Ferroelectric properties of highly c-axis oriented Bi4−xLaxTi3O12 film-based capacitors

Highly c-axis oriented lanthanum-modified bismuth titanate (Bi_4−xLa_xTi₃O₁₂) films having a variety of lanthanum (La) contents were grown on Pt/TiO₂/SiO₂/Si(100) substrates using metal-organic sol deposition and subsequent annealing at 650 °C for 1 h. After systematically examining the ferroelectric properties of Bi_4−xLa_xTi₃O₁₂ films as a function of the La-content, it was concluded that the film with x=0.85 had the largest remanent polarization in the direction parallel to the c-axis. The Pt/Bi_3.15La_0.85Ti₃O₁₂/Pt capacitor showed a well-saturated polarization-electric field (P-E) switching curve with the switching remanent polarization (2P_r) value of 33 μC/cm² and the coercive field (E_c) of 68 kV/cm at an applied voltage of 10 V. More importantly, the capacitor exhibited fatigue-free behavior up to 6.5×10¹⁰ read/write switching cycles at a frequency of 1 MHz. The capacitor also demonstrated an excellent charge-retaining ability and a strong resistance against the imprinting failure.     

Study of (Bi2O3)(BaxMo1−xO3) polycrystalline ceramic as relaxor ferroelectric

Solid solutions of bismuth layered (Bi₂O₃)(Ba_xMo_1−xO₃) (0.2≤x≤0.8, x is in step of 0.2) ceramics were prepared by conventional solid-state reaction of the constitutive oxides at optimized temperatures with a view to study its electrical properties. Powder X-ray diffraction has been employed for physical characterization and an average grain size of ∼16 to 22 nm was obtained. XRD study reveals the single phase structure of the samples. Dielectric properties such as dielectric constant (ε′), dielectric loss (tanδ) and ac electrical conductivity (σ_ac) of the prepared ceramics sintered at various temperatures in the frequency range 10¹–10⁷ Hz have been studied. A strong dispersion observed in the dielectric properties shows the relaxor type behavior of the ceramic. The presence of maxima in the dielectric permittivity spectra indicates the ferroelectric behavior of the samples. Impedance plots (Cole–Cole plots) at different frequencies and temperatures were used to analyze the electric behavior. The value of grain resistance increases with the increase in Ba ion concentration. The conductivity mechanism shows a frequency dependence, which can be ascribed to the space charge mainly due to the oxygen vacancies. The relaxation observed for the M″ (ω) or Z″ (ω) curves is correlated to both localized and long range conduction. A single ‘master curve’ for the normalized plots of all the modulus isotherms observed for a given composition indicates that the conductivity relaxation is temperature independent.     

Ferroelectric properties of Bi3.25−x/3La0.75Ti3−xNbxO12 films prepared by pulsed laser deposition

Bi₄Ti₃O₁₂ (BiT), Bi_3.25La_0.75Ti₃O₁₂ (BLT), Bi_4−x/3Ti_3−xNb_xO₁₂ (BTN) and Bi_3.25−x/3La_0.75Ti_3−xNb_xO₁₂ (BLTN) thin films have been prepared by pulsed laser deposition. BTN and BLTN films exhibit a maximum in the remanent polarization P_r at a Nb content x=0.018. At this Nb content, the BLTN film has a P_r value (25 μC/cm²) that is much higher than that of BiT and a coercive field similar to that of BiT. The polarization of this BLTN film is fatigue-free up to 10⁹ switching cycles. The high fatigue resistance is mainly due to the substitution of Bi³⁺ ions by La³⁺ ions at the A site and the enhanced P_r arises largely from the replacement of Ti⁴⁺ ions by Nb⁵⁺ ions at the B site. The mechanisms behind the effects of the substitution at the two sites are discussed.     

Compositional dependence of ferroelectric properties of highly c-axis oriented Bi4−xNdxTi3O12 film capacitors

Highly c-axis oriented neodymium-modified bismuth titanate (Bi_4−xNd_xTi₃O₁₂) films having a variety of neodymium (Nd) contents were successfully grown on Pt/TiO₂/SiO₂/Si(100) substrates using metal-organic sol decomposition. After systematically examining ferroelectric properties of the c-axis oriented Bi_4−xNd_xTi₃O₁₂ film capacitors as a function of the Nd-content, we concluded that the capacitor with x=0.85 had the largest remanent polarization. The Bi_3.15Nd_0.85Ti₃O₁₂ capacitor fabricated using a top Pt electrode showed well-saturated polarization-electric field (P-E) switching curves with the remanent polarization (P_r) of 51 μC/cm² and the coercive field (E_c) of 99 kV/cm at an applied voltage of 10 V. More importantly, the Pt/Bi_3.15Nd_0.85Ti₃O₁₂/Pt capacitor exhibited fatigue-free behavior up to 4.5×10¹⁰ read/write switching cycles at a frequency of 1 MHz. The capacitor also demonstrated an excellent charge-retaining ability and a strong resistance against the imprinting failure.     

