First-principles investigation of oxidized Si- and Ge-terminated diamond (100) surfaces.

Diamond is a semiconductor material with remarkable structural, thermal, and electronic properties that has garnered significant interest in the field of electronics. Although hydrogen (H) and oxygen (O) terminations are conventionally favored in transistor designs, alternative options, such as silicon (Si) and germanium (Ge), are being explored because of their resilience to harsh processing conditions during fabrication. Density-functional theory was used to examine the non-oxidized and oxidized group-IV (Si and Ge)-terminated diamond (100) surfaces. The (3 × 1) reconstructed surfaces feature an ether configuration and show relative stability compared with the bare surface. Hybrid-functional calculations of the electronic properties revealed reduced fundamental bandgaps (<1 eV) and lower negative electron affinities (NEAs) than those of H-terminated diamond surfaces, which is attributed to the introduction of unoccupied Si (Ge) states and the depletion of negative charges. Furthermore, oxidation of these surfaces enhanced the stability of the diamond surfaces but resulted in two structural configurations: ether and ketone. Oxidized ether configurations displayed insulating properties with energy gaps of ∼4.3 ± 0.3 eV, similar to H-terminated diamond (100) surfaces, whereas bridged ether configurations exhibited metallic properties. Oxidization of the metallic ketone configurations leads to the opening of relatively smaller gaps in the range of 1.1-1.7 eV. Overall, oxidation induced a shift from NEAs to positive electron affinities, except for the reverse-ordered ketone surface with an NEA of -0.94 eV, a value comparable to the H-terminated diamond (100) surfaces. In conclusion, oxidized group-IV-terminated diamond surfaces offer enhanced stability compared to H-terminated surfaces and display unique structural and electronic properties that are influenced by surface bonding.