Spinel Ferrite Films Research Articles

Ultra-thin lithium aluminate spinel ferrite films with perpendicular magnetic anisotropy and low damping

Ultra-thin films of low damping ferromagnetic insulators with perpendicular magnetic anisotropy have been identified as critical to advancing spin-based electronics by significantly reducing the threshold for current-induced magnetization switching while enabling new types of hybrid structures or devices. Here, we have developed a new class of ultra-thin spinel structure Li0.5Al1.0Fe1.5O4 (LAFO) films on MgGa2O4 (MGO) substrates with: 1) perpendicular magnetic anisotropy; 2) low magnetic damping and 3) the absence of degraded or magnetic dead layers. These films have been integrated with epitaxial Pt spin source layers to demonstrate record low magnetization switching currents and high spin-orbit torque efficiencies. These LAFO films on MGO thus combine all of the desirable properties of ferromagnetic insulators with perpendicular magnetic anisotropy, opening new possibilities for spin based electronics.

Robust Ferrimagnetism and Switchable Magnetic Anisotropy in High‐Entropy Ferrite Film

AbstractFerrimagnetic insulator materials are the enabling technology for the development of next‐generation magnetic devices with low power consumption, high operation speed, and high miniaturization capability. To achieve a high‐density memory device, a combined realization of robust saturation magnetization (Ms), controllable magnetic anisotropy, and high resistivity (ρ) are highly demanded. Despite significant efforts that have been made recently, simultaneously achieving significant enhancements in these properties in a soft magnetic insulator material still remains a great challenge, severely limiting their practical application. Herein, a high‐entropy strategy in an ultra‐thin spinel ferrite (CrMnFeCoNi)3O4 film is reported that exhibits concurrently a superior saturation magnetization (MS = 1198 emu cm−3), low coercivity (HC = 90 Oe), and excellent resistivity (ρ = 1233 Ω cm), as well as switchable magnetic anisotropy. The comprehensive lattice probing and microstructure analysis studies reveal that such desirable ferromagnetic properties originate from the high‐quality structurally ordered but compositionally disordered single‐crystal epitaxial structure. The switchable magnetic anisotropy demonstrated in the high‐entropy ferrite film can be attributed to the new antiferromagnetic rock‐salt phase. This work unveils the critical benefits of the high‐entropy strategy for magnetic oxide thin films, which opens up new opportunities for the development of high‐performance magnetic materials.

Homogeneous solution assembled Turing structures with near zero strain semi-coherence interface

Turing structures typically emerge in reaction-diffusion processes far from thermodynamic equilibrium, involving at least two chemicals with different diffusion coefficients (inhibitors and activators) in the classic Turing systems. Constructing a Turing structure in homogeneous solutions is a large challenge because of the similar diffusion coefficients of most small molecule weight species. In this work, we show that Turing structure with near zero strain semi-coherence interfaces is constructed in homogeneous solutions subject to the diffusion kinetics. Experimental results combined with molecular dynamics and numerical simulations confirm the Turing structure in the spinel ferrite films. Furthermore, using the hard-soft acid-base theory, the design of coordination binding can improve the diffusion motion of molecules in homogeneous solutions, increasing the library of Turing structure designs, which provides a greater potential to develop advanced materials.

Understanding the coexistence of unipolar and bipolar resistive switching in NiFe2O4 resistive memory devices

In this Letter, spinel ferrite NiFe2O4 films prepared through pulsed laser deposition are used to fabricate Pt/NiFe2O4/Pt devices with the coexistence of unipolar resistive switching (URS) and bipolar resistive switching (BRS). The device demonstrated nonvolatile and stable resistive switching (RS) properties under URS and BRS modes. The current–voltage (I–V) fitting analysis and temperature dependence measurements suggested that one Pt/NiFe2O4/Pt RRAM cell follows two significantly different RS and carrier transport mechanisms under URS and BRS modes. Under URS mode, the carrier mechanism alternates between the high resistance state (HRS) with Schottky emission and low resistance state (LRS) with the Ohmic mechanism. In contrast, under BRS mode, carrier transport at HRS and LRS is dominated by space-charge-limited current and nearest-neighboring hopping, respectively. Finally, a physical model, combining oxygen ion (O2−) migration and electric field distribution simulated by COMSOL Multiphysics, is proposed to further clarify the coexistence of two distinct RS and carrier transport mechanisms in the single Pt/NiFe2O4/Pt RRAM device.

