Dielectric properties and phase transitions of (Pb0.87La0.02Ba0.1)(Zr0.6Sn0.4−xTix)O3 ceramics with compositions near AFE/RFE phase boundary

The electrical properties and phase transition behavior of (Pb_0.87La_0.02Ba_0.1)(Zr_0.6Sn_0.4−xTi_x)O₃ solid solutions (PLBZST, 0.04≤x0.2) were investigated by the X-ray diffraction, permittivity, pyroelectric current, and P-E electric hysterisis loops. As the composition x increased from 0.04 to 0.2, the antiferroelectric ceramics (x≤0.07, AFE) with tetragonal phase changed to the ferroelectric relaxors (RFE, 0.09≤x). AFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to −100 °C) due to a frustration between AFE and FE state. With an increase in composition x, electrically field-induced AFE-FE switching field (E_AFE-FE) and AFE-paraelectric (PE) phase transition temperature (T_c) are depressed in the temperature (T)-Ti composition (x) phase diagram, a FE-AFE-PE triple phase point (T_tr) with the lowest transition temperature occurred at x=0.09. The pyroelectric currents under an application of various external electric field (E) were measured to identify a T-E phase diagram of the PLBZST compound.     

Dielectric properties of SrBi2−xPrxNb2O9 ceramics (x=0, 0.04 and 0.2)

SrBi_2−xPr_xNb₂O₉ (x=0, 0.04 and 0.2) ceramics were prepared by a solid state reaction method. X-ray diffraction analysis indicated that single-phase layered perovskite structure ferroelectrics were obtained. A relaxor behavior of frequency dispersion was observed among Pr-doped SrBi₂Nb₂O₉. The degree of frequency dispersion ΔT increased from 0 for x=0-7 °C for x=0.2, and the extent of relaxor behavior γ increased from 0.94 for x=0-1.45 for x=0.2. The substitution of Pr ions for Bi³⁺ ions in the Bi₂O₂ layers resulted in a shift of the Curie point to lower temperatures and a decrease in remanent polarization. In addition, the coercive field 2E_c reduced from 110 kV/cm for an undoped specimen to 90 kV/cm for x=0.2.     

Bias field effects on the dielectric properties of 0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3 single crystals with different orientations

The domain states and phase transitions in 0.67Pb(Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ single crystals were investigated by studying their relative permittivity under various dc bias at constant heating and cooling rates. The orientation dependence of the bias field effect was revealed by examining the temperature dependence of relative permittivity as a function of crystal orientation (the 〈111〉, 〈011〉 and 〈001〉 directions) and dc bias field. The crystals basically have a macrodomain rhombohedral ferroelectric state in the ferroelectric phase under zero dc bias. External bias field could modulate the domain state and induce a stable macrodomain state in the crystals. Also, it is proposed that the dc bias applied along the 〈001〉 or 〈011〉 direction could induce a tetragonal ferroelectric phase or an orthorhombic ferroelectric phase, respectively, in an intermediate temperature range.     

Effects of composition on phase structure and electrical properties of (K0.5Na0.5)0.90Li0.06Sr0.02Nb(1−x)SbxO3 ceramics

Lead-free (K_0.5Na_0.5)_0.90Li_0.06Sr_0.02Nb_(1−x)Sb_xO₃ (KNLSN-Sb_x) ceramics were synthesized by ordinary sintering technique. The compositional dependence of phase structure and electrical properties of the ceramics was systematically investigated. All samples possessed pure perovskite structure, showing room temperature symmetries of orthorhombic at x<0.01, coexistence of orthorhombic and tetragonal phases at x=0.01, and tetragonal at 0.02≤x≤0.05. The temperature of the polymorphic phase transition (PPT) was shifted to lower temperature and dielectric relaxor behavior was induced by increasing Sb content. The samples near the coexistence region (x=0.01) exhibited enhanced electrical properties: d₃₃∼145 pC/N, k_p∼38% and P_r∼20.4 μC/cm².     

