Search Results (12)

Thin film technology shows great promise in fabricating electronic devices such as gas sensors. Here, we report the fabrication of surface acoustic wave (SAW) sensors based on thin films of (1 − x) Ba(Ti_0.8Zr_0.2)O_3−x(Ba_0.7Ca_0.3)TiO₃ (BCTZ50, x = 50) and Polyethylenimine (PEI). The layers were deposited by two laser-based techniques, namely pulsed laser deposition (PLD) for the lead-free material and matrix assisted pulsed laser evaporation (MAPLE) for the sensitive polymer. In order to assay the impact of the thickness, the number of laser pulses was varied, leading to thicknesses between 50 and 350 nm. The influence of BCTZ film’s crystallographic features on the characteristics and performance of the SAW device was studied by employing substrates with different crystal structures, more precisely cubic Strontium Titanate (SrTiO₃) and orthorhombic Gadolinium Scandium Oxide (GdScO₃). The SAW sensors were further integrated into a testing system to evaluate the response of the BCTZ thin films with PEI, and then subjected to tests for N₂, CO₂ and O₂ gases. The influence of the MAPLE’s deposited PEI layer on the overall performance was demonstrated. For the SAW sensors based on BCTZ/GdScO₃ thin films with a PEI polymer, a maximum frequency shift of 39.5 kHz has been obtained for CO₂; eight times higher compared to the sensor without the polymeric layer. Full article

Fine-tuning of grain sizes can significantly influence the interaction between different dielectric phenomena, allowing the development of materials with tailored dielectric resistivity. By virtue of various synthesis mechanisms, a pathway to manipulate grain sizes and, consequently, tune the material’s dielectric response is revealed. Understanding these intricate relationships between granulation and dielectric properties can pave the way for designing and optimizing materials for specific applications where tailored dielectric responses are sought. The experimental part involved the fabrication of dense BCT-BZT ceramics with different grain sizes by varying the synthesis (conventional solid-state reaction route and sol-gel) and consolidation methods. Both consolidation methods produced well-crystallized specimens, with Ba_0.85Ca_0.15O₃Ti_0.9Zr_0.1 (BCTZ) perovskite as the major phase. Conventional sintering resulted in microstructured and submicron-structured BCT-BZT ceramics, with average grain sizes of 2.35 μm for the solid-state sample and 0.91 μm for the sol-gel synthesized ceramic. However, spark plasma sintering produced a nanocrystalline specimen with an average grain size of 67.5 nm. As the grain size decreases, there is a noticeable decrease in the maximum permittivity, a significant reduction in dielectric losses, and a shifting of the Curie temperature towards lower values. Full article

Lead-free barium calcium titanate zirconate (BCTZ) ceramics doped with a single rare-earth element generally exhibit excellent piezoelectric properties. However, their electrical properties deteriorate at an excessive dopant content, limiting their application. In this study, amphoteric neodymium (Nd³⁺) and yttrium (Y³⁺)-codoped BCTZ-NYx ceramics were synthesized via a solid-state reaction at 1240 °C. The influences of the Y³⁺ content (x) on the structural features, electrical properties, mechanical properties, and thermophysical properties were investigated. At a small x (<0.18 mol%), Y³⁺ could enhance the fracture strength and electrical properties by eliminating oxygen vacancies, defect dipoles, and/or structural defects. However, the outstanding performance deteriorated with excessive x. Additionally, the mechanism of the defect chemistry at different x was deduced. At an yttrium content of 0.18 mol%, the ceramic exhibited high piezoelectricity and ferroelectricity with low domain-switching activation energy (E_a = 0.401 eV), indicating that it could replace commercial lead-based piezoelectric ceramics. Full article

Ba_0.92Ca_0.08Ti_0.95Zr_0.05O₃ (BCZT8-5) ceramic materials have been scarcely studied as lead-free piezo/ferroelectrics despite their enhanced Curie temperature (>100 °C) with respect to most studied BCZT compositions. In this work, homogeneous dense BCZT8-5 ceramics with grain size in the range of 20 μm, and optimum ferroelectric, dielectric, and electromechanical performance, were prepared by the mixed oxides route using moderate synthesis (1250 °C-2 h) and sintering (1400 °C-2 h) conditions. Thickness-poled thin disks and monomodal shear plate resonators were used for the determination of piezoelectric coefficients, coupling factors, elastic, and dielectric permittivity coefficients, including all losses, by iterative analysis of impedance curves at resonance. Furthermore, the thermal evolution of the piezoelectric characteristics at resonance was determined to assess the enhanced working range of the ceramics (≈100 °C). Ferroelectric hysteresis loops and strains vs. electric-field butterfly loops were also measured and showed soft behavior with E_c = 2 kV/cm, P_r = 12 μC/cm² after a maximum applied field of 3 kV was used. The ceramics showed a high endurance of P-E cycles to electrical fatigue up to 10⁷ cycles. Moreover, dielectric properties as a function of temperature were also accomplished and showed nearly normal ferroelectric behavior, characteristic of samples with low crystallographic disorder. Overall, these ceramics showed high sensitivity and higher stability than other currently studied BCZT compositions. Full article

