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.     

Microstructure, domain structures and ferroelectric properties in (Pb0.8,La0.1,Ca0.1)TiO3/Pb(Zr0.2,Ti0.8)O3 bilayered thin film

Ferroelectric (Pb_0.8,La_0.1,Ca_0.1)TiO₃/Pb(Zr_0.2,Ti_0.8)O₃ (PLCT/PZT) bilayered thin film was prepared on Pt(111)/Ti/SiO₂/Si(100) substrate by RF magnetron sputtering technique. Pure perovskite crystalline phase, determined by X-ray diffraction, was formed in the PLCT/PZT bilayer. The bilayered film exhibited a very dense and smooth surface morphology with a uniform grain size distribution. The ferroelectric domain structures were investigated by a combination of vertical and lateral piezoresponse force microscopy (VPFM and LPFM, respectively). It is demonstrated by both VPFM and LPFM observations that out-of-plane and in-plane lamellar ferroelectric domains coexist in the bilayered thin film. The PLCT/PZT bilayered film possesses good ferroelectric properties with relatively high spontaneous polarization (2P_s = 82 µC/cm²) and remnant polarization (2P_r = 26.2 µC/cm²).     

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.     

Dynamic magneto-electric multiferroics PZT/CFO multilayered nanostructure

Highly oriented PbZr_0.53Ti_0.47O₃/CoFe₂O₄ (PZT/CFO) multilayered nanostructures (MLNs) were grown on MgO substrate by pulsed laser ablation using La_0.5Sr_0.5CoO₃ (LSCO) as conducting bottom electrode. The effect of various PZT/CFO (PC) sandwich configurations having three, five, and nine layers while maintaining total thickness of PZT and CFO be identical has been systematically investigated. X-ray diffraction (XRD) and micro-Raman spectra revealed the existence of pure PZT and CFO phases without any intermediate phase. Intact MLNs were observed by transmission electron microscopy (TEM) with little inter-diffusion near the interfaces at nano-metric scale without any impurity phase. Impedance spectroscopy, modulus spectroscopy, and conductivity spectroscopy were carry out over a wide range of temperatures (100–600 K) and frequencies (100 Hz–1 MHz) to investigate the grain and grain boundary effect on electrical properties of MLNs. Temperature dependent real dielectric permittivity and dielectric loss illustrated step-like behavior and relaxation peaks near the step-up characteristic, respectively. Cole–Cole plots indicate that most of the dielectric response came from the bulk (grain) MLNs below 300 K, whereas the grain boundary and the electrode–MLNs effects are prominent at elevated temperatures. The dielectric loss relaxation peak shifted to higher frequency side with increase in temperature, it was out of the experimental frequency window above 300 K. Our Cole–Cole fitting of dielectric loss spectra indicated marked deviation from the ideal Debye-type of relaxation, which is more at elevated temperature. Master modulus spectra supported the observation from the impedance spectra; it also indicated that the magnitude of the grain boundary compared to grain becomes more prominent with increase in number of layers. We have explained these electrical properties of MLNs by Maxwell–Wagner type contributions arising from the interfacial charge at the interface of the ML structures. Three different types of frequency dependent conduction processes were observed at elevated temperatures (>300 K), which fitted well with the double power law, indicating that the low frequency (<1 kHz) conductivity may be due to long-range ordering (frequency independent), mid frequency conductivity (<10 kHz) may be due to short-range hopping, and high frequency (<1 MHz) conduction due to the localized relaxation hopping mechanism. Ferroelectric polarization decreased slowly in reducing the temperature from 300 to 200 K, with complete collapse of polarization at ~100 K, but there was complete recovery of the polarization during heating, which was repeatable over many different experiments. At the same time, the temperature dependent remanent magnetization of the MLNs showed slow enhancement in the magnitude till 200 K with three-fold increase at 100 K compared to room temperature. This enhancement in remanent magnetization and decrease in remanent ferroelectric polarization on lowering the temperature indicate temperature dependent dynamic switching of ferroelectric polarization. The magnetic and ferroelectric properties of MLNs were quite different compared to individual layers suggesting its improper ferroelectric characteristics. The fatigue test showed almost 0–20% deterioration in polarization. Fatigue and strong temperature and frequency dependent magneto-electric coupling suggest MLNs utility for Dynamic Magneto-Electric Random Access Memory (DMERAM).     

