Microstructures, ferromagnetic, and ferroelectric properties in polyvinylpyrrolidone-assisted CoFe2O4/Pb(Zr0.53Ti0.47)O3 multiferroic composite thick films

CoFe₂O₄/Pb(Zr_0.53Ti_0.47)O₃ (CFO/PZT) multiferroic composite thick films with different CFO mass fractions have been prepared onto Pt/Ti/SiO₂/Si substrate by a hybrid sol–gel process and spin coating technique. Polyvinylpyrrolidone (PVP) was employed to be an assistance to the sol–gel solution for enhancing the film thickness and promising a crack-free film surface. After annealing at 650 °C in air for 1 h, phase structure, microstructure, magnetic and ferroelectric properties as well as leakage current of multiferroic thick films were investigated. X-ray diffraction indicated a deeply buried distribution of CFO particles in the PZT matrix. Scanning electronic microscopes showed crack-free surfaces and a decreasing film thickness from 7.2 μm to 6.2 μm with increasing CFO content. Furthermore, the saturated magnetization and remanent magnetization were also hence increased. In addition, mass fraction of CFO in PZT matrix was also estimated from 0.36% to 4.58% according to the relationship between M _s and magnetic content. Ferroelectric hysteresis loops revealed saturated polarization (P _s) and remanent polarization (P _r) were diluted by CFO till its mass fraction rising to 1.8%. After that, polarization was increased with further increasing CFO content. Enhanced leakage was demonstrated to be partially contributed to them. A critical content of 1.8% was hence confirmed, where ferroelectric and magnetic properties can be balanced, indicating a possible stress-transferred magnetoelectric coupling effect in this composite.     

Strain-induced artificial multiferroicity in Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript>/Pb(Fe<Subscript>0.66</Subscript>W<Subscript>0.33</Subscript>)O<Subscript>3</Subscript> layered nanostructure at ambient temperature

Layered nanostructures (LNs) of the commercial ferroelectric Pb(Zr_0.53Ti_0.47)O₃ (PZT) and the natural ferroic relaxor Pb(Fe_0.66W_0.33)O₃ (PFW) were fabricated with a periodicity of PZT/PFW/PZT (~5/1/5 nm, thickness ~250 nm) on MgO substrates by pulsed laser deposition. The dielectric behavior of these LNs were investigated over a wide range of temperatures and frequencies, observing Debye-type relaxation with marked deviation at elevated temperatures (>400 K). High dielectric constant and very low dielectric loss were observed below 100 kHz and 400 K, whereas the dielectric constant decreases and loss increases with increase in frequency, similar to relaxor ferroelectrics. Asymmetric ferroelectric hysteresis loops across UP and DOWN electric field were observed with high remanent polarization (P_r) of about 33 μC/cm². High imprint (~5–7 V across 250 nm thin films) were seen in ferroelectric hysteresis that may be due to charge accumulation at the interface of layers or significant amount of strain (~3.21) across the layers. Room temperature ferromagnetic hysteresis was observed with remanent magnetization 5.32 emu/cc and a coercive field of ~550 Oe. Temperature and field dependent leakage current densities showed very low leakage ~10⁻⁷–10⁻⁵ A/cm² over 500 kV/cm. We observed imprint in hysteresis that may be due to charge accumulation at the interface of layers or active role of polar nano regions (PNRs) situated in the PFW regions.     

Magnetoelectric properties of CoFe2O4–Pb(Zr0.52Ti0.48)O3 multilayered composite film via sol–gel method

CoFe₂O₄–Pb(Zr_0.52Ti_0.48)O₃ (CFO–PZT) multilayered composite film was prepared on Pt/Ti/SiO₂/Si substrate via a sol–gel method and spin-coating technique. Results show that PZT and CFO phases exist in the composite film, calcined at 700 °C, besides substrate phase, and no obvious impurity phases can be detected. The composite film exhibits layered structure with obvious boundary between CFO and PZT films. Ferroelectric and ferromagnetic properties were simultaneously observed in the composite film, evidencing the ferroelectric and ferromagnetic properties in the composite film. The composite film exhibits both good magnetic and electric properties, as well as, magnetoelectric (ME) effect. The saturation magnetization value of the composite film is lower than that of the pure CFO film derived by the same processing as a result of the effect of the nonferromagnetic PZT layers. Ferroelectric hysteresis loops reveal that saturated polarization and remanent polarization of the composite film are lower than those of the pure PZT films. The composite film exhibits a very large ME effect, which makes the composite film attractive for technological applications as devices.     

