Structural and electrical properties of sol–gel-derived Al-doped bismuth ferrite thin films

Al-doped BiFeO₃ (BiFe_(1?x)Al_xO₃) thin films with small doping content (x=0, 0.05, and 0.1) were grown on Pt(111)/TiO₂/SiO₂/Si substrates at the annealing temperature of 550 °C for 5 min in air by the sol–gel method. The crystalline structure, as well as surface and cross section morphology were studied by X-ray diffraction and scanning electron microscope, respectively. The dielectric constant of BiFeO₃ film was approximately 71 at 100 kHz, and it increased to 91 and 96 in the 5% and 10% Al-doped BiFeO₃ films, respectively. The substitution of Al atoms in BiFeO₃ thin films reduced the leakage current obviously. At an applied electric field of 260 kV/cm, the leakage current density of the undoped BiFeO₃ films was 3.97×10^?4 A/cm², while in the 10% Al-substitution BiFeO₃ thin films it was reduced to 8.4×10^?7 A/cm². The obtained values of 2P_r were 63 μC/cm² and 54 μC/cm² in the 5% and 10% Al-doped BiFeO₃ films at 2 kHz, respectively.     

Dielectric properties and tunability of Ba(ZrxTi1−x)O3 ceramics under high DC electric field

Ba(Zr_xTi_1−x)O₃ (BZT) (x = 0.25, 0. 3, 0.35, 0.4) ceramics were prepared by the traditional ceramic processing and their structural, surface morphological, dielectric properties, tunable properties as well as the mechanism of their nonlinear dielectric constant under DC electric field were systemically examined. The Zr ions substitution of Ti ions has a strong effect on the dielectric properties and the grain sizes. The results show Ba(Zr_xTi_1−x)O₃ (x = 0.25, 0.3, 0.35) ceramics to be promising candidates for the DC electric field tunable materials for microwave electronics application, because they exhibit high tunability (27.6%, 26.3%, 19.4%, respectively) as the strength of electric field is up to 2 kV/mm, low dielectric loss (0.001–0.002, 0.001–0.002, 0.004–0.005, respectively) at 10 kHz at room temperature and low temperature coefficient of capacitance.     

Tunable multiferroic properties of Mn substituted BiFeO3 thin films

The current study explored the influence of Mn substitution on the electrical and magnetic properties of BiFeO₃ (BFO) thin films synthesized using low cost chemical solution deposition technique. X-ray diffraction analysis revealed that pure rhombohedral phase of BiFeO₃ was transformed to the tetragonal structure with P4mm symmetry on Mn substitution. A leakage current density of 5.7×10⁻⁴ A/cm² which is about two orders of magnitude lower than pure BFO was observed in 3% Mn doped BFO thin film at an external electric field >400 kV/cm. A well saturated (p-E) loops with saturation polarization (P_sat) and remanent polarization (2P_r) as high as 60.34 µC/cm² and 25.06 µC/cm² were observed in 10% Mn substituted BFO thin films. An escalation in dielectric tunability (n_r), figure of merit (K) and quality factor (Q) were observed in suitable Mn doped BFO thin films. The magnetic measurement revealed that Mn substituted BFO thin films showed a large saturation magnetization compared to pure BFO thin film. The highest saturation ~31 emu/cc was observed for 3% Mn substituted BFO thin films.     

Enhanced ferroelectric properties of Ce-substituted BiFeO3 thin films on LaNiO3/Si substrates prepared by sol–gel process

The effects of Ce substitution on the structural and electrical properties of multiferroic BiFeO₃ thin films grown on LaNiO₃/Si(1 0 0) substrates by a sol–gel process have been reported. X-ray diffraction data confirmed the substitutions of Ce into the Bi site with the elimination of all secondary phases under a substitution ratio x = 15%. The dielectric constants of the films increased from 90 to ～260 below 100 kHz with 5% molar Ce substitution and the films showed enhanced dielectric behavior. We observed a substantial increase in the remnant polarization (P_r) with Ce substitution and obtained a maximum value of ～71 μC/cm² by 5% molar Ce incorporation. The leakage current behavior at room temperature of the films was studied and it was found that the leakage current density decreased from 10^?6 to 10^?8 A/cm² for 5% molar Ce-substituted films under a field 150 kV/cm. The reduction of dc leakage current of Ce-substituted films is explained on the basis of relative phase stability and improved microstructure of the material.     

