Direct visualization of polaron formation in the thermoelectric SnSe

TL;DR

This study visualizes polaron formation in SnSe, revealing how strong electron-phonon coupling influences carrier localization and contributes to its high thermoelectric efficiency.

Contribution

It provides direct experimental evidence of polaron formation and anisotropic electron-phonon interactions in SnSe, a key factor in its thermoelectric performance.

Findings

Large quasi-1D polarons form within 300 fs

Smaller 3D polarons develop over 4 ps

Strong anisotropic electron-phonon coupling influences carrier localization

Abstract

SnSe is a layered material that currently holds the record for bulk thermoelectric efficiency. The primary determinant of this high efficiency is thought to be the anomalously low thermal conductivity resulting from strong anharmonic coupling within the phonon system. Here we show that the nature of the carrier system in SnSe is also determined by strong coupling to phonons by directly visualizing polaron formation in the material. We employ ultrafast electron diffraction and diffuse scattering to track the response of phonons in both momentum and time to the photodoping of free carriers across the bandgap, observing the bimodal and anisotropic lattice distortions that drive carrier localization. Relatively large (\SI{18.7}{\angstrom}), quasi-1D polarons are formed on the \SI{300}{\femto\second} timescale with smaller (\SI{4.2}{\angstrom}) 3D polarons taking an order of magnitude longer (\SI{4}{\pico\second}) to form. This difference appears to be a consequence of the profoundly anisotropic electron-phonon coupling in SnSe, with strong Fr\"ohlich coupling only to zone center polar optical phonons. These results demonstrate that carriers in SnSe at optimal doping levels results in a high polaron density and that strong electron-phonon coupling is also critical to the thermoelectric performance of this benchmark material and potentially high-performance thermoelectrics more generally.