Julia Glaum

Effect of Nb-donor and Fe-acceptor dopants in (Bi1/2Na1/2)TiO3-BaTiO3-(K0.5Na0.5)NbO3 lead-free piezoceramics

The role of Fe as an acceptor and Nb as a donor in [0.94−x](Bi1/2Na1/2)TiO3–0.06BaTiO3−x (K0.5Na0.5)NbO3 (100xKNN) (x=0.02 and 0.03) lead-free piezoceramics was investigated. X-ray diffraction analyses show that all the profiles are best-fitted with a cubic symmetry where Fe doping tends to induce a lattice expansion, while Nb doping does the opposite. The strain and polarization characteristics are enhanced and suppressed by the acceptor and donor dopants, respectively. The improvement in the electrical properties with acceptor doping is accompanied by the stabilization of a ferroelectric order. Electron paramagnetic resonance spectroscopic analysis suggests that the stabilization of the ferroelectric order by the Fe dopant originates from the formation of (FeTi′–VO••)• defect dipoles.

Origin of large recoverable strain in 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3 near the ferroelectric-relaxor transition

Piezoceramics of composition 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3 demonstrate large recoverable strain at elevated temperature (T > 75 °C), which is absent at room temperature. In situ neutron diffraction was used to measure changes in the crystallographic and domain structures during electric field application at temperatures ranging from 25 °C to 100 °C. Quantitative evaluation of the ferroelastic domain volume fraction in the field-induced phases enabled calculation of the strain contribution from non-180° domain switching. The large recoverable strain is shown to be associated with the reversible nature of the phase transformation. These findings have implications to additional BNT-xBT-based composition and other relaxor ferroelectrics.

Fatigue-free unipolar strain behavior in CaZrO3 and MnO2 co-modified (K,Na)NbO3-based lead-free piezoceramics

The unipolar fatigue behavior of CaZrO3 and MnO2 co-modified (K,Na,Li)(Nb,Ta)O3 lead-free piezoceramics was investigated systematically. The well-known charge agglomeration model is shown to explain the overall changes observed during unipolar fatigue, such as the development of bias field as well as the anisotropy in bipolar strain hysteresis and field-dependent dielectric permittivity. In addition, it is found that the unipolar strain exhibits only small degradation within 3% at the field amplitude of 2 kV/mm up to 107 cycles. This exceptionally good fatigue resistance is identified due to the presence of additional process, assigned as a “softening” effect that competes against the usual fatigue effect.

Aging of poled ferroelectric ceramics due to relaxation of random depolarization fields by space-charge accumulation near grain boundaries

Migration of charged point defects triggered by the local random depolarization field is shown to plausibly explain aging of poled ferroelectric ceramics providing reasonable time and acceptor concentration dependences of the emerging internal bias field. The theory is based on the evaluation of the energy of the local depolarization field caused by mismatch of the polarizations of neighbor grains. The kinetics of charge migration assumes presence of mobile oxygen vacancies in the material due to the intentional or unintentional acceptor doping. Satisfactory agreement of the theory with experiment on the Fe-doped lead zirconate titanate is demonstrated.

Reduction of the piezoelectric performance in lead-free (1-x)Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 piezoceramics under uniaxial compressive stress

The effect of a uniaxial compressive stress on the properties of BZT-BCT samples across the morphotropic phase boundary (MPB) is investigated using direct piezoelectric coefficient measurements. In contrast to many lead zirconate titanate compositions, the piezoelectric coefficient decreases monotonically with increasing stress and does not show an initial increase or plateau. Electrically softer rhombohedral and MPB compositions are found to be more susceptible to a decrease in piezoelectric coefficient under an increasing pre-stress than tetragonal compositions. Depoling due to ferroelastic domain switching alone, as observed by x-ray diffraction, does not explain this reduction, but instead a decreasing domain wall density is proposed to be responsible for reduced piezoelectric coefficients under increasing compressive stress. The relaxation of the piezoelectric response after complete unloading supports this proposed mechanism.

Two-step polarization reversal in biased ferroelectrics

Polarization reversal in polycrystalline ferroelectrics is shown to occur via two distinct and sequential domain reorientation steps. This reorientation sequence, which cannot be readily discriminated in the overall sample polarization, is made apparent using time-resolved high-energy x-ray diffraction. Upon application of electric fields opposite to the initial poling direction, two unique and significantly different time constants are observed. The first (faster time constant) is shown to be derived by the release of a residual stress due to initial electrical biasing and the second (slower time constant) due to the redevelopment of residual stress during further domain wall motion. A modified domain reorientation model is given that accurately describes the domain volume fraction evolution during the reversal process.

Domain fragmentation during cyclic fatigue in 94%(Bi1/2Na1/2)TiO3-6%BaTiO3

The fatigue of the lead-free piezoceramic 94%(Bi1/2Na1/2)TiO3-6%BaTiO3 was investigated under bipolar electric fields. Degradation of the polarization, strain, and permittivity was measured during the fatigue process, and correlated with structural data measured at incremental points in the fatigue process using neutron diffraction. The results suggest a two-stage fatigue mechanism whereby, following a field-induced phase transformation to a poled ferroelectric state, the domain structure becomes progressively fragmented by a repetitive process of domain wall pinning and subdivision.

Effect of bipolar electric fatigue on polarization switching in lead-zirconate-titanate ceramics

From comparison of experimental results on polarization switching in fresh and electrically fatigued lead-zirconate-titanate (PZT) over a wide range of applied fields and switching times it is concluded that fatigue alters the local field distribution inside the sample due to the generation of discrete defects, such as voids and cracks. Such defects have a strong influence on the overall electric field distribution by their shape and dielectric permittivity. On this hypothesis, a new phenomenological model of polarization switching in fatigued PZT is proposed. The model assumes that the fatigued sample can be composed of different local regions which exhibit different field strengths but otherwise can be considered as unfatigued. Consequently the temporal response of a fatigued sample is assumed to be the superposition of the field-dependent temporal responses of unfatigued samples weighted by their respective volume fraction. A certain part of the volume is excluded from the overall switching process due to the domain pinning even at earlier stages of fatigue, which can be recovered by annealing. Suitability of the proposed model is demonstrated by a good correlation between experimental and calculated data for differently fatigued samples. Plausible cause of the formation of such regions is the generation of defects such as microcracks and the change in electrical properties at imperfections such as pores or voids.

Barrier heights, polarization switching, and electrical fatigue in Pb(Zr,Ti)O3 ceramics with different electrodes

The influence of Pt, tin-doped In2O3, and RuO2 electrodes on the electrical fatigue of bulk ceramic Pb(Zr,Ti)O3 (PZT) has been studied. Schottky barrier heights at the ferroelectric/electrode interfaces vary by more than one electronvolt for different electrode materials and do not depend on crystallographic orientation of the interface. Despite different barrier heights, hysteresis loops of polarization, strain, permittivity, and piezoelectric constant and the switching kinetics are identical for all electrodes. A 20% reduction in polarization after 106 bipolar cycles is observed for all the samples. In contrast to PZT thin films, the loss of remanent polarization with bipolar switching cycles does not significantly depend on the electrode material.

De-aging of Fe-doped lead-zirconate-titanate ceramics by electric field cycling: 180°- vs. non-180° domain wall processes

Acceptor-doped ferroelectrics tend to show pronounced aging behavior. The microscopic effects of aging are commonly related to oxygen vacancies, however, there are still open questions with respect to their impact on domain wall movements. To elucidate the latter, the reverse process of de-aging by electric field cycling is investigated here on Pb(Zr0.54Ti0.46)O3 doped with iron in different concentrations. Measurements of the hysteretic behavior of large-signal parameters, i.e., polarization and strain, as well as small-signal parameters, i.e., electrical permittivity and piezoelectric coefficient, are used to distinguish between reversible and irreversible movement of 180°- and non-180° domain walls. The results indicate that for low doping concentrations, the de-aging behavior of 180° domain wall motion is governed by irreversible domain wall motion and a coarsening of the domain structure, while for non-180° domain walls the change in reversible domain wall mobility is the dominant de-aging mechanism....