High-throughput computational discovery of CuI-based ternary $p$-type transparent conductors

Abstract

P-type transparent conducting materials (TCMs) remain scarce, limiting progress in transparent electronics and tandem photovoltaics. Here, we perform a high-throughput computational search across CuI-based ternary X--Cu--I compounds using the minima hopping method combined with density functional theory. Filtering for thermodynamic stability, optical transparency, and light hole effective mass, we identify 58 candidate p-type TCMs, of which 49 are previously unreported. Twenty are p-type degenerate semiconductors with intrinsic hole carriers, including Cu$_2$FI$_2$ (calculated gap 3.75 eV, hole effective mass $0.262\,m_0$). We further use this dataset to revisit the chemical modulation of the valence band (CMVB) design rules, originally formulated for Cu-based delafossite oxides. Four generalizations emerge: linear Cu coordination is not required, as tetrahedral coordination (CN = 4) is compatible with p-type TCM character; the mechanism extends to halide-based systems with I $5p$ anion states; the Cu $d$ state energy center $ε_d$ is a quantitative descriptor for valence band dispersion; and Cu undercoordination in monovalent-anion hosts drives intrinsic p-type carrier generation through stoichiometric charge balance. These results establish a generalized computational framework for the design of p-type halide TCMs.