Clamping enables enhanced electromechanical responses in antiferroelectric thin films.

Thin-film materials with large electromechanical responses are fundamental enablers of next-generation micro-/nano-electromechanical applications. Conventional electromechanical materials (for example, ferroelectrics and relaxors), however, exhibit severely degraded responses when scaled down to submicrometre-thick films due to substrate constraints (clamping). This limitation is overcome, and substantial electromechanical responses in antiferroelectric thin films are achieved through an unconventional coupling of the field-induced antiferroelectric-to-ferroelectric phase transition and the substrate constraints. A detilting of the oxygen octahedra and lattice-volume expansion in all dimensions are observed commensurate with the phase transition using operando electron microscopy, such that the in-plane clamping further enhances the out-of-plane expansion, as rationalized using first-principles calculations. In turn, a non-traditional thickness scaling is realized wherein an electromechanical strain (1.7%) is produced from a model antiferroelectric PbZrO3 film that is just 100 nm thick. The high performance and understanding of the mechanism provide a promising pathway to develop high-performance micro-/nano-electromechanical systems.

Exploring the Pb1- x Srx HfO3 System and Potential for High Capacitive Energy Storage Density and Efficiency.

The hafnate perovskites PbHfO3 (antiferroelectric) and SrHfO3 ("potential" ferroelectric) are studied as epitaxial thin films on SrTiO3 (001) substrates with the added opportunity of observing a morphotropic phase boundary (MPB) in the Pb1- x Srx HfO3 system. The resulting (240)-oriented PbHfO3 (Pba2) films exhibited antiferroelectric switching with a saturation polarization ≈53 µC cm-2 at 1.6 MV cm-1 , weak-field dielectric constant ≈186 at 298 K, and an antiferroelectric-to-paraelectric phase transition at ≈518 K. (002)-oriented SrHfO3 films exhibited neither ferroelectric behavior nor evidence of a polar P4mm phase . Instead, the SrHfO3 films exhibited a weak-field dielectric constant ≈25 at 298 K and no signs of a structural transition to a polar phase as a function of temperature (77-623 K) and electric field (-3 to 3 MV cm-1 ). While the lack of ferroelectric order in SrHfO3 removes the potential for MPB, structural and property evolution of the Pb1- x Srx HfO3 (0 ≤ x < 1) system is explored. Strontium alloying increased the electric-breakdown strength (EB ) and decreased hysteresis loss, thus enhancing the capacitive energy storage density (Ur ) and efficiency (η). The composition, Pb0.5 Sr0.5 HfO3 produced the best combination of EB  = 5.12 ± 0.5 MV cm-1 , Ur  = 77 ± 5 J cm-3 , and η = 97 ± 2%, well out-performing PbHfO3 and other antiferroelectric oxides.