Magnetic,magnetoelectric and dielectric behavior of CoFe2O4–Pb(Fe1/2Nb1/2)O3 particulate and layered composites

Magnetic, magnetoelectric and dielectric properties of multiferroic CoFe₂O₄–Pb(Fe_1/2Nb_1/2)O₃ composites prepared as bulk ceramics were compared with those of tape cast and cofired laminates consisting of alternate ferrite and relaxor layers. X-ray diffraction analysis and Scanning Electron Microscope observations of ceramic samples revealed two-phase composition and fine grained microstructure with uniformly distributed ferrite and relaxor phases. High and broad maxima of dielectric permittivity attributed to dielectric relaxation were found for ceramic samples measured in a temperature range from −55 to 500 °C at frequencies 10 Hz–2 MHz. Magnetic hysteresis, zero-field cooled (ZFC) and field cooled (FC) curves, and dependencies of magnetization on temperature for both magnetoelectric composites were measured with a vibrating sample magnetometer in an applied magnetic field up to 80 kOe at 4–400 K. The hysteresis loops obtained for composites are typical of a mixture of the hard magnetic material with a significant amount of the paramagnet. The bifurcation of ZFC–FC magnetizations observed for both composites implies spin-glass behavior. Magnetoelectric properties at room temperature were investigated as a function of dc magnetic field (0.3–7.2 kOe) and frequency (10 Hz–10 kHz) of ac magnetic field. Both types of composites exhibit a distinct magnetoelectric effect. Maximum values of magnetoelectric coefficient attained for the layered composites exceed 200 mV/(cm Oe) and are almost three times higher than those for particulate composites.     

Effect of film thickness on interface and electric properties of BiFeO3 thin films

Bismuth ferrite (BFO) thin films were fabricated by RF-magnetron sputtering deposition method on Pt/Ti/SiO₂/Si(1 0 0) substrate. The effect of the thickness of BFO films varying from 85 to 280 nm on electrical properties was investigated. Saturated coercive fields were found to increase with the BFO film thickness. The dielectric constant of BFO thin films measured at 1 kHz decreased with decreasing thickness from 98 to 86, while tangent losses increased from 0.013 to 0.021. The presence of bismuth oxide at the interface between BFO films and Pt bottom electrodes was responsible for the high leakage currents in thin BFO thin films as was demonstrated by X-ray diffraction, grazing-incident X-ray diffraction, and secondary ion mass spectroscopy analysis.     

Effect of Sc substitution on the structure,electrical, and magnetic properties of multiferroic BiFeO3 thin films grown by a sol–gel process

Multiferroic BiFeO₃ (BFO), Bi_1−xSc_xFeO₃ (BSF), and BiFe_1−xSc_xO₃ (BFS) (x=0.3 mol%) thin films are prepared on Pt/Ti/SiO₂/Si substrates using a sol–gel technique. The effect of Sc substitution along with the annealing ambient (N₂ and O₂) on the structure, electrical, and magnetic properties of the films are reported. X-ray diffraction (XRD) analysis reveals that the films can be prepared with the single-phase perovskite structure by annealing at 700 °C for 10 min either in O₂ or N₂ ambient. The unit cell volume increases on the substitution of Sc, which are 61.39, 62.50, and 62.57 (Å)³ for BFO, BSF, and BFS, respectively. X-ray photoelectron spectroscopy (XPS) study reveals that the chemical environments of Bi and Fe are different in BFO, BSF, BFS films. Similarly, XPS spectra for Sc2p lines in BSF and BFS also have different peak positions; this indicates Sc doping has certain chemical impact on BSF and BFS films. Systematic studies of Sc substitution along with the effect of annealing ambient on the dielectric constant (ε) and dielectric loss (tan δ), leakage current, remnant polarization (P_r), coercive field (E_c), and magnetic properties of the films are carried out. The room temperature values of ε and tan δ at 1 kHz for BFO and BFS films annealed in N₂ ambient are (∼208; 0.035) and (∼235; 0.023), respectively. The comparative value of leakage current for the BFO and BFS films at an applied field strength of 50 kV/cm are 2.997×10⁻⁴ and 1.87×10⁻⁵ A/cm², respectively. Room temperature value of coercive magnetization for BFS films has one order small compared to that of the BFO films; this indicates BFS films are magnetically soft and more suitable for potential device applications. Finally, among the studied compositions, the BFS films annealed in N₂ ambient show the best property.     