Microstructures and microwave dielectric properties of La1-xBx(Mg0.5Sn0.5)O3 ceramics

The microwave dielectric properties of La_1-xB_x(Mg_0.5Sn_0.5)O₃ ceramics were examined with a view to their exploitation for mobile communication. The La_1-xB_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.995B_0.005(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. A maximum apparent density of 6.58 g/cm³, a dielectric constant (ε_r) of 19.8, a quality factor (Q × f) of 41,800 GHz, and a temperature coefficient of resonant frequency (τ_f) of −86 ppm/°C were obtained for La_0.995B_0.005(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1500 °C for 4 h.     

La substitution in four-layers Aurivillius phase SrBi4Ti4O15

Ceramics with the nominal composition of SrBi_4−xLa_xTi₄O₁₅ have been prepared within the range of 0≤x≤1.8, and the dielectric properties are investigated. Single phase SrBi_4−xLa_xTi₄O₁₅ solid solution exists until the secondary phase of La_2/3TiO₃ appears at x=1.6. The Curie temperature is 520 °C for pure SrBi₄Ti₄O₁₅, and it shifts to low temperature with increasing x, which is due to the smaller structural distortion caused by La³⁺ substitution. In addition, the dielectric constant anomaly is suppressed with the substitution. No dielectric relaxation behavior is observed. When x≥1.2, the paraelectric state is attained in the present ceramics. La³⁺ substitution effects on the SrBi₄Ti₄O₁₅ ceramics are also compared with the previous work on Bi_4−xLa_xTi₃O₁₂.     

Dielectric properties of lanthanum-doped CaCu3Ti4O12 synthesized by semi-wet route

Effect of La³⁺ doping at Ca²⁺ site in CaCu₃Ti₄O₁₂ has been examined. Compositions with x=0.10, 0.20 and 0.30 were synthesized in the system Ca_(1−3x/2)La_xCu₃Ti₄O₁₂ by semi-wet method. Powder X-ray diffraction confirmed the formation of monophasic compounds. The structure remains cubic similar to CaCu₃Ti₄O₁₂. Lattice parameter increases slightly with increasing La³⁺ concentration. Microstructure has been studied using scanning electron microscopy (SEM). Average grain size is in the range 2-4 μm for various compositions. Energy-dispersive spectrometer (EDS) studies confirm the stoichiometry of the synthesized materials. Dielectric constant, dielectric loss and conductivity of the samples decrease with increasing lanthanum concentrations.     

Dielectric spectroscopy on Bi3Zn2Sb3O14 ceramic: an approach based on the complex impedance

The dielectric properties and loss of Bi_1.5ZnSb_1.5O₇ a poor-semiconducting ceramic were investigated by impedance spectroscopy, in the frequency range from 5 Hz to 13 MHz. Electric measurements were performed from 100 to 700 °C. Pyrochlore type phase was synthesized by the polymeric precursor method. Dense ceramic with 97% of the theoretical density was prepared by sintering via constant heating rate. The dielectric permittivity dependence as a function of frequency and temperature showed a strong dispersion at frequency lower than 10 kHz. The losses exhibit slight dependence with the frequency at low temperatures presenting a strong increase at temperatures higher than 400 °C. A decrease of the loss magnitude occurs with increasing frequency. Relaxation times were extracted using the dielectric functions Z″(ω) and M″(ω). The plots of the relaxation times τ_Z′ and τ_M″ as a function of temperature follow the Arrhenius law, where a single slope is observed with activation energy values equal to 1.38 and 1.37 eV, respectively.     

Dielectric and optical behaviors in relaxor ferroelectric Pb(In1/2Nb1/2)1−xTixO3 crystal

Dielectric permittivities (ε′,ε″) have been measured as functions of temperature (140-535 K) and frequency (500 Hz-2.0 MHz) in a (001)-cut Pb(In_1/2Nb_1/2)_0.7Ti_0.3O₃ (PINT30%) single crystal grown by the modified Bridgman method with Pb(Mg_1/3Nb_2/3)_0.71Ti_0.29O₃ (PMNT29%) seed crystal. A diffused phase transition was observed in the temperature region of ∼430-460 K with strong frequency dispersion. Above the Burns temperature T_B≅510 K, the dielectric permittivity was found to follow the Curie-Weiss behavior, ε′=C/(T−T_C), with parameters C=3.9×10⁵ and T_C=472 K. Below T_B≅510 K, polar nanoclusters are considered to appear and are responsible for the diffused dielectric anomaly. Optical transmission, refractive indices, and the Cauchy equations were obtained as a function of wavelength at room temperature. The unpoled crystal shows almost no birefringence, indicating that the average structural symmetry is optically isotropic. The crystal exhibits a broad transparency in the wavelength range of ∼0.4-6.0 μm.     

