CoFe2O4 Films Research Articles

Thickness-dependent morphological, structural, and optical properties of cobalt ferrite films

ABSTRACT A facile and prudent approach has been developed to deposit cobalt ferrite (CoFe2O4) films on the surface of the precursor solution by purging ammonia vapors over it. The vigorous technique to control the thickness of the film attributes spectacular characteristics to this approach. The study of CoFe2O4 films has been carried out by using FE-SEM, AFM, XRD, and UV-Visible spectroscopy. FE-SEM micrographs confirm the formation of the thin films composed of nanoparticles. The AFM micrographs indicate an increase in the root mean square roughness value with purged NH3 concentration due to the aggregation of nanoparticles. The observed XRD spectra show a cubic spinel structure of CoFe2O4 films with an increase in crystallite size in the range of 20–45 nm on increasing the NH3 concentration. UV – Visible spectroscopic investigations show a decrease in the band gap energy from 2.84 to 2.37 eV on account of the increased concentration of NH3 vapors.

Modification induced by electronic excitation in CoFe2O4 thin films: Structural, morphological, and magnetic properties

AbstractThe present study focuses on the modification induced by 200 MeV Ag15+ and 100 MeV O7+ ion irradiations on the structural, surface morphological, and magnetic properties of radio frequency sputtered CoFe2O4 (CFO) thin films grown on SiO2/Si (100) substrates. X‐ray diffraction shows amorphization of the CFO thin films when irradiated with Ag ions and varies with fluences. This effect is absent in the case of O ion irradiated CFO films. These results are consistent with the measurements from the Raman spectroscopy, where the intensities of Eg and T2g modes are significantly reduced and further disappear in the high fluence. The surface morphology of the O ion irradiated films is dramatically different from the pristine and Ag ion irradiated films where the surfaces appear in nanopillars‐like patterns. The topography of the O ion irradiated films appears to be like hill and valley structures, the roughness first increases (from 10.11 to 24.39 nm). Then it decreases to 18.93 nm on further increasing ion fluence. The coercivity, remnant magnetization, and saturation magnetization increase upon irradiation at low fluence 5 × 1011 ions/cm2 for both the ion beams and then downturn with the increase of fluence 5 × 1012 ions/cm2. The changes in the magnetic and structural characteristics are ascribed to the defects induced by ion irradiation. These results are understood based on the structural and surface modifications induced by the electronic excitation of Ag and O ions. The study depicts that a controlled selection of ions and beam fluence can tailor the structure, morphology, and magnetic properties of ferrite films.

Structure, optical and magnetic properties of PVA/CuO/CoFe2O4 nanocomposite films for flexible magneto-electronic applications

Pure polyvinyl alcohol (PVA) and its nanocomposites with CuO and/or CoFe2O4 films have been prepared with different weights of ≤ 5 %. The structure of the films shows an orthorhombic phase of semi-crystalline polymer for PVA, a monoclinic phase for CuO, and a cubic phase of CoFe2O4 in nanocomposite films with particle sizes ≤ 25.5 nm, as determined by the XRD technique. Surface morphology by TEM of representative films shows the crystalline structure and nanoparticles and nanorods of individual CuO and/or CoFe2O4 compounds. The optical transmission and reflection properties of films have been measured, and the optical band gap has been estimated, showing that variable values (1.4–4 eV) can be controlled by controlling the percentage of CuO and/or CoFe2O4 in films. Magnetic investigation shows diamagnetic behavior for PVA and paramagnetic behavior for PC1, PC3, while PC5 has a very weak ferromagnetic response. Whereas nanocomposites with different contents of CoFe2O4 exhibit smooth ferromagnetic behavior with increasing Ms values. Ferromagnetic behavior has been confirmed via a convex Arrott–Belov–Kouvel plot. The improvement of magnetic properties makes the prepared films suitable to be used in various fields, such as antenna system miniaturization and flexible magneto-electronic applications.