Structural, magnetic and electric properties of HoMnO3 films on SrTiO3(001)

HoMnO₃ films were grown on pure and Nb-doped SrTiO₃ (001) substrates by pulsed laser deposition. The films grew epitaxially with the c-axis along the substrate normal. Varying the deposition temperature between 650 and 850 °C did not significantly affect the structural and magnetic properties of the films, whereas growth in oxygen partial pressures below 0.01 mbar lead to a degradation of the structural properties. Some of the films had a ferromagnetic-like magnetic phase transition at about 45 K, probably related to Mn₃O₄ precipitates; this magnetic response was isotropic. The Ho sublattice was found to be paramagnetic down to 5 K, but showing a pronounced anisotropy with the c-axis being the hard axis. The films showed a distinct dielectric anomaly at 16 K that depended on voltage and slightly on frequency in the range between 1 kHz and 1 MHz. The magnetoelectric effect was large with an in-plane field of 8 T suppressing the dielectric anomaly completely.     

The magnetoelectric coupling in rhombohedral–tetragonal phases coexisted Bi0.84Ba0.20FeO3

Ba doped Bi_1.04−xBa_xFeO₃ ceramics with x up to 0.30 have been prepared by the tartaric acid modified sol–gel method. The X ray diffraction patterns show that the structure transforms from rhombohedral to tetragonal with increasing the Ba substitution concentration from 10% to 30% and the coexistence of distorted rhombohedral and tetragonal phases in 20% Ba substituted BiFeO₃, which was further confirmed by the Raman spectra. Bi_0.84Ba_0.20FeO₃ exhibits the highest magnetization (1.6 emu/g under magnetic field of 12 kOe) compared with the other samples of different Ba substitution concentration. Significant enhancement of the ferroelectricity has been observed in 20% and 30% Ba substituted BiFeO₃ with saturate polarization close to 6.6 μC/cm² for Bi_0.74Ba_0.30FeO₃. The magnetoelectric coupling of Bi_0.84Ba_0.20FeO₃ has been measured and the maximum decrease of magnetization under magnetic field of 9.8 kOe was about 0.06 emu/g with increasing applied electric field to 11 kV/cm, and the magnetoelectric coefficient is 1.5×10⁻¹² s/m.     

Optical and electrical properties of plasma-oxidation derived HfO2 gate dielectric films

High-k gate dielectric HfO₂ thin films have been deposited on Si(1 0 0) by using plasma oxidation of sputtered metallic Hf thin films. The optical and electrical properties in relation to postdeposition annealing temperatures are investigated by spectroscopic ellipsometry (SE) and capacitance-voltage (C-V) characteristics in detail. X-ray diffraction (XRD) measurement shows that the as-deposited HfO₂ films are basically amorphous. Based on a parameterized Tauc-Lorentz dispersion mode, excellent agreement has been found between the experimental and the simulated spectra, and the optical constants of the as-deposited and annealed films related to the annealing temperature are systematically extracted. Increases in the refractive index n and extinction coefficient k, with increasing annealing temperature are observed due to the formation of more closely packed thin films and the enhancement of scattering effect in the targeted HfO₂ film. Change of the complex dielectric function and reduction of optical band gap with an increase in annealing temperature are discussed. The extracted direct band gap related to the structure varies from 5.77, 5.65, and 5.56 eV for the as-deposited and annealed thin films at 700 and 800 °C, respectively. It has been found from the C-V measurement the decrease of accumulation capacitance values upon annealing, which can be contributed to the growth of the interfacial layer with lower dielectric constant upon postannealing. The flat-band voltage shifts negatively due to positive charge generated during postannealing.     

