Exploring the Morphotropic Phase Boundary in Epitaxial PbHf 1 − x Ti x O 3 Thin Films

: Epitaxial PbHf 1 − x Ti x O 3 /SrTiO 3 (001) thin-film heterostructures are studied for a potential morphotropic phase boundary (MPB) akin to that in the PbZr 1 − x Ti x O 3 system. End members, PbHfO 3 and PbTiO 3 , were found to possess orthorhombic ( Pbam ) and tetragonal ( P 4 mm ) crystal structures and antiferroelectric and ferroelectric ( ∼ 87 μ C/cm 2 ) behavior, respectively. PbHf 0.75 Ti 0.25 O 3 and PbHf 0.25 Ti 0.75 O 3 solid solutions were both found to be ferroelectric with rhombohedral ( R 3 c , ∼ 22 μ C/cm 2 ) and tetragonal ( P 4 mm , ∼ 46 μ C/ cm 2 ) structures, respectively. For intermediate PbHf 1 − x Ti x O 3 compositions (e.g., x = 0.4, 0.45, 0.5, and 0.55), a structural transition was observed from rhombohedral (hafnium-rich) to tetragonal (titanium-rich) phases. These intermediate compositions also exhibited mixed-phase structures including R 3 c , monoclinic ( Cm ), and P 4 mm symmetries and, in all cases, were ferroelectric with remanent (5 − 22 μ C/cm 2 ) and saturation (18.5 − 36 μ C/cm 2 ) polarization and coercive field (24 − 34.5 kV/cm) values increasing with x . While the dielectric constant was the largest for PbHf 0.6 Ti 0.4 O 3 , the MPB is thought to be near x = 0.5 after separation of the intrinsic and extrinsic contributions to the dielectric response. Furthermore, piezoelectric displacement − voltage hysteresis loops were obtained for all chemistries revealing displacement values as good as PbZr 0.52 Ti 0.48 O 3 films in the same geometry. Thereby, the PbHf 1 − x Ti x O 3 system is a viable alternative to the PbZr 1 − x Ti x O 3 system offering comparable performance.

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