PbZr0.4Ti0.6O3 dielectric reflectors with large photonic band gap and high average optical reflectivity

PbZr_0.4Ti_0.6O₃ multilayer, comprising of three PbZr_0.4Ti_0.6O₃ stacks with a slight difference in their periodic thickness, has been designed and fabricated on FTO substrate based on one single chemical solution and on the simple spinning‐coating and annealing technique. The obtained multilayer exhibits a high reflectivity band with 110 nm photonic stop‐band width and average reflectivity of over 80% at room temperature, rendering the novel arrange of PbZr_0.4Ti_0.6O₃ multilayer system a promising candidate as tunable dielectric mirrors, optical cavities and selective filters.     

Insight for the construction of R-T phase boundary in KNN piezoceramics from the view of energy band structure and electron density

The crystal structures and associated energy band structures of classic lead-based PZT (PbZr_0.5Ti_0.5O₃) and lead-free KNN (K_0.5Na_0.5NbO₃) piezoelectric ceramics prepared by a solid-state method are systematically studied based on the First-principles calculations. For better understanding relations between energy band structures and the phase structures in the PbZr_0.5Ti_0.5O₃ and KNN, the components PT (PbTiO₃)/PZ (PbZrO₃) and KN (KNbO₃)/NN (NaNbO₃) are also calculated. The results suggest that the vital contribution to R-T morphotropic phase boundary (MPB) in PbZr_0.5Ti_0.5O₃ comes from the hybridization of A-site and B-site ions, which causes stretching and tilting of oxygen octahedron and therefore leads to the formation of R and T phases. The KNN behaves differently. Moreover, it's concluded that the band structure highly inherited from tetragonal PbTiO₃ plays an important role in the construction of the R-T phase boundary according to the comparison of PbZr_0.5Ti_0.5O₃ and KNN. In general, the work inspires an idea from the view of energy band structure to realize R-T phase coexistence as well as improved piezoelectric properties in KNN-based lead-free piezoceramics.     

High‐energy storage density and excellent temperature stability in antiferroelectric/ferroelectric bilayer thin films

The antiferroelectric/ferroelectric (PbZrO₃/PbZr_0.52Ti_0.48O₃) bilayer thin films were fabricated on a Pt(111)/Ti/SiO₂/Si substrate using sol‐gel method. PbZr_0.52Ti_0.48O₃ layer acts as a buffered layer and template for the crystallization of PbZrO₃ layer. The PbZrO₃ layer with improved quality can share the external voltage due to its smaller dielectric constant and thinner thickness, resulting in the enhancements of electric field strength and energy storage density for the PbZrO₃/PbZr_0.52Ti_0.48O₃ bilayer thin film. The greatly improved electric breakdown strength value of 2615 kV/cm has been obtained, which is more than twice the value of individual PbZr_0.52Ti_0.48O₃ film. The enhanced energy storage density of 28.2 J/cm³ at 2410 kV/cm has been achieved in PbZrO₃/PbZr_0.52Ti_0.48O₃ bilayer film at 20°C, which is higher than that of individual PbZr_0.52Ti_0.48O₃ film (15.6 J/cm³). Meanwhile, the energy storage density and efficiency of PbZrO₃/PbZr_0.52Ti_0.48O₃ bilayer film increase slightly with the increasing temperature from 20°C to 120°C. Our results indicate that the design of antiferroelectric/ferroelectric bilayer films may be an effective way for developing high power energy storage density capacitors with high‐temperature stability.     

Radiation shielding and structural features for different perovskites doped YBa2Cu3Oy composites

The increased demand for ionizing radiation in various fields led to the search for new shielding substances. In this study, five samples of perovskite oxides (BaTiO₃, SrTiO₃, BaTiO₃–SrTiO₃, and PbZr_0.2Ti_0.8O₃) doped YBa₂Cu₃O_y ceramics were prepared to explore their structure and ability for exploitation in the radiation shielding field. The structural properties were explored by using the XRD technique. The XRD results showed an orthorhombic structure for all prepared ceramics. The crystallite size reduces gradually from 96.19 to 66.63 nm with adding different perovskite oxides into the composites. The density shows a variation from about 5.89 to 6.23 g/cm³. The mass attenuation coefficient (MAC) was defined experimentally (MAC)_exp and theoretically (MAC)_the to check its validity. The maximum relative difference between (MAC)_exp and (MAC)_the is 7.83%. YBa₂Cu₃O₇/(PbZr_0.2Ti_0.8O₃)_2% and YBa₂Cu₃O₇/(BaTiO₃–SrTiO₃)_2% samples showed superior gamma shielding properties and mass stopping power (MSP) for charged particles, respectively, while the pristine YBa₂Cu₃O₇ sample has a better fast neutron removal cross-section (Σ_R). From the obtained results, it can be seen a slight variation in shielding properties, indicating the ability to use the different ceramic samples as radiation shielding materials.     

