Size effect on the thermal conductivity of a type-I clathrate

TL;DR

This study demonstrates that reducing the size of a type-I clathrate to mesoscopic wire scales significantly lowers its phonon thermal conductivity, enhancing its potential for thermoelectric applications.

Contribution

It introduces a top-down fabrication method to create mesoscopic wires of a type-I clathrate and confirms size-dependent thermal conductivity reduction at room temperature.

Findings

40% reduction in thermal conductivity for 630 nm wires at room temperature

Size effects influence phonon transport in clathrate wires

Size reduction affects low-energy rattling modes and acoustic phonons

Abstract

Clathrates are a materials class with an extremely low phonon thermal conductivity, which is a key ingredient for a high thermoelectric conversion efficiency. Here, we present a study on the type-I clathrate La$_{1.2}$Ba$_{6.8}$Au$_{5.8}$Si$_{38.8}\square_{1.4}$ directed at lowering the phonon thermal conductivity even further by forming mesoscopic wires out of it. Our hypothesis is that the interaction of the low-energy rattling modes of the guest atoms (La and Ba) with the acoustic modes, which originate mainly from the type-I clathrate framework (formed by Au and Si atoms, with some vacancies $\square$), cuts off their dispersion and thereby tilts the balance of phonons relevant for thermal transport to long-wavelength ones. Thus, size effects are expected to set in at relatively long length scales. The structuring was carried out using a top-down approach, where the wires, ranging from 1260 nm to 630 nm in diameter, were cut from a piece of single crystal using a focused ion beam technique. Measurements of the thermal conductivity were performed with a self-heating $3\omega$ technique down to 80 K. Indeed, they reveal a reduction of the room-temperature phonon thermal conductivity by a sizable fraction of $\sim$40 % for our thinnest wire, thereby confirming our hypothesis.