Anisotropic in-plane misfit strains dependence of phase diagrams and dielectric behavior in epitaxial Pb(Zr1−xTix)O3 thin films

A phenomenological Landau–Devonshire thermodynamic theory is used to describe the effects of anisotropic in-plane misfit strains on equilibrium polarization states and dielectric properties of single domain epitaxial Pb(Zr_1−xTi_x)O₃ thin films grown on dissimilar orthorhombic substrates. Compared with the “isotropic in-plane misfit strains-temperature” phase diagrams, the characteristic features of “misfit strain-misfit strain” and “misfit strain-temperature” phase diagrams under the circumstance of strain anisotropy are the presence of four different phases (a^′$a^{\prime }$, a^″$a^{″}$, a^′c$a^{\prime }c$, and a^″c$a^{″}c$) and the direct 90° polarization switching between c   phase and a^′$a^{\prime }$ phase (or a^″$a^{″}$ phase), between a^′$a^{\prime }$ phase and a^″$a^{″}$ phase. The misfit strain dependence of polarization components, the small-signal dielectric responses and the tunabilities at room temperature are also calculated. We find that the phase diagrams and dielectric properties largely depend on anisotropic in-plane misfit strains as well. Moreover, the strain anisotropy will lead to the polarization and dielectric anisotropy.     

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.     

Investigation on optical transmission spectra of (1−x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystals

The optical transmission spectra from 0.3 to 11 μm of relaxor ferroelectric single crystals (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMN-xPT) were systematically studied at room temperature in this paper. The crystal is transparent between 0.45 and 5.5 μm and becomes completely absorbing around 0.4 μm in near UV region and 10 μm in infrared region. But the wavelength cutoff in near UV is much sharper than the long wavelength cutoff. As compared with other configurations, tetragonal single crystals possess the optimal transmission properties. The optical transmittance in the wavelength region from 0.45 to 5.5 μm is about 70%. The results show that tetragonal PMN-xPT single crystals are promising for a wide range of optical applications. Some discussions about the oxygen-octahedra structure that determines the basic energy level of the crystals are also presented on the optical properties of PMN-xPT single crystals.     

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.     

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.     

Investigations of structural, dielectric and ferroelectric behavior of europium substituted SrBi2Ta2O9 ferroelectric ceramics

Europium substituted samples of the compositions Sr_1−xEu_xBi₂Ta₂O₉ (x=0.0,0.025,0.050,0.10 and 0.20) were synthesized by solid state reaction method and studied for their structural, dielectric and ferroelectric properties. The X-ray diffractograms confirmed the formation of single phase layered perovskite structure in all the samples. The temperature variation of dielectric constant shows that the Curie temperature (T_c) decreases on increasing concentration of europium. The dielectric loss reduces significantly with europium addition. The P-E studies of the Eu-substituted SBT ceramics show that the remanent polarization increases with increasing concentration of europium.     

Interrelation of antiferrodistortive and ferroelectric phase transitions in Sr1−xAxTiO3 (A=Ba, Pb)

A dielectric and ultrasonic velocity study of antiferrodistortive and ferroelectric phase transitions in Sr_1−xA_xTiO₃ (A=Ba, Pb) is reported. It is shown that both phase transitions co-exist at x<0.03 but at the higher concentration the ferroelectric phase transition entirely suppresses the antiferrodistortive phase transition. The experimentally obtained phase diagrams are discussed in the framework of the Landau phenomenological theory.     

TiO2-nonstoichiometry dependence on piezoelectric properties and depolarization temperature of (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06Ti_xO_1+2x lead-free piezoceramics with x varying from 0.97 to 1.03 were fabricated and characterized in order to investigate the effects of TiO₂-nonstoichiometry on the piezoelectric properties and depolarization temperature of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ composition. X-ray diffraction (XRD) analysis showed that all samples have a single phase of perovskite structure with rhombohedral symmetry. Piezoelectric and dielectric measurements revealed that deficiency of TiO₂ leads to an increase in the piezoelectric coefficient (d₃₃), free relative permittivity (), and loss tangent (tan δ) besides an increase in the electromechanical coupling coefficient (k_p) within a certain amount, while excess of TiO₂ results in a decrease in k_p, d₃₃, and , but an increase in tan δ. Depolarization temperature (T_d) measurement indicated a decrease and an increase in T_d as a result of increasing TiO₂ deficiency and TiO₂ excess, respectively. This TiO₂-nonstoichiometry also induced changes in the remanent polarization (P_r) and coercive field (E_c) of the ceramics.     

