First-principle investigation of structural, electronic, and phase stabilities in chalcopyrite semiconductors: insights from Meta-GGA functionals

Abstract

We undertake a comprehensive first-principles investigation into the factors influencing the optoelectronic efficiencies of PQR2 chalcopyrite semiconductors. The structural attributes, electronic properties, and phase stabilities are explored using various meta-GGA exchange-correlation (XC) functionals within the density functional framework. In particular, we assess the relative performance of these XC functionals in obtaining estimates of various relevant parameters. The structural parameter u in chalcopyrite semiconductors is a noteworthy aspect, as it is intrinsically tied to the extent of orbital hybridization between distinct atoms and thereby strongly
influences the electronic properties. In general, the application of widely used GGA-PBE XC functional to
these chalcopyrites results in unreliable predictions of band gaps and ’u’ parameters due to delocalization errors
that in turn arise due to the inclusion of d and f core electrons. While hybrid functionals offer remarkable ac-
curacy through state-of-the-art methods, their main drawback lies in their computational expense and resource
demands. Our findings strongly suggest that in comparison to GGA-PBE, the meta-GGA XC functionals per-
form quite well and provide results that closely align with experimental values. In particular, the r2SCAN and
rMGGAC XC functionals are preferable and superior for investigating chalcopyrites and other solid-state sys-
tems. This preference is rooted in their excellent performance and substantially reduced computational costs
compared to hybrid functionals.