Combinatorial exploration of flux material for Bi4Ti3O12 single crystal film growth

The combinatorial approach to materials synthesis was employed for the quick screening of a flux material for liquid phase-mediated epitaxy of Bi₄Ti₃O₁₂ single crystal film. A series of ternary flux libraries composed of two self-fluxes (Bi₂O₃ and Bi₄Ti₃O₁₂) and an impurity flux (VO_x, WO_x, CuO_x, BiPO_x, BaO, MoO_x) were fabricated on the SrTiO₃ (0 0 1) substrates. Then, stoichiometric Bi₄Ti₃O₁₂ was grown on each one of these flux libraries at a temperature presumed to melt the flux. High-throughput characterization with the concurrent X-ray diffraction (XRD) method resulted in the discovery of a novel flux material, CuO, containing Bi₂O₃, for Bi₄Ti₃O₁₂ single crystal film.     

Influence of frequency, temperature and composition on electrical properties of polycrystalline Co0.5CdxFe2.5−xO4 ferrites

Polycrystalline ferrites with general formula Co_0.5Cd_xFe_2.5−xO₄ (0.0?x?0.5) were prepared by sol-gel method. The dielectric properties ε′, ε″, loss tangent tan δ and ac conductivity σ_ac have been studied as a function of frequency, temperature and composition. The experimental results indicate that ε′, ε″, tan δ and σ_ac decrease as the frequency increases; whereas they increase as the temperature increases. These parameters are found to increase by increasing the concentration of Cd content up to x=0.2, after which they start to decrease with further increase in concentration of Cd ion. The dielectric properties and ac conductivity in studied samples have been explained on the basis of space charge polarization according to Maxwell and Wagner's two-layer model and the hoping between adjacent Fe²⁺ and Fe³⁺ as well as the hole hopping between Co³⁺and Co²⁺ ions at B-sites. The values of activation energies E_f for conduction process are determined from Arrhenius plots, and the variations in these activation energies as a function of Cd content are discussed. The complex impedance analysis is used to separate the grain and grain boundary of the system Co_0.5Cd_xFe_2.5−xO₄. The variations of both grain boundary and grain resistances with temperature and composition are evaluated in the frequency range 42 Hz-5 MHz.     

Complex permittivity, permeability and wide band microwave absorbing property of La substituted U-type hexaferrite

Polycrystalline samples of U-type hexaferrite series: (Ba_1−3xLa_2x)₄Co₂Fe₃₆O₆₀ with 0.10≤x≤0.20 in step of 0.05, are prepared by conventional solid state reaction route. Partial substitution of Ba²⁺ ions with La³⁺ ions enhances the electron hopping and reduces the magnetic interaction in the samples over the entire X-band frequencies; leading to wide band microwave absorption in all sample. Relative complex permittivity (ε_r=ε′−jε″) and permeability (μ_r=μ′−jμ″) of the prepared samples were measured using Vector Network Analyzer (VNA, Agilent PNA-L N5230A) for X-band (8.2-12.4 GHz) frequency range. The maximum absorption of 99.8% was obtained for x=0.10 sample for thickness t_m=1.8 mm and all sample showed absorption ≥96%. The reflection loss (R_L) calculated using the measured parameter (ε_r=ε′−jε″ and μ_r=μ′−jμ″) shows good agreement when compared with the return loss measured directly using VNA for sample x=0.20. The material can be expected to find relevance in suppression of electromagnetic interference (EMI) shielding and reduction of radar signatures.     