Electrical properties of high Curie temperature (1−x)Pb(In1/2Nb1/2)O3-xPbTiO3 single crystals grown by the solution Bridgman technique

0.65Pb(In_1/2Nb_1/2)O₃-0.35PbTiO₃ (PINT65/35) (starting composition) single crystals were grown successfully through the solution Bridgman technique using PbO flux and PMNT67/33 seed crystals. Because of the composition variation, the final composition of achievable crystals is in a range of 0.32-0.34 with the corresponding T_c range of 265-269 °C. The (001) plates of as-grown PINT66/34 single crystals show high Curie temperature (T_c=269 °C) and rhombohedral-tetragonal phase transition temperature (T_rt=134 °C). Besides, good electrical properties with high dielectric constant (ε>3000), low dielectric loss (tan δ∼1.2%), high piezoelectric constant (d₃₃∼2000 pC/N) and large electromechanical coupling factor (k_t≈59%) at room temperature have been obtained on the (001) plates. The sound velocity, acoustic impedance and other piezoelectric parameters were also measured on the (001) plates in this study, which provide us more detailed information about PINT66/34 single crystals.     

Phase transformation in (0.90−x)Pb(Mg1/3Nb2/3)O3-xPbTiO3-0.10PbZrO3 piezoelectric ceramic: X-ray diffraction and Raman investigation

Piezoelectric ceramics with compositions of (0.90−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃-0.10PbZrO₃, x=0.28, 0.31, 0.34, 0.37, 0.40 and 0.43, were prepared using the conventional columbite precursor method, and their structural phase transformation and piezoelectric behaviors near the morphotropic phase boundary (MPB) have been systematically investigated as a function of PbTiO₃ content. X-ray diffraction (XRD) results demonstrate that the structure of the ceramics experiences a gradual transition process from rhombohedral phase to tetragonal phase with the increasing of PbTiO₃ content, and that compositions with x=0.34-0.40 lie in the MPB region of this ternary system. A Raman spectra investigation of the ceramic samples testified to the transformation process of rhombohedral phase to tetragonal phase by comparing the relative intensities of tetragonal E(2TO₁) mode and rhombohedral phase R_h mode. The structure information was also correlated to the parabola change of the piezoelectric constant; the maximum piezoelectric constants were obtained near the MPB region.     

Spectroscopic studies of (AsSe)100−xAgx thin films

Thin (AsSe)_100−xAg_x films have been grown onto quartz substrates by vacuum thermal evaporation or pulsed laser deposition from the corresponding bulk materials. The amorphous character of the coatings was confirmed by X-ray diffraction investigations. Their transmission was measured within the wavelength range 400-2500 nm and the obtained spectra were analyzed by the Swanepoel method to derive the optical band gap E_g and the refractive index n. We found that both parameters are strongly influenced by the addition of silver to the glassy matrix: E_g decreases while n increases with Ag content. These variations are discussed in terms of the changes in the atomic and electronic structure of the materials as a result of silver incorporation.     

Maxwell-Wagner characterization of dielectric relaxation in Ni0.8Zn0.2Fe2O4/Sr0.5Ba0.5Nb2O6 composite

Dense composites were prepared through incorporating the dispersed Ni_0.8Zn_0.2Fe₂O₄ ferromagnetic particles into Sr_0.5Ba_0.5Nb₂O₆ ferroelectric matrix. Extrinsic dielectric relaxation and associated high permittivities of the materials are reported in the composites. We used an ideal equivalent circuit to explain electrical responses in impedance formalism. A Debye-like relaxation in the permittivity formalism was also found. Interestingly, real permittivity (ε′) of the sample containing 30% Ni_0.8Zn_0.2Fe₂O₄ shows obvious independence of the temperature at 100 kHz. Dielectric relaxation and high-ε′ properties of the composites are explained in terms of the Maxwell-Wagner (MW) polarization model.     