Influence of substrate temperature on structures and dielectric properties of pyrochlore Bi1.5Zn1.0Nb1.5O7 thin films prepared by pulsed laser deposition

The influence of substrate temperature on structural and dielectric properties of cubic pyrochlore Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin films prepared by pulsed laser deposition process has been investigated. BZN thin films were deposited on Pt/Ti/SiO₂/Si(1 0 0) substrate and in situ annealed at 700 °C. The results indicate that the substrate temperature has a significant effect on the structural and dielectric properties of BZN thin films. The films exhibit a cubic pyrochlore structure in the substrate temperature range from 550 °C to 700 °C and at the annealing temperature of 700 °C. With further increase of substrate temperature to 750 °C, the phases of Bi₂O₃, BiNbO₄ and Bi₅Nb₃O₁₅ can be detected in the XRD pattern due to the Zn loss. The dielectric constant and loss tangent of the films deposited at 650 °C are 192 and 6 × 10⁻⁴ at 10 kHz, respectively. The tunability is 10% at a dc bias field of 0.9 MV/cm.     

The dc magnetic field,temperature and film thickness dependence of microwave surface resistance of YBCO and DyBCO thin films

We investigated the dc magnetic field and temperature dependences of the microwave surface resistance (R_s) of YBa₂Cu₃O_y (YBCO) and DyBa₂Cu₃O_y (DyBCO) superconducting thin films. The YBCO and DyBCO thin films, each with a thickness of 300, 500, or 700 nm, were deposited on MgO (1 0 0) substrates by the thermal co-evaporation method. The R_s was measured using the dielectric resonator method. A dc magnetic field of up to 5.0 T was applied parallel to the c-axis of the superconducting thin films. The results showed that the R_s value had almost the same temperature dependence at various thicknesses in a zero-external field. The R_s of the YBCO and DyBCO thin films increased with the applied dc magnetic field. The DyBCO thin films showed weaker magnetic field dependence of R_s than the YBCO thin films. The R_s ratio (defined as R_s(5 T)/R_s(0 T)) linearly increased with the film thickness. These results show that pinning strength decreased with an increasing film thickness.     

Correlation between microstructure and optical properties of nano-crystalline TiO2 thin films prepared by sol-gel dip coating

Titanium dioxide thin films have been prepared from tetrabutyl-orthotitanate solution and methanol as a solvent by sol-gel dip coating technique. TiO₂ thin films prepared using a sol-gel process have been analyzed for different annealing temperatures. Structural properties in terms of crystal structure were investigated by Raman spectroscopy. The surface morphology and composition of the films were investigated by atomic force microscopy (AFM). The optical transmittance and reflectance spectra of TiO₂ thin films deposited on silicon substrate were also determined. Spectroscopic ellipsometry study was used to determine the annealing temperature effect on the optical properties and the optical gap of the TiO₂ thin films. The results show that the TiO₂ thin films crystallize in anatase phase between 400 and 800 °C, and into the anatase-rutile phase at 1000 °C, and further into the rutile phase at 1200 °C. We have found that the films consist of titanium dioxide nano-crystals. The AFM surface morphology results indicate that the particle size increases from 5 to 41 nm by increasing the annealing temperature. The TiO₂ thin films have high transparency in the visible range. For annealing temperatures between 1000 and 1400 °C, the transmittance of the films was reduced significantly in the wavelength range of 300-800 nm due to the change of crystallite phase and composition in the films. We have demonstrated as well the decrease of the optical band gap with the increase of the annealing temperature.     

Effect of magnetic annealing on phonon behaviors of nanocrystalline BiFeO3

Influence of magnetic annealing at 823 K up to 10 T (T) on the phonon behaviors of nanocrystalline BiFeO₃ was investigated by Raman spectroscopy. The frequencies of fundamental Raman modes increase obviously with increasing annealing magnetic field, and the intensity of the 1260 cm⁻¹ two-phonon mode decreases. The pronounced anomalies of Raman phonon modes under magnetic annealing are attributed to the change of the spin-phonon coupling due to the modulation of spiral spin order. Furthermore, the temperature dependence of Raman peak positions, for the two prominent modes (147 and 176 cm⁻¹), show no notable anomaly around T_N except the sample annealed under 10 T magnetic field; meanwhile, in this sample, another obvious phonon anomaly occurs at ∼150 K (another magnetic phase transition point), which indicate that stronger magnetic annealing with 10 T intensely enhances the spin-phonon coupling, and possibly increases magnetoelectric coupling of nanocrystalline BiFeO₃ due to severely modulation of spiral spin order.     