Dielectric, ferromagnetic and ferroelectric properties of the (1 ? x)Ba0.8Sr0.2TiO3–xCoFe2O4 multiferroic particulate ceramic composites

The (1 − x)Ba_0.8Sr_0.2TiO₃–xCoFe₂O₄ ceramic composites (x = 0–1) were prepared by standard solid state reaction method. X-ray diffraction and SEM indicate the Ba_0.8Sr_0.2TiO₃ (BST) phase and CoFe₂O₄ (CFO) phase coexist in the composites. The dielectric constant and dielectric loss for the composites were studied as a function of frequency (40 Hz–1 MHz) and temperature (30–600 °C). Magnetic and ferroelectric tests show that the ceramic composites display ferromagnetic and ferroelectric properties simultaneously. The saturated polarization of the composites decrease with ferrite concentration increasing, while the remnant polarization of the composites increase with increasing ferrite concentration. The enhanced ferroelectricity of composites may be attributed to space charge contribution in the composites.     

Damping properties of epoxy-based composite embedded with sol–gel-derived Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript> thin film annealed at different temperatures

Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films were prepared on Pt/Ti/SiO₂/Si substrate by sol–gel method. The effect of annealing temperature on microstructure, ferroelectric and dielectric properties of PZT films was investigated. When the films were annealed at 550–850 °C, the single-phase PZT films were obtained. PZT films annealed at 650–750 °C had better dielectric and ferroelectric properties. The sandwich composites with epoxy resin/PZT film with substrate/epoxy resin were prepared. The annealing temperature of PZT films influenced their damping properties, and the epoxy-based composites embedded with PZT film annealed at 700 °C had the largest damping loss factor of 0.923.     

Investigation of temperature-dependent polarization, dielectric, and magnetization behavior of multiferroic layered nanostructure

The PbZr_0.53Ti_0.47O₃(PZT)/CoFe₂O₄(CFO) layered nanostructures show lowering of dielectric constant and polarization, and an enhanced magnetization with a decrease in temperature from 400 K to 100 K. The temperature dependence of the real part of the dielectric constant illustrates a step-like behavior, whereas the imaginary part gives a relaxation peak near the step maxima temperature. A slow decrease in the polarization was observed from 300 K to 200 K, with an eventual collapse of polarization at ~ 100 K, and a complete polarization recovery with heating, these phenomena is reproducible over cycles of experiment. Remanent magnetization of the layered nanostructure was found to be three times higher at 100 K than that at room temperature. There is a slow enhancement in remanent (internal) magnetization with lowering of temperature, resulting in slow polarization switch and finally the collapse. The temperature-dependent dielectric, polarization and magnetization were different from the parent layer, indicating a kind of dynamic magneto-electric coupling in the layered nanostructures.     

Heterolayered PZT thin films of different thicknesses and stacking sequence

The effects of stacking sequence and thickness toward the texture and electrical properties of heterolayered PbZr _x Ti_1−x O₃ (PZT) films, consisting of alternating PbZr_0.7Ti_0.3O₃ and PbZr_0.3Ti_0.7O₃ layers, have been studied. Thickness dependence is observed in the ferroelectric and dielectric behavior of the heterolayered PZT films whereby the remanent polarization (P _r) and relative permittivity (ε) increase with thickness, while coercive field (E _c) decreases. When baked at 500 °C and thermally annealed at 650 °C, the heterolayered PZT films regardless of their stacking sequence exhibit perovskite phase with (001)/(100) preferred orientation. Interestingly, the stacking sequence of the heterolayered PZT films dictates the morphology of the films which eventually affects the ferroelectric and dielectric performance. The heterolayered PZT film with PbZr_0.7Ti_0.3O₃ as the first layer (heterolayered PZ₇₀T₃₀ film) exhibits a large grain size in the range of 1–3 μm and shows superior properties as compared to the heterolayered PZT films with PbZr_0.3Ti_0.7O₃ as the first layer (heterolayered PZ₃₀T₇₀ film), which exhibits a much smaller grain size. From the sub-switching field measurement according to the Rayleigh law, there appears a lower concentration or mobility of domain walls in the small-grained heterolayered PZ₃₀T₇₀ films.     