Ferroelectric and dielectric properties of La/Mn co-doped Bi4Ti3O12 ceramics

La/Mn co-doped Bi4Ti3O12 ceramics,Bi3.25La0.75Ti3-xMnxO12(x=0.02,0.04,0.06,0.08),were prepared by the solid-state reaction method.The influence of manganese substitution for the titanium part in Bi 3.25 La 0.75 Ti 3 O 12 on the sintering behaviour,microstructure,Raman spectra and electrical properties was investigated.The experimental results show that the phase composition of all samples with and without manganese doping,sintered at 1000 ℃,consists of a single phase with a bismuth-layered structure belonging to the crystalline phase Bi4Ti3O12.There is no evidence of any impurity phase,but a small change in crystallographic orientation is observed.The Curie temperature of Bi3.25La0.75Ti3-xMnxO12 ceramics is steadily shifted to lower temperature with increasing Mn-doping content.Moreover,the remnant polarisation(Pr) of Bi3.25La0.75Ti2.92Mn0.08O12 samples increases with Mn-doping content,and the Bi3.25La0.75Ti2.92Mn0.08O12 sample exhibits the largest P r of 16.6 μC/cm 2.     

Ferroelectric-relaxor behavior of (Na0.5K0.5)NbO3-based ceramics

We report that ferroelectric-relaxor behavior is induced by doping of SrO and TiO₂, or BaO and TiO₂ into classic ferroelectric (Na_0.5K_0.5)NbO₃. It is found that [(Na_0.5K_0.5)_0.9Sr_0.1](Nb_0.9Ti_0.1)O₃ ceramics exhibit a pronounced ferroelectric-relaxor behavior, comparable to that of [(Na_0.5K_0.5)_0.9Ba_0.1](Nb_0.9Ti_0.1)O₃ ceramics. Our results indicate that the relaxor behavior is closely related to the appearance of micropolar regions in these systems. The relaxor behavior should arise from the dynamic response of micropolar clusters. Raman spectra of [(Na_0.5K_0.5)_1−xSr_x](Nb_1−xTi_x)O₃ ceramics measured in the wavenumber range from 100 to 1200 cm⁻¹ confirm that the first order scattering is dominant in phonon bands should result from both short-range ordered region (micropolar regions) and disordered matrix. The frequency dependence of dielectric permittivity measurements show that the relaxor behavior of SrO and TiO₂, or BaO and TiO₂ doped (Na_0.5K_0.5)NbO₃ ceramics is not a Debye type in the radio frequency range.     

Complex permittivity, permeability and microwave absorbing properties of (Mn2−xZnx)U-type hexaferrite

Complex permittivity, permeability and microwave absorbing properties of a U-type hexaferrite series Ba₄Mn_(2−x)Zn_xFe₃₆O₆₀ (with 0≤x≤2 in step of 0.5) have been examined in the X-band (8.2-12.4 GHz) frequency range. The series have been prepared using conventional solid state reaction route. Microstructural variations with composition have been found with X-ray diffraction (XRD) and scanning electron microgram (SEM). The complex permittivity (ε^?=ε′−jε″) and permeability (μ^?=μ′−jμ″) were measured using vector network analyzer (Agilient Make model PNA E8364B). These parameters were then used for calculating the reflection loss for determination of microwave absorbing properties. Addition of Zn resulted in an increase in reflection loss from −4 dB (or 60 % absorption) in sample with x= 0 to −32 dB (99.92% absorption) in sample with x=1 when the sample thickness was 1.7 mm. Multiple peaks of resonance were obtained in the dielectric and magnetic loss spectra for all samples with x>0. The result indicates that the sample with composition Ba₄MnZnFe₃₆O₆₀, i.e., x=1, can be used effectively for microwave absorption and suppression of electromagnetic interference.     

AC conductivity and dielectric properties of bulk tungsten trioxide (WO3)

AC conductivity and dielectric properties of tungsten trioxide (WO₃) in a pellet form were studied in the frequency range from 42 Hz to 5 MHz with a variation of temperature in the range from 303 K to 463 K. AC conductivity, σ_ac(ω) was found to be a function of ω^s where ω is the angular frequency and s is the frequency exponent. The values of s were found to be less than unity and decrease with increasing temperature, which supports the correlated barrier hopping mechanism (CBH) as the dominant mechanism for the conduction in WO₃. The dielectric constant (ε′) and dielectric loss (ε″) were measured. The Cole–Cole diagram determined complex impedance for different temperatures.     

