Electrodynamic Response of the Charge Ordering Phase: Dielectric and Optical Studies of alpha-(BEDT-TTF)2I3

TL;DR

This study investigates the anisotropic dielectric and optical responses of alpha-(BEDT-TTF)2I3 across its charge-ordered transition, revealing charge dynamics, gap formation, and relaxation modes linked to charge density waves and domain-wall motions.

Contribution

It provides detailed experimental insights into the charge and lattice dynamics of alpha-(BEDT-TTF)2I3, highlighting the nature of charge order and associated excitations with novel dielectric relaxation modes.

Findings

Charge order onset at 136 K evidenced by vibrational splitting.

An isotropic optical gap of ~75 meV opens below TCO.

Two dielectric relaxation modes linked to charge density wave and domain walls.

Abstract

We report on the anisotropic response, the charge and lattice dynamics of normal and charge-ordered phases with horizontal stripes in single crystals of the organic conductor alpha-(BEDT-TTF)2I3 determined by dc resistivity, dielectric and optical spectroscopy. An overdamped Drude response and a small conductivity anisotropy observed in optics is consistent with a weakly temperature dependent dc conductivity and anisotropy at high temperatures. The splitting of the molecular vibrations nu27(Bu) evidences the abrupt onset of static charge order below TCO=136 K. The drop of optical conductivity measured within the ab plane of the crystal is characterized by an isotropic gap that opens of approximately 75 meV with several phonons becoming pronounced below. Conversely, the dc conductivity anisotropy rises steeply, attaining at 50 K a value 25 times larger than at high temperatures. The dielectric response within this plane reveals two broad relaxation modes of strength Deltaepsilon_LD ~= 5000 and Deltaepsilon_SD ~= 400, centered at 1 kHz < f_LD < 100 MHz and f_SD ~= 1 MHz. The anisotropy of the large-mode (LD) mean relaxation time closely follows the temperature behavior of the respective dc conductivity ratio. We argue that this phason-like excitation is best described as a long-wavelength excitation of a 2kF bond-charge density wave expected theoretically for layered quarter-filled electronic systems with horizontal stripes. Conversely, based on the theoretically expected ferroelectric-like nature of the charge-ordered phase, we associate the small-mode (SD) relaxation with the motion of domain-wall pairs, created at the interface between two types of domains, along the a and b axes. We also consider other possible theoretical interpretations and discuss their limitations.