Pb()O3-type Perovskites: Part II. Short-range Order Parameter as a Criterion of the Distinction Between Relaxor and Normal Ferroelectrics

A classification scheme of Pb()O3-type perovskites with respect to the B-site order parameters was proposed based on the theoretical calculation of the short-range order parameter (σ) using the pair-correlation model. The calculated order parameters predict that a Pb()O3-type perovskite without any charge difference between B′ and B″ cations [e.g., Pb(Zr1/2Ti1/2)O3 (PZT)] is represented by a completely disordered state with the absence of a finite coherence length. On the other hand, a Pb()O3-type perovskite system having different ionic charges is characterized either by the short-range ordering with a nanoscale coherence length or by the macroscopic long-range ordering, depending on the magnitude of ionic charge difference between B′ and B″ ions. The normal ferroelectricity in Pb()O3-type complex perovskites was then correlated either with a completely disordered state (σ = 0) or with a perfectly ordered state (σ = 0), whereas the relaxor behavior was attributed to the nanoscale short-range ordering (0 < σ < 1) in the configuration of the B-site cations.