Effects of surface vibrations on interlayer mass transport: Ab initio molecular dynamics investigation of Ti adatom descent pathways and rates from TiN/TiN(001) islands

We carried out density-functional ab initio molecular dynamics (AIMD) simulations of Ti adatom (T i_ad ) migration on, and descent from, square TiN 〈100 〉 epitaxial islands on TiN(001) at temperatures (T ) ranging from 1200 to 2400 K. Adatom-descent energy barriers determined via ab initio nudged-elastic-band calculations at 0 Kelvin suggest that Ti interlayer transport on TiN(001) occurs essentially exclusively via direct hopping onto a lower layer. However, AIMD simulations reveal comparable rates for T i_ad descent via direct hopping vs push-out/exchange with a Ti island-edge atom for T ≥1500 K . We demonstrate that this effect is due to surface vibrations, which yield considerably lower activation energies at finite temperatures by significantly modifying the adatom push-out/exchange reaction pathway.