Chemical Vapor Deposition of Cobalt and Nickel Ferrite Thin Films: Investigation of Structure and Pseudocapacitive Properties

AbstractTransition metal ferrites, such as CoFe2O4 (CFO) and NiFe2O4 (NFO), have gained increasing attention as potential materials for supercapacitors. Since chemical vapor deposition (CVD) offers advantages like interface quality to the underlying substrates and the possibility for coverage of 3D substrates, two CVD processes are reported for CFO and NFO. Growth rates amount to 150 to 200 nm h−1 and yield uniform, dense, and phase pure spinel ferrite films according to X‐ray diffraction (XRD), Raman spectroscopy, Rutherford backscattering spectrometry and nuclear reaction analysis (RBS/NRA) and scanning electron microscopy (SEM). Atom probe tomography (APT) and synchrotron X‐ray photoelectron spectroscopy (XPS) give insights into the vertical homogeneity and oxidation states in the CFO films. Cation disorder of CFO is analyzed for the first time from synchrotron‐based XPS. NFO is analyzed via lab‐based XPS. Depositions on conducting Ni and Ti substrates result in electrodes with pseudocapacitive behavior, as evidenced by cyclovoltammetry (CV) experiments. The interfacial capacitances of the electrodes are up to 185 µF cm−2.

Atomic Structure and Electron Magnetic Circular Dichroism of Individual Rock Salt Structure Antiphase Boundaries in Spinel Ferrites

AbstractSpinel ferrites are an important class of materials, whose magnetic properties are of interest for industrial applications. The antiphase boundaries (APBs) that are commonly observed in spinel ferrite films can hinder their applications in spintronic devices and sensors, as a result of their influence on magnetic degradation and magnetoresistance of the materials. However, it is challenging to correlate magnetic properties with atomic structure in individual APBs due to the limited spatial resolution of most magnetic imaging techniques. Here, aberration‐corrected scanning transmission electron microscopy and electron energy‐loss magnetic chiral dichroism are used to measure the atomic structure and electron magnetic circular dichroism (EMCD) of a single APB in NiFe2O4 that takes the form of a rock salt structure interlayer and is associated with a crystal translation of (1/4)a[011]. First principles density functional theory calculations are used to confirm that this specific APB introduces antiferromagnetic coupling and a significant decrease in the magnitude of the magnetic moments, which is consistent with an observed decrease in EMCD signal at the APB. The results provide new insight into the physical origins of magnetic coupling at an individual defect on the atomic scale.

Evidence for strain control of magnetic anisotropy in epitaxial nickel ferrite thin films grown on strontium titanate substrates

This report is on strain control of magnetic order parameters in 50 nm epitaxial NiFe2O4 (NFO) films grown on (001), (110), and (111) SrTiO3 (STO) single-crystal substrates by pulsed laser deposition. The related in-plane strains for NFO films on (001), (110), and (111) STO substrates are found to be ―1.36 %, 1.35 %, and 1.52 %, respectively, where the lattice mismatch between film and substrate is as high as 6.7 %. Our analysis of magnetization and ferromagnetic resonance on all the NFO films reveals the presence of a uniaxial anisotropy field, which is perpendicular to the film plane. The anisotropy field decreases with the increase of strain in NFO films. Specifically, NFO films on STO (111) and STO (001) have the lowest and highest uniaxial anisotropy fileds of 1.4 kOe and 6.1 kOe, respectively. These experimental values of anisotropy field are a factor of 5–10 times smaller than those of the calculated ones due to the film defects induced by the high lattice mismatch. The studies of magnetic anisotropy of spinel ferrite films are of interest for spintronics and microwave devices.

Ferrimagnetic insulators for spintronics: Beyond garnets

Ferrimagnetic insulators have gained much attention as material platforms with efficient magnetization dynamics. To date, epitaxial iron garnet thin films are the most widely used materials in the emerging field of “insulator spintronics.” However, further advances in this field require overcoming the disadvantages of garnets—e.g., their complex structure, high growth temperature, incompatibility with other crystalline materials, and relatively weak perpendicular magnetic anisotropy. In this Perspective, we make the case that epitaxial thin films of spinel ferrites and hexagonal ferrites are viable materials for insulator spintronics with complementary advantages over the oft-used garnets. Specifically, spinel ferrites have a simpler structure, can crystallize at lower temperatures, and are more amenable to coherent integration with various materials; hexagonal ferrites possess enormous perpendicular anisotropy of bulk origin, in contrast to garnets where the strength of anisotropy is restricted by interfacial strain. The expanded repertoire of materials for insulator spintronics will enable new physical insights and potential applications, beyond what is currently possible with garnets.