This work was devoted to the first multi-parametric unitary comparative analysis of a selection of sintered piezoceramic materials synthesised by solid-state reactions, aiming to delineate the most promising biocompatible piezoelectric material, to be further implemented into macro-porous ceramic scaffolds fabricated by 3D printing technologies. The piezoceramics under scrutiny were: KNbO₃, LiNbO₃, LiTaO₃, BaTiO₃, Zr-doped BaTiO₃, and the (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃ solid solution (BCTZ). The XRD analysis revealed the high crystallinity of all sintered ceramics, while the best densification was achieved for the BaTiO₃-based materials via conventional sintering. Conjunctively, BCTZ yielded the best combination of functional properties—piezoelectric response (in terms of longitudinal piezoelectric constant and planar electromechanical coupling factor) and mechanical and in vitro osteoblast cell compatibility. The selected piezoceramic was further used as a base material for the robocasting fabrication of 3D macro-porous scaffolds (porosity of ~50%), which yielded a promising compressive strength of ~20 MPa (higher than that of trabecular bone), excellent cell colonization capability, and noteworthy cytocompatibility in osteoblast cell cultures, analogous to the biological control. Thereby, good prospects for the possible development of a new generation of synthetic bone graft substitutes endowed with the piezoelectric effect as a stimulus for the enhancement of osteogenic capacity were settled. Full article

Lead-free piezoelectric ceramics with nominal composition at morphotropic phase boundary Ba_0.85Ca_0.15Ti_0.9Zr_0.1O₃ (BCTZ) prepared by different processing routes and sintered either by conventional solid-state reaction or by spark plasma sintering (SPS) techniques were comparatively investigated to observe the role of structural modifications and of microstructures on the dielectric, ferroelectric, piezoelectric and electrocaloric responses. The ceramics presented relative densities from 75% to 97% and showed variations in their phase composition as a result of variable mixing and different synthesis and sintering parameters providing local compositional heterogeneity. As result, all of the ceramics showed diffuse phase transition and ferroelectric switching responses, with parameters affected mostly by density (P_r between 3.6 to 10.1 μC/cm²). High values for the electrocaloric response in the Curie range were found for the ceramics with predominantly orthorhombic character. Field-induced structural modifications were probed by tunability anomalies and by XRD experiments in remanence conditions. Piezoelectric effects with notably high figure of merit values were assigned to the better densification and poling efficiency of BCTZ ceramics. Full article

In the preparation of (Ba,Ca)(Zr,Ti)O₃ lead-free piezoelectric ceramics, different Ca²⁺ and Zr⁴⁺ contents will greatly affect the phase structure, microstructure, and electrical properties of the ceramics. XRD shows that all samples have pure perovskite phase structure, and the (Ba_0.85Ca_0.15)(Zr_yTi_1−y)O₃ ceramics morphotropic phase boundary region from tetragonal phase to rhombohedral phase near 0.08 ≤ y ≤ 0.1. From the dielectric temperature curve, the phase transition temperature (T_O-T) was found near room temperature at 0.12 ≤ x ≤ 0.18 for the (Ba_1−xCa_x)(Zr_0.1Ti_0.9)O₃ ceramics. Both Ca²⁺ and Zr⁴⁺ increase have a significant decrease on the Curie temperature T_c. All samples were revealed as relaxers with diffusivities in the range 1.29 ≤ γ ≤ 1.82. Different from the undoped ceramics, ceramics doped with Ca and Zr ions exhibit saturated P–E hysteresis loops, and their ferroelectric properties are significantly optimized. In particular, the (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ ceramic demonstrated optimal properties, namely d₃₃ = 330 pC/N, k_p = 0.41, ε_r = 4069, P_r = 4.8 μC/cm², and E_c = 3.1 kV/cm, indicating that it is a viable lead-free piezoelectric contender. Variations in Ca and Zr content have a significant effect on the crystal grain sizes and densities of ceramics, which is strongly associated with their piezoelectricity. Full article

