Hydrogen Sensing via Heterolytic H2 Activation at Room Temperature by Atomic Layer Deposited Ceria

Ultrathin atomic layer deposited ceria films (< 20 nm) are capable of H2 heterolytic activation at room temperature, undergoing a significant reduction regardless of the absolute pressure, as measured under in‐situ conditions by near ambient pressure X‐ray photoelectron spectroscopy. ALD‐ceria can gradually reduce as a function of H2 concentration under H2/O2 environments, especially for diluted mixtures below 10%. At room temperature, this reduction is limited to the surface region, where the hydroxylation of the ceria surface induces a charge transfer towards the ceria matrix, reducing Ce4+ cations to Ce3+. Thus, ALD‐ceria replicates the expected sensing mechanism of metal oxides at low temperatures without using any noble metal decorating the oxide surface to enhance H2 dissociation. The intrinsic defects of the ALD deposit seem to play a crucial role since the post‐annealing process capable of healing these defects leads to decreased film reactivity. The sensing behavior was successfully demonstrated in sensor test structures by resistance changes towards low concentrations of H2 at low operating temperatures without using noble metals. These promising results call for combining ALD‐ceria with more conductive metal oxides, taking advantage of the charge transfer at the interface and thus modifying the depletion layer formed at the heterojunction.