[en] 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.
Research Center/Unit :
PhyTheMa
Disciplines :
Physics
Author, co-author :
Mukherjee, Debangshu; The Pennsylvania State University > Department of Materials Science and Engineering
Prokhorenko, Sergei ; Université de Liège - ULiège > Département de physique > Physique théorique des matériaux
Miao, Leixin; The Pennsylvania State University > Department of Materials Science and Engineering
Wang, Ke; The Pennsylvania State University > Materials Research Institute > Materials Characterization Laboratory
Bousquet, Eric ; Université de Liège - ULiège > Département de physique > Physique théorique des matériaux
Gopalan, Venkatraman; The Pennsylvania State University > Department of Materials Science and Engineering
Alem, Nasim; The Pennsylvania State University > Department of Materials Science and Engineering
Language :
English
Title :
Atomic-scale measurement of polar entropy
Publication date :
03 September 2019
Journal title :
Physical Review. B, Condensed Matter
ISSN :
0163-1829
eISSN :
1095-3795
Publisher :
American Physical Society, United States - Maryland
Volume :
100
Pages :
104102
Peer reviewed :
Peer Reviewed verified by ORBi
Tags :
Tier-1 supercomputer CÉCI : Consortium des Équipements de Calcul Intensif
F.R.S.-FNRS - Fonds de la Recherche Scientifique FWB - Fédération Wallonie-Bruxelles
Funding text :
Céci facilities funded by F.R.S-FNRS (Grant No. 2.5020.1) and Tier-1 supercomputer of the Fédération Wallonie-Bruxelles funded by the Walloon Region (Grant No. 1117545)
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