Oxygen Vacancy Defects Boosted High Performance p‑Type Delafossite CuCrO₂ Gas Sensors

p-type ternary oxides can be extensively explored as alternative sensing channels to binary oxides with diverse structural and compositional versatilities. Seeking a novel approach to magnify their sensitivities toward gas molecules, e.g., volatile organic compounds (VOCs), will definitely expand their applications in the frontier area of healthcare and air-quality monitoring. In this work, delafossite CuCrO₂ (CCO) nanoparticles with different grain sizes have been utilized as p-type ternary oxide sensors. It was found that singly ionized oxygen vacancies (V_o^•) defects, compared with the grain size of CCO nanoparticles, play an important role in enhancing the charge exchange at the VOCs molecules/CCO interface. In addition to suppressing the hole concentration of the sensor channel, the unpaired electron trapped in V_o^• provides an active site for chemisorptions of environmental oxygen and VOCs molecules. The synergetic effect is responsible for the observed increase of sensitivity. Furthermore, the sensitive (V_o^• defect-rich) CCO sensor exhibits good reproducibility and stability under a moderate operation temperature (<325 °C). Our work highlights that V_o^• defects, created via either in situ synthesis or postannealing treatment, could be explored to rationally boost the performance of p-type ternary oxide sensors.