Sputter‐Deposited α‐MoO3 Interlayers for van der Waals Epitaxy and Film Transfer

AbstractIntegration of functional thin films onto flexible substrates is driven by the need to improve the performance and durability of flexible electronic devices. A van der Waals epitaxy technology that accomplishes the transfer of oxide or metal thin films via exfoliation or dissolution of sacrificial α‐MoO3 layers produced by sputtering is presented. The α‐MoO3 thin films, consisting of weakly bonded 2D layers, grow epitaxially on SrTiO3 (001) substrates, exhibiting mosaic domains rotated by 90°. Metallic Au films grown on the α‐MoO3 are transferred by mechanical exfoliation or by dissolving the α‐MoO3 in water at 45 °C. Spinel‐structured CoFe2O4 thin films grown on α‐MoO3 layers are easily transferred to flexible substrates via mechanical exfoliation, and the magnetic anisotropy of the transferred CoFe2O4 films is modulated by bending.

Photo-induced oxygen vacancy formation and anomalous photoconductivity in solution-processed CoFe2O4 thin films

Designing an optoelectronic device requires adequate information about the photo-response of the active material. Here, we have studied the optical and optoelectrical properties of the solution-processed inverse spinel structured CoFe2O4 (CFO) thin film and correlated it with the photovoltaic performance of CFO active material-based all-oxide solar cell. The optical absorption spectra of spin-coated CFO films show the existence of a direct bandgap of 2.64 eV with a maximum absorption coefficient >105/cm. A simple spin-coated CFO/TiO2p–n heterojunction shows an open circuit voltage of over 0.95 V under 1 sun illumination. However, photo-induced oxygen vacancy formation and the desorption of surface oxygen lead to additional electron generation and hole capture, respectively, in the p-type CFO, resulting in an anomalous photocurrent decay under white light illumination, resulting in a low short-circuit current density. This study provides a fundamental understanding of photo-carrier dynamics in solution-processed CFO thin films and apprehends the photophysics of designing spinel-ferrite-based optoelectronic devices.

Structural, Magnetic, and Magnetostriction Properties of Flexible, Nanocrystalline CoFe2O4 Films Made by Chemical Processing.

We report on the simple, single-step, and cost-effective fabrication, characterization, and performance evaluation of cobalt ferrite (CoFe2O4; CFO) nanocrystalline (NC) thin films on a flexible mica substrate. The chemical solution-based drop-casting method employed to fabricate crystalline CFO films and their characterization was performed by studying the phase formation, surface morphology, and magnetic parameters, while sensor applicability was evaluated using combined magnetic and magnetostrictive properties. X-ray diffraction (XRD) indicates the single-phase and nanocrystalline nature of CFO films, where the crystallite size is ∼60 nm. The optimum conditions employed resulted in CFO NC films with surface particles exhibiting a spherical shape morphology with a homogeneous size distribution, as revealed by scanning electron microscopy analyses. Raman spectroscopic characterization of the chemical bonding indicates all of the active bands that are characteristic of the ferrite phase confirm the spinel structure, which is in agreement with XRD studies. The saturation magnetization (M S) and coercivity (H C), which are extracted from the field-dependent magnetization data, of CFO NC films were found to be 15.8 emu/g and 1.6 kOe, respectively, while the first-order magnetocrystalline anisotropy constant K 1 was ∼1.07 × 106 erg/cm3. The magnetostriction strain curve indicates that the CFO NC films exhibit a strain value of ∼86 ppm at an applied magnetic field of 8 kOe, indicating their suitability for flexible sensor devices.