Electric and magnetic properties of Pb(Zr0.52Ti0.48)O3-CoFe2O4 particle composite thin film on the SrTiO3 substrate

We deposited a thin epitaxial Pb(Zr_0.52Ti_0.48)O₃ (PZT) layer on the (0 0 1) SrTiO₃ (STO) substrate doped with Nb (0.5 wt.%), then grew composite thin film of CoFe₂O₄ (CFO) and PZT phases on it. X-ray diffraction and high resolution transmission electron microscopy showed that the PZT and CFO phases in the film had perfect epitaxial structures. CFO nanoparticles were embedded in PZT matrix randomly, which was useful to enhance the insulativity of the composite film. The composite thin film exhibited good ferromagnetic and ferroelectric properties. The dielectric constants of the composite thin film kept unchangeable in a wide bias electric field, but increased in a magnetic field, namely, magnetodielectric effect. The possible reasons for the magnetodielectric effect were discussed.     

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.     

Hysteresis loops of polarization and magnetization in (BiNd0.05)(Fe0.97Mn0.03)O3/Pt/CoFe2O4 layered epitaxial thin film grown by pulsed laser deposition

(BiNd_0.05)(Fe_0.97Mn_0.03)O₃ (BNFM)/Pt/CoFe₂O₄ (CFO) layered thin film was fabricated on (100) SrTiO₃ substrate by pulsed laser deposition. BNFM, Pt, and CFO layers were epitaxially grown on the substrate. Almost no increase of leakage current due to the formation of heteroepitaxial structure was found, and well-saturated hysteresis loops in the polarization vs electric field and magnetization vs magnetic field curves coexist at room temperature. The remnant polarization and remnant magnetization values were 55 μC/cm², and 70-145 mA/m, respectively.     

Magnetoelectric effect in Pb(Zr0.95Ti0.05)O3 and CoFe2O4 heteroepitaxial thin film composite

Multiferroic epitaxial films, include SrRuO₃/Pb(Zr_0.95Ti_0.05)O₃/CoFe₂O₄ has been successfully deposited on SrTiO₃ substrate by pulsed-laser deposition technique. The results show that the prepared films exhibit a single phase. The Pb(Zr_0.95Ti_0.05)O₃ (PZT) film was highly textured with (1 0 0) orientation and gives good ferroelectric properties with saturated polarization of 15 μC/cm². The magnetic coercivity of CoFe₂O₄ film on Pb(Zr_0.95Ti_0.05)O₃ has been dampened to 0.9 kOe. The anisotropic magnetically behavior of CoFe₂O₄ film was changed to isotropic by using high Zr concentrated PZT as underneath layer. Heterostructure films show a good ferromagnetic and ferroelectric coupling that lead to the large magnetoelectricity of 287 mV/cm Oe.     

Processing and magneto-electric properties of sol–gel-derived Pb(Zr0.52Ti0.48)O3–Ni0.8Zn0.2Fe2O4 2-2 type multilayered films

Pb(Zr_0.52Ti_0.48)O₃–Ni_0.8Zn_0.2Fe₂O₄ (PZT–NZFO) multilayered thin films with various volume fractions of the PZT phase (100, 74, 58, 48, 33, and 0%) were prepared on Pt/Ti/SiO₂/Si substrates using sol–gel spin-coating method. X-ray diffraction shows polycrystalline structure and scanning electron microscopy reveals good multilayer morphology of the composite thin film as annealed at 700 °C in air. The thickness of the composite films was estimated in the range of ~400 to ~600 nm. The ferroelectric and magnetic properties were measured as function of the volume fractions of the PZT phase. The magnetoelectric (ME) effect was investigated under various bias magnetic fields. The maximum ME voltage coefficient (α _E  = dE/dH) is 278 mV/cmOe for the composite film with the volume fractions of the PZT phase of ~48%.     

