Effect of Ligand Polarity on the Internal Dipoles and Ferroelectric Distortion in BaTiO3 Nanocubes

Jiang, Bo; Usher-Ditzian, Tedi-Marie; Jothi, Palani Raja; Kavey, Benard; Caruntu, Gabriel; Page, Katharine L.

doi:10.1002/chem.202100692

Effect of Ligand Polarity on the Internal Dipoles and Ferroelectric Distortion in BaTiO₃ Nanocubes

Journal Article · Mon Apr 05 00:00:00 EDT 2021 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.202100692· OSTI ID:1846547

^[1]; ^[1]; ^[2]; Kavey, Benard ^[3]; ^[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)

Here, 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 (BF₄^-) ligand capping on the surface of various sizes of BaTiO₃ 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 BaTiO₃ nanocubes, mimicking the well-established order-disorder local structure found in bulk BaTiO₃. Interestingly, the intermediate-range order in nanocubes is found to be orthorhombic, rather than tetragonal. It is concluded that polar ligands adsorbed at BaTiO₃ surfaces stabilize the correlation length scale of local rhombohedral distortions in ferroelectric nanoparticles relative to nonpolar ligands.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: Central Michigan University; Research Development and Innovation Funding (Romania); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1846547

Alternate ID(s):: OSTI ID: 1781922

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 32 Vol. 27; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Effect of Ligand Polarity on the Internal Dipoles and Ferroelectric Distortion in BaTiO3 Nanocubes

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Effect of Ligand Polarity on the Internal Dipoles and Ferroelectric Distortion in BaTiO₃ Nanocubes