Preparation of substituted barium ferrite BaFe12−x(Ti0.5Co0.5)xO19 by citrate precursor method and compositional dependence of their magnetic properties

As a possible candidate for the left-handed metamaterial with negative permeability, a series of Ti, Co-substituted M-type barium hexaferrite BaFe_12−x(Ti_0.5Co_0.5)_xO₁₉ (x=0, 1, 2, 3, 4 and 5) was prepared by citrate precursor method. The formation processes of the substituted barium hexaferrite compounds from the precursors were followed by the measurements of powder X-ray diffraction (XRD), Infrared absorption spectra (FT-IR), and thermogravimetry and differential thermal analysis (TG/DTA) coupled with mass spectroscopy (MS). In the case of the non-substituted sample, the formation of the barium hexaferrite is regulated by the thermal decomposition of BaCO₃ and the solid-state reactions of BaO and Fe₂O₃ in the temperature range from 800 to 1100 K. The formation temperature of the substituted BaFe_12−x(Ti_0.5Co_0.5)_xO₁₉ is higher than that for the non-substituted sample and increases with the value of x, due to the effects of carbonate ions incorporated by the partial substitution of Fe³⁺ by (Ti_0.5Co_0.5)³⁺. On heating up to ca. 1200 K, all the substituted samples transform into the magenetoplumbite phase as is the non-substituted sample. The compositional dependence of the magnetic properties of the substituted barium hexaferrite was investigated by the magnetization measurement. The decrease in the magnetic anisotropy was confirmed by the change in the magnetization curve and coercivity H_C with the composition x. A negative permeability spectrum was observed in the BaFe₉(Ti_0.5Co_0.5)₃O₁₉ in the frequency range from 2 to 4 GHz.     

Dielectric and piezoelectric properties of barium-modified Aurivillius-type Na0.5Bi4.5Ti4O15

In this study, monophasic Ba_x(Na_0.5Bi_0.5)_1−xBi₄Ti₄O₁₅ (x=0.03, 0.06, 0.09 and 0.12) ceramics fabricated from the powders synthesized via the solid-state reaction route exhibited relaxor behavior. X-ray diffraction analysis revealed that the barium-modified Na_0.5Bi_4.5Ti₄O₁₅ ceramics have a pure four-layer Aurivillius phase structure. Dielectric properties and phase transitions were studied and are explained in terms of lattice response of these ceramics. A shift in ferroelectric–paraelectric phase transition (T_c) to lower temperatures and a corresponding increase in permittivity peak with increasing concentration of Ba²⁺ are also observed. The decrease of orthorhombicity in the lattice structure by the larger Ba²⁺ ion incorporation, indicating an approach of a and b parameters, results in lower Curie temperature. The piezoelectric activity of Na_0.5Bi_4.5Ti₄O₁₅ (NBT) ceramics was significantly improved by the modification of barium. The Curie temperature T_c and piezoelectric coefficient d₃₃ for the composition with x=0.12 were found to be 635 °C and 21 pC/N, respectively. The relationship of polarization with lattice response is discussed.     

Electrical conductivity and complex electric modulus of titanium doped nickel-zinc ferrites

The samples Ni_1+x−yZn_yTi_x Fe_2−2xO₄; y=0.1, 0.0≤x≤0.5 were prepared in a single-phase spinel structure as indicated from X-ray analysis. Electrical conductivity and dielectric measurements at different temperatures from 300 K to 600 K in the frequency range from 42 Hz to 5 MHz have been analyzed. The relation of conductivity with temperature revealed a semiconductor to semimetallic behavior as Ti⁴⁺ concentration increases. The conduction mechanism depends mainly on the valence exchange between the different metal ions in the same site or in different sites. The dielectric constant as a function of temperature and frequency showed that there is a strong dependence on the compositional parameter x. The electrical modulus has been employed to study the relaxation dynamics of charge carriers. The result indicates the presence of correlation between motions of mobile ion charges. The activation energies extracted from M′(ω) and M″(ω) peaks are found to follow the Arrhenius law. The electrical conductance of the samples found to be dependent on the temperature and frequency.     

Fabrication and properties of PLT/PLZT/PLT structures obtained by RF magnetron sputtering

Ferroelectric Pb_0.84La_0.16Ti_0.96O₃/Pb_0.96La_0.04(Zr_0.52Ti_0.48)_0.99O₃/Pb_0.84La_0.16Ti_0.96O₃ (PLT/PLZT/PLT) structures were fabricated on platinum-coated silicon wafers by RF magnetron sputtering. A Pb_0.84La_0.16Ti_0.96O₃ layer was used as a seed layer to improve the crystallization and enhance the ferroelectric properties of the PLZT film. With the PLT seed layers, the films showed excellent ferroelectric properties in terms of large remnant polarization (2P_r) of 52.7 μC/cm², lower coercive field (2E_c) of 130 kV/cm for an applied field of 500 kV/cm. Moreover, the PLT/PLZT/PLT structures exhibited good fatigue endurance after 10¹⁰ switching cycles, which was attributed to the double-sided PLT layers. They improved the electrical fatigue by eliminating the pyrochlore phase, reduced the strong (111) orientation, and assimilated the oxygen vacancies from the PLZT layer.