Barium strontium titanate and non-ferroelectric oxide ceramic composites for use in phased array antennas

Abstract

A ceramic ferroelectric phase shifting device has been demonstrated using Ba_1?xSr_xTiO₃ (BSTO) ceramics. ¹ As part of an effort to optimize the device performance, various composites of BSTO and other nonelectrically active oxide ceramics have been formulated. In general the composites have reduced dielectric constants, ε′, where ε = ε′-iε″ and reduced loss tangents, tan δ, compared to BSTO. The low dielectric constant and low loss tangent reduce the overall impedance mismatch and insertion loss of the device. In addition, the tunability (change in the dielectric constant with applied voltage) is maintained at a relatively high level (15% with an applied electric field of 1.5 V/μm) for dielectric constants of 200. The combination of electronic properties of these materials offer substantially higher operating frequencies, 10 GHz and above. The microstructures including grain size and phase analysis have been examined using SEM and EDX. X-ray diffraction has been used to identify the presence of any secondary phases formed in the composites. The analysis of the phase formation and compositional variations will be related to the electronic properties of the materials.     

Microstructure and Properties of Solution Deposited, Nb-Doped PZT Thin Films

Nb doped PZT films with Nb concentrations of 0, 5, 8 and 12 mol% are being processed via chemical solution deposition on platinized Silicon substrates. An original processing route including seed layer and additional PbO coating is presented whereby homogeneous, pyrochlore free microstructures with 111/100 texture are obtained. The temperature dependence of the dielectric constant shows diffuse peaks corresponding to the paraelectric to ferroelectric transition. The transition temperature is found to decrease from 325°C to 220°C with increasing Nb content. Nb is however found to lead to a substantial increase in the dielectric constant in comparison to non-doped PZT. The dependence of the dielectric constant on DC bias field is also reported. Strong asymmetries towards positive values both in the values of the dielectric constant and coercive fields are obtained at room temperature, and become replenished at 100°C. This is interpreted in terms of space charge effects on the pinning of domain walls. Furthermore, the loss tangent shows a relaxation peak which shifts to higher frequencies with increasing Nb content, and suggests that Nb-doping affects the dielectric properties of the interfacial layer. Finally, Nb addition is found to lead to slant hysteresis loops with lower remnant polarization and coercive field.     

Dielectric and piezoelectric properties of ceramic-polymer composites with 0–3 connectivity type

Piezoelectric ceramic-polymer composites with 0–3 connectivity were fabricated from lead zirconate titanate (PZT) and poly(vinylidene-fluoride-chlorotrifluoroethylene [P(VDF-CTFE)] copolymer. PZT-P(VDF-CTFE) composites were prepared using the hot press method under various pressure levels of P(VDF-CTFE) at 170°C. The composites were investigated for density, as well as their dielectric and piezoelectric properties, while the particle size of the PZT powder and volume fraction were varied. The connectivity model for the composites was evaluated on the basis of the measured dielectric properties. The piezoelectric voltage constant (g ₃₃ ) was found to achieve a maximum value with a volume fraction of 60 %. In addition, the PZT-P(VDF-CTFE) composite with a 60 % volume fraction was found to yield optimum d ₃₃ × g ₃₃ value of 7.27 pm²/N.     

Ferroelectric and dielectric properties of sol-gel and excimer-laser-deposited lead zirconate titanate and barium titanate films

Abstract

Switched remanent polarization was measured as a function of accumulated switching cycles for a variety of ferroelectric films using sinusoidally driven hysteresis loops. Switched remanent polarization and dielectric constant and loss were also obtained as a function of the cycling frequency. PZT films with niobium additives appeared to lose switched remanent polarization with accumulated cycles at a lesser rate than films without niobium. The switched remanent polarization was found to decrease with increasing frequency, which we attribute to the effect of grain size. Also, a decrease of dielectric constant with increasing frequency and an increase of dielectric constant with increased applied voltage are attributed to the effects of domain wall motion contributions to dielectric constant.     