Magnetic field induced ferroelectric and dielectric properties in Pb(Zr0.5Ti0.5)O3 films containing Fe3O4 nanoparticles

About 1.05 µm-thick Pb(Zr_0.5Ti_0.5)O₃ (PZT) films containing Fe₃O₄ nanoparticles were deposited on LaNiO₃-coated silicon substrates through a sol-gel technique. Fe₃O₄ nanoparticles were effectively dispersed into PZT solution under the involvement of polyvinylpyrrolidone. X-ray diffraction confirmed the coexistence of PZT and Fe₃O₄ phases without other impurity phases. Scanning electron microscope revealed that the thick composite films possess well-defined and crack-free microstructure. The composite films exhibit good ferroelectric and ferromagnetic properties at room temperature. An obvious magnetodielectric effect has been demonstrated in the Pb(Zr_0.5Ti_0.5)O₃/Fe₃O₄ composite films. Magnetic field induced change in ferroelectric polarization loop may support the possible magnetoelectric coupling between PZT and Fe₃O₄ phases.     

Effect of excess Pb in PbTiO<Subscript>3</Subscript> precursors on ferroelectric and fatigue property of sol–gel derived PbTiO<Subscript>3</Subscript>/PbZr<Subscript>0.3</Subscript>Ti<Subscript>0.7</Subscript>O<Subscript>3</Subscript>/PbTiO<Subscript>3</Subscript> thin films

A series of Pb_(1+x)TiO₃/PbZr_0.3Ti_0.7O₃/Pb_(1+x)TiO₃ (PTO/PZT/PTO) and PbZr_0.3Ti_0.7O₃ (PZT) thin films were prepared by a sol–gel method. Different excess Pb content (x) (x = 0, 0.05, 0.10, 0.15, 0.20) were added to the PbTiO₃ (PTO) precursors to investigate their effect on ferroelectric and fatigue properties of the PTO/PZT/PTO thin films. X-ray diffraction results show that the crystallization behavior of the PTO/PZT/PTO thin films is greatly affected by the excess Pb content (x) in PTO precursors. Topographic images show that the PTO/PZT/PTO thin films with excess Pb content x = 0.10 appears the densest and the most uniform grain size surface morphology. The ferroelectric and fatigue properties of the films correlate straightforwardly to the crystallization behaviors and excess Pb content (x) in the PTO precursors. The excess Pb content (x) in the PTO layers which acts as a nucleation site or seeding layer for PZT films affects the crystallization of the PTO layer and ultimately affects the perovskite phase formation of the PZT films. With the proper excess Pb content (x = 0.10–0.15) in the PTO precursors, the pure perovskite structure PTO/PZT/PTO thin films, with dense, void-free, and uniform fine grain size are obtained, and a well-saturated hysteresis loop with higher remnant polarization is achieved. Using an appropriate Pb content, the fatigue has been avoided by controlling the inter-diffusion and surface volatilization.     

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.     

Sol–gel synthesis and electrical characterization of (Pb, Ca)TiO3 thin films

Calcium modified lead titanate films have been prepared on Pt/Ti/SiO₂/Si substrates using a sol–gel route. The sols were prepared from propanediol solutions of Pb(CH₃COO)₂·xH₂O, Ti(OC₃H₇)₂(CH₃COCHCOCH₃)₂ and Ca(NO₃)₂·xH₂O. Tetragonal phase (Pb, Ca)TiO3 films could be produced by firing the coatings at 650°C for 30 min. The limiting thickness of crack-free single layers was ∼0.4 μm, but 3 μm thick films could be made by a multiple deposition technique. Dielectric and ferroelectric parameters were determined for single layer 0.5 μm films for compositions up to 30 mol% Ca. The average values of remanent polarization, P_r and coercive field, E_c decreased with increasing Ca content from ∼11 μC cm⁻² and ∼125 Kv cm⁻¹ for a 10 mol% Ca composition to ∼8 μC cm⁻² and 80 kV cm⁻¹ for 30 mol% Ca films. It was noted that the statistical variation in electrical values across each film was greater than in PZT films made by a similar sol–gel route. Reasons for this are discussed in terms of the incidence of physical defects in the films. This revised version was published online in November 2006 with corrections to the Cover Date.     

