Effect of Nb doping on structural and electric properties of PZT (65/35) ceramic

The aim of this study is to determine the effect of Nb⁵⁺ doping on PZT (65/35) based bulk materials in their structure, micro structure and electrical properties. The Nb content was chosen 0-9 mole%. These materials were prepared by conventional mixed oxide method. X ray diffraction studies suggest the compound to be of rhombohedral perovskite phase. Excess addition of Nb result in pyrochlore and fluorite phase develops in PZT (65/35) sample. Detailed studies of dielectric constant as a function of temperature (40degC to 500degC) and frequency (100 Hz to 1 MHz) suggest that the compounds undergo diffuse type of phase transition. Maximum dielectric constant and resistivity were found to be strongly dependent on doping and measuring frequencies. Using complex impedance analysis micro structural parameters such as bulk and grain boundary resistance, bulk charge carrier concentration and relaxation time were determined     

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.     

Effects of complex doping on microstructural and electrical properties of PZT ceramics

The influence of complex dopants including donor and acceptor ions on microstructure and electrical properties of PZT (Zr/Ti = 53/47) ceramics was investigated. The prepared PZT ceramics modified with complex soft dopants, La⁺³ and Nb⁺⁵, showed that the piezoelectric properties were enhanced and stable with the compositional variations, which made it possible to establish the higher reliability and reproducibility of the piezoelectric performances. For 1.0 mol% La and 1.2 mol% Nb doped composition, the maximum value, k _P = 0.66, was obtained. Unlike single element doping, the complex doping of both the donor and acceptor ions caused various compensation effects for the piezoelectric properties of the PZT ceramics. The improved piezoelectric properties, i.e., enhanced Q _m with remaining higher k _p , were obtained in the PZT composition complexly doped with La⁺³ and Fe⁺³. For 1.0 mol% La and 2.0 mol% Fe doped PZT composition, relatively high Q _m and k _p values of 580 and 0.53, respectively, were obtained. It was also shown that the PZT composition had the rather lowered dielectric constant, ε _r = 800, and considerably low loss, tanδ = 0.003. By changing the dopants compositions, the properties can also be tailored over wider range.     

Influence of Post-Annealing on the Characteristics of Pb(Zr,Ti)O3 Thin Films Deposited by Liquid Delivery MOCVD Using a Cocktail Solution

Ferroelectric PZT thin films were deposited by liquid delivery MOCVD using a cocktail solution. The cocktail solution consisted of Pb(METHD)₂, Zr(METHD)₄ and Ti(MPD)(METHD)₂ diluted with ethylcyclohexane. The films deposited on Pt/Ti/SiO₂/Si at a substrate temperature of 500°C consisted of PZT, PbO and PbPt_x, and showed poor properties. However, after annealing at 450°C in air for thirty minutes, the PbPt_x phase disappeared while the volume of the PbO phase increased. The hysteresis properties were also improved by annealing at 450°C. After annealing at 600°C in air for thirty minutes, the PbPt_x and the PbO phases disappeared perfectly and the PZT thin films showed good hysteresis properties with the remanent polarization of 30 μC/cm² and the coercive field of 88 kV/cm.     

Preparation of Zr-rich PZT and La-doped PbTiO3 thin films by RF magnetron sputtering and their properties for pyroelectric applications

Abstract

Zr-rich PZT and La-doped PT films were fabricated on a PLT/Pt/Ti/SiO₂/Si or Pt/Ti/SiO₂/Si substrate by an RF planar magnetron sputtering equipment using powder targets with compositions of PbZr_{0 94}Ti_0.06O₃, PbZr_0.92Ti_0.08O₃ and Pb_0.85La_0.15 Ti_0.96O₃ with excess PbO of 20 mol%. The dielectric constants of PZT and PLT films showed anomalies at the transition temperatures of around 246 and 300°C, and their dielectric constants at room temperature were 350 and 1070, respectively. Significant pytroelectric currents were observed in both as-grown PZT and PLT films even without a poling treatment. The pyroelectric coefficients of those films were 10 and 30 nC/cm²K, respectively. Therefore, Zr-rich PZT and [111]-oriented PLT films sputtered on Pt/Ti/SiO₂/Si substrates possess desirable properties for potential applications to pyroelectric devices.     

Synthesis and thermal stability of perovskite PbZr0.52Ti0.48O3 (PZT) powders via precipitation routes

Synthesis of PbZr_0.52Ti_0.48O₃ (PZT) powders was realized via coprecipitation route or two-stage precipitation route. The thermal behavior and phase evolution of the PZT precursor were investigated with DTA/TG and followed with XRD, respectively. The thermal stabilities of the synthesized PZT powders were evaluated with TG. It concluded that the PZT powder prepared via two-stage precipitation route is of pure perovskite phase and of good thermal stability because the combination of Zr⁴⁺ and Ti⁴⁺ ions is enhanced and Pb(OH)₂ is encapsulated by (Zr_0.52Ti_0.48)O(OH)₂. However, the PZT powder obtained via coprecipitation route is of poor thermal stability due to the formation and evaporation of PbO.     

Recent progress in sputtering PZT thin films for ferroelectric memories

Abstract

This paper describes amorphous Pb(Zr, Ti)O₃ (PZT) thin films deposited by cosputtering Pb(Zr_0.5 Ti_0.5)O₃ and PbO targets. By optimizing the amount of the excess Pb and the deposition temperature, PZT thin films with a single perovskite phase were obtained successfully on Ir substrates and Pt substrates at 520°C. 250-nm-thick PZT films crystallized by rapid thermal annealing (RTA) at 600°C for 20 s exhibited excellent ferroelectric properties: a coercive voltage of 1.0 V, a remanent polarization density of about 40 μC/cm², and a polarization switching endurance over 1x109 cycles. Although a heat treatment in a reductive ambient causes degradation of ferroelectric properties of PZT thin films, their degraded ferroelectric properties can be easily recovered from by a 1-min RTA in an oxygen at 400°C.     

Influence of the Lead Source Materials on the Microstructure and Ferroelectric Properties of PZT Films Sputter-Deposited Using Lead and Lead Oxide

In this investigation, PZT films were sputter-deposited on Si/SiO₂/Ti/Pt substrates using a dual-target system. The dual targets Pb/PZT(PbZr_0.54Ti_0.46O₃) and PbO/PZT(PbZr_0.54Ti_0.46O₃) were used to reveal the effects of various lead compensation source materials on the microstructure and ferroelectric properties of the films. The structures of the films were characterized by X-ray diffractometry (XRD) and field emission scanning electron microscopy (FESEM). The chemical binding state was determined using X-ray photoelectron spectrometry (XPS). Ferroelectric polarizability was measured using a Radiant Technology RT66A tester. The influence of deposition temperatures on the microstructure and ferroelectric properties of the films was studied. Perovskite PZT films were successfully deposited using the Pb/PZT and the PbO/PZT dual target sputtering systems at a substrate temperature of between 500 and 580C. Structural change was elucidated as a function of deposition temperatures and the lead sources were correlated with the ferroelectric properties of the film. The ferroelectric characteristics of the PZT films deposited using the PbO/PZT dual target were better than those of films deposited using the Pb/PZT dual target, because the former films had a higher bonding energy.     

Anomalous fatigue behavior in Zn doped PZT

Abstract

Doping lead zirconate titanate (PZT) has often been examined in order to investigate changes in the electrical behavior of thin film ferroelectric capacitors.¹ In this study, PZT has been doped with Hf, Nb, and Zn. After reviewing the results of the initial studies, Zn doping of PZT was further investigated. Physical and electrical studies of Zn doped PZT have been conducted. These studies include x-ray diffraction analysis, hysteresis, pulsed switching, fatigue and retention measurements. Endurance measurements indicate an anomalous fatigue behavior of some Zn doped PZT thin film capacitors.     

Pyroelectric properties and X-ray photoelectron spectroscopic study of R.F. magnetron-sputtering-derived PZT thin films deposited on various interlayers

PZT thin films and interlayers were fabricated by the radio frequency (r.f.) Magnetron-sputtering from the Pb_1.1Zr_0.53Ti_0.47O₃, PbO and TiO₂ target. As a result of the XPS depth profile analysis, we can confirm that the substrate temperature affects the oxidation condition of each element of interlayers and the PZT film. Compared to the PZT/Pt structure, the dielectric and pyroelectric properties of PZT thin films inserted by interlayers were measured to a relatively high value. In particular, the PZT/PbO structure had the highest pyroelectric properties (P = 189.4 μC/cm²K; F _D = 12.7×10⁻⁶ Pa^−1/2; F _V = 0.018 m²/C).     

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.     

Effect of excess PbO on microstructure and orientation of PZT(60/40) films

Lead zirconate titanate [PZT(60/40)] films were deposited by RF-magnetron sputtering using single oxide targets with various levels of excess PbO. The excess PbO in the film played an important role in the pyrochlore-to-perovskite transformation, nucleation and growth processes, orientation control, and crack formation. When 5% or 20% excess PbO was added to the target, pyrochlore phases were created and the films were severely cracked. However, the films had a perovskite structure without any pyrochlore phases when 10% or 15% excess PbO was added to the targets. More interestingly, the crystallographic orientation was strongly dependant on the excess PbO content. A film with a (111) preferred orientation was produced when 10% excess PbO was added to the target. On the other hand, a film with a (100) preferred orientation was deposited by the target with 15% excess PbO. The dielectric, ferroelectric and piezoelectric properties of these films with different orientations and microstructures were examined and correlated with the film structure.     

Effect of Nb Doping on (Sr,Ba)TiO3 (BST) Ceramic Samples

The effect of doping the Sr_0.3Ba_0.7Ti_(1–5y/4)Nb _y O₃ ceramic with different concentration of Nb is studied by scanning electron microscopy (SEM), X-ray diffraction and thermoelectric analysis. It is observed that the grain size decreases as the Nb concentration increases. The critical temperature T _c has a linear decrease at a rate of 19°C/mol% of Nb. The temperature dependence of the dielectric permittivity presents strongly broadened curves, which suggest a non Curie-Weiss behavior near the transition temperature. The diffuse phase transition coefficient () was also determined and its value leads to the conclusion that the degree of disorder in the system increases with the presence of the Nb cation.     

Effect of excess-PB and prenucleation layer on properties of Pb(ZryTi1-y)O3 thin films prepared by mod process

Abstract

A modified metal-organic decomposition process, MOD has been successfully utilized to improve the ferroelectric properties of Pb(Zr_0.52Ti_0.48)O₃, PZT, thin films. Multilayer PZT/Pt(Si) films, which contain 0.12 μm layer of spin coated PbO-excess (10 mol%) precursors on top of 0.12 μm layer of stoichiometric PZT precursors, exhibit superior ferroelectric properties (P_r=14.2 μC/cm²; E_c=62 kV/cm) to the single layer PZT/Pt(Si) films of the same thickness (0.24 μm), which are either stoichiometric or 10 mol% Pb-enriched. The ferroelectric properties are further improved when the PZT films were synthesized using a thin pulsed laser deposited (PLD) prenucleation layer (0.06 μm). The subsequently MOD-prepared PZT films posses high remanent polarization (P_r=23.2–26.6 μC/cm²) and low coercive field (E_c=62.9–69.0 kV/cm).     

Reactive Calcination Derived PZT Ceramics

Perovskite PZT ceramics are synthesized from stoichiometric oxide ratios of Pb, Zr, and Ti. The oxide powders are mixed mechanically and calcinated, and then sintered to form the desired perovskite phase using conventional solid-state reaction and reactive calcination routes. Highly reactive powders are produced by reacting the materials near the temperature of maximum volumetric expansion. At this point, an almost single phase with relatively high homogeneous structure is obtained. Also, the highly reactive powders allow densification to occur at temperatures as low as 950C without the need to the additions of excess lead oxides. The dielectric properties of the PZT ceramics prepared by reactive calcination route are measured and compared with the conventional route.     

Microstructural and dielectric studies of A-site calcium doped PbZr0.94Ti0.06O3 ceramics

The microstructure-property relationship of calcium doped PbZr_0.94Ti_0.06O₃ (PZT 94/6) ceramics has been studied. It was found that calcium doping on the A-site turns the ferroelectric PZT 94/6 into antiferroelectric. {hk0} superlattice reflections were observed in the selected area diffraction pattern (SADP) of PZT 94/6 which indicated an in-phase oxygen octahedra tilting in the ferroelectric PZT 94/6. When 4 mol% of calcium was added as a dopant, the material became antiferroelectric at room temperature, with the characteristic {hk0} superlattice reflections observed in the SADP. The P-E hysteresis loop measurement also supports this conclusion. As the temperature increased, an AFE-FE phase transition occurred and this was accompanied by a hunch-like dielectric anomaly at around 140^∘C.     

Preparation of Bulk Pb(Zr, Ti)O3 with Crystallographic Texture by Templated Grain Growth Method

Polycrystalline Pb(Zr, Ti)O₃ (PZT) ceramics with 111-texture were prepared by the templated grain growth (TGG) method using the platelike Ba₆Ti₁₇O₄₀ (B6T17) particles as templates. Textured PZT was obtained by sintering of green compacts containing matrix PZT, aligned B6T17, and excess PbO. Excess PbO formed a liquid phase and promoted the dissolution of PZT grains and the precipitation on B6T17 grains. A similarity of the arrangement of ions on (001) of B6T17 and (111) of PZT gave 111-texture to matrix PZT.     

Fatigue properties of Sb doped PZT thin films deposited by dc reactive sputtering

Abstract

Sb doped reactive sputtering-derived Pb(Zr, Ti)O₃ (Zr/Ti=48/52) thin films were investigated with the intention of improving ferroelectric properties. Also, the atomic valence of Sb in PZT thin film was confirmed as trivalent cation (Sb³⁺) by x-ray photoelectron spectroscopy (XPS). According to the tolerance factor t, Sb³⁺ tends to occupy the B-site of ABO₃ perovskite structure and acts as an acceptor that generates oxygen vacancies and holes. Transmission Electron Microscope(TEM) was used to observe the structural changes of PZT thin films by Sb addition. The leakage current densities and P_r of PZT thin films increased as the Sb contents increased. 0.7at% Sb doped PZT(PZST07) thin films exhibited improved fatigue properties (about 10% degradation of the remanent polarization after 10¹⁰ switching cycles).     

Preparation and properties of sol-gel derived PZT thin films for decoupling capacitor applications

Abstract

The use of ceramic thin films as decoupling capacitors offers the possibility of capacitor integration within the integrated circuit (IC) package, and potentially, directly onto the IC itself. Since these configurations minimize series inductance, higher operational speeds are possible. In the present study we have investigated the dielectric and leakage characteristics of sol-gel PZT films. For compositions near the morphotropic phase boundary, dielectric constants of 1000, and loss tangents of about 0.02, were observed. The current-voltage behavior of the capacitors was characterized by a non-linear response, and significant asymmetry in both the leakage and breakdown characteristics as a function of bias sign was observed. Breakdown fields for PZT 53/47 thin films were typically ～800 kV/cm at 25°C. We have also studied the effects of La and Nb dopant additions and alternate firing strategies on film leakage characteristics. Donor doping at 2–5 mol% lowered leakage currents by a factor of 10³ For films prepared by a multilayering approach, firing each layer to crystallization resulted in leakage currents that were a factor of 10² lower than films prepared by the standard process.     

Microstructures and Piezoelectric Properties of Microwave-Sintered Pb(Mn1/3Nb2/3)0.1Zr0.52Ti0.38O3 Ceramics

In this work, we study the microstructural modifications and the electrical properties of Pb(Mn_1/3Nb_2/3)_0.1Zr_0.52Ti_0.38O₃ + 1.5 wt% PbO (PMNZT) ceramics processed using microwave sintering (MS) and conventional sintering (CS) techniques. Dielectric and piezoelectric properties were evaluated via an impedance/gain phase analyzer and the corresponding microstructures were examined using transmission electron microscopy (TEM). The experimental results imply that smaller grain size and less loss of PbO obtained for specimens using MS process. The MS specimens (1200°C-15 min) show the remanent polarization (P_r) of 24.1 μC/cm², coercive field (E_c) of 15.2 kV/cm, dielectric constants (?_r) of 432 and electromechanical coupling coefficient (k_p) of 0.47, which are superior to CS specimens (1200°C-2 h) with P_r = 19.5 μC/cm², E_c = 16.1 kV/cm, ?_r = 395 and k_p = 0.45. The results revealed that the MS process shows capability of fabrication of good quality PMNZT ceramics with advantages of lowing process temperature and shorten process time. TEM investigations of MS specimens show that smaller grain size and simpler domain arrangements exist inside the specimens. From the energy aspect, the domain structure in piezoelectric ceramics below the temperature of a ferroelectric structural phase transformation is a result of energy minimization. Homogeneous elastic strain energy is reduced at the expense of domain boundary energy during the phase transformation. Density of domain boundaries, 71° (109°) domains in particular, depends on and increases with the grain size. Base on the above argument, therefore, CS specimens exhibit more complicated domain arrangements because they possess larger grain size than MS specimens do. The microstructural investigations suggest that the electrical property difference is intimately related to different sintering methods since the complicated domain arrangements could hinder domain moving and deteriorate electrical performance. In addition, the microstructural characteristics in both MS and CS specimens will be discussed further in the context.