Domain-induced control of latent heat in freestanding BaTiO${}_3$ membranes

Abstract

Thin ferroelectric BaTiO${}_3$ films often exhibit continuous transitions instead of the first-order behavior of bulk crystals, a discrepancy usually attributed to epitaxial strain or dimensionality. Using quasi-adiabatic nanocalorimetry on freestanding BaTiO${}_3$ membranes-free of clamping and substrate heat sinking-we show that domain morphology, not thickness or boundary conditions, controls the transition order. Thick membranes with large, monodomain-like regions display clear latent heat, whereas thinner membranes with dense 180${}^{\circ }$ domain patterns show a continuous transition despite undergoing the same tetragonal-cubic structural change confirmed by x-ray diffraction. Piezoresponse force microscopy links this behavior to domain-size evolution, and a Ginzburg-Landau analysis demonstrates how reduced domain size lowers the free-energy barrier, rounding a nominally first-order instability. These results identify domain morphology as the key determinant of ferroelectric transition order in oxide membranes and establish design guidelines for enhancing caloric effects through domain engineering.

13 pages, 8 figures