Origin of low dielectric loss and giant dielectric response in (Nb+Al) co‐doped strontium titanate

(Nb+Al) co‐doped SrTiO₃ ceramics with a nominal composition of Sr(Nb_0.5Al_0.5)_xTi_1‐xO₃ (x = 0, 0.02, 0.04, and 0.06) were fabricated using the conventional solid‐state reaction method; giant permittivity (10500) and low dielectric loss (0.03) were obtained at x = 0.06. Dielectric and impedance spectroscopy, X‐ray photoelectron spectroscopy, and Raman spectroscopy, were employed to study why the dielectric property improved. The results indicate that the giant dielectric response occurs because of the combined effects of the off‐center Ti³⁺ reorientation and conduction of electrons with the polar ordering structure Ti³⁺/Ti⁴⁺. In contrast, the low dielectric loss can be attributed to electron localization that occurs because of the defect dipole . These fundamental understandings will benefit the design of doped SrTiO₃ ceramics with desired performance.     

Bismuth doped PbZr0.70Ti0.30O3 ceramics and their properties driven by high temperature local polarity

Lead zirconate-titanate PbZr_0.70Ti_0.30O₃ ceramics doped with bismuth oxide has been investigated. Dielectric and optical measurements were performed to check the dopant influence on phase transitions and pre-transitional effects. It has been postulated that the temperature at which maximum permittivity occurs is not connected with structural phase transitions.     

Temperature Stable Dielectric Behavior of Sol–Gel Derived Compositionally Graded SrTiO3/Na0.5Bi0.5TiO3/SrTiO3 Thin Films

Polycrystalline sol–gel‐derived SrTiO₃/Na_0.5Bi_0.5TiO₃/SrTiO₃ (ST/NBT/ST) thin films were designed to achieve the electrical isolation of the NBT, and to mediate the temperature dependency of the dielectric properties. Proper thermal annealing of particulate phase enabled us to achieve compositionally graded elemental profiles between individual ST and NBT layers. The dielectric and ferroelectric properties were investigated with respect to the electrical behavior of the monophasic ST and NBT thin films. The dielectric characteristics of the multilayer thin film were marked by a temperature stable behavior (temperature coefficient of dielectric constant of 780 ppm/°C) in the measured ?50°C to 200°C range, frequency‐independent response at room temperature and improved dielectric loss characteristics compared with the NBT; however, on the expense of decreased permittivity and a reduced ferroelectric stability. Nevertheless, stable dielectric properties were achieved and properties of multilayer may well be exploited in functional devices that demand insensitive operation over wide temperature and frequency ranges.     

Enhanced photodielectric effect in (0.88–x)Bi0.5Na0.5TiO3–0.12BaTiO3 –xBa(Ti0.5Ni0.5)O3–δ (BNBTNO) ceramics

In this work, solid solutions of (0.88–x)Bi_0.5Na_0.5TiO₃–0.12BaTiO₃– xBa(Ti_0.5Ni_0.5)O_3–δ were designed and prepared. These compositions exhibit ferroelectricity at room temperature, with the tetragonal symmetry. The c/a values are varied from ～1.0067 (x?=?0.1) to ～1.0208 (x?=?0.04). A transition from the high–temperature relaxor state to the low–temperature ferroelectric state is demonstrated by the temperature dependence of dielectric data and Raman spectrum. The direct bandgap decreases from 3.40?eV for x?=?0 to 3.16?eV for x?=?0.1. The Ba(Ti_0.5Ni_0.5)O_3–δ addition leads an additional optical absorption peak in the visible range. The obvious photodielectric effect was discovered. In particular, the relative permittivity of the x?=?0.1 composition rises from ～756 to ～807 under light illumination.     