Structural,dielectric, vibrational and magnetic properties of Sm doped BiFeO3 multiferroic ceramics prepared by a rapid liquid phase sintering method

Rare earth Sm substituted Bi_1−xSm_xFeO₃ with x=0, 0.025, 0.05, 0.075 and 0.10 polycrystalline ceramics were synthesized by a rapid liquid phase sintering method. The effect of varying composition of Sm substitution on the structural, dielectric, vibrational, optical and magnetic properties of doped BiFeO₃ (BFO) ceramics have been investigated. X-ray diffraction patterns of the synthesized rare earth substituted multiferroic ceramics showed the pure phase formation with distorted rhombohedral structure with space group R3c. Good agreement between the observed and calculated diffraction patterns of Sm doped BFO ceramics in Rietveld refinement analysis of the X-ray diffraction patterns and Raman spectroscopy also confirmed the distorted rhombohedral perovskite structure with R3c symmetry. Dielectric measurements showed improved dielectric properties and magnetoelectric coupling around Néel temperature in all the doped samples. FTIR analysis establishes O–Fe–O and Fe–O stretching vibrations in BiFeO₃ and Sm-doped BiFeO₃. Photoluminescence (PL) spectra showed visible range emissions in modified BiFeO₃ ceramics. The magnetic hysteresis measurements at room temperature and 5 K showed the increase in the magnetization with the increase in doping concentration of Sm which is due to the structural distortion and partial destruction of spin cycloid caused by Sm doping in BFO ceramics.     

Leakage current and dielectric breakdown in lanthanum doped amorphous aluminum oxide films prepared by sol–gel

Dielectric Al_2−2xLa_2xO₃ (x=0.00, 0.005, 0.02, 0.05, and 0.10) thin films were fabricated on Pt/Ti/SiO₂/Si substrates by sol–gel spin coating. The surface morphology of Al_2−2xLa_2xO₃ thin film was observed by field emission scanning electron microscopy. The chemical state of the lanthanum in aluminum oxide films was analyzed using X-ray photoelectron spectroscopy (XPS), indicating that lanthanum reacts with absorbed water to form lanthanum hydroxide. J–E measurements were used to investigate the current conduction mechanism and breakdown behavior. The results show that La doping changes the conduction mechanism and makes influences on leakage current. The dominating conduction process of 10% La doped Al₂O₃ films turns into the space charge limited current (SCLC) mechanism in the field region ranging from 25 to 150 MV/m. The leakage current of the films with 10% La doping decreases by three orders of magnitude from 10⁻⁶ to 10⁻⁹ at the electric field of 25 MV/m. The breakdown strength increases with the increasing content of lanthanum.     

Dielectric and Magnetic properties of (1 − x)BiFeO3–xBa0.8Sr0.2TiO3 ceramics

The polycrystalline samples of (1 ? x)BiFeO₃–xBa_0.8Sr_0.2TiO₃ (x = 0, 0.1, 0.2, 0.25, 0.3, 0.4 and x = 1) were prepared by the conventional solid state reaction method. The effect of substitution in BiFeO₃ by Ba_0.8Sr_0.2TiO₃ on the structural, dielectric and magnetic properties was investigated. X-ray diffraction study showed that these compounds crystallized at room temperature in the rhombohedral distorted perovskite structure for x ≤ 0.3 and in cubic one for x = 0.4. As Ba_0.8Sr_0.2TiO₃ content increases, the dielectric permittivity increases. This work suggests also that the Ba_0.8Sr_0.2TiO₃ substitution can enhance the magnetic response at room temperature. A remanent magnetization M_r and a coercive magnetic field H_C of about 0.971 emu/g and 2.616 kOe, respectively were obtained in specimen with composition x = 0.1 at room temperature.     

