Defect energy formalism for CALPHAD thermodynamics of dilute point defects: Theory

Abstract

The thermodynamics of point defects is crucial for determining the functional properties of materials. Defect stability is typically assessed using grand-canonical defect formation energy, which requires deducing the equilibrium chemical potential or Fermi level. This process is complicated by the interplay of chemical potential and Fermi level and their dependence on composition and temperature. The grand-canonical formation energy is added to the bulk Gibbs energy, creating a defect-centric framework where each new defect state needs a distinct Gibbs energy formulation. The CALPHAD method offers a more flexible alternative by integrating defect energies into the total Gibbs energy model, allowing easier extrapolation to complex compositions. CALPHAD unifies the analysis of chemically and electronically driven defects using chemical composition as the primary variable. However, the Compound Energy Formalism (CEF) used in CALPHAD has limitations, such as a lack of clear connections between defect formation energies and Gibbs energy parameters and an exponential increase in complexity with added chemical or charge variations. We present the theoretical derivation of the Defect Energy Formalism (DEF), which overcomes CEF limitations by establishing explicit relationships between absolute defect energies - independent of chemical potential and Fermi level - and the Gibbs energy parameters of defective compounds. This results in a first-principles model for dilute defects, eliminating the need for model fitting to experimental or simulation data. DEF reduces the complexity of CEF by applying the superposition of absolute defect energies, making it feasible for modeling multi-component and chemically complex compounds. This paper presents a formal derivation of DEF and offers guidelines for its application, promising more accurate and efficient thermodynamic modeling of defective materials.