Structural and magnetic properties of CoFe2O4 thin films grown on isostructural lattice-matched substrates

Epitaxial thin films of cobalt ferrite (CoFe2O4) are grown on two isostructural substrates, (001)-oriented MgGa2O4 and ZnGa2O4, using pulsed laser deposition. The substrates have a lattice mismatch of 1.26% and 0.70% with bulk CoFe2O4 (CFO) crystal. We have systematically investigated the structural and magnetic properties of the epitaxial CFO films on these substrates. X-ray diffraction and transmission electron microscopy result analysis reveal that the films deposited on spinel ZnGa2O4 are essentially free of defects and are under a small compressive strain, while films on MgGa2O4 show partial strain relaxation along with defect formation. Room temperature magnetization data indicate that CFO grown on ZnGa2O4 substrates have a bulk-like saturation magnetization of 420 emu/cc and a uniaxial substrate-induced anisotropy value of −22.9× 106 erg/cm3 with an anisotropy field as low as 60 kOe.

Dielectric, piezoelectric and magnetic behavior of CoFe2O4/BNT–BT0.08 monolayer thin films composites

We report in this paper on the monolayer composites thin films that have the magnetic spinel CoFe2O4 and the piezoelectric perovskite BNT-BT0.08 as constituent phases. Composite thin films of CoFe2O4 and BNT-BT0.08, with molar ratios of 0.5:1, 1:1 and 1.5:1, have been deposited by spin coating method from a sol precursor, mixture type, of CoFe2O4 and BNT-BT0.08. The monolayer thin films, deposited on Si/SiO2/TiO2/Pt substrate, were characterized using selected methods, such as: X-ray diffraction, scanning electron microscopy, atomic force microscopy/piezoelectric force microscopy, dielectric spectroscopy, and vibrating sample magnetometer. X-ray diffraction demonstrated the two phases: cubic CoFe2O4 and rhombohedral BNT-BT0.08. Furthermore, the Si/SiO2/TiO2/Pt/BNT-BT0.08/CoFe2O4 monolayers show a simultaneous enhancement of both the magnetization and coercivity with the increase of the magnetic phase, accompanied by a decrease of the dielectric constant. The obtained results reveal that the investigated monolayer structures present superior properties compared to those of bilayer composites.

Surface-to-bulk core level shift in CoFe2O4 thin films

In spite of the absence of significant segregation of either cobalt oxide or iron oxide, core level photoemission binding energy shifts tend to indicate that the surface is significantly different from the bulk for CoFe2O4(111) thin films grown on Al2O3(0001). CoFe2O4(111) thin films show a surface-to-bulk core level shift in both the Co 2p and Fe 2p core level photoemission spectra. Surface weighted components in the core level photoemission spectra of both Co 2p3/2 and Fe 2p3/2 can be distinguished from the bulk components, by angle-resolved x-ray photoemission spectroscopy, for CoFe2O4(111) thin films. The surface termination of CoFe2O4(111) contains both Co and Fe with no evidence of strong preferential surface termination of either an iron or cobalt oxide, except for CoFe2O4(111) in the thin film limit. With extensive annealing above room temperature, the cobalt oxide component of very thin CoFe2O4(111) films, grown on Al2O3 (0001), will lose oxygen.

The emergence of high room temperature in-plane and out-of-plane magnetostriction in polycrystalline CoFe2O4 film

The polycrystalline CoFe2O4 (CFO) film on cantilever substrate of silicon was grown using pulsed laser deposition (PLD) method and investigated its in-plane and out-of-plane magnetostrictive strain at room temperature (300 K) using the indigenous optical Cantilever Beam Magnetometer (CBM). The film shows a high compressive magnetostrictive strain of ‒ 387 ppm and ‒ 708 ppm for in-plane and out-of-plane configurations, respectively. Considerably, the magnetostrictive strain loops (λ‒H) possess a certain degree of hysteresis with a symmetric butterfly shape. The origin of large compressive magnetostriction of CFO film is attributed to the non-180° domain wall motion followed by 90° domain rotation. The large values of saturation magnetostrictive strain make CFO film a suitable candidate in sensor design for different purposes.

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.