Co-doping effects of A-site Y3+ and B-site Al3+ on the microstructures and dielectric properties of CaCu3Ti4O12 ceramics

Different doping elements have been used to reduce the dielectric losses of CaCu₃Ti₄O₁₂ ceramics, but their dielectric constants usually are undesirably decreased. This work intends to reduce their dielectric losses and simultaneously enhance their dielectric constants by co-doping Y³⁺ as a donor at A site and Al³⁺ as an acceptor at B site for substituting Ca²⁺ and Ti⁴⁺, respectively. Samples with different doping concentrations x = 0, 0.01, 0.02, 0.03, 0.05 and 0.07 have been prepared. It has been shown that their dielectric losses are generally reduced and their dielectric constants are simultaneously enhanced across the frequency range up to 1 MHz. The doped sample with x = 0.05 exhibits the highest dielectric constant, which is well over 10⁴ for frequency up to 1 MHz and is about 20% higher than the undoped sample. Impedance spectra indicate that the doped samples have much higher grain boundary resistance than the undoped one.     

Electrical and nonlinear current-voltage characteristics of La-doped BiFeO3 ceramics

Multiferroic Bi_1-xLa_xFeO₃(x=0, 0.05, 0.1, 0.2, and 0.3) ceramics with particle sizes of ~67–19 nm were prepared by a simple co-precipitation method. The effects of La dopant on the microstructure, giant dielectric response, and electrical properties were investigated. The grain size of Bi_1-xLa_xFeO₃ ceramics significantly decreased with increasing La doping ions. The Bi_0.95La_0.05FeO₃ ceramic exhibited the highest leakage current density value. Interestingly, it strongly decreased as the concentration of La increased. The nonlinear coefficient of La doped BFO slightly decreased with increasing La. This shows a space-charge-limited conduction mechanism, which is involved in low electric field regions for all samples investigated. La substitution significantly enhanced the breakdown field. It was found that the potential barrier height at the grain boundary was slightly reduced from 0.3 to 0.16 eV by substitution of La ions. Using impedance spectroscopy analysis, except for the Bi_0.7La_0.3FeO₃ ceramic, the grain boundary resistance at room temperature was affected by dc bias, whereas the grain resistance of all samples was independent of dc bias. This result was well consistent with the variation in low-frequency dielectric constant and loss tangent value due to the effect of dc bias. These results were closely related to the existence of the interfacial polarization at the grain boundary.     

Influence of Y doping on structural,vibrational, optical and magnetic properties of BiFeO3 ceramics prepared by Mechanical Activation

Y substituted BiFeO₃ (Bi_1−xY_xFeO_3; x=0.0–0.1) polycrystalline ceramics were synthesized by Mechanical Activation. The effect of varying composition of Y substitution on the structural, vibrational, optical and magnetic properties of doped BiFeO₃ (BFO) ceramics has been investigated. Rietveld refinement of X-ray diffraction patterns reveals that all samples crystallize in distorted rhombohedral structure with R3c symmetry and no structural transition has been observed. Raman spectroscopy also confirmed the distorted perovskite structure with R3c space group. Optical studies in the spectral range 1–4.5 eV were dominated by two d-d and three charge transfer (C-T) transitions. The optical band gap decreases from 2.11 to 2.01 eV with increasing Y substitution. Room temperature magnetic measurements showed weak ferromagnetic ordering and enhancement in magnetization with increasing Y concentration. Mechanical activation leads to significantly altered magnetic properties, particularly in higher Y-doping samples. The Mössbauer spectra demonstrate the suppression of spiral spin modulation of the magnetic moments resulting in enhanced ferromagnetism with increasing doping concentration. Significant increase in Néel temperature T_N in the substituted compounds was discussed on the basis of structural distortions.     