Preparation and characteristics of fine-grained ferroelectric glass-ceramic composites via a modified hybrid route at low temperature sintering

Dense, homogeneous and fully developed fine-grained ferroelectric Pb(Zr_0.53Ti_0.47)O₃?Cbased glass-ceramics have been successfully prepared at a low-sintering temperature of 850?C900°C by a modified hybrid process in air. The influence of the PbO-B₂O₃-SiO₂ (abbreviated as PBS) glass-gel content on the microstructure, dielectric, and ferroelectric properties of such glass-ceramics has been investigated. The temperature dependence of the dielectric constant indicated that the fine-grained Pb(Zr_0.53Ti_0.47)O₃ (abbreviated as PZT(53/47)) based glass-ceramic shows the characteristic dispersion at the Curie point. Ferroelectric hysteresis loop analyses have been performed to manifest the ferroelectric nature of the highly crystallized PZT(53/47) phase prepared by this modified novel hybrid process despite containing higher wt% glass-gel contents. The best dielectric and ferroelectric properties in a typical sample with 5% by weight of glass-gel content were found to have dielectric constant and loss tangent of 920 and 0.02 at 1 kHz, respectively. The saturation polarization (P _s ), and remanent polarization (P _r ) as well as the coercive field (E _c ) are 21.9 ??C/cm², 10.8 ??C/cm² and 2.19 kV/mm, respectively.     

Solid Freeform Encapsulation of 1-3-0 PZT Composites

Two types of encapsulated lead zirconate titanate (PZT) composite hydrophones have been built and tested: a straight walled 1-3-0 PZT composite design and a curved wall 1-3-0 PZT design. The solid freeform fabrication (SFF) technique was used to construct the polymer encapsulation for the two prototype designs.In the 1-3 composites soft PZT bars are embedded in a polymer matrix with a surrounding air gap. The polymer encapsulations were fabricated on a SFF stereolithography machine in order to enclose the gap and the PZT. Air gaps between the polymer and the PZT were shown to increase the hydrostatic piezoelectric response (d _h) by absorbing the lateral hydrostatic stress. Because of the small percentage of PZT, these composites had a low density (neutral buoyancy), low dielectric constant, and, therefore, a lower dielectric constant, and a corresponding higher hydrostatic voltage coefficient, g _h.The curved-wall composite design decoupled the PZT component more effectively from the lateral pressure, and thereby improved upon the direct piezoelectric effect. The large cap surface and the curved-wall further improved the amplification of the mechanical loading on the PZT element. The effective hydrostatic charge coefficient d _h, reached about 1100 pC/N which amplified the d ₃₃ coefficient, and greatly enhanced the d _h g _h figure of merit.     

High dielectric response of cobalt aluminate mullite (CAM) nanocomposite over cobalt aluminate mullite polymer (CAMP) nanocomposite in PVDF matrix

In this communication we have compared the dielectric behavior of cobalt aluminate mullite (CAM) nanocomposite and cobalt aluminate mullite polymer (CAMP) nanocomposite with different molar concentration of Co ⁺² ions. The study of dielectric property of the CAM samples as well as that of the CAMP samples at room temperature shows that at all concentrations the dielectric constant is higher than pure mullite and there is a critical concentration of Co ⁺², where maximum enhancement of dielectric property occurs. This paper demonstrates that the loading of a conductive component into a highly insulating matrix is an effective way to fabricate composites with high permittivity as well as a charge storage material. We have designed a device using CAM as the electrode material and CAMP as the separator to compare it with a commercial Li-polymer ion mobile battery. We observed that the charge storage ability of the composite system is better than the commercial Li-polymer ion mobile battery. Our device persists for more than 24 h while the maximum voltage recorded by the device is 0.885 V, whereas the maximum voltage recorded by the conventional commercial Li-polymer ion mobile battery is 0.566 V.     

Optimized PZT Thin Films for Pyroelectric IR Detector Arrays

A planar multi target sputtering technology was used to deposit highly (111) oriented Pb(Zr _x Ti_1–x )O₃ (PZT) thin films with x ranging from 0–0.6. The preparation of a stable Pt/ZrO₂ electrode is described and analyzed in terms of stress and stress-temperature behavior. The PZT films with low Zr content are under compressive stress after deposition. The dielectric constant and loss peaks occur at a composition close to the morphotropic phase boundary. Films on the tetragonal side of the phase diagram with a Zr content up to about 25% exhibited a strong self polarization and strong voltage shifts in the C(V) curves. High pyroelectric coefficients of >2×10^–4 C/(m²K) have been measured on these films without additional poling. The self polarization fades out with increasing Zr content. The low values of the pyroelectric coefficient for the PZT film with 60% Zr is discussed in terms of the possible crystallographic variants after distortion and the tensile stress state during the phase transition. Based on the systematic study of stress and electrical properties of PZT films with a wide range of composition presented in this paper, films with a Zr content up to about 25% turned out to give the best properties for the use in pyroelectric detector arrays.     