Orientation controlling of Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript> thin films prepared on silicon substrates with the thickness of La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> electrodes

Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films were prepared on La_0.5Sr_0.5CoO₃ (LSCO) coated Si substrates by a sol–gel route. The thickness of LSCO electrode was found to modify the preferential orientation of PZT thin films, which consequently affected the dielectric and ferroelectric properties. (100) textured PZT films with dense columnar structure could be obtained on the top of (110) textured LSCO with thickness of 230 nm. PZT thin films prepared on the optimized LSCO films exhibit the enhanced dielectric constant and remnant polarization of 980 and 20 μC/cm², respectively.     

Damping property of epoxy-based composite embedded with sol–gel-derived Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript> thin film

The Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films were prepared on Pt/Ti/SiO₂/Si substrate by sol–gel method. The effect of the annealing holding time on microstructure, ferroelectric and dielectric properties was investigated. The single-phase PZT films were obtained with different annealing holding time. PZT films annealed for 30–90 min had better dielectric and ferroelectric properties. The epoxy/PZT film/epoxy sandwich composites were prepared, and the annealing holding time of PZT films influenced the damping property of the composites. The epoxy-based composites embedded with PZT films annealed for 90 min had largest damping loss factor of 0.906.     

Effect of drawing on the dielectric properties and polarization of pressed solution cast β-PVDF films

Poly(vinylidene fluoride), PVDF, samples containing exclusively the polar β phase were obtained by crystallization from N,N-dimethylformamide (DMF) solution at 60 °C and subsequent pressing. Some of these samples were uniaxially drawn at 120 °C at draw ratio of 4, resulting in oriented films. Oriented and unoriented samples were characterized as to relative fraction of β phase, degree of crystallinity and orientation by infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and wide-angle X-ray diffraction (WAXD). The dependence on frequency of the real ( e_\textr^￠ \varepsilon_{\text{r}}^{\prime} ) and imaginary ( e_\textr^￠￠ \varepsilon_{\text{r}}^{\prime\prime} ) components of the relative permittivity of the samples was determined between 10⁴ and 1.7 × 10⁷ Hz. The coercive field and stable and metastable remanent ferroelectric polarization were determined from the hysteresis loop obtained by the ramp voltage technique, described in detail in this work. The results allowed verification of the effect of drawing on structure and of the resulting structure on the dielectric properties, remanent polarization, and coercive field of β-PVDF. A possible effect of the crystal–amorphous interphase region on the metastable remanent polarization is suggested. The results obtained with the oriented and unoriented samples were compared with those obtained for films commercialized by Piezotech S.A.     

Anomalies in the elastic and inelastic properties of ferromagnet-ferroelectric composites

We have studied the elastic and inelastic properties of composite materials of the Co _x (PZT)_{1 − x} system (x = 0.23–0.79) possessing a nonequilibrium nanogranular structure with an average grain size of ∼3 nm. The results of mechanical tests performed in a temperature range of 300–900 K revealed a significant increase in the level of mechanical losses (Q ⁻¹) above 750 K, which is caused by the thermoactivated migration of point defects. An additional heat treatment leads to grain coarsening and the appearance of a ferroelectric state in the dielectric matrix. The temperature dependences of Q ⁻¹ in annealed samples exhibit two maxima, one of which is due to the interaction of domain boundaries with lattice defects and the other is related to the motion of interfaces in the region of the ferroelectric phase transition.     

Effect of film thickness on ferroelectric domain structure and properties of Pb(Zr0.35Ti0.65)O3/SrRuO3/SrTiO3 heterostructures

Epitaxial Pb(Zr_0.35Ti_0.65)O₃ (PZT) thin films with tetragonal symmetry and thicknesses ranging from 45 to 230 nm were grown at 540 °C on SrRuO₃-coated (001)SrTiO₃ substrates by pulse-injected metalorganic chemical vapor deposition. The effect of the film thickness on the ferroelectric domain structure and the dielectric and ferroelectric properties were systematically investigated. Domain structure analysis of epitaxial PZT films was accomplished with high-resolution X-ray diffraction reciprocal space mapping and high-resolution transmission electron microscopy. Fully polar-axis (c-axis)-oriented epitaxial PZT thin films with high ferroelectric polarization values [e.g., remanent polarization (P _r) ~ 90 μC/cm²] were observed for film thicknesses below 70 nm. Films thicker than 70 nm had a c/a/c/a polydomain structure and the relative volume fraction of c-domains monotonously decreased to about 72% on increasing the film thickness up to 230 nm , and finally P _r diminished to about 64 μC/cm² for the 230-nm-thick epitaxial film. These polarization values were in good agreement with the estimated values taking into account the volume fraction of the c-axis-oriented domains while assuming a negligible contribution of 90° domain reorientation caused by an externally applied electric field.     