Synthesis,structural and electrical properties of Bi1−xDyxFeO3 multiferroic ceramics

Polycrystalline ceramic samples of dysprosium (Dy³⁺) doped bismuth ferrite of general formula Bi_1?xDy_xFeO₃ (x=0.00, 0.01, 0.05 and 0.1) have been prepared by standard solid state reaction method. Powder X-ray diffraction (XRD) analysis reveals that all the samples crystallize in the rhombohedral structure with noncentrosymmetric R3c space group. The refined lattice parameters decrease with the increase of Dy concentration within the same structure symmetry. The bond lengths among atoms for all the compounds were calculated by the Rietveld analysis. The frequency and temperature dependent dielectric constants (real and imaginary parts) have been measured. The real part of dielectric constant reveals that the Neel temperature decreases with the increase of Dy-substitution down to ～200 °C for 10% substitution to the Bi site.     

Structural and electromagnetic properties of Ni0.5Zn0.5HoxFe2-xO4 ferrites

Ni-Zn ferrites with a nominal composition of Ni_0.5Zn_0.5Ho_xFe_2-xO₄ (x = 0–0.06) were prepared by conventional solid state reaction through using analytical-grade metal oxides powders as raw materials. The phase composition, microstructure, magnetic properties and dielectric performance of the as-prepared samples were investigated. The doped Ho³⁺ ions could enter into the crystal lattice of the resultant spinel ferrites, causing the expansion of the unit cell, reaching a saturated state when x = 0.015; and the additional Ho³⁺ ions would form a foreign HoFeO₃ phase at the grain boundary. The grain size and densification of the samples initially decreased after a small amount of Ho³⁺ ions was doped, but then increased with more Ho³⁺ ions added. The saturation magnetization decreased gradually with increasing substitution level of Ho³⁺ ions. The Curie temperature and coercivity raised initially and declined later with increasing content of Ho³⁺ ions in the samples, reaching their maximums of 305 °C with x = 0.015 and 2.99 Oe with x = 0.03, respectively. The variation of complex permeability versus Ho³⁺ ions substitution level presented an opposite trend to that of coercivity. The dielectric loss increased slightly after the introduction of a small amount of Ho³⁺ ions, but reduced significantly with more Ho³⁺ ions doped.     

Effects of Nd3+-substitution for Bi-site on the leakage current,ferroelectric and dielectric properties of Na0.5Bi0.5TiO3 thin films

Perovskite Na_0.5(Bi_1?xNd_x)_0.5TiO₃ (x = 0, 0.01, 0.03, 0.05; xNd: NBT) ferroelectric films were synthesized on indium tin oxide (ITO)/glass substrates via chemical solution deposition. Structural characterization shows the similar phase-pure perovskite structures in all the films and gradually decreased grain sizes with Nd³⁺ doping amount increasing. For all the films, the leakage behaviors are dominant by the Ohmic conduction in low electric field region and interface-limited Fowler-Nordheim tunneling mechanism in high electric field region. Additionally, the space-charge-limited conduction is involved in 0.03Nd: NBT sample. Compared with the sample of x = 0, the resistivity can be improved through Nd³⁺-substitution in NBT. Enhanced ferroelectricity can be obtained from the dynamic polarization-electric field test, and the reversible domains switching in film can be confirmed by static dielectric constant-electric field measurement. Especially, the 0.03Nd: NBT possesses optimal electrical performances with a large remanent polarization (P_r = 26.7 μC/cm²) and a high dielectric tunability (19.6% at 100 kHz).     

Enhanced dielectric and energy-storage properties in BiFeO3-modified Bi0.5(Na0.8K0.2)0.5TiO3 thin films

Lead free Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ thin films doped with BiFeO₃ (abbreviated as BNKT-xBFO) (x = 0, 0.02, 0.04, 0.08, 0.10) were deposited on Pt(111)/Ti/SiO₂/Si substrates by sol-gel/spin coating technique and the effects of BiFeO₃ content on the crystal structure and electrical properties were investigated in detail. The results showed that all the BNKT-xBFO thin films exhibited a single perovskite phase structure and high-dense surface. Reduced leakage current density, enhanced dielectric and ferroelectric properties were achieved at the optimal composition of BNKT-0.10BFO thin films, with a leakage current density, dielectric constant, dielectric loss and maximum polarization of < 2 × 10⁻⁴ A/cm³, ~ 978^, ~ 0.028 and ~ 74.13 μC/cm² at room temperature, respectively. Moreover, the BNKT-0.10BFO thin films possessed superior energy storage properties due to their slim P-E loops and large maximum polarization, with an energy storage density of 22.12 J/cm³ and an energy conversion efficiency of 60.85% under a relatively low electric field of 1200 kV/cm. Furthermore, the first half period of the BNKT-0.10BFO thin film capacitor was about 0.15 μs, during which most charges and energy were released. The large recoverable energy density and the fast discharge process indicated the potential application of the BNKT-0.10BFO thin films in electrostatic capacitors and embedded devices.     

