Electron-phonon interaction contribution to the total energy of group IV semiconductor polymorphs: evaluation and implications

TL;DR

This paper introduces a new electron-phonon interaction correction to total energy calculations in density functional theory, significantly impacting the predicted stability of semiconductor polytypes.

Contribution

It develops and applies a formalism to include electron-phonon interaction corrections in total energy calculations, going beyond the Quasi-Harmonic Approximation.

Findings

EPI corrections significantly affect energy differences between polytypes.

EPI correction confirms the metastability of cubic SiC-3C and stability of hexagonal SiC-4H.

Results align with experimental data on SiC polytypes.

Abstract

In density functional theory (DFT) based total energy studies, the van der Waals (vdW) and zero-point vibrational energy (ZPVE) correction terms are included to obtain energy differences between polymorphs. We propose and compute a new correction term to the total energy, due to electron-phonon interactions (EPI). We rely on Allen's general formalism, which goes beyond the Quasi-Harmonic Approximation (QHA), to include the free energy contributions due to quasiparticle interactions. We show that, for semiconductors and insulators, the EPI contributions to the free energies of electrons and phonons are the corresponding zero-point energy contributions. Using an approximate version of Allen's formalism in combination with the Allen-Heine theory for EPI corrections, we calculate the zero-point EPI corrections to the total energy for cubic and hexagonal polytypes of Carbon, Silicon and Silicon Carbide. The EPI corrections alter the energy differences between polytypes. In SiC polytypes, the EPI correction term is more sensitive to crystal structure than the vdW and ZPVE terms and is thus essential in determining their energy differences. It clearly establishes that the cubic SiC-3C is metastable and hexagonal SiC-4H is the stable polytype. Our results are consistent with the experimental results of Kleykamp. Our study enables the inclusion of EPI corrections as a separate term in the free energy expression. This opens the way to go beyond the QHA by including the contribution of EPI on all thermodynamic properties.