Realizing the Control of Electronic Energy Level Structure and Gas-Sensing Selectivity over Heteroatom-Doped In₂O₃...

Understanding the effect of substitutional doping on gas-sensing performances is essential for designing high-activity sensing nanomaterials. Herein, formaldehyde sensors based on gallium-doped In₂O₃ inverse opal (IO-(Ga _xIn_{1- x})₂O₃) microspheres were purposefully prepared by a simple ultrasonic spray pyrolysis method combined with self-assembled sulfonated polystyrene sphere templates. The well-aligned inverse opal structure, with three different-sized pores, plays the dual role of accelerating the diffusion of gas molecules and providing more active sites. The Ga substitutional doping can alter the electronic energy level structure of (Ga _xIn_{1- x})₂O₃, leading to the elevation of the Fermi level and the modulation of the band gap close to a suitable value (3.90 eV), hence, effectively optimizing the oxidative catalytic activity for preferential CH₂O oxidation and increasing the amount of adsorbed oxygen. More importantly, the gas selectivity could be controlled by varying the energy level of adsorbed oxygen. Accordingly, the IO-(Ga_0.2In_0.8)₂O₃ microsphere sensor showed a high response toward formaldehyde with fast response and recovery speeds, and ultralow detection limit (50 ppb). Our findings finally offer implications for designing Fermi level-tailorable semiconductor nanomaterials for the control of selectivity and monitoring indoor air pollutants.