Enhanced Born Charge and Proximity to Ferroelectricity in Thallium Halides

TL;DR

This study reveals that thallium halides exhibit giant Born effective charges and are close to ferroelectric instability, which may enhance their electronic properties and suitability for radiation detection applications.

Contribution

The paper demonstrates that thallium halides have significantly enhanced Born charges due to hybridization, bringing them near ferroelectricity, a novel insight into their electronic structure.

Findings

Born effective charges are over twice the nominal ionic charges.

Lattice polarization occurs with 2% lattice expansion.

Thallium halides are close to ferroelectric instability.

Abstract

Electronic structure and lattice dynamics calculations on thallium halides show that the Born effective charges in these compounds are more than twice larger than the nominal ionic charges. This is a result of cross-band-gap hybridization between Tl-p and halogen-p states. The large Born charges cause giant splitting between longitudinal and transverse optic phonon modes, bringing the lattice close to ferroelectric instability. Our calculations indeed show spontaneous lattice polarization upon lattice expansion starting at 2%. It is remarkable that the apparently ionic thallium halides with a simple cubic CsCl structure and large differences in electronegativity between cations and anions can be very close to ferroelectricity. This can lead to effective screening of defects and impurities that would otherwise be strong carrier traps and may therefore contribute to the relatively good carrier transport properties in TlBr radiation detectors.