High dielectric constant and high‐Q in microwave ceramics of SrTiO3 co‐doped with aluminum and niobium

Al/Nb co‐doped SrTiO₃ microwave ceramics with the composition of SrTi_1–x(Al_0.5Nb_0.5)_xO₃ (x = 0.03, 0.05, 0.1, and 0.15) have been synthesized via a standard solid‐state reaction method. The substitution of (Al_0.5Nb_0.5)⁴⁺ in B‐site inhibits the reduction in Ti⁴⁺ ions and the growth of grain size, then the transport of mobile charge carriers is limited, and thus the Q value is improved. For the SrTi_0.9(Al_0.5Nb_0.5)_0.1O₃ ceramics, in addition to their high dielectric constant (ε_r ~185), they exhibit correspondingly a high Qf value (~ 9077 GHz) at 2.9 GHz, making the microwave ceramics suitable for myriad device miniaturization and high‐performance wireless communication.     

Temperature dependence of field‐responsive mechanisms in lead zirconate titanate

An electric field loading stage was designed for use in a laboratory diffractometer that enables in situ investigations of the temperature dependence in the field response mechanisms of ferroelectric materials. The stage was demonstrated by measuring PbZr_1?xTi_xO₃ (PZT) based materials—a commercially available PZT and a 1% Nb‐doped PbZr_0.56Ti_0.44O₃ (PZT 56/44)—over a temperature range of 25°C to 250°C. The degree of non‐180° domain alignment (η₀₀₂) of the PZT as a function of temperature was quantified. η₀₀₂ of the commercially available PZT increases exponentially with temperature, and was analyzed as a thermally activated process as described by the Arrhenius law. The activation energy for thermally activated domain wall depinning process in PZT was found to be 0.47 eV. Additionally, a field‐induced rhombohedral to tetragonal phase transition was observed 5°C below the rhombohedral‐tetragonal transition in PZT 56/44 ceramic. The field‐induced tetragonal phase fraction was increased 41.8% after electrical cycling. A large amount of domain switching (η₀₀₂=0.45 at 1.75 kV/mm) was observed in the induced tetragonal phase.     

Microstructure Evolution of In Situ Pulsed‐Laser Crystallized Pb(Zr0.52Ti0.48)O3 Thin Films

Integration of lead zirconate titanate (PZT) films with temperature‐sensitive substrates (CMOS, polymers) would benefit from growth at substrate temperatures below 400°C. In this work, in situ pulsed‐laser annealing [Rajashekhar et al. (2013) Appl. Phys. Lett., 103 [3] 032908] was used to grow crystalline lead zirconate titanate (PbZr_0.52Ti_0.48O₃) thin films at a substrate temperature of ~370°C on PbZr_0.30Ti_0.70O₃‐buffered platinized silicon substrates. Transmission electron microscopy analysis indicated that the films were well crystallized into columnar grains, but with pores segregated at the grain boundaries. Lateral densification of the grain columns was significantly improved by reducing the partial pressure of oxygen from 120 to 50 mTorr, presumably due to enhanced adatom mobility at the surface accompanying increased bombardment. It was found that varying the fractional annealing duration with respect to the deposition duration produced little effect on lateral grain growth. However, increasing the fractional annealing duration led to shift of 111 PZT X‐ray diffraction peaks to higher 2θ values, suggesting residual in‐plane tensile stresses in the films. Thermal simulations were used to understand the annealing process. Evolution of the film microstructure is described in terms of transient heating from the pulsed laser determining the nucleation events, while the energy of the arriving species dictates grain growth/coarsening.     

Electrical and Optical Properties of Transparent Conducting p‐Type SrTiO3 Thin Films

We report a systematic study of the electrical and optical properties of epitaxial perovskite p‐type In‐doped SrTiO₃ thin films (SrIn_xTi_1?xO₃, 0 ≤ x ≤ 0.15) grown on single‐crystal (100)‐oriented LaAlO₃ substrates using a hybrid method which combines pulsed laser deposition and molecular beam epitaxy in a range of deposition conditions. X‐ray diffraction analysis confirms the epitaxial growth of high crystal quality films. Four‐point probe and Hall Effect measurements demonstrate that the films are p‐type semiconductors with a low resistivity of ~10^?2 Ω·cm and a high carrier concentration of ~10¹⁹ cm^?3. The optical transmittance spectra reveal that the films are highly transparent (?70%) in the visible region.     

