Nanoscale ordering of planar octupolar molecules for nonlinear optics at higher temperatures

TL;DR

This paper explores how to achieve orientational ordering of octupolar molecules at higher temperatures for nonlinear optical applications, using statistical models and different poling scenarios, to enhance NLO signals at room temperature.

Contribution

It introduces models for orientational ordering of octupolar molecules at elevated temperatures, analyzing poling mechanisms and estimating nonlinear susceptibilities for potential room-temperature NLO use.

Findings

Weak octupolar order emerges at Helium temperatures.

Strong electric fields are needed for dipoling at Nitrogen temperatures.

Modifications like increasing octupole size can raise poling temperature.

Abstract

We develop scenarios for orientational ordering of an in-plane system of small flat octupolar molecules at the low-concentration limit, aiming towards nonlinear-optical (NLO) applications at room temperatures. The octupoles interact with external electric poling fields and intermolecular interactions are neglected. Simple statistical-mechanics models are used to analyze the orientational order in the very weak poling limit, sufficient for retrieving the NLO signals owing to the high sensitivity of NLO detectors and measurement chains. Two scenarios are discussed. Firstly, the octupolar poling field is imparted by a system of point charges; the setup is subject to cell-related constraints imposed by mechanical strength and dielectric breakdown limit. The very weak octupolar order of benchmarking TATB molecules is shown to emerge at Helium temperatures. The second scenario addresses the dipoling of octupolar molecules with a small admixture of electric dipolar component. It requires a strong field regime to become effective at Nitrogen temperature range. An estimation of the nonlinear susceptibility coefficient matrix for both scenarios is done in the high-temperature (weak interaction) limit formalism. We argue that moderate modifications of the system like, e.g., an increase of the size of the octupole, accompanied by dipole-assisted octupoling, can increase the poling temperature above Nitrogen temperatures.