Effects of layering and magnetic annealing on the texture of CoPt films

The effect of magnetic field annealing of magnetron sputtered CoPt alloy films and Co/Pt bilayers on the crystallographic texture of the obtained chemically ordered (L1₀) CoPt films is presented. In CoPt alloy films the main effect of the magnetic field is to suppress (1 1 1) growth in the early stages of L1₀ formation whereas the development of (0 0 1) versus (1 0 0) texture is related to chemical ordering strain. A higher degree of (0 0 1) texture is obtained by magnetically annealing Co/Pt bilayers since the initial (1 1 1) texture in the as-sputtered films is avoided and Co-Pt alloying occurs in the presence of the magnetic field.     

Effects of co-substitution on the electrical properties of BiFeO3 thin films prepared by chemical solution deposition

Ferroelectric BiFeO₃ thin films with Nd-Cr (or Sm-Cr) co-substitution (denoted by BNdFCr and BSmFCr, respectively) were deposited on the Pt(2 0 0)/TiO₂/SiO₂/Si(1 0 0) substrates by a chemical solution deposition method. X-ray diffraction patterns revealed the formation of BNdFCr and BSmFCr thin films without any secondary phases. The co-substituted BNdFCr (or BSmFCr) thin films, which were annealed at 550 °C for 30 min in N₂ atmosphere, exhibited enhanced electrical properties compared to BFO thin films with the remanent polarization (2P_r) and coercive electric field (2E_c) of 196, 188 μC/cm² and 600, 570 kV/cm with the electric field of 800 kV/cm, respectively. The leakage current densities of BNdFCr and BSmFCr thin films measured at room temperature were approximately three orders of magnitude lower than that of BFO thin film, and the leakage current at room temperature of the thin films exhibited three distinctive conduction behaviors. Furthermore, the values of pulse polarizations [i.e., +(P*-P^{^}) or −(P*-P^{^})] of BNdFCr and BSmFCr thin films were reasonably unchanged up to 1.4 × 10¹⁰ switching cycles.     

Magnetoelectric effect in perovskite quantum paraelectric EuTiO3

On the basis of successful theoretical explanation of the observed large magnetic-field effect (by ∼7% with 1.5 T) on the dielectric constant below the Néel temperature T_N of 5.5 K, we have demonstrated convincingly the magnetoelectric effect in an antiferromagnetic quantum paraelectric EuTiO₃ system. The mutual control of electric and magnetic properties is revealed by the variation of the electric-field-induced polarization with applied magnetic fields as well as the change of the magnetic-field-induced spin moments under the control of electric fields. It is found that the applied electric field (magnetic field) acts like a fictitious magnetic field (electric field) on the EuTiO₃ system. The magnetoelectric susceptibility is deduced to be proportional to the product of the magnetization, electrical polarization, magnetic susceptibility and dielectric susceptibility.     

Underlayer diffusion-induced enhancement of coercivity in high anisotropy FePt thin films

The L1₀ ordered FePt films have been prepared at 300 °C with a basic structure of CrRu/MgO/FePt, followed by a post-annealing process at temperatures from 200 to 350 °C. The magnetic properties and the microstructure of the films were investigated. It is found that coercivity of FePt films increases greatly from 3.57 to 9.1 kOe with the increasing annealing temperature from 200 to 350 °C. The loop slope of the M–H curves decreases with the increasing annealing temperature, which is due to the grain isolation induced by MgO underlayer diffusion during the annealing process. The underlayer diffusion could be a useful approach to prepare the FePt-based composite films for high-density recording media.     

