Temperature and thickness dependence of the sensitivity of nitrogen dioxide graphene gas sensors modified by atomic layer deposited zinc oxide films

Abstract

The Chemical Vapor Deposition (CVD) grown graphene nitrogen dioxide (NO₂) gas sensors modified by zinc oxide (ZnO) thin films via atomic layer deposition (ALD) were fabricated and their sensitivity dependence on the temperature and ZnO film thickness was investigated. The anomalous p-type response of the ALD ZnO modified graphene sensors (ZnO/graphene) to NO₂ at room temperature was found which might be attributed to the n to p conductance transition due to the reaction between oxygen vacancies and oxygen in the ZnO films. At elevated temperature, ZnO/graphene sensors exhibited p to n conductance transition and the transition temperature increased from 200 °C for pristine graphene, 300 °C for 5 ALD cycles and 1 nm ZnO/graphene, to 350 °C for 3, 5 and 10 nm ZnO/graphene. Meanwhile, the sensors' sensitivity revealed strong temperature dependence with the optimal temperature of 100 °C for ultra thin 5 ALD cycles ZnO/graphene (including pristine graphene) and 200 °C for other ZnO/graphene sensors (ZnO films thickness ≥ 1 nm). Such transition and sensitivity dependence on temperature could be ascribed to the change of carrier type and concentration in the ZnO/graphene with the variation of the temperature. Besides, strong sensitivity dependence on the ZnO film thickness at various temperatures was also demonstrated with the optimal ZnO film thicknesses of 5 ALD cycles for relatively low temperature of 100 °C and 3 nm for higher temperatures of 200 °C and 300 °C. The mechanism responsible for the sensors' sensitivity dependence on the temperature and ZnO film thickness was discussed.