Enhanced ferroelectric properties of (Pb0.90La0.10)Ti0.975O3 multilayered thin films prepared by RF magnetron sputtering

The (Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PLT/PT), PbTiO₃/(Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PT/PLT/PT) multilayered thin films with a PbO_x buffer layer were in situ deposited by RF magnetron sputtering at the substrate temperature of 600 °C. With this method, highly (1 0 0)-oriented PLT/PT and PT/PLT/PT multilayered thin films were obtained. The PbO_x buffer layer leads to the (1 0 0) orientation of the films. The dielectric, ferroelectric and pyroelectric properties of the PLT multilayered thin films were investigated. It is found that highly (1 0 0)-oriented PT/PLT/PT multilayered thin films possess higher remnant polarization 2P_r (44.1 μC/cm²) and better pyroelectric coefficient at room temperature p (p = 2.425 × 10⁻⁸ C/cm² K) than these of PLT and PLT/PT thin films. These results indicate that the design of the PT/PLT/PT multilayered thin films with a PbO_x buffer layer should be an effective way to enhance the dielectric, ferroelectric and pyroelectric properties. The mechanism of the enhanced ferroelectric properties was also discussed.     

Electro-optic characterization of tetragonal (1−x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystals by a modified Sénarmont setup

The refractive indices of tetragonal (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMN-xPT) single crystals were measured with a prism coupler and their linear electro-optic (EO) properties were investigated from 20 to 80 °C by the automated scanning Sénarmont system with an ac field. The composition and temperature effect on the EO coefficients were also discussed. It has been found that their EO coefficients are much larger than that of widely used LiNbO₃ single crystal and the calculated half-wave voltages are also much lower, which enable the operation at lower voltages and the smaller device dimensions. Since the excellent EO properties are very stable and such high quality single crystals with large-size have been obtained, the PMN-xPT single crystals are a very promising candidate for EO modulation applications. By linking to the polarization-related quadratic EO coefficients, we find that the linear EO properties are related with the spontaneous polarization and dielectric constants.     

Refractive index and dielectric constants of GaxIn1−xP: Disorder effect

A pseudopotential scheme, which incorporates compositional disorder as an effective potential, is used so as to calculate the optical properties of Ga_xIn_1−xP ternary alloys in the zinc-blende structure. Generally, the agreement between our results and the existing data in the literature is reasonable. The composition dependence of the studied features showed a non-monotonic behaviour for most studied features. Reasons for these findings are discussed. Moreover, the effect of the compositional disorder on the features of interest has been examined and found to be important for the calculation of optical properties of Ga_xIn_1−xP.     

Third-order optical nonlinearities of lead-free (Na1−xKx)0.5Bi0.5TiO3 thin films

(Na_1−xK_x)_0.5Bi_0.5TiO₃ (NKBT) (x = 0.1, 0.2, and 0.3) thin films with good surface morphology and rhombohedral perovskite structure were fabricated on quartz substrates by a sol-gel process. The fundamental optical constants (the band gaps, linear refractive indices and absorption coefficients) of the films were obtained through optical transmittance measurements. The nonlinear optical properties were investigated by Z-scan technique performed at 532 nm with a picosecond laser. A two-photon absorption effect closely related with potassium-doping content was found in thin films, and the nonlinear refractive index n₂ increases evidently with potassium-doping. The real part of the third-order nonlinear susceptibility χ⁽³⁾ is much larger than its imaginary part, indicating that the third-order optical nonlinear response of the NKBT films is dominated by the optical nonlinear refractive behavior. These results show that NKBT thin films have potential applications in nonlinear optics.