Structure,magnetic properties and magnetostriction of Fe81Ga19 thin films

The structure, magnetic properties and magnetostriction of Fe₈₁Ga₁₉ thin films have been investigated by using X-ray diffraction analysis, scanning electron microscope (SEM), vibrating sample magnetometer and capacitive cantilever method. It was found that the grain size of as-deposited Fe₈₁Ga₁₉ thin films is 50–60 nm and the grain size increases with increase in the annealing temperature. The remanence ratio (M_r/M_s) of the thin films slowly decreases with increase in the annealing temperature. However, the coercivity of the thin films goes the opposite way with increase in the annealing temperature. A preferential orientation of the Fe₈₁Ga₁₉ thin film fabricated under an applied magnetic field exists along 〈1 0 0〉 direction due to the function of magnetic field during sputtering. An in-plane-induced anisotropy of the thin film is well formed by the applied magnetic field during the sputtering and the formation of in-plane-induced anisotropy results in 90° rotations of the magnetic domains during magnetization and in the increase of magnetostriction for the thin film.     

An XPS study of Au alloyed Al-O sputtered coatings

The focus of this research is the X-ray photoelectron spectroscopy (XPS) analysis of thin films consisting of Au metal clusters embedded in a dielectric matrix of Al-O coatings. The coatings were deposited by co-sputtering an Al + Au target in a reactive atmosphere with Au contents up to 8 at.%. The Al-O matrix was kept amorphous even after annealing at 1000 °C. In the as-deposited films the presence of Au clusters with sizes smaller than 1-2 nm (not detected by XRD) was demonstrated by XPS. With increasing annealing temperature, Au clustering in the dielectric matrix was also confirmed by XPS, in agreement with XRD results.     

Modification in structure of La and Nd co‐doped epitaxial BiFeO3 thin films probed by micro Raman spectroscopy

The influence of La and Nd co‐substitution on structure, electric and magnetic properties of epitaxial thin films of BiFeO₃ (BFO) was examined. We demonstrate structural phase transition in co‐doped La and Nd BFO thin films using Raman spectroscopy. Based on group theoretical analysis of the number and symmetry of Raman lines, we provide strong experimental evidence that the structure has been changed from rhombohedral to monoclinic due to co‐doping in BFO. The change in structure was also reflected in morphology of these films. Room temperature magnetic hysteresis curves showed that doped films exhibit enhanced ferromagnetic properties with remnant magnetization of ~10 emu/cm³ and coercive field of 1.2 kOe. The enhanced magnetic properties highlight the potential applications of doped BLNFO thin film for smart devices. Copyright © 2015 John Wiley & Sons, Ltd.     

Amorphous Ni-Al underlayer-accelerated L10 ordering transition of FePt thin films

In the present study, we succeeded in accelerating the L1₀ ordering transition of FePt thin films by employing amorphous Ni-Al as underlayers. The coercivity H_c = 5 kOe and ordering parameter S = 0.67 of FePt thin films deposited on a Ni-Al underlayer with a thickness of ∼5 nm after 380 °C annealing for 30 min are significantly higher than those H_c = 0.4 kOe and S = 0.35 of the films without the Ni-Al underlayer. The L1₀ ordering process of and the coercivity of FePt thin films can be significantly tuned by varying the thickness of the Ni-Al underlayer.     

Strain effects on multiferroic BiFeO3 films

The field of multiferroics has experienced a rapid progress resulting in the discovery of many new physical phenomena. BiFeO₃ (BFO) compound, which is one of the few room-temperature single-phase multiferroics, has contributed subsequently to this progress. As a result, significant review articles have been devoted specifically to this famous system. This chapter is dedicated to the strain effects on the structure stability and property changes of BFO thin films. It is a short and non-exhaustive topical overview that may be seen as an invitation for interested readers to go beyond. There is a very active and prolific research in this field and we apologize to the authors whose relevant work is not cited here. After a short introduction, we will thus review the effect of strain on BFO films by describing the consequences on the structure and the phase transitions as well as on polar, magnetic and magnetoelectric properties.     

Study on dielectric and magnetic properties of Ho3Fe5O12 ceramics

Ho₃Fe₅O₁₂ ceramics with garnet structure were prepared by the solid-state reaction method. The results revealed the existence of Fe²⁺ ions have intensive influence on dielectric and magnetic properties of Ho₃Fe₅O₁₂ ceramics, which could be further confirmed by oxygen treatment. With a magnetic field lower than 10 kOe, the ME coefficient reaches 33 ps m⁻¹ at room temperature. And the ME coupling was further verified by dielectric anomaly near Néel temperature.