Impact of Defects on Magnetic Properties of Spinel Zinc Ferrite Thin Films

The recent developments in the study of magnetic properties in the spinel zinc ferrite system are explored. Engineering of ionic valence and site distribution allows tailoring of magnetic interactions. Recent literature is reviewed, and own investigations are presented for a conclusive understanding of the mechanisms responsible for the magnetic behavior in this material system. By varying the Zn‐to‐Fe ratio, the deposition, as well as thermal annealing conditions, ZnFe2O4 thin films with a wide range of crystalline quality are produced. In particular, the focus is on the magnetic structure in relation to spectroscopic properties of disordered ZnFe2O4 thin films. Comparing the cation distribution in film bulk (optical transitions in the dielectric function) and near‐surface region (X‐ray absorption), it is found that an inhomogeneous cation distribution leads to a weaker magnetic response in films of inverse configuration, whereas defects in the normal spinel are likely to be found at the film surface. The results show that it is possible to engineer the defect distribution in the magnetic spinel ferrite film structure and tailor their magnetic properties on demand. It is demonstrated that these properties can be read out optically, which allows controlled growth of the material and applications in future magneto‐optical devices.

Effect of Structural Inhomogeneities on the Spin-Wave and Magnetic Properties of Monocrystalline Spinel Ferrite Films in the Microwave Range

We have studied magnetic parameters of monocrystalline manganese spinel ferrite films differing in composition and structural perfection and assessed the effect of dislocation distribution on the frequency dependence of the ferromagnetic resonance (FMR) linewidth in the microwave range. The results demonstrate that, if an external magnetic field is perpendicular to the film surface, electron paramagnetic resonance (EPR) absorption lines correspond to ferromagnetic and spin wave resonances (SWRs). SWR is due to nanostructural surface inhomogeneities. The EPR spectrum of a tangently magnetized film represents a single dipole exchange oscillation spectrum. Parameters of dipole and exchange modes have been determined.

Temperature dependent resonant microwave absorption in perpendicular magnetic anisotropy epitaxial films of a spinel ferrite

We report on the temperature (T), magnetic field (μ0H), and angle (Θ, Φ) dependent resonant absorption of X-band microwaves in spinel ferrite epitaxial films subjected to two distinct states of growth strain. The polar angle (Θ) dependence of the resonance field (Hres) in films with ∼0.5% ab-plane expanded unit cell establishes a distinct perpendicular magnetic anisotropy (PMA). The anisotropy field (Han┴) for Θ = 0° increases monotonically on lowering the temperature from 300 K to 90 K following the behavior of the saturation magnetization (Ms) keeping Han┴/Ms ≈ 1. The narrow resonance linewidth (μ0ΔHres┴ = 3.7 mT at 300 K) and its negligible (±0.3 mT) variation with temperature establish the magnetic softness of these PMA films. The dependence of Hres on Θ, Φ, and T in films subjected to compressive stress shows in-plane cubic anisotropy whose strength is nonmonotonic in temperature. The ∼2.0% compression of the unit cell basal plane also appears to accentuate noncollinearity of sublattice magnetization of such films as indicated by the T-dependence of ΔHres. The thicker films with PMA display spin wave resonances whose position allows determination of the spin wave stiffness constant together with independent determination of Han┴. The resonance characteristics of the PMA films qualify them as potential candidates for frequency agile microwave devices and magnonic circuit elements.