Stress Effects on Stabilizing Antiferroelectric Phase in Multilayer Ceramics

Controllable phase transformation between antiferroelectric (AFE) and ferroelectric (FE) states suggests multifunctional properties valuable for many device applications. Compared to AFE bulk ceramics with large voltage required for driving electric field‐induced phase transition, implementation of structures comprising multiple thin AFE ceramic layers can realize applications by reducing the switching operation voltage in the feasible range. Here, it is found that a compressive residual stress is developed in multilayer (Pb_0.97,La_0.02)(Zr_0.66,Sn_x,Ti_0.34?x)O₃ (PLZST) ceramic co‐fired with multiple Pd/Ag electrode layers, and the compressive residual stress can stabilize AFE phase. AFE phase forms in the PLZST multilayer ceramic with composition corresponding to FE in the bulk materials. Thermodynamic analysis based on free energy of FE and AFE phases well explains the FE to AFE phase transformation observed in the multilayer ceramic under the compressive stress. The findings exhibit a new strategy to tune structure and functional properties of multilayer ceramics through stress engineering for achieving device applications.     

Orientation-dependent,field-induced phase transitions in soft lead zirconate titanate piezoceramics

In situ high-energy X-ray diffraction (XRD) was performed on lead-zirconate-titanate-based ferroelectric materials with composition near the morphotropic phase boundary (MPB). The utilization of the two-dimensional area detector in in situ field-dependent experiments enables the complete analysis of the material response with respect to all azimuthal angles at each field amplitude. The studies reveal that the field-induced phase transition from tetragonal to rhombohedral is dependent on crystal orientation in Nb-doped PbZr_0.53Ti_0.47O₃ that is in close compositional proximity to the MPB. However, only domain wall motion is activated in Nb-doped PbZr_0.50Ti_0.50O₃, which is further in composition from the MPB. This synchrotron-based XRD characterization approach illustrates the importance in evaluating the orientation-dependence of phase transitions in piezoelectric and ferroelectric polycrystalline materials.     

Oxygen plasma-assisted ultra-low temperature sol-gel-preparation of the PZT thin films

PbTi_1-xZr_xO₃ (PZT) thin films prepared by sol-gel method have paid much attention due to the excellent performances in piezoelectric, dielectric, ferroelectric and electro-optical. However, the high crystallization temperature of the PZT thin films restricts the compatibility with modern COMS technology. In this work, PbZr_0.52Ti_0.48O₃ (PZT) ferroelectric thin films were successfully prepared by sol-gel method at an ultra-low temperature (～450 °C) in an oxygen plasma-assisted environment. A large spontaneous polarization ～30 μC/cm² and a large dielectric breakdown ～2,900 kV/cm were obtained in the sample annealed at 450 °C for 25 h. We believe that the oxygen plasma-assisted ultra-low temperature (OPAULT) annealing process is a promising way for the sol-gel technology applied in the modern COMS devices.     

Design,synthesis, microstructure and electrical properties of thermal-strained PZT films

The integration units with functional and structural material components have been developed largely recently. In the present study, 200 nm-thick polycrystalline PbZr_0.52Ti_0.48O₃ (PZT) films with a dense columnar structure were grown on LaNiO₃ (LNO) buffered heat-resistant steel substrates via a low-cost chemical solution approach. The behavior of the functional PZT films when combined with the structural steel was investigated mainly by TEM and electrical measurement. A large in-plane compressive stress was obtained in the PZT films due to the thermal expansion mismatch of about 88.2 % between the thin films and the steel substrates, which intensifies the orientation of the films toward c-axis. Sub-10 nm 90° nanodomains were alternately distributed in [001] grains which is beneficial to the piezoelectric performance, and the equivalent d₃₃ value is ～44.4 pm V^?1. A remnant polarization (P_r) of ～67.3μC/cm² and a dielectric constant of ～425 were obtained. The enhanced electrical properties are associated with the stress-induced improved c-axis spontaneous polarization and crystal orientation in the hybrid system. This work may provide a theoretical basis for further integrating functional elements into metallic materials, which is valuable for covering the gap between academic research and industrial mass production.     

SrLa(R0.5Ti0.5)O4 (R=Mg,Zn) microwave dielectric ceramics with complex K2NiF4‐type layered perovskite structure

