Effect of Ligand Polarity on the Internal Dipoles and Ferroelectric Distortion in BaTiO3 Nanocubes
Abstract
Abstract Surface adsorbates and surrounding matrix species have been demonstrated to affect the properties of nanoscale ferroelectrics and nanoscale ferroelectric composites; potentially counteracting performance losses that can occur in small particle sizes. In this work, the effects of nonpolar oleic acid (OA) and polar tetrafluoroborate (BF 4 − ) ligand capping on the surface of various sizes of BaTiO 3 nanocubes have been investigated with combined neutron diffraction and neutron pair distribution function (PDF), density functional theory (DFT), and ab initio molecular dynamics (AIMD) methods. The low real space PDF region provides an unobstructed view of rhombohedral (split short and long) Ti−O distances in BaTiO 3 nanocubes, mimicking the well‐established order‐disorder local structure found in bulk BaTiO 3 . Interestingly, the intermediate‐range order in nanocubes is found to be orthorhombic, rather than tetragonal. It is concluded that polar ligands adsorbed at BaTiO 3 surfaces stabilize the correlation length scale of local rhombohedral distortions in ferroelectric nanoparticles relative to nonpolar ligands.
- Authors:
-
[1];
[1];
[2];
[3];
[4]
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of Tennessee, Knoxville, TN (United States)
- Central Michigan Univ., Mount Pleasant, MI (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Central Michigan University; Research Development and Innovation Funding (Romania)
- OSTI Identifier:
- 1846547
- Alternate Identifier(s):
- OSTI ID: 1781922
- Grant/Contract Number:
- AC05-00OR22725; PN-III−P4-ID-PCCF2016-0175; KC040602
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Volume: 27; Journal Issue: 32; Journal ID: ISSN 0947-6539
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ab initio calculations; ferroelectric distortion; local correlation; nanocubes; neutron total scattering
Citation Formats
Jiang, Bo, Usher-Ditzian, Tedi-Marie, Jothi, Palani Raja, Kavey, Benard, Caruntu, Gabriel, and Page, Katharine L. Effect of Ligand Polarity on the Internal Dipoles and Ferroelectric Distortion in BaTiO3 Nanocubes. United States: N. p., 2021.
Web. doi:10.1002/chem.202100692.
Jiang, Bo, Usher-Ditzian, Tedi-Marie, Jothi, Palani Raja, Kavey, Benard, Caruntu, Gabriel, & Page, Katharine L. Effect of Ligand Polarity on the Internal Dipoles and Ferroelectric Distortion in BaTiO3 Nanocubes. United States. https://doi.org/10.1002/chem.202100692
Jiang, Bo, Usher-Ditzian, Tedi-Marie, Jothi, Palani Raja, Kavey, Benard, Caruntu, Gabriel, and Page, Katharine L. Mon .
"Effect of Ligand Polarity on the Internal Dipoles and Ferroelectric Distortion in BaTiO3 Nanocubes". United States. https://doi.org/10.1002/chem.202100692. https://www.osti.gov/servlets/purl/1846547.
@article{osti_1846547,
title = {Effect of Ligand Polarity on the Internal Dipoles and Ferroelectric Distortion in BaTiO3 Nanocubes},
author = {Jiang, Bo and Usher-Ditzian, Tedi-Marie and Jothi, Palani Raja and Kavey, Benard and Caruntu, Gabriel and Page, Katharine L.},
abstractNote = {Abstract Surface adsorbates and surrounding matrix species have been demonstrated to affect the properties of nanoscale ferroelectrics and nanoscale ferroelectric composites; potentially counteracting performance losses that can occur in small particle sizes. In this work, the effects of nonpolar oleic acid (OA) and polar tetrafluoroborate (BF 4 − ) ligand capping on the surface of various sizes of BaTiO 3 nanocubes have been investigated with combined neutron diffraction and neutron pair distribution function (PDF), density functional theory (DFT), and ab initio molecular dynamics (AIMD) methods. The low real space PDF region provides an unobstructed view of rhombohedral (split short and long) Ti−O distances in BaTiO 3 nanocubes, mimicking the well‐established order‐disorder local structure found in bulk BaTiO 3 . Interestingly, the intermediate‐range order in nanocubes is found to be orthorhombic, rather than tetragonal. It is concluded that polar ligands adsorbed at BaTiO 3 surfaces stabilize the correlation length scale of local rhombohedral distortions in ferroelectric nanoparticles relative to nonpolar ligands.},
doi = {10.1002/chem.202100692},
journal = {Chemistry - A European Journal},
number = 32,
volume = 27,
place = {United States},
year = {Mon Apr 05 00:00:00 EDT 2021},
month = {Mon Apr 05 00:00:00 EDT 2021}
}
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