Entropy is a fundamental thermodynamic quantity that is a measure of the accessible microstates available to a system, with the stability of a system determined by the magnitude of the total entropy of the system. This is valid across truly mind boggling length scales, from nanoparticles to galaxies. However, quantitative measurements of entropy change using calorimetry are predominantly macroscopic, with direct atomic-scale measurements being exceedingly rare. Here, we experimentally quantify the polar configurational entropy (in meV/K) using sub-angstrom resolution aberration corrected scanning transmission electron microscopy in a single crystal of the prototypical ferroelectric LiNbO3 through the quantification of the niobium and oxygen atom column deviations from their paraelectric positions. Significant excursions of the niobium-oxygen polar displacement away from its symmetry-constrained direction are seen in single domain regions which increase in the proximity of domain walls. Combined with first-principles theory plus mean field effective Hamiltonian methods, we demonstrate the variability in the polar order parameter, which is stabilized by an increase in the magnitude of the configurational entropy. This study presents a powerful tool to quantify entropy from atomic displacements and demonstrates its dominant role in local symmetry breaking at finite temperatures in classic, nominally Ising ferroelectrics.
All Science Journal Classification (ASJC) codes
- Electronic, Optical and Magnetic Materials
- Condensed Matter Physics