Fabrication and characterization of flexible piezoelectric composites with natural rubber matrix

Abstract

This work aims to fabricate and characterize flexible piezoelectric composites with natural rubber (NR) matrix. Different amounts of Pb(Mg_1/3Nb_2/3)_0.65Ti_0.35O₃ (PMNT) powders were added in NR matrices. Porosity, tensile strength and percent elongation at break of composites tended to decrease with increasing PMNT content. The dielectric constant of the NR materials was found to be 3.5. It was raised up to 4.2, 5.0, 4.5, 4.8 and 5.1 when 60, 80, 100, 120 and 150 phr PMNT powders were added. However, dielectric loss of NR materials did not change with PMNT additions. Among this composite system, the NR/100PMNT composite showed the best piezoelectric properties, which its output voltage, piezoelectric coefficient (d₃₃) and piezoelectric voltage coefficient (g₃₃) values were equal to 1.61 V, 2.1?×?10^?4 pC/N and 5.4?×?10^?6 V?m/N, respectively. This composition composite is a promising material suitable for further improvement to be used as piezoelectric generators in energy harvesting applications.     

Experimental and numerical studies of dielectric properties of BaTiO/sub 3/-platinum composites at microwave frequencies

The conductor loading method has been used for creating a lossy dielectric material with a desired loss tangent. This method may also be applicable for developing high dielectric constant materials. In this paper, we will present the experimental results of the dielectric properties of BaTiO/sub 3/ and BaTiO/sub 3/ -platinum (BaTiO/sub 3/-Pt) composites. These composite materials were designed to increase the real part of the effective dielectric constant at high frequency. Three different platinum volume fractions were used, 3, 5 and 10%, to make BaTiO/sub 3/-Pt composites, in addition to a pure BaTiO/sub 3/ material. To characterize the BaTiO/sub 3/-Pt composites, microwave frequency measurements were conducted using the waveguide transmission technique. The experimental and numerical results verify that it is possible to increase the dielectric constant using the conductor loading method.     

Effect of re-oxidation on dielectric properties in Ni-MLCC

The effect of re-oxidation treatment on the solubility of dopants and the dielectric properties of rare-earths (La, Ho) and V-substituted BaTiO₃ solid solutions, assuming the shell phase of X7R dielectrics, was investigated. Ho-V-substituted samples showed larger increase of the lattice parameter and T _c by re-oxidation treatment compared with La-V-substituted samples. Electron spin resonance measurements revealed that the oxidation of V³⁺ to V⁴⁺ or V⁵⁺ appeared in the range in which the increase of lattice parameter by re-oxidation treatment was observed. This suggests that the increase of T _c is due to the change of preferential occupational site of Ho ion from A-site to B-site, being accompanied with the oxidation of V³⁺. We also investigated the effect of re-oxidation treatment on the electrical properties and microstructure in Ni-MLCC samples, using rare-earths (La, Ho, Yb) and acceptors (Mn, V) doped BaTiO₃ based X7R dielectrics. The change in temperature characteristic of the dielectric constant by re-oxidation treatment was observed for the MLCC samples containing V with smaller content. In the case of Ho-V- and Yb-V-doped samples showed larger increase of the dielectric constant at around 120 °C compared with La-V-doped samples. The relationship between the microstructure and electrical properties of the MLCC sample was investigated by impedance measurement at elevated temperature.     

Novel 3D PZT thin film structure for micromechanics

In this work, fabrication and properties of 3-dimensional structures coated with piezoelectric Pb(Zr,Ti)O₃ (PZT) thin films have been studied in order to improve the piezoelectric coupling into the third dimension. Calotte layers have been chosen as demonstration devices. The base diameters range from 40 to 120 μm, the height varies between 10 to 40 μm. A dynamic, in-situ co-sputtering process allowing for in-situ growth was applied. Micromoulds were formed by wet etching in silicon. The etchant was a HNA solution (HF, HNO₃, CH₃COOH) on a silicon dioxide mask. Calottes were obtained with the desired geometry and smooth surface state after few minutes etching time, and the use of chemical mechanical polishing (CMP). After deposition of the PZT membrane, deep silicon dry etching was then used to liberate the calotte layer. The dielectric constant and loss tangent of the calotte capacitors amounted to 830 and 5%, respectively (10 kHz). The fundamental resonance frequencies varied between 2.5 and 16.5 MHz, and were found to be inversely proportional to the base area of the calotte, the proportionality factor being 0.08 Hz m².     