Tunable ferroelectric capacitors, which exhibit a decrease in the dielectric permittivity under an electric field, are widely used in electronics for RF tunable applications. Current devices use barium strontium titanate (BST) as the tunable dielectric, but new applications call for tunable materials with specific performance improvements. It is then of crucial importance to dispose of a large panel of electrically characterized materials to identify the most suited compound for a given set of device specifications. Here, we report on the dielectric tuning properties of Ba_1−xCa_xTi_1−yZr_yO₃ (BCTZ) thin films libraries (0 ≤ x ≤ 30% and 0 ≤ y ≤ 28.5%) synthesized by combinatorial pulsed laser deposition (CPLD). An original CPLD approach allowing reliable and statistical ternary phase diagrams exploration is reported. The effects of Ca and Zr content on tunability, breakdown voltage and dielectric losses are explicated and shown to be beneficial up to a certain amount. Compounds close to (Ba_0.84Ca_0.16)(Ti_0.8Zr_0.2)O₃ exhibit the highest figures of merit, while a zone with compositions around (Ba_0.91Ca_0.09)(Ti_0.81Zr_0.19)O₃ show the best compromise between tuning ratio and figure of merit. These results highlight the potential of BCTZ thin films for electrically tunable applications. Full article

In this paper we report the development of thin films composed of two piezoelectric materials, namely (Ba(Ti_0.8Zr_0.2)O₃-x(Ba_0.7Ca_0.3)TiO₃ (BCTZ) and polyvinylidene difluoride (PVDF), thus obtaining high piezoelectric hybrid heterostructures for making them a viable option for wearable pressure sensors. The piezoelectric output response as a function of different weight percentage of BCTZ ceramic powders (x = 0.50 BCTZ50 and x = 0.55 BCTZ55) in the PVDF matrix was investigated. The highest value of the piezoelectric coefficient d33 and the capacitance, with low dielectric loss was obtained for the heterostructure composed of PVDF/BCTZ50. Full article

Ba_1−xCa_xTi_0.9Zr_0.1O₃ (x = 0.10, 0.15, 0.18) solid solutions were synthesized by the conventional solid-state method. A perovskite-type structure was determined using the X-ray diffraction (XRD) technique. The addition of Ca²⁺ reduced the grain size (22.6, 17.9 and 13.3 μm, respectively) for all well-sintered ceramics (≈98%). Moreover, the stability temperature ranges for the tetragonal phase were promoted by displacing the ferroelectric-ferroelectric phase’s transition temperatures while T_C was maintained (86 °C). The electrical performance of the material improved as the stoichiometric composition was positioned near the morphotropic phase boundary (x = 0.15): ε_r ≈ 16,500 (T_C) at 1 kHz. For T > T_C, a thermally activated relaxation process occurred. In addition, the bulk and grain boundary processes were responsible for the conduction mechanisms. The composition x = 0.15 showed an activation energy of Ea = 1.49 eV with a maximum conductivity of σ_max = 2.48 × 10⁻² S·cm⁻¹ at 580 °C. Systematic studies at high temperature for dielectric properties were accomplished for analyzing electrical inhomogeneities associated with the grain, grain boundaries or surfaces, which are important for device design and a fundamental electrical characterization. Full article

The search for improved piezoelectric materials is based on the morphotropic phase boundaries (MPB) between ferroelectric phases with different crystal symmetry and available directions for the spontaneous polarization. Such regions of the composition x − T phase diagrams provide the conditions for minimal anisotropy with respect to the direction of the polarization, so that the polarization can easily rotate maintaining a substantial magnitude, while the near verticality of the T_MPB(x) boundary extends the temperature range of the resulting enhanced piezoelectricity. Another consequence of the quasi-isotropy of the free energy is a reduction of the domain walls energies, with consequent formation of domain structures down to nanoscale. Disentangling the extrinsic and intrinsic contributions to the piezoelectricity in such conditions requires a high level of sophistication from the techniques and analyses for studying the structural, ferroelectric and dielectric properties. The elastic characterization is extremely useful in clarifying the phenomenology and mechanisms related to ferroelectric MPBs. The relationship between dielectric, elastic and piezoelectric responses is introduced in terms of relaxation of defects with electric dipole and elastic quadrupole, and extended to the response near phase transitions in the framework of the Landau theory. An account is provided of the anelastic experiments, from torsional pendulum to Brillouin scattering, that provided new important information on ferroelectric MPBs, including PZT, PMN-PT, NBT-BT, BCTZ, and KNN-based systems. Full article

Lead-free piezoelectric materials attract more and more attention owing to the environmental toxicity of lead-containing materials. In this work, we review our first attempts of single crystal grown by the top-seeded solution growth method of BaTiO₃ substituted with zirconium and calcium (BCTZ) and (K_0.5Na_0.5)NbO₃ substituted with lithium, tantalum, and antimony (KNLSTN). The growth methodology is optimized in order to reach the best compositions where enhanced properties are expected. Chemical analysis and electrical characterizations are presented for both kinds of crystals. The compositionally-dependent electrical performance is investigated for a better understanding of the relationship between the composition and electrical properties. A cross-over from relaxor to ferroelectric state in BCTZ solid solution is evidenced similar to the one reported in ceramics. In KNLSTN single crystals, we observed a substantial evolution of the orthorhombic-to-tetragonal phase transition under minute composition changes. Full article