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

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