Magnetic force microscopic analysis and the magnetoelectric sensor of PLZT – Spinel ferrite composite films

Abstract Composite films of Pb0.93La0.07Zr0.6Ti0.4O3 (PLZT) with spinel ferrites viz. Ni0.6Zn0.4Fe2O4 (NZFO), Co1.1Mn0.1Fe1.8O4 (CMFO), and Co0.9Zn0.1Fe2O4 (CZFO) respectively, were synthesized by the sol-gel spin coating technique. The layered structure of PLZT and spinel ferrite has been deposited onto silicon (1 1 1) substrate. X-ray diffraction analysis was used to confirm the formation of required phases in the light of JCPDS data. Microstructural investigation carried out using Magnetic Force Microscopy (MFM) operated topography mode depicts presence of grains having size of about 20–25 nm. The dielectric properties of the samples under investigation were recorded in the wide range of temperature measurements, in order to confirm existence of well grown ferroelectric phase and understand phase transition behavior. The magnetoelectric interactions have been investigated using phase signal of Magnetic Force Microscopy (MFM). Variation of MFM phase contrast and phase angle have been investigated as a function of electric field applied between magnetic tip and substrate, which gives an idea about nature of magnetoelectric interactions. The change in the magnetic domain as a function of applied electric field has been used to understand the magnetoelectric interactions present in the layered thin films of PLZT and spinel ferrite composite structure. Maximum phase angle change of 80°, 100° and 18° has been observed in the composite films of PLZT-NZFO, PLZT-CMFO and PLZT-CZFO respectively in presence of the applied voltage of 5 V/−5 V with respect to 0 V. Maximum value of magnetoelectric coefficient estimated for composite films of PLZT and NZFO composite was found to be 98 mV/cm Oe amongst the sample under investigation.

Formation of antiphase boundaries in CuFe2O4 films induced by rough MgAl2O4 (001) substrates

Antiphase boundaries in spinel ferrites have been considered as the functional elements with great potential for applications in spintronic devices. Engineering the antiphase boundaries is a big challenge in experiments. Here, we report on that a high density of antiphase boundaries in CuFe2O4 films have been prepared on rough surface of MgAl2O4 (001) substrates. By means of advanced electron microscopy these antiphase boundaries are found to be of {011}14〈011〉-type and bound by interfacial dislocations with Burgers vector of a/4〈011〉 that contribute to relaxation of in-plane and out-of-plane lattice strain in the heterostructure. Our results provide evidence that the rough substrate surface can be applied for the formation of antiphase boundaries in the CuFe2O4/MgAl2O4 system to tune the magnetic and electrical transport properties of epitaxial spinel ferrite films.

Pseudomorphic spinel ferrite films with perpendicular anisotropy and low damping

We report on epitaxial thin films of spinel ferrite Ni0.65Zn0.35Fe1.2Al0.8O4 with strain-induced perpendicular magnetic anisotropy (PMA) and low magnetic damping. Static magnetometry and broadband ferromagnetic resonance experiments show a distinct change in the preferred direction of magnetization from in-plane to out-of-plane when the coherent strain in films changes from ∼2% compressive on (001) MgAl2O4 to ∼0.5% tensile on (001) MgGa2O4 substrates. Significant deviations from the spin-only value (2.0) of the g-factor suggest spin-orbit effects and further support our conclusion of strain-driven magnetic anisotropy in these films. The low Gilbert damping parameter of α = 5 × 10−3 in these ferrite films, combined with their PMA, makes them promising for spintronic and frequency-agile microwave device applications.

Voltage control of magnetism in NiZn ferrite/mica/PMNPT heterostructure with giant tunability and narrow linewidth

Recently, large magnetoelectric coupling of a spinel/piezoelectric heterostructure has been reported. However, the linewidth of the spinel is very large due to lattice mismatch when ferrite is directly deposited on piezoelectric substrates. This indicates a large magnetic loss, which impedes the spinel/piezoelectric heterostructure from useful device applications. Mica is a well-known 2D material, which can be split manually layer by layer without the substrate clamping effect. In this report, NiZn ferrite was deposited on a mica substrate by a spin-spray deposition technique. Spin-spray deposition is a wet chemical synthesis technique involving several chemical reactions for generating high-quality crystalline spinel ferrite films with various compositions directly from an aqueous solution. The thickness of ferrite is 2 μm, and the linewidth of the ferromagnetic resonance (FMR) is 115 Oe which is suitable for RF/microwave devices. The large FMR field tuning of 605 Oe was observed in NiZn ferrite/mica/PMN-PT heterostructures with minimal substrate clamping effect by reducing the thickness of the mica substrate. These multiferroic heterostructures exhibiting combined giant magnetoelectric coupling and narrow ferromagnetic resonance linewidth offer great opportunities for flexible RF magnetic devices.