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.     

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.     

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.     

Enhanced ferroelectric properties of epitaxial Pb(Zr,Ti)O3 film with LaAlO3 buffer

PbZr_0.52Ti_0.48O₃ films (PZT) have been grown epitaxially on SrRuO₃/LaAlO₃ (SRO/LAO) substrates using pulse laser deposition. In order to improve the ferroelectric properties of the PZT, one LAO buffer was introduced into the interface of PZT/SRO. The dependence of the electrical properties of the PZT films on the buffer thickness was studied. When a 10-nm-thick buffer was used, the remnant polarization (Pr) of the PZT film reached 58 ± 5 μC/cm², 2 times larger than the sample without any buffer layer. The leakage current was reduced 1-2 orders of magnitude. Besides, the PZT film with 10-nm-thick LAO buffer also exhibited good fatigue endurance after 10⁹ switching cycles. These results could propose one effective way to improve the properties of ferroelectric films deposited on oxide electrodes.     

Highly a-oriented SrBi2Ta2O9 thin film on (111) Pt/TiO2/SiO2/Si substrate by eclipse pulsed laser deposition

A highly a-oriented SrBi₂Ta₂O₉ thin film with a polycrystalline structure was deposited on a preferentially oriented (111) Pt/TiO₂/SiO₂/Si substrate by eclipse pulsed laser deposition (PLD) method. The SrBi₂Ta₂O₉ thin film exhibited flat and smooth surface with the surface roughness of about 0.5 nm resulting from reducing particulates generated by on-axis PLD. The SrBi₂Ta₂O₉ thin film showed a good ferroelectric property with the high remanent polarization of 12 μC/cm² and the low coercive electric field of 140 kV/cm. For the highly a-oriented SBT thin film, domain switching and reading were performed by Kelvin probe force microscope (KFM). The KFM data indicate a good ferroelectric property of the highly a-oriented SrBi₂Ta₂O₉ thin film with high KFM signals that reflect ferroelectric polarizations.     

Multiferroic properties of ErMnO3

Measurements of magnetic and dielectric properties of single crystalline ErMnO₃ establish the Néel and ferroelectric transition temperatures to be 77 K and 588 K respectively. The dielectric constant of ErMnO₃ shows an anomalous jump at T_N. At higher temperatures, the dielectric constant undergoes a significant decrease on application of magnetic fields. The study clearly exhibits multiferroic and magnetoelectric nature of ErMnO₃.     

Enhanced ferro- and piezoelectric properties in (100)-textured Nb-doped Pb(ZrxTi1 − x)O3 films with compositions at morphotropic phase boundary

To develop high-performance piezoelectric films on conventional Pt(111)/Ti/SiO₂/Si(100) substrates, sol-gel-derived highly [100]-textured Nb-doped Pb(Zr_xTi_1 − x)O₃ (PNZT) thin films with different Zr/Ti ratios ranging from 20/80 to 80/20 were prepared and characterized. The phase structure, ferroelectric and piezoelectric properties of the PZNT films were investigated as a function of Zr/Ti ratios, and it was confirmed that there was distinct phase transition of the PNZT system from tetragonal to rhombohedral when the Zr/Ti ratio varied across the morphotropic phase boundary (MPB). The Nb-doped PZT films showed enhanced remanent polarization but reduced coercive field, whose best values reached 75 μC/cm² and 82 kV/cm, respectively at the composition close to MPB. In addition, the [100]-textured PNZT film at MPB also shows a high piezoelectric coefficient up to 161 pm/V. All these properties are superior to those for undoped PZT films.