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  1. In many commercially utilized ferroelectric materials, the motion of domain walls is an important contributor to the functional dielectric and piezoelectric responses. This paper compares the temperature dependence of domain wall motion for BaTiO3 ceramics with different grain sizes, point defect concentrations, and formulations. The grain boundaries act as significant pinning points for domain wall motion such that fine-grained materials show smaller extrinsic contributions to the properties below the Curie temperature and lower residual ferroelectric contributions immediately above the Curie temperature. Oxygen vacancy point defects make a modest change in the extrinsic contributions of undoped BaTiO3 ceramics. In formulated BaTiO3, extrinsic contributions to the dielectric response were suppressed over a wide temperature range. It is believed this is due to a combination of reduced grain size, the existence of a core-shell microstructure, and a reduction in domain wall continuity over the grain boundaries.

     
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    Free, publicly-accessible full text available November 15, 2024
  2. Abstract

    Thin films based on PbZr1−xTixO3and K1−xNaxNbO3are increasingly being commercialized in piezoelectric MEMS due to the comparatively low drive voltages required relative to bulk actuators, as well as the facile approach to making sensor or actuator arrays. As these materials are incorporated into devices, it is critically important that they operate reliably over the lifetime of the system. This paper discusses some of the factors controlling the electrical and electromechanical reliability of lead zirconate titanate (PZT)-based piezoMEMS films. In particular, it will be shown the gradients in the Zr/Ti ratio through the depth of the films are useful in increasing the lifetime of the films under DC electrical stresses.

     
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    Free, publicly-accessible full text available September 21, 2024
  3. Lead zirconate titanate (PZT) films with high Nb concentrations (6–13 mol%) were grown by chemical solution deposition. In concentrations up to 8 mol% Nb, the films self-compensate the stoichiometry; single phase films were grown from precursor solutions with 10 mol% PbO excess. Higher Nb concentrations induced multi-phase films unless the amount of excess PbO in the precursor solution was reduced. Phase pure perovskite films were grown with 13 mol% excess Nb with the addition of 6 mol% PbO. Charge compensation was achieved by creating lead vacancies when decreasing excess PbO level; using Kroger-Vink notation, NbTi• are ionically compensated by VPb″ to maintain charge neutrality in heavily Nb-doped PZT films. With Nb doping, films showed suppressed {100} orientation, the Curie temperature decreased, and the maximum in the relative permittivity at the phase transition broadened. The dielectric and piezoelectric properties were dramatically degraded due to increased quantity of the non-polar pyrochlore phase in multi-phase films; εr reduced from 1360 ± 8 to 940 ± 6, and the remanent d33,f value decreased from 112 to 42 pm/V when increasing the Nb concentration from 6 to 13 mol%. Property deterioration was corrected by decreasing the PbO level to 6 mol%; phase pure perovskite films were attained. εr and the remanent d33,f increased to 1330 ± 9 and 106 ± 4 pm/V, respectively. There was no discernable difference in the level of self-imprint in phase pure PZT films with Nb doping. However, the magnitude of the internal field after thermal poling at 150 °C increased significantly; the level of imprint was 30 kV/cm and 11.5 kV/cm in phase pure 6 mol% and 13 mol% Nb-doped films, respectively. The absence of mobile VO••, coupled with the immobile VPb″ in 13 mol% Nb-doped PZT films, leads to lower internal field formation upon thermal poling. For 6 mol% Nb-doped PZT films, the internal field formation was primarily governed by (1) the alignment of (VPb″−VO•• )x and (2) the injection and subsequent electron trapping by Ti4+. For 13 mol% Nb-doped PZT films, hole migration between VPb″ controlled internal field formation upon thermal poling. 
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    Free, publicly-accessible full text available June 1, 2024
  4. Anomalously abrupt nucleation and growth kinetics in polarization switching of wurtzite ferroelectrics are demonstrated. The anomaly inspires an extension of the traditional model to a regime that simultaneous non-linear nucleation and growth occur.

     
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    Free, publicly-accessible full text available July 31, 2024
  5. Free, publicly-accessible full text available May 1, 2024
  6. In undoped lead zirconate titanate films of 1–2  μm thick, domain walls move in clusters with a correlation length of approximately 0.5–2  μm. Band excitation piezoresponse force microscopy mapping of the piezoelectric nonlinearity revealed that niobium (Nb) doping increases the average concentration or mobility of domain walls without changing the cluster area of correlated domain wall motion. In contrast, manganese (Mn) doping reduces the contribution of mobile domain walls to the dielectric and piezoelectric responses without changing the cluster area for correlated motion. In both Nb and Mn doped films, the cluster area increases and the cluster density drops as the film thickness increases from 250 to 1250 nm. This is evident in spatial maps generated from the analysis of irreversible to reversible ratios of the Rayleigh coefficients. 
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  7. Free, publicly-accessible full text available August 1, 2024
  8. Phase pure PbZr 0.52 Ti 0.48 O 3 (PZT) films with up to 13 mol. % Nb were prepared on Pt-coated Si substrates using chemical solution deposition; charge compensation for Nb was accomplished by reducing the concentration of lead in the film. For high Nb doping levels, (1) superoxidation of the PZT film surface makes the PZT/Pt interface more p-type and, hence reduces electron injection over the Schottky barrier, (2) the bulk charge transport mechanism changes from electron trapping by Ti 4+ to hole migration between lead vacancies, and (3) the ionic conductivity due to migration of oxygen vacancies decreases. For [Formula: see text] Nb, electrical degradation was controlled via field-induced accumulation of oxygen vacancies near the cathode, which, in turn, leads to Schottky barrier lowering and electron trapping by Ti 4+ . In phase pure 13 mol. % Nb doped PZT films, on the other hand, the increase in the leakage current during electrical degradation was dominated by hole migration between lead vacancies ([Formula: see text]. A much lower lifetime and drastic increase in the leakage current upon electrical degradation was observed in mixed phase PNZT films, which was attributed to (1) a more electrically conductive pyrochlore phase and (2) a high concentration of lead vacancies. 
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  9. Piezoelectric microelectromechanical systems (piezoMEMS) enable dense arrays of actuators which are often driven to higher electrical fields than their bulk piezoelectric counterparts. In bulk ceramics, high field driving causes internal heating of the piezoelectric, largely due to field-induced domain wall motion. Self-heating is then tracked as a function of vibration velocity to determine the upper bound for the drive levels. However, the literature is limited concerning self-heating in thin film piezoMEMS. In this work, it is shown that self-heating in piezoMEMS transducer arrays occurs due to domain wall motion and Ohmic losses. This was demonstrated via a systematic study of drive waveform dependence of self-heating in piezoMEMS arrays. In particular, the magnitude of self-heating was quantified as a function of different waveform parameters (e.g., amplitude, DC offset, and frequency). Thermal modeling of the self-heating of piezoMEMS using the measured hysteresis loss from electrical characterization as the heat source was found to be in excellent agreement with the experimental data. The self-heating model allows improved thermal design of piezoMEMS and can, furthermore, be utilized for functional heating, especially for device level poling. 
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