparticles.

Magnetic nanoparticles (MNPs) are widely investigated due to their potential use in various applications, ranging from electronics to biomedical devices. The magnetic properties of MNPs are strongly dependent on their size and shape (i.e., morphology), thus appropriate tools to investigate their morphology are fundamental to understand the physics of these systems. Recently a new approach to study nanoparticle morphology by Transmission Electron Microscopy (TEM) analysis has been proposed, introducing the so-called Aspect Maps (AMs). In this paper, a further evolution of the AM method is presented, allowing determination of the nanoparticles' 3D shape by TEM image. As a case study, this paper will focus on magnetite nanoparticles (Fe3O4), with a mean size of ∼45 nm extracted from Magnetospirillum gryphiswaldense magnetostatic bacteria (MTB). The proposed approach gives a complete description of the nanoparticles' morphology, allowing estimation of an average geometrical size and shape. In addition, preliminary investigation of the magnetic properties of MTB nanoparticles was performed, giving some insight into interparticle interactions and on the reversal mechanism of the magnetization.

Ferromagnetism and Conductivity in Hydrogen Irradiated Co-Doped ZnO Thin Films.

Impressive changes in the transport and ferromagnetic properties of Co-doped ZnO thin films have been obtained by postgrowth hydrogen irradiation at temperatures of 400 °C. Hydrogen incorporation increases the saturation magnetization by one order of magnitude (up to ∼1.50 µB/Co) and increases the carrier density and mobility by about a factor of two. In addition to the magnetic characterization, the transport and structural properties of hydrogenated ZnO:Co have been investigated by Hall effect, local probe conductivity measurements, micro-Raman, and X-ray absorption spectroscopy. Particular care has been given to the detection of Co oxides and metal Co nanophases, whose influence on the increase in the transport and ferromagnetic properties can be excluded on the ground of the achieved results. The enhancement in ferromagnetism is directly related to the dose of H introduced in the samples. On the contrary, despite the shallow donor character of H atoms, the increase in carrier density n is not related to the H dose. These apparently contradictory effects of H are fully accounted for by a mechanism based on a theoretical model involving Co-VO (Co-O vacancy) pairs.

Designing new ferrite/manganite nanocomposites.

Two kinds of nanocomposites of transition metal oxides were synthesized and investigated. Each nanocomposite comprises nanoparticles of La0.67Ca0.33MnO3 and CoFe2O4 in similar volume fractions, however arranged with different morphologies. The temperature-dependent magnetic and electrical properties of the two systems are found to greatly differ, suggesting different degrees of interaction and coupling of their constituents. This is confirmed by magnetic field-dependent experiments, which reveal contrasted magnetization reversal and magnetoresistance in the systems. We discuss this morphology-physical property relationship, and the possibility to further tune the magnetism and magneto-transport in such nanocomposites.

Magnetic properties of granular CoCrPt:SiO 2 thin films deposited on GaSb nanocones.

We report on the effect of microstructure and geometrically induced modifications of the magnetic properties of granular CoCrPt:SiO2 films with weakly interacting magnetic grains deposited on pre-structured GaSb nanocone templates fabricated by an ion erosion technique. By tuning the irradiation conditions, nanocone patterns of different cone sizes were prepared (from 28 to 120 nm in diameter and 32 to 330 nm high, respectively). The influence of the intergranular exchange coupling was also investigated by varying the SiO2 content from 8 to 12 at.%. Deposition of CoCrPt:SiO2 on samples with small nanocones leads to a close magnetic grain packing, which results in the formation of extended magnetic domains larger than the average distance between the GaSb cones. In contrast, on larger nanocones, the magnetic coating grows on the side-walls, with a large separation between neighboring cones, leading to magnetic single-domain regions, which are correlated to the underlying structure. Magnetometry indicates that both remanence and coercivity decrease with increasing cone size and/or SiO2 content due to a combined effect of the angular distribution of the magnetic easy axis of the grains and the intergranular exchange coupling strength.

Magnetic interactions in silica coated nanoporous assemblies of CoFe2O4 nanoparticles with cubic magnetic anisotropy.

Magnetic interactions in silica coated spherical nanoporous assemblies of CoFe(2)O(4) nanoparticles have been investigated by low temperature field dependent remanent magnetization (M(DCD) and M(IRM)) and magnetization relaxation measurements. The synthesis procedure leads to the formation of spherical aggregates of about 50-60 nm in diameter composed of hexagonal shaped nanocrystals with shared edges. The negative deviation from the non-interacting case in the Henkel plot indicates the predominance of dipole-dipole interactions favouring the demagnetized state, although the presence of exchange interactions in the porous system cannot be excluded. The activation volume, derived from time dependent magnetization measurements, turns out to be comparable with the particle physical volume, thus indicating, in agreement with static and dynamic irreversible magnetization measurements, that the magnetization reversal actually involves individual crystals.