Annealing-temperature-modulated optical,electrical properties,and leakage current transport mechanism of sol–gel-processed high-k HfAlOx gate dielectrics

Deposition of HfAlO_x gate dielectric films on n-type Si and quartz substrates by sol-gel technique has been performed and the optical, electrical characteristics of the as-deposited HfAlO_x thin films as a function of annealing temperature have been investigated. The optical properties of HfAlO_x thin films related to annealing temperature are investigated by ultraviolet-visible spectroscopy (UV–vis) and spectroscopy ellipsometry (SE). By measurement of UV–vis, average transmission of all the HfAlO_x samples are about 85% owing to their uniform composition. And the increase in band gap has been observed with the increase of annealing temperature. Moreover, the increase of refractive index (n) and density with the increase of annealing temperature are obtained by SE measurements. Additionally, the electrical properties based on Al/Si/HfAlO_x/Al capacitor are analyzed by means of the high frequency capacitance-voltage (C-V) and the leakage current density-voltage (J-V) characteristics. Results have shown that 400 °C-annealed sample demonstrates good electrical performance, including larger dielectric constant of 12.93 and lower leakage current density of 3.75×10⁻⁷ A/cm² at the gate voltage of 1 V. Additionally, the leakage current conduction mechanisms as functions of annealing temperatures are also discussed systematically.     

Synthesis and properties of multiferroic 0.7BiFeO3−0.3BaTiO3 thin films by Mn doping

Multiferroic BiFeO₃?BaTiO₃ thin films that simultaneously exhibit ferroelectricity and ferromagnetism at room temperature were prepared by chemical solution deposition. Perovskite single-phase 0.7BiFeO₃?0.3BaTiO₃ thin films were successfully fabricated in the temperature range 600–700 °C on Pt/TiO_x/SiO₂/Si substrates. As the crystallization temperature was increased, grain growth proceeded, resulting in higher crystallinity at 700 °C. Although the 0.7BiFeO₃?0.3BaTiO₃ thin films exhibited poor polarization (P)?electric field (E) hysteresis loops owing to their low insulating resistance. The leakage current at high applied fields was effectively reduced by Mn doping at the Fe site of the 0.7BiFeO₃?0.3BaTiO₃ thin films, leading to improved ferroelectric properties. The 5 mol% Mn-doped 0.7BiFeO₃?0.3BaTiO₃ thin films simultaneously exhibited ferroelectric polarization and ferromagnetic magnetization hysteresis loops at room temperature.     

Study of electrical transport properties of Eu+3substituted MnZn-ferrites synthesized by co-precipitation technique

Eu substituted MnZn-ferrites with nominal composition Mn_0.78Zn_0.22Eu_x Fe_(2?x)O₄ (x=0.0, 0.02, 0.04, 0.06, 0.08 and 0.10) were prepared by co-precipitation technique. The effect of Europium substitution on electrical transport properties of Mn–Zn ferrites is reported. XRD analysis reveals fcc phase in all the samples along with few traces of second phase. The lattice constant shows decreasing trend with the substitution of Eu due to partial solubility of Eu-ions in the lattice. Room temperature resistivity both at 10 and 20 V shows on average an increasing trend. This increase in resistivity is attributed to the unavailability of Fe⁺³ ions in the lattice due to Eu-substitution. The dc resistivity decreases with temperature for all the samples at 10 V and 20 V indicating the semiconducting behavior of these samples. Room temperature dc resistivity and activation energies show similar trend both at 10 V and 20 V indicating that the samples with high resistivity have high activation energies and vice versa. The dielectric constant (ε′), complex dielectric constant (ε″) and loss tangent of these samples decreased with the increase of Eu-concentration, following the Maxwell–Weigner model.     