Mechanical stability of ferrimagnetic CoFe2O4 flexible thin films

We fabricated high-quality ferrimagnetic CoFe2O4 (CFO) thin films on a mica substrate using a pulsed laser deposition technique. High-resolution X-ray diffraction and transmission electron microscopy revealed that the film grew epitaxially with the relationships of CFO <1-10> || Mica [010] and CFO [111] || Mica [001]. The films were highly flexible in terms of both inward and outward bending, and exhibited clear ferrimagnetic hysteresis with weak anisotropy in both the in-plane and out-of-plane directions. We observed that the magnetization of CFO films was robust against mechanical stimuli without microcracks. The remnant magnetization and coercive field were within 8% and 11% over a strain of ±0.54%. As the number of bending cycles increased, the magnetic easy axis became more closely aligned to the out-of-plane direction, without any noticeable change in domain size.

Reduced magnetocrystalline anisotropy of CoFe2O4 thin films studied by angle-dependent x-ray magnetic circular dichroism

Spinel-type CoFe2O4 is a ferrimagnetic insulator with the Néel temperature exceeding 790 K, and it shows strong cubic magnetocrystalline anisotropy (MCA) in bulk materials. However, when a CoFe2O4 film is grown on other materials, its magnetic properties are degraded so that so-called magnetically dead layers are expected to be formed in the interfacial region. We investigate how the magnetic anisotropy of CoFe2O4 is modified at the interface of CoFe2O4/Al2O3 bilayers grown on Si(111) using x-ray magnetic circular dichroism. We find that the thinner CoFe2O4 films have significantly smaller MCA values than bulk materials. The reduction in MCA is explained by the reduced number of Co2+ ions at the Oh site, as reported by a previous study [Wakabayashi et al., Phys. Rev. B 96, 104410 (2017)].

All‐alkoxide based deposition and properties of a multilayer La0.67Sr0.33MnO3/CoFe2O4/La0.67Sr0.33MnO3 film

AbstractSingle and multilayer films of La0.67Sr0.33MnO3 and CoFe2O4 were deposited by spin‐coating. The all‐alkoxide precursors allowed inorganic gel films of extreme homogeneity to be formed and converted to phase pure complex oxides at low temperatures. La0.67Sr0.33MnO3 films were made with La‐ and Ca‐methoxy‐ethoxides and Mn19O12(moe)14(moeH)10 as precursors at 800 °C. The CoFe2O4 films were obtained at extremely low 275 °C, using a new CoFe2‐methoxyethoxide precursor. The decomposition and microstructural development on heating was described by TG, TEM, XRD and IR spectroscopy. XRD showed no spurious phases and the unit‐cell dimensions coincided quite well with literature values of the targeted phases. The structural, magnetic and electronic properties of these films established their phase purity and high quality with physical properties comparable to films deposited by physical deposition methods. The magnetic and magneto transport results are presented for single, bi‐ and tri‐ layer structures. The magnetically soft La0.67Sr0.33MnO3 layer was exchange coupled to the magnetically hard CoFe2O4 layer, giving rise to interesting switching behaviour in magnetism and magneto‐transport properties.

Effects of Post-deposition Annealing on Epitaxial CoO/Fe3O4 Bilayers on SrTiO3(001) and Formation of Thin High-Quality Cobalt Ferrite-like Films

In order to explore an alternative pathway to prepare ultrathin CoFe2O4 films, epitaxial CoO/Fe3O4 bilayers with varying film thickness of the CoO film were grown on Nb-doped SrTiO3(001) substrates...

