Phase transition behavior of Pb(Hf, Sn, Ti, Nb)O₃ ceramics at morphotropic phase boundary

Abstract

The phase transition and dielectric properties of Pb0.988(Hf0.945SnxTi0.03‐xNb0.025)O3 ceramics (0 ≤ x ≤ 0.03, correspondingly abbreviated as H1, H2, H3, and H4) at the morphotropic phase boundary were systematically investigated. X‐ray diffraction results and P‐E hysteresis loops show that the dominate orthorhombic antiferroelectric phase and a small amount of the tetragonal FE phase coexist in Pb0.988(Hf0.945SnxTi0.03‐xNb0.025)O3 ceramics. As the Sn content increases, the antiferroelectricity is significantly enhanced, accompanied with an increased Curie temperature and sharply reduced peak dielectric constant. H1 and H2 experience an irreversible field‐induced AFE‐FE phase transition at the ambient temperature, and the transition from a metastable FE phase to the original AFE phase is observed in H2 when heated to 60°C. H3 and H4 experience an invertible AFE‐FE phase transition, along with an enhanced forward phase switching field EF. Moreover a decreased backward phase switching field EA for H4 is detected as the electric field increases due to the AFE/FE coexistence. These results reveal the unique phase transition characteristics of AFE materials near the phase boundary, which is helpful for better understanding of AFE/FE materials.

Decoding the Double/Multiple Hysteresis Loops in Antiferroelectric Materials

“…and/or B-site doping (Sn 4+ , Ti 4+ , Nb 5+ , etc. ), − and is classified roughly into two categories, namely double and multiple hysteresis loops, respectively, in terms of reversible phase transitions. ,− The two kinds of P–E loops exhibit remarkable differences in the energy-storage performance. As can be seen in Figure a,b, those compositions (circled ones) with multiple hysteresis loops always have superior energy-storage performance to the compositions exhibiting double hysteresis loops (uncircled ones).…”

Investigation on antiferroelectricity of Pb0.97La0.02(Hf1−xTix)O3ceramics with low Ti content (0 ≤ x ≤ 0.1)

“…23 Yang et al investigated the phase transition and dielectric properties of Pb 0.988 (Hf 0.945 Sn x Ti 0.03−x Nb 0.025 )O 3 ceramics (0 ≤ x ≤ 0.03) at the morphotropic phase boundary (MPB) and found the Sn content enhanced the antiferroelectricity. 24 Ge et al fabricated PbHf 1−x Sn x O 3 (PHS) AFE ceramics, and the double P-E loop was modified via the variation of Sn content. In the composition with x = 0.07, a high recoverable energy storage density of 10.2 ± 0.4 J/cm 3 with a high energy efficiency of 78.9% is achieved at 320 kV/cm.…”

“…Yang et al. investigated the phase transition and dielectric properties of Pb 0.988 (Hf 0.945 Sn x Ti 0.03− x Nb 0.025 )O 3 ceramics (0 ≤ x ≤ 0.03) at the morphotropic phase boundary (MPB) and found the Sn content enhanced the antiferroelectricity 24 . Ge et al.…”

High‐temperature dielectric properties and impedance spectroscopy of PbHf1−xSnxO3ceramics

“…It is reported that PbHfO 3 single crystal undergoes two structural transformations in broad frequency and temperature range: at about 163°C from the antiferroelectric (AFE1) to another intermediate antiferroelectric phase (AFE2) and at about 209°C from the AFE2 to the paraelectric (PE) phase [5, 12]. For more profound research, researchers are usually doping different ions to improve the dielectric properties of PbHfO 3 , such as Ti‐doped PbHfO 3 antiferroelectric crystals [13], (1− x )PbSc 0.5 Ta 0.5 O 3 –( x )PbHfO 3 ceramics [14], PbHfO 3 –BaHfO 3 and PbHfO 3 –SrHfO 3 [15] and so on. In comparison with PbHfO 3 single crystal, phase‐transition temperatures of PbHf 1− x Sn x O 3 (PSH, with x = 0.025) single crystal showed a slight decrease and reached about 153 and 201°C, respectively, for AFE1 to AFE2 phase and AFE2 to PE phase [5].…”

“…Considering the excellent characteristics of PSH single crystal, we conducted PSH ceramics as our research. In previous work, both Ti‐doped [13] and Sn‐doped [6] PbHfO 3 crystals show excellent FE and antiferroelectric properties due to Sn or Ti doping plays a crucial role in changing properties of PbHfO 3 , especially in structural phase transitions. Fan et al reported a new cloverleaf AFE domain structure in PbHfO 3 ceramics.…”