Low-temperature crystallization of sol-gel-derived lead zirconate titanate thin films using 2.45 GHz microwaves

Lead zirconate titanate (PZT) thin films of thickness 420 nm were deposited on Pt/Ti/SiO₂/Si substrate using a spin coating sol-gel precursor solution, and then annealed using 2.45 GHz microwaves at a temperature of 450 °C for 30 min. The film has a high perovskite content and high crystallinity with a full width at half maximum of 0.35°. The surface roughness of the PZT thin film was 1.63 nm. Well-saturated ferroelectric properties were obtained with a remanent polarization of 46.86 μC/cm² and coercive field of 86.25 kV/cm. The film also exhibited excellent dielectric properties with a dielectric constant of 1140 and a dissipation factor of 0.03. These properties are superior to those obtained by conventional annealing at a temperature of 700 °C for 30 min.     

Effects of sintering temperature on microstructure and electrical properties of 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3 modified with CuO

The structural, dielectric and ferroelectric properties of Pb(Mg_1/3Nb_2/3)_0.9Ti_0.1O₃ (PMNT) ceramics prepared with CuO as a sintering aid at various sintering temperatures between 950 °C and 1150 °C are investigated. The lattice parameters slightly increase with the sintering temperature >1050 °C. A significant increase in the grain size is observed when the sintering temperature is increased from 1000 °C to 1050 °C. The maximum dielectric constant reaches the highest value of ∼22,000 for the ceramic sintered at 1050 °C. For the ceramics sintered at >1050 °C, the temperature of maximum dielectric constant and the diffuseness parameters tend to increase with the increasing sintering temperature. The optimal sintering temperature for this ceramic is 1050 °C, which displays significant improvements in ferroelectric properties at room temperature, i.e. the increase in the remanent polarization and the ferroelectric loop squareness.     

Temperature dependence of ferroelectric and dielectric properties of textured 0.98(0.94Na0.5Bi0.5TiO3–0.06BaTiO3)–0.02K0.5Na0.5NbO3 thick film

Textured 0.98(0.94Na_0.5Bi_0.5TiO₃–0.06BaTiO₃)–0.02K_0.5Na_0.5NbO₃ thick film was prepared by reactive templated grain growth (RTGG) method. The effect of temperature on ferroelectric and dielectric behaviors of the thick film was investigated. Its dielectric constant as a function of temperature displayed typical relaxation behavior, which was similar to that of NBT-based bulk ceramics. Remnant polarization, saturation polarization, and coercive field of the thick film all decreased with increasing temperature. Dielectric constant and tunability of the film were also dependent on temperature. Electric field dependence of dielectric constant of the thick film suggested a transition from ferroelectric to antiferroelectric phase at around the depolarization temperature. A strong increase in leakage current density with increasing temperature was observed, which could be related to the enhanced activity of conductivity carriers.     

Properties of neodymium-doped Ca<Subscript>0.15</Subscript>Sr<Subscript>1.85</Subscript>Bi<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>18</Subscript> ferroelectric ceramics

Bismuth-layered compound Ca_0.15Sr_1.85Bi_4−xNd_xTi₅O₁₈ (CSBNT, x = 0–0.25) ferroelectric ceramics samples were prepared by solid-state reaction method. The effects of Nd³⁺ doping on their ferroelectric and dielectric properties were investigated. The remnant polarization Pr of CSBNT ceramics increases at beginning then decreases with increasing of Nd³⁺ doping level, and a maximum Pr value of 9.6 μC/cm² at x = 0.05 was detected with a coercive field Ec = 80.2 kV/cm. Nd³⁺ dopant not only decreases the Curie temperature linearly, but also the dielectric constant (ε_r) and dielectric loss tangent (tan δ). The magnitudes of ε_r and tan δ at the frequency of 100 kHz are estimated to be 164 and 0.0083 at room temperature, respectively.     