Thin films of novel ferroelectric composites

Abstract

Composites of BSTO combined with other non electrically active oxides have demonstrated adjustable electronic properteis which can be tailored for use in various electronic devices.^[1,2] These novel composites of barium strontium titanate (BSTO) and oxide III compounds have already exhibited promising results in their ceramic form.^[3] The additive oxides modify the dielectric constant, tunability (change in the dielectric constant with applied voltage), and dielectric loss of the material. One application has been for use in phased array antennas and insertion has been accomplished into several working antenna systems.^[4] To further accommodate the frequencies required by these phased array antennas, thin films of the composites have been fabricated. Preliminary studies have indicated that thin films of such composites exhibit similar behavior as their bulk ceramic counterparts.^[5] The purpose of this study is to investigate the properties of the BSTO/oxide III based compounds in thin film form.     

Study of piezoelectric fibre/cement 1–3 composites

To improve the compatibility between the sensor material and civil engineering structural material, a new functional cement-based composite for smart structure applications has been studied. Piezoelectric lead zirconate titanate (PZT) fibres, fabricated using a slurry method, are embedded in a cement matrix to form PZT/cement 1–3 composites. By incorporating PZT fibres into the cement matrix, composites with low PZT volume fractions ranging from 0.05 to 0.22 have been fabricated. The 1–3 composites have good piezoelectric properties that agree quite well with theoretical modeling. The thickness electromechanical coupling coefficient of the composites could reach ～0.5 even for low volume fraction of PZT. These composites have potential to be used as sensors in civil structure health monitoring systems.     

Fabrication and evaluation of PZT/Ag composites and functionally graded piezoelectric actuators

Metallic Ag as the second phase was added into PZT ceramic matrix to fabricate piezoelectric composites and functionally graded actuators by gradually altering Ag concentration, aimed to improve mechanical properties and to solve possible interfacial debonding usually observed in conventional bimorph-type piezoelectric actuator. The PZT/Ag composites were obtained by directly co-firing PZT and Ag powders at 1200^∘C for 1 h. The fracture strength σ _f and fracture toughness K _IC , as well as the corresponding piezoelectric properties, were firstly evaluated upon the PZT/Ag composites for Ag concentrations of 0–30 vol%. The mechanical properties for the PZT/Ag composites were found to be greatly enhanced compared with pure PZT ceramics: from 69 to 129 MPa for σ _f and from 1.0 to 3.7 MPa.m^1/2 for K _IC . With increasing Ag concentration, the piezoelectric constant d ₃₃ of PZT/Ag composites was found to decrease from 419 to 86 pC/N. Then, a functionally graded actuator was fabricated and evaluated in terms of electric-induced curvature k. The PZT/Ag FGM actuator with size of 12 mm × 3 mm × 1 mm has a curvature k of 0.03–0.17 m⁻¹ that corresponds to applied voltages of 100–500 V. A comprehensive comparison was made on the mechanical property enhancements by the metal particles dispersion, and the bending displacements produced by the FGM actuators between the PZT/Ag and previously fabricated PZT/Pt systems.     

Preparation and characterization of PZT ferroelectric thin films by plasma enhanced metalorganic chemical vapor deposition

Abstract

PZT thin films with a uniform distribution of components were prepared by plasma enhanced chemical vapor deposition (PECVD) using Pb(C₂H₅)₄, Z (O-i-C₄H₉)₄, Ti(O-i-C₃H₇)₄, and oxygen. The crystallization of films was occure after annealing in the temperature range between 450 and 550°C under O₂ ambient for 1 hr. The significant change of Pb concentration in PECVD PZT thin films was not observed in the relation to annealing temperature and time. The dielectric constant PECVD PZT thin films increased with the Ti content, showed the maximum value in the vicinity of morphotropic phase boundary (MPB) composition of PZT material, and decreased with the Ti content. The leakage current density of PZT (65/35) thin film of 180 nm in thickness was 3·37 × 10^?7 A/cm² at the applied voltage of 3 V. Remanent polarization increased with increasing of Zr content in the film and coercive field was nearly independent of the composition. The typical values of electrical properties were ε_r = 570, E_c = 90 kV/cm, and P_r = 19 μC/cm² in the PECVD PZT (54/46) thin film of 220 nm in thickness.     

