Carbon Vacancy Formation in Binary Transition Metal Carbides from Density Functional Theory

TL;DR

This study uses density functional theory to analyze carbon vacancy formation in binary transition metal carbides, revealing how vacancy formation depends on crystal structure, metal group, and growth conditions, aligning with experimental observations.

Contribution

It provides a comprehensive theoretical analysis of carbon vacancy trends in various transition metal carbides, highlighting the influence of crystal structure and growth conditions on vacancy formation.

Findings

C vacancies are easier to form in B1-structured carbides with more valence electrons.

C vacancies are energetically unfavorable in WC-structured carbides regardless of conditions.

Experimental vacancy concentrations align with theoretical predictions under different growth environments.

Abstract

We have investigated the trends in the formation of carbon vacancies in binary transition metal (TM) carbides using density functional calculations for two common TM carbide crystal structures, namely the B1 (rock-salt) and WC structure types. The TM are taken from group IV (Ti, Zr, Hf), V (V, Nb, Ta) and VI (Cr, Mo, W) of the periodic table, as well as Sc from group III. For B1-structured TM carbides, the general trend is that it is easier for C vacancies to be formed as the number of valence electrons in the system increases. The exception is ScC where C vacancies are rather easy to form. It is also clear that the formation of C vacancies depends on the growth conditions: For TM-rich conditions, B1-structured carbides will always favour C vacancy formation. For C-rich conditions it is energetically favourable to form C vacancies in ScC, VC, NbC, CrC, MoC and WC. Experimentally large C vacancy concentrations are found in B1-structured TM carbides and our calculations are in line with these observations. In fact, TiC, ZrC, HfC and TaC are the only B1-structured TM carbides that do not spontaneously favour C vacancies and then only for C-rich conditions. C vacancies may still be present in these systems, however, due to the high temperatures used when growing TM carbides. In the case of WC-structured TM carbides, C vacancy formation is not energetically favourable irrespective of the growth conditions, which is the reason why this structure is only found close to a one-to-one metal-to-carbon ratio. ...