TY - JOUR

T1 - Impact of d‑states on transition metal impurity diffusion in TiN

AU - Nayak, Ganesh Kumar

AU - Holec, David

AU - Zelený, Martin

N1 - Publisher Copyright: © 2023, The Author(s).

PY - 2023/5/22

Y1 - 2023/5/22

N2 - In this work, we studied the energetics of diffusion-related quantities of transition-metal impurities in TiN, a prototype ceramic protective coating. We use ab-initio calculations to construct a database of impurity formation energies, vacancy-impurity binding energies, migration, and activation energies of 3d and selected 4d and 5d elements for the vacancy-mediated diffusion process. The obtained trends suggest that the trends in migration and activation energies are not fully anti-correlated with the size of the migration atom. We argue that this is caused by a strong impact of chemistry in terms of binding. We quantified this effect for selected cases using the density of electronic states, Crystal Orbital Hamiltonian Population analysis, and charge density analysis. Our results show that the bonding of impurities in the initial state of a diffusion jump (equilibrium lattice position), as well as the charge directionality at the transition state (energy maximum along the diffusion jump pathway), significantly impact the activation energies.

AB - In this work, we studied the energetics of diffusion-related quantities of transition-metal impurities in TiN, a prototype ceramic protective coating. We use ab-initio calculations to construct a database of impurity formation energies, vacancy-impurity binding energies, migration, and activation energies of 3d and selected 4d and 5d elements for the vacancy-mediated diffusion process. The obtained trends suggest that the trends in migration and activation energies are not fully anti-correlated with the size of the migration atom. We argue that this is caused by a strong impact of chemistry in terms of binding. We quantified this effect for selected cases using the density of electronic states, Crystal Orbital Hamiltonian Population analysis, and charge density analysis. Our results show that the bonding of impurities in the initial state of a diffusion jump (equilibrium lattice position), as well as the charge directionality at the transition state (energy maximum along the diffusion jump pathway), significantly impact the activation energies.

UR - http://www.scopus.com/inward/record.url?scp=85160070855&partnerID=8YFLogxK

U2 - 10.1038/s41598-023-34768-7

DO - 10.1038/s41598-023-34768-7

M3 - Article

VL - 2023

JO - Scientific reports (London : Nature Publishing Group)

JF - Scientific reports (London : Nature Publishing Group)

SN - 2045-2322

IS - 13

M1 - 8244

ER -