RHEED oscillations in spinel ferrite epitaxial films grown by conventional planar magnetron sputtering

Real-time in situ reflection high energy electron diffraction (RHEED) observations of Fe3O4, γ-Fe2O3, and (Co,Fe)3O4 films on MgO(001) substrates grown by a conventional planar magnetron sputtering was studied. The change in periodical intensity of the specular reflection spot in the RHEED images of three different spinel ferrite compounds grown by two different sputtering systems was examined. The oscillation period was found to correspond to the 1/4 unit cell of each spinel ferrite, similar to that observed in molecular beam epitaxy (MBE) and pulsed laser deposition (PLD) experiments. This suggests that the layer-by-layer growth of spinel ferrite (001) films is general in most physical vapor deposition (PVD) processes. The surfaces of the films were as flat as the surface of the substrate, consistent with the observed layer-by-layer growth process. The observed RHEED oscillation indicates that even a conventional sputtering method can be used to control film thickness during atomic layer depositions.

Observation and manipulation of magnetic domains in sol gel derived thin films of spinel ferrites

Thin films of spinel ferrites, namely zinc substituted nickel, cobalt ferrite, and manganese substituted cobalt ferrite, were synthesized using sol-gel derived spin-coating techniques. The films were characterized using x-ray diffraction, field emission scanning electron microscopy, Fourier transform infrared spectroscopy and Raman spectroscopy techniques for the analysis of structural, morphological and vibrational band transition properties, which confirm the spinel phase formation of the films. The magnetic force microscopy (MFM) technique was used to observe the magnetic domain structure present in the synthesized films. Further, the films were subjected to an external DC magnetic field of 2 kG to orient the magnetic domains and analyzed using an ex situ MFM technique.

Fabrication of Epitaxial Fe3O4 Film on a Si(111) Substrate

The application of magnetic oxides in spintronics has recently attracted much attention. The epitaxial growth of magnetic oxide on Si could be the first step of new functional spintronics devices with semiconductors. However, epitaxial spinel ferrite films are generally grown on oxide substrates, not on semiconductors. To combine oxide spintronics and semiconductor technology, we fabricated Fe3O4 films through epitaxial growth on a Si(111) substrate by inserting a γ-Al2O3 buffer layer. Both of γ-Al2O3 and Fe3O4 layer grew epitaxially on Si and the films exhibited the magnetic and electronic properties as same as bulk. Furthermore, we also found the buffer layer dependence of crystal structure of Fe3O4 by X-ray diffraction and high-resolution transmission electron microscope. The Fe3O4 films on an amorphous-Al2O3 buffer layer grown at room temperature grew uniaxially in the (111) orientation and had a textured structure in the plane. When Fe3O4 was deposited on Si(111) directly, the poly-crystal Fe3O4 films were obtained due to SiOx on Si substrate. The epitaxial Fe3O4 layer on Si substrates enable us the integration of highly functional spintoronic devices with Si technology.

Microwave magnetic properties of spinel ferrite films deposited by one-step electrochemical method

Spinel ferrites have been widely used in microwave devices due to their excellent electromagnetic properties. In this study, two kinds of spinel ferrite films, Fe3O4 and Co xFe3-xO4, were grown on Pt(111)/Ti/SiO2/Si substrates by one-step electrochemical deposition method. The XRD and SEM characterizations demonstrated that the orientation of the ferrite films changed from (111) to (100) with the increase of depositing time. The cobalt content within Co xFe3-xO4 films was studied in detail by EDS analysis. The ferromagnetic resonance (FMR) responses of the ferrite films were measured by the flip-chip method using a vector network analyzer (VNA). It showed that the FMR frequency of Fe3O4 films reached to 10.5GHz under an out-plane magnetic field of 5 kOe, while it reached to 27GHz under an in-plane magnetic field of 5kOe for Co xFe3-xO4 films. Meanwhile, whether the magnetic field was applied parallelly or perpendicularly, the resonant peaks were increased linearly with increasing the magnetic field, indicating that the films are promising candidates for applications in tunable wave-absorbing materials or other tunable frequency devices.

High-magnetization oxide spinel ferrite films

High-magnetization oxide spinel ferrite films