Dielectric Properties of Yttrium Vanadate Crystals from 15 K to 295 K

Yttrium Vanadate (YVO₄) is a birefringent crystal, which has similar dielectric constant as that of Sapphire. In this paper we have reported the measurement of the real part of permittivity and loss tangent of YVO₄ crystal in the temperature range 15–295 K at a frequency of 16.3 GHz. We have used the dielectric post resonator technique for the microwave characterisation of the YVO₄ dielectric rod. The multifrequency Transmission Mode Q-Factor (TMQF) technique has been used for data processing and hence precise values of permittivity and loss tangent are achieved. Easily machineable YVO₄ is characterized by low losses at microwave frequencies. At temperature of 15 K and frequency of 16.3 GHz the permittivity was 9.23 and loss tangent was 2 × 10^{− 5}. YVO₄ is identified as a potential candidate to replace expensive Sapphire in many microwave applications.     

Effect of Ba2+ – Sr2+ co-substitution on the structural and dielectric properties of Lead Titanate

Growing interest in developing new materials for device applications led to study of ferroelectric oxides in a wide range and variety of compositions. In the present work, polycrystalline samples of lead barium strontium titanate (Pb_1-xBa_0.5xSr_0.5xTiO₃) solid solution system have been synthesized. Phase formation studies and crystal structure analysis were carried out by X ray diffractometry at room temperature, which suggested formation of single phase compound with tetragonal structure up to x?=?0.8 and cubic structure for x?=?1.0. The XRD pattern has been analyzed by employing Rietveld method. The phase transition in the system was confirmed by Differential Scanning Calorimetry (DSC). Samples with 0.0????x????0.8 are in ferroelectric state whereas with x?=?1.0 is found to be in paraelectric state at room temperature. Co-substitution of Ba²⁺ and Sr²⁺ into lead titanate shows reduction in anisotropy as well as porosity. The dielectric studies of the system as a function of temperature and frequency were carried out in the range 323?K to 773?K and 100?Hz to 1?MHz respectively. Variation of dielectric constant and loss tangent with temperature shows peaking effect near Curie temperature. Frequency dependant dielectric studies clearly show that the dielectric constant and loss tangent decrease exponentially with increased frequency.     

Characteristics of ferroelectric gate mos and mosfets

Abstract

Electrical characteristics of metal-insulator-semiconductor (MIS) capacitors of a variety of ferroelectric materials like lead zirconate titanate (PZT), lead titanate (PT) and barium magnesium fluoride (BMF) on p-silicon have been studied. PZT was deposited by r.f. magnetron sputtering from a composite target and PT from co-evaporation. The films were annealed in oxygen atmosphere in the temperature range 550–700°C for various times. PZT and PT films which are directly deposited on silicon showed low effective dielectric constant.¹⁰ For normal applied bias voltages (±5 V), the C-V curves did not show significant hysteresis. The effective dielectric constant was improved significantly by the incorporation of a buffer layer. BMF film was deposited in ultra high vacuum on a heated substrate and the film was encapsulated by a zirconium oxide layer. The C-V curves for these MIS capacitors shows hysteresis and the direction of hysteresis corresponds to ferroelectric polarization.     

EFFECTS OF PZT BUFFER LAYERS ON PZFNT FERROELECTRIC THIN FILMS

ABSTRACT

PZFNT thin films were fabricated on 5-inch Pt/Ti/SiO₂/Si and PZT/Pt/Ti/SiO₂/Si substrates by RF magnetron sputtering method and rapid thermal annealing process. By investigating the two thin films at various annealing temperatures, the results show that the annealing temperature of PZFNT thin films without PZT buffer layers is about 730°C, which is higher than that of PZFNT films with PZT buffer layers. By use of PZT buffer layers, the annealing temperature of PZFNT films is decreased greatly, and the dielectric and ferroelectric properties are improved. In the optimum process, the thin films with PZT buffer layers have a dielectric constant of 1199 and dielectric loss of 3.0% at 1 KHz. The remanent polarization and coercive field of the thin films are 21.1 μC/cm² and 53.5 KV/cm respectively. The films have the significant potential for FRAM and pyroelectric infrared detectors.