Adsorption of ammonia at GaN(0001) surface in the mixed ammonia/hydrogen ambient - a summary of ab initio data

TL;DR

This study uses ab initio calculations to analyze ammonia adsorption on GaN(0001) surfaces with mixed coverage, revealing how Fermi level pinning influences dissociative and molecular adsorption energies and configurations.

Contribution

The paper introduces a comprehensive ab initio analysis of ammonia adsorption on GaN(0001), highlighting the role of Fermi level pinning and electron transfer in adsorption mechanisms.

Findings

Adsorption energy depends on Fermi level pinning and charge transfer.

Dissociative adsorption occurs at certain surface regions, molecular at others.

Adsorption configurations vary with surface coverage and Fermi level position.

Abstract

Adsorption of ammonia at NH3/NH2/H covered GaN(0001) surface was analyzed using results of ab initio calculations. The whole configuration space of partially NH3/NH2/H covered GaN(0001) surface was divided into zones differently pinned Fermi level: at Ga broken bond state for dominantly bare surface (region I), at VBM for NH2 and H covered (region II), and at CBM for NH3 covered surface (region III). The extensive ab intio calculations show validity of electron counting rule (ECR) for all mixed coverage, for bordering these three regions. The adsorption was analyzed using newly identified dependence of the adsorption energy on the charge transfer at the surface. For region I and II ammonia adsorb dissociatively, disintegrating into H adatom and HN2 radical for large fraction of vacant sites while for high coverage the ammonia adsorption is molecular. The dissociative adsorption energy strongly depends on the Fermi level at the surface (pinned) and in the bulk (unpinned) while the molecular adsorption energy is determined by bonding to surface only, in accordance to the recently published theory. The molecular adsorption is determined by the energy of covalent bonding to the surface. Ammonia adsorption in region III (Fermi level pinned at CBM) leads to unstable configuration both molecular and dissociative which is explained by the fact that Ga-broken bond sites are doubly occupied by electrons. The adsorbing ammonia brings 8 electrons to the surface, necessitating transfer of the electrons from Ga-broken bond state to Fermi level, energetically costly process. Adsorption of ammonia at H-covered site leads to creation of NH2 radical at the surface and escape of H2 molecule. The process energy is close to 0.12 eV, thus not large, but the inverse process is not possible due to escape of the hydrogen molecule.