Electrical properties of lead zirconate titanate thick films prepared by hybrid sol–gel method with multiple infiltration steps

High-quality ferroelectric thick films are required for various piezoelectric applications including high-frequency transducers and microelectromechanical systems. In this work, we report the fabrication of dense crack-free lead zirconate titanate (PZT) thick films on Pt-coated Si substrates using commercial PZT powder dispersed in a sol–gel precursor solution without viscous additives. Preannealed films were infiltrated with the same solution and heat treated at 500 °C. Dielectric and ferroelectric properties of the films are found to be strongly dependent on the number of infiltration steps reaching sufficiently high values: dielectric constant ∼2270 and remanent polarization ∼35 μC cm⁻². Moderate coercive field of 60 kV cm⁻¹ and low dielectric loss ∼0.04 are observed in these films. Effective longitudinal piezoelectric coefficient d₃₃ also depends on the number of infiltrations demonstrating remanent value of ∼80 pm V⁻¹ for eight infiltration steps. The results show the suitability of hybrid sol–gel method for the fabrication of PZT thick films for dielectric and piezoelectric applications.     

Structure and dielectric properties of potassium niobate nano glass–ceramics

Glasses in the composition of 25K₂O-25Nb₂O₅-50SiO₂ (mol %) have been prepared by melt quenching technique and isothermally heat-treated at 800 °C for different duration (0–200 h). The formed nanocrystalline KNbO₃ phase, crystallite size and morphology are examined by X-ray diffraction, Fourier transform infrared reflection spectroscopy, field emission scanning and transmission electron microscopes. The frequency and temperature dependent dielectric constant and loss tangent are measured in the frequency and temperature ranges 0.1–1000 kHz and 200–500 °C respectively. The dielectric constant and loss tangent are found to decrease with increasing frequency and increase with increasing temperature. The dielectric constant and loss tangent versus temperature curve at different frequency revealed the phase transition of KNbO₃ from paraelectric cubic to ferroelectric tetragonal around 425 and 397 °C (Curie temperature) for nano glass–ceramics obtained after 1 and 200 h heat-treatment respectively.     

Ferroelectric and dielectric properties of Bi4-xNdxTi3O12 thin films prepared by sol–gel method

Bi_4-xNd_xTi₃O₁₂ (BNT-x, x = 0, 0.25, 0.50, 0.75 and 1.0) thin films were prepared on Pt/Ti/SiO₂/Si substrates by a sol–gel method. The microstructure, ferroelectric and dielectric properties of BNT-x thin films were investigated. The single-phase BNT-x thin films were obtained. With increasing Nd content, the preferred orientation changed from random to (117) and surface morphologies changed from the mixture of rod- and plate-like grains to rod-like grains. The Nd substitution improved the ferroelectric and dielectric properties of BTO films. BNT-x films showed better electrical properties at x = 0.50—1.0. BNT-0.75 film exhibited the best electrical properties with remanent polarization (2P _r) of 26.6 μC/cm², dielectric constant (ε _r) of 366 (at 1 MHz), dielectric loss (tanδ) of 0.034 (at 1 MHz), leakage current density (J) of ±3.0 × 10⁻⁶ A/cm² (at ± 5 V) and fatigue-free characteristics.     

An investigation on electrical properties of microwave treated natural ilmenite (FeTiO3)

It has been observed that microwaves of 2.45 GHz heat dielectric materials. On subjecting natural ilmenite to microwave irradiation, the mineral is observed to heat, with a surface temperature in proportion to the irradiation time. With irradiation times from 40 to 240 seconds (increased in steps of 40 sec), the surface temperature measured on the samples were between 280 and 520 K. Electrical measurements made on the samples before and after irradiation show that the electrical properties are modified by the microwave irradiation. The real conductivity (σ′), dielectric constant (ɛ′) and the dielectric loss (ɛ″) plotted against frequency generally showed universal dielectric behaviour [1 and references therein] similar to that observed in other systems studied in the literature but using conventional heating techniques. Plots of σ′, ɛ′ and ɛ″ against the surface temperature of the sample showed frequency independent peaks around 460 K. The experimental dielectric loss (ɛ″) results fit a peak function of the form: