Piezoelectric nonlinearity and frequency dispersion of the direct piezoelectric response of BiFeO3 ceramics

We report on the frequency and stress dependence of the direct piezoelectric d33 coefficient in BiFeO3 ceramics. The measurements reveal considerable piezoelectric nonlinearity, i.e., dependence of d33 on the amplitude of the dynamic stress. The nonlinear response suggests a large irreversible contribution of non-180{\deg} domain walls to the piezoelectric response of the ferrite, which, at present measurement conditions, reached a maximum of 38% of the total measured d33. In agreement with this interpretation, both types of non-180{\deg} domain walls, characteristic for the rhombohedral BiFeO3, i.e., 71{\deg} and 109{\deg}, were identified in the poled ceramics using transmission electron microscopy (TEM). In support to the link between nonlinearity and non-180{\deg} domain wall contribution, we found a correlation between nonlinearity and processes leading to deppining of domain walls from defects, such as quenching from above the Curie temperature and high-temperature sintering. In addition, the nonlinear piezoelectric response of BiFeO3 showed a frequency dependence that is qualitatively different from that measured in other nonlinear ferroelectric ceramics, such as "soft" (donor-doped) Pb(Zr,Ti)O3 (PZT); possible origins of this dispersion are discussed. Finally, we show that, once released from pinning centers, the domain walls can contribute extensively to the electromechanical response of BiFeO3; in fact, the extrinsic domain-wall contribution is relatively as large as in Pb-based ferroelectric ceramics with morphotropic phase boundary (MPB) composition, such as PZT. This finding might be important in the search of new lead-free MPB compositions based on BiFeO3 as it suggests that such compositions might also exhibit large extrinsic domain-wall contribution to the piezoelectric response.Comment: 38 pages, 11 figure

Role of charged defects on the electrical and electromechanical properties of rhombohedral Pb(Zr,Ti)O3 with oxygen octahedra tilts

Oxygen octahedra tilting is a common structural phenomenon in perovskites and has been subject of intensive studies, particularly in rhombohedral Pb(Zr,Ti)O3 (PZT). Early reports suggest that the tilted octahedra may strongly affect the domain switching behavior as well as the dielectric and piezoelectric properties of PZT ceramics. In a way similar to that proposed for tilts, however, charged defects, associated with oxygen vacancies, may also inhibit the motion of the domain walls, resulting macroscopically in pinched hysteresis loops and reduced piezoelectric response. Here, we revisit the early studies on rhombohedral PZT ceramics with tilted octahedra by considering a possible role of both tilts and charged defects on domain-wall motion. We show that the observed pinched hysteresis loops are likely associated with the presence of defect complexes containing charged oxygen vacancies, and not tilts, as suggested in some cases. Regardless of the presence or absence of long-range ordered tilts in rhombohedral PZT, the effect of charged defects is also prominent in weak-field permittivity and piezoelectric properties, particularly at sub-Hertz driving conditions where the conductivity, related to the motion of oxygen vacancies, gives rise to strong frequency dispersion

Structure and Dynamics of Ferroelectric Domains in Polycrystalline Pb(Fe_1/2Nb_1/2)O₃

A complex domain structure with variations in the morphology is observed at ambient temperature in monoclinic Pb(Fe1/2Nb1/2)O3. Using electron microscopy and piezoresponse force microscopy, it is possible to reveal micrometre-sized wedge, lamellar-like, and irregularly shaped domains. By increasing the temperature, the domain structure persists up to 80 °C, and then starts to disappear at around 100 °C due to the proximity of the ferroelectric–paraelectric phase transition, in agreement with macroscopic dielectric measurements. In order to understand to what degree domain switching can occur in the ceramic, the mobility of the domain walls was studied at ambient temperature. The in situ poling experiment performed using piezoresponse force microscopy resulted in an almost perfectly poled area, providing evidence that all types of domains can be easily switched. By poling half an area with 20 V and the other half with −20 V, two domains separated by a straight domain wall were created, indicating that Pb(Fe1/2Nb1/2)O3 is a promising material for domain-wall engineering

Construction and Functionality of a Ceramic Resonant Pressure Sensor for Operation at Elevated Temperatures

Piezoelectric ceramic resonant pressure sensors have shown potential as sensing elements for harsh environments, such as elevated temperatures. For operating temperatures exceeding ~250 °C, conventional and widely used Pb(Zr,Ti)O3 (PZT) piezoelectrics should be replaced. Here, a ceramic pressure sensor from low-temperature co-fired ceramics (LTCC) was constructed by integrating a piezoelectric actuator made from bismuth ferrite (BiFeO3) on a diaphragm. This ferroelectric material was selected because of its high Curie temperature (TC = 825 °C) and as a lead-free piezoelectric extensively investigated for high-temperature applications. In order to construct a sensor with suitable pressure sensitivity, numerical simulations were used to define the optimum construction dimensions. The functionality of the pressure sensor was tested up to 201 °C. The measurements confirmed a pressure sensitivity, i.e., resonance frequency shift of the sensor per unit of pressure, of −8.7 Hz/kPa up to 171 °C. It was suggested that the main reason for the hindered operation at the elevated temperatures could lie in the thermo-mechanical properties of the diaphragm and the adhesive bonding at the actuator-diaphragm interconnection

Nanocrystalline cobalt-oxide powders by solution-combustion synthesis and their application in chemical sensors

The present study demonstrates the relationship between the combustion reaction mechanism induced by the exothermicity of the cobalt nitrate-glycine solution-combustion reactions and morphological details of the nanocrystalline Co3O4. The thermal decomposition pathway and the amount of the heat liberated in combustion are defined by the exothermic reaction between gaseous NH3 and N2O species. A direct evidence that the exothermicity of the combustion reaction plays an important role in formation of the powders with different morphology was obtained from the scanning and transmission electron microscopies. In contrast to stoichiometric reaction, where the short-string Co3O4 particles form hard agglomerates, the energetically softer 50% fuel lean reaction is responsible for weak bonds between Co3O4 particles and formation of the loose cauliflower-like agglomerates. The latter powder with the specific surface area of 64.4 m(2)/g and the average crystallite size of similar to 11 nm was used for the processing of drop-coated sensors, which showed a superior sensor response toward 20 ppm of acetone in 25% r.h. humidity and at low operating temperature of 150 degrees C

Determining the stoichiometry of (K,Na)NbO(3) using optimized energy-dispersive x-ray spectroscopy and electron energy-loss spectroscopy analyses in a transmission electron microscope

This paper describes an optimized analytical procedure for determining the composition of alkaline niobate-based lead-free piezoceramics by energy-dispersive X-ray spectroscopy (EDXS) in a transmission electron microscope (TEM). To discriminate the material-specific composition from the artifacts introduced during the EDXS/TEM analyses, the effects of radiation damage and the absorption of the characteristic X-ray lines were studied in detail. The optimized, quantitative EDXS analysis was tested on sodium potassium niobate with the nominal composition K(0.5)Na(0.5)NbO(3) (KNN) by applying KNbO(3) and NaNbO(3) as standards. The results obtained indicate that KNbO(3) is more radiation sensitive than NaNbO(3). A similar degradation was confirmed in KNN, where the loss of potassium was higher than that of sodium. In addition, the degradation of the KNN was associated with a severe oxygen loss and the reduction of niobium. To achieve highly reliable, quantitative analyses and to preserve good counting statistics, the optimum conditions for the EDXS/TEM analyses were found at an electron dose rate of 0.4 pA/nm(2) and an acquisition time of around 200 s in the specimen thickness range between 30 and 200 nm

Magnetic contributions in multiferroic gadolinium modified bismuth ferrite ceramics

Bi0.88Gd0.12FeO3 multiferroics are of interest for next-generation electronics and are shown with a remnant magnetization 0.2 emu·g−1, coercive field 8 kOe, Curie temperature 370 °C and magnetization of 0.7 emu·g−1 at magnetic fields 30 kOe. Scanning probe microscopy confirmed the intrinsic multiferroicity in the perovskite phase with coexistence of ferroelectric/ferroelastic and ferromagnetic domain structures. Strong magnetic hysteresis was produced by thermal cycling to 1000 °C due to degeneration of the perovskite phase into iron oxide inclusions, highlighting the importance of processing, thermal history and thermodynamic stability for minimizing the amount of parasitic magnetic secondary phases