Ab Initio Studies of Work Function Changes Induced by Single and Co-Adsorption of NO, CO, CO₂, NO₂, H₂S, and O₃ on ZnGa₂O₄(111) Surface for Gas Sensor Applications.

Abstract

In this study, first-principles density functional theory (DFT) calculations were employed to investigate the effects of single and binary gas adsorption of NO, CO, CO₂, NO₂, H₂S, and O₃ on the ZnGa₂O₄(111) surface. For single-gas adsorption, O₃ adsorbed on surface Ga sites induces a pronounced work-function increase of 0.97 eV, whereas H₂S adsorption at surface O sites yields the strongest adsorption energy (-1.21 eV), highlighting their distinct electronic interactions with the surface. For binary co-adsorption, the NO₂-O₃ pair adsorbed at Ga-coordinated sites produces the largest work-function shift (1.88 eV), while adsorption at Zn sites results in the most stable configuration, with an adsorption energy reaching -3.98 eV. These results indicate that co-adsorption of highly electronegative gases can significantly enhance charge transfer and sensing response. In contrast, mixed oxidizing-reducing gas pairs, such as NO₂-H₂S, lead to a markedly suppressed work-function variation (-0.02 eV), suggesting reduced sensor sensitivity due to compensating charge-transfer effects. Overall, this work demonstrates that gas-sensing behavior on ZnGa₂O₄(111) is governed not only by individual gas-surface interactions but also by cooperative and competitive effects arising from binary co-adsorption, providing insights into realistic multi-gas sensing environments.