Effect of non-magnetic Al3+ doping on structural,optical, electrical,dielectric and magnetic properties of BiFeO3 ceramics

Pure BiFeO₃ (BFO) and Al doped BFO samples were synthesized via citrate precursor method and sintered at 500 °C for two hours. Effect of Al doping on the structural, optical, electrical, dielectric and magnetic properties were investigated. X-ray diffraction (XRD) confirmed the distorted rhombohedral structure without any merging of peaks which indicates no structural transformation. Average crystallite size was found to be in the range 28–39 nm. Field emission scanning electron microscopy (FESEM) images illustrated the dense, agglomerated, spherically shaped with reduced grain size nanoparticles. Increased value of dielectric constant with low dielectric tangent loss was observed for the Al doped BFO samples. The value of dielectric constant was found to be 51 at 100 kHz for x = 0.1 sample. Temperature dependent dielectric constant showed a dielectric anomaly, indicating the antiferromagnetic transition. The remanent polarization and the corresponding coercive field for x = 0.1 was found to be 0.0625 µC/cm² and 56.154 kV/cm at an operating voltage of 1000 V. The improved electrical properties with low leakage current density were ascribed to the stabilization of the pervoskite structure and reduced oxygen vacancies.     

Dielectric behavior and impedance spectroscopy in lead-free BNT–BT–NBN perovskite ceramics for energy storage

The dielectric behavior, impedance spectroscopy and energy-storage properties of 0.85[(1−x)Bi_0.5Na_0.5TiO₃–xBaTiO₃]–0.15Na_0.73Bi_0.09NbO₃ [(BNT–xBT)–NBN] ternary ceramics were investigated. Temperature dependent permittivity curves displayed two depressed anomalies, resulting in significantly improved dielectric temperature stability. (BNT–9BT)–NBN showed a permittivity of 1680 at 150 °C with Δε/ε_150 °C varying no more than ±10% up to 340 °C. From the complex impedance analysis, grain and grain boundary shared the same time constant. The high temperature resistivity followed the Arrhenius law with E_a=1.7–2.0 eV, suggesting intrinsic band-type electronic conduction. The maximum energy-storage density of all the samples reached 1.1–1.4 J/cm³, accompanied with good temperature stability in the range of 25–140 °C. These results indicate that (BNT–xBT)–NBN system should be a promising lead-free material for energy-storage capacitor applications.     

Enhanced temperature stability and fatigue-resistant behavior in MgTiO3-doped 0.948(K0.5Na0.5)NbO3–0.052LiSbO3 lead-free ceramics

0.948(K_0.5Na_0.5)NbO₃–0.052LiSbO₃–xMgTiO₃ (x=0, 0.005 and 0.010) (abbreviated as KNLNS–xMT) lead-free piezoelectric ceramics were prepared by normal sintering. The effect of MT addition on KNLNS ceramics was investigated through dielectric, ferroelectric and electric field-induced strain characterizations. The grain size decreased slightly after the addition of MT, and more uniform grains were obtained. Impedance measurements made over a wide range of temperatures (425–525 °C) showed the presence of both bulk and grain boundary effects in the materials. The activation energies E_a were 0.483 and 0.507 eV for KNLNS and KNLNS–0.005MT ceramics respectively, indicating that the conduction process was due to oxygen vacancies in the higher temperature region. The P_r and unipolar strain of the MT modified ceramics exhibited lower temperature sensibility than KNLNS ceramics in the temperature range 30–120 °C. Meanwhile, the MT doped samples showed less degradation in both switchable polarization and unipolar strain after 10⁶ switching cycles than those of KNLNS. It is expected that the KNLNS–xMT ceramics is promising candidate for lead-free piezoceramics and could be used in practical applications.