Strong modulation of magnetism in multiferroic CoFe2O4/0.7 Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 oxide composite films

Multiferroic magnetoelectric composite films have been becoming the research focus as the candidates for sensors, memories, spintronics and microwave devices. Compared to ferroelectric single crystal consisting of the heterostructure, the functional composite film realizes the magnetism control under only a few volts which brings the advantage of safety and low energy consumption in the memory devices. Here, the CoFe2O4/0.7PbMg1/3Nb2/3O3-0.3PbTiO3 oxide composite thin films were deposited on SrRuO3-buffered SrTiO3 substrate by pulsed laser deposition method. The structural, ferroelectric, magnetic and magnetoelectric properties have been studied respectively. The polarization reversibility of ferroelectric domain was investigated in the PMN-PT films by piezoresponse force microscopy. The coercive field of the CoFe2O4 film ranges from 900 Oe to 975 Oe under the applied direct current voltage. By performing the alternative current voltage modulated magneto-optical Kerr effect test, the dominating coupling mechanism in the composite films influenced by the CoFe2O4 film thickness was discussed. Our study indicates the potential application of electric field assisted magnetic data storage device.

Ferroelectric, ferromagnetic, and magnetoelectric properties of Bi3.15Nd0.85Ti2.9Zr0.1O12–CoFe2O4 composite films with large magnetoelectric coupling effect

The magnetoelectric composite films of Bi3.15Nd0.85Ti2.9Zr0.1O12 (BNTZO)–CoFe2O4 (CFO) were deposited on the substrates of Pt/Ti/SiO2/Si (111) by means of the sol–gel method. The results show that, in the composite films, there are tri-axial compressive stresses in the CFO films. Nevertheless, there are bi-axial tensile stresses and uniaxial compressive stress in the BNTZO films. The composite films possess compact microstructure and flat interface without forming intermediate layer. The composite films have good magnetoelectric properties besides both good ferroelectric and ferromagnetic properties. When Hdc is 738 Oe, the composite film of BNTZO-CFO possesses the maximum of αE, 114 mV cm−1 Oe−1, which is helpful for the application in multi-functional devices.

Deposition-environment-dependent structural and magnetic property modification of [111]-oriented epitaxial CoFe2O4 films

We examined the magnetic, structural, and chemical properties of CoFe2O4 films deposited on Al2O3 substrates using RF-magnetron sputtering under Ar and Ar + O2 environments. Perpendicular magnetic anisotropy with large magnetization was observed in the case of the film deposited under the Ar + O2 environment. However, no significant anisotropy appeared in the film deposited under the Ar environment. Interestingly, depth-dependent X-ray photoelectron spectra showed nearly identical stoichiometric ratios of Co/Fe and oxygen vacancies regardless of the deposition environment. Structurally, high-quality crystallinity with in-plane compressive strain, and lower surface and interfacial roughness were induced in the film deposited under the Ar + O2 environment. Cross-sectional transmission electron microscopy and X-ray reflectivity measurements showed that oxygen not only suppressed the deposition rate but also increased the electron density of the film, resulting in better crystallinity. Hence, the presence of oxygen during deposition should be considered as one of the essential parameters for improving the structural and magnetic properties of ferrite films.

Annealing heating rate dependence of microstructure and multiferroic properties in Bi4Ti2.9Fe0.1O12/CoFe2O4 layered magnetoelectric composite films prepared by chemical solution deposition method

Lead-free magnetoelectric composite films of CoFe2O4 (CFO) and Bi4Ti2.9Fe0.1O12 (BTF) were prepared on the LaNiO3-coated Si substrate by chemical solution deposition. Though the CFO layer randomly grows on the LaNiO3 layer, the oriented growth of the BTF layer can be regulated by rapid annealing treatment. The results indicated that the annealing heating rate significantly affects the c-axis orientation of the BTF layer, thereby resulting in obvious changes in microstructure, leakage behavior, dielectricity and ferroelectricity of the BTF/CFO films. The BTF/CFO film prepared at the heating rate of 40 °C/s presents the most compact structure, minimum leakage current, maximum dielectric constant and the highest residual polarization of 28.8 μC/cm2. Moreover, the excellent magnetoelectric coupling performance along with the highest magnetoelectric coupling voltage coefficient αE of 20.1 V/cm∙Oe can be achieved in these conditions.

WITHDRAWN: Formation of CoFe2O4 and NiFe2O4 films under the application of magnetic field for tuning the lattice oxygen

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