The detection of hydrogen in a fast, efficient and accurate way is vital for its safe handling in industrial processes and in its use as an energy carrier. Thin film metal hydrides are able to probe the hydrogen pressure, often relying on a change of the optical properties of a sensing layer comprised of palladium and alloys thereof. Apart from hysteresis, these palladium-based thin films suffer from a limited operating range. Here, we study the optical and structural properties of palladium capped hafnium and tantalum thin films. Both tantalum and hafnium thin films offer a stable and hysteresis-free optical response to hydrogen over a much larger pressure range than palladium-based films. Remarkably, the hydrogen content in both cases proves to be linear with the optical signal. In a wider perspective, these results illustrate that palladium-capped transition metals provide ample opportunities to design optical hydrogen sensors with desired properties.

Hydrogen detection is essential for its implementation as an energy vector. So far, palladium is considered to be the most effective hydrogen sensing material. Here we show that palladium-capped hafnium thin films show a highly reproducible change in optical transmission in response to a hydrogen exposure ranging over six orders of magnitude in pressure. The optical signal is hysteresis-free within this range, which includes a transition between two structural phases. A temperature change results in a uniform shift of the optical signal. This, to our knowledge unique, feature facilitates the sensor calibration and suggests a constant hydrogenation enthalpy. In addition, it suggests an anomalously steep increase of the entropy with the hydrogen/metal ratio that cannot be explained on the basis of a classical solid solution model. The optical behaviour as a function of its hydrogen content makes hafnium well-suited for use as a hydrogen detection material.

This work deals with the thermodynamics of hydride formation in 3-D nanoconfined Mg. Two ensembles of nearly monodisperse Mg nanodots (NDs) with different diameters (60 and 320 nm), were grown by the template nanopatterning method, using ultra-thin alumina membranes (UTAMs) with ordered porosity as evaporation masks. Multilayer NDs consisting of 30 nm Mg, 5 nm Ti and 5 nm Pd were deposited on UTAM-coated glass substrates by molecular beam epitaxy. The lateral surface of the NDs is constituted by native MgO. The morphology of the NDs was characterized by field emission scanning electron microscopy and atomic force microscopy. Hydride formation and decomposition was studied at low temperature (363–393 K) by means of optical hydrogenography. Compared to bulk Mg, the plateau pressure for hydrogen absorption in NDs exhibits an upward shift, which is larger for small NDs. Differently, the desorption plateau pressure is almost the same for