Dense SrLa(R_0.5Ti_0.5)O₄ (R=Mg, Zn) ceramics were prepared by a standard solid‐state reaction method. The single phase with complex K₂NiF₄‐type layered perovskite structure and I4/mmm space group was revealed by XRD, and the refined structure was analyzed by Rietveld analysis. Significantly improved dielectric constant was obtained in SrLa(R_0.5Ti_0.5)O₄ ceramics compared to the analogues SrLaAlO₄ and SrLaGaO₄, which is attributed to the increasing normalized bond lengths of Sr/La‐O(1) and Sr/La‐O(2a) bonds and the higher polarizability of (R_0.5Ti_0.5)³⁺ than Al³⁺ and Ga³⁺. In addition, τ_f converts to a positive value with the increase in dielectric constant. The following microwave dielectric properties were obtained in the dense ceramics: ε_r=25.5, Qf=72 000 GHz, τ_f=29 ppm/°C for SrLa(Mg_0.5Ti_0.5)O₄, and ε_r=29.4, Qf=34 000 GHz, τ_f=38 ppm/°C for SrLa(Zn_0.5Ti_0.5)O_4. Furthermore, the stability of K₂NiF₄‐type structure in MLnBO₄ [M=Ca, Sr, Ba; Ln=Y, Sm, Nd, La; B=Al, Ga, (Mg_0.5Ti_0.5), (Zn_0.5Ti_0.5)] compounds was discussed in relation to the tolerance factor of perovskite layer and the radius ratio of M²⁺ and Ln³⁺, based on which near‐zero τ_f values are expected to be obtained in SrLa(R_0.5Ti_0.5)O₄‐SrLaAlO₄ and SrLa(R_0.5Ti_0.5)O₄–SrLaGaO₄ unlimited solid solutions.     

Effect of Mechanical Constraint on Domain Reorientation in Predominantly {111}‐Textured Lead Zirconate Titanate Films

Ferroelectric/ferroelastic domain reorientation was measured in 2.0 μm thick tetragonal {111}‐textured PbZr_0.30Ti_0.70O₃ thin films using synchrotron X‐ray diffraction (XRD). Lattice strain from the peak shift in the 111 Bragg reflection and domain reorientation were quantified as a function of applied electric field amplitude. Domain reorientation was quantified through the intensity exchange between the 112 and 211 Bragg reflections. Results from three different film types are reported: dense films that are clamped to the substrate (as‐processed), dense films that are partially released from the substrate, and films with 3% volume porosity. The highest amount of domain reorientation is observed in grains that are misoriented with respect to the {111} preferred (domain engineered) orientation. Relative to the clamped films, films that were released from the substrate or had porosity exhibited neither significant enhancement in domain reorientation nor in 111 lattice strain. In contrast, similar experiments on {100}‐textured and randomly oriented films showed significant enhancement in domain reorientation in released and porous films. Therefore, {111}‐textured films are less susceptible to changes in properties due to mechanical constraints because there is overall less domain reorientation in {111} films than in {100} films.     

Low‐Temperature Dielectric Relaxations Associated with Mixed‐Valent Structure in Na0.5Bi0.5Cu3Ti4O12

We, herein, present comparative investigations on the Na_0.5Bi_0.5Cu₃Ti₄O₁₂ ceramic samples with and without 10 mol% excess of Na/Bi. The samples were prepared by the standard solid‐state reaction technique. The dielectric properties of the sample were investigated in the temperature (93–320 K) and frequency (20 Hz–10 MHz) windows. Three thermally activated dielectric relaxations observed in Na_0.5Bi_0.5Cu₃Ti₄O₁₂ with the activation energies of 0.104, 0.267, and 0.365 eV for the low‐, middle‐, and high‐temperature dielectric relaxations, respectively. Only the low‐temperature relaxation was observed in both Na and Bi excessive samples. X‐ray photoemission spectroscopy results revealed the mixed‐valent structures of Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺ in Na_0.5Bi_0.5Cu₃Ti₄O₁₂ sample, but only Ti³⁺/Ti⁴⁺ in Na and Bi excessive samples. Our results showed that the dielectric properties of the investigated samples are strongly linked with these mixed‐valent structures. The high‐ and low‐temperature relaxations were attributed to be a polaron‐type relaxation due to localized carriers hopping between Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺, respectively. The middle‐temperature relaxation is suggested to be a dipole‐type relaxation caused by the defect complex of bismuth and oxygen vacancies.     

PZT thick films on LTCC substrates with an interposed alumina barrier layer

PZT thick films (PbZr_0.53Ti_0.47O₃ with the addition of 6% PbO and 2% Pb₅Ge₃O₁₁) with a low sintering temperature were printed and fired on LTCC substrates (951, Du Pont), covered with an alumina barrier layer. The electrical characteristics (remanent polarisation, coercive field, dielectric constant and dielectric loss) of these PZT thick films, together with sets prepared on “unprotected” LTCC substrates and on alumina substrates were compared. Whereas the electrical characteristics of the films on LTCC substrates deteriorated significantly due to interactions between the LTCC substrates and the PZT layers the values obtained for the LTCC/alumina barrier structures were comparable with those on ceramic alumina substrates.