Toward a unified description of nonlinearity and frequency dispersion of piezoelectric and dielectric responses in Pb(Zr,Ti)O3

A phenomenological approach is proposed describing both nonlinearity and frequency dispersion in dielectric and piezoelectric properties of lead zirconate titanate, Pb(Zr,Ti)O₃ (PZT), thin films and ceramics. The approach couples the frequency dependent response in form of the power law, 1/ω^β, with the rate-independent nonlinear response described by the Rayleigh law. The main experimental trends are well described by the model.     

Conduction mechanism in antiferrolectric PbZrO3 thin films—analysis of charge carrier trapping phenomenon

Abstract

Antiferroelectric compositions, such as PbZrO₃, are attractive candidates in charge storage devices and actuator/transducer applications in MEMs technology. Thin films of PbZrO₃were deposited on Pt coated Si substrates by a pulsed excimer ablation process. The process of field induced ferroelectric phase switching involves the domain wall reorientation in the polycrystalline thin films. The presence of grain boundaries and various defects in the polycrystalline thin films acts as the pinning sources for the various domain walls. These defects capture the charge carriers in the presence of external applied field and hinders further switching of the dipoles in the domains, thereby increases the response times and threshold voltages for the devices operations. Understanding of the trapping phenomenon in these films is very essential. Using Lampert's theory of space charge limited conduction both shallow and deep trap energies were estimated approximately from charge transport analysis.     

Excimer laser ablation processed ferroelectric and antiferroelectric thin films

Abstract

The dielectric and electrical properties of excimer laser ablated processed paraelectric (Ba_0.5, Sr_0.5)TiO₃, ferroelectric Bi-layered SrBi₂(Ta_0.5Nb_0.5)₂O₉, and antiferroelectric (PbZrO₃) thin films have been investigated. The effect of processing parameters on the microstructure of the films and the functional properties has been presented in detail. Some of the recent studies of stress induced effects, dielectric, hysteresis and ac and dc electrical properties have been highlighted in conjunction with microstructures of the films.     

Dielectric and Piezoelectric Properties of PZT Composite Thick Films with Variable Solution to Powder Ratios

The use of PZT films in sliver-mode high-frequency ultrasonic transducers applications requires thick, dense, and crack-free films with excellent piezoelectric and dielectric properties. In this work, PZT composite solutions were used to deposit PZT films >10 μm in thickness. It was found that the functional properties depend strongly on the mass ratio of PZT sol–gel solution to PZT powder in the composite solution. Both the remanent polarization, P _r, and transverse piezoelectric coefficient, e _{31, f} , increase with increasing proportion of the sol–gel solution in the precursor. Films prepared using a solution-to-powder mass ratio of 0.5 have a remanent polarization of 8 μC/cm², a dielectric constant of 450 (at 1 kHz), and e _{31, f} =−2.8 C/m². Increasing the solution-to-powder mass ratio to 6, the films were found to have remanent polarizations as large as 37 μC/cm², a dielectric constant of 1250 (at 1 kHz) and e _{31, f} =−5.8 C/m².     

Fabrication of High Aspect Ratio Ferroelectric Microtubes by Vacuum Infiltration using Macroporous Silicon Templates

Ordered arrays of high aspect ratio (>10:1) ferroelectric Pb(Zr_0.52Ti_0.48)O₃ (PZT) tube structures were fabricated by vacuum infiltration of macroporous silicon (Si) templates. Improved phase purity was achieved when PZT microtubes were pyrolyzed at 300°C and partially released from the Si template to prevent a chemical reaction between the Pb and the Si during subsequent high-temperature crystallization. The free-standing microtubes were crystallized by rapid thermal annealing at 750°C for 1–3 min. Perovskite phase formation was confirmed by X-ray diffraction and transmission electron microscopy methods. Coaxial structures comprised of metallic LaNiO₃, PZT, and Pd layers were also processed to enable future electrical characterization of the ferroelectric microtubes.     

Designing piezoelectric films for micro electromechanical systems

Piezoelectric thin films are of increasing interest in low-voltage micro electromechanical systems for sensing, actuation, and energy harvesting. They also serve as model systems to study fundamental behavior in piezoelectrics. Next-generation technologies such as ultrasound pill cameras, flexible ultrasound arrays, and energy harvesting systems for unattended wireless sensors will all benefit from improvements in the piezoelectric properties of the films. This paper describes tailoring the composition, microstructure, orientation of thin films, and substrate choice to optimize the response. It is shown that increases in the grain size of lead-based perovskite films from 75 to 300 nm results in 40 and 20% increases in the permittivity and piezoelectric coefficients, respectively. This is accompanied by an increase in the nonlinearity in the response. Band excitation piezoresponse force microscopy was used to interrogate the nonlinearity locally. It was found that chemical solution-derived PbZr(0.52)Ti(0.48)O(3) thin films show clusters of larger nonlinear response embedded in a more weakly nonlinear matrix. The scale of the clusters significantly exceeds that of the grain size, suggesting that collective motion of many domain walls contributes to the observed Rayleigh behavior in these films. Finally, it is shown that it is possible to increase the energy-harvesting figure of merit through appropriate materials choice, strong imprint, and composite connectivity patterns.     

Antiferroelectric lead zirconate thin films by excimer laser ablation

Abstract

Utilization of antiferroelectric thin films was proposed for high charge storage capacitors and transducer applications. The volume changes that are associated with the AFE? FE and FE ? AFE phases are high enough to use them in MEMs device technology. Lead zirconate was the first identified antiferroelectric compound with a reported dielectric phase transition temperature of ～ 230°C. In this article, deposition of lead zirconate thin films by a pulsed excimer laser ablation technique is reported. The antiferroelectric nature of the lead zirconate thin films were confirmed by the presence of double hysteresis loop in polarization vs. applied electric field response as well as double butterfly behavior in capacitance vs. voltage characteristics. The variations in the polarization hysteresis with temperature were elucidated in detail. The switching times between the field induced FE and AFE phases (backward switching) were studied at various applied electric fields.     

Properties of Chemical Solution Deposited Polycrystalline Neodymium-Modified Bi4Ti3O12

Thin films of neodymium-modified bismuth titanate Bi_3.44Nd_0.56Ti₃O₁₂ (BNT) were grown on Pt/TiO₂/SiO₂/Si substrates using chemical solution deposition method. The capacitors made by applying top Au electrodes on BNT films showed significantly improved values of the remanent polarization as compared to that using bismuth titanate Bi₄Ti₃O₁₂ (BT) films. The 2P _r value for the BNT capacitors was determined to be equal to 38 C/cm² at an applied voltage of 24 V, whereas, for Bi₄Ti₃O₁₂ (BT) capacitors a value of 20 C/cm² was measured at the same applied voltage. The maximum piezoelectric and pyroelectric coefficients of 22 pm/V and 112 C/m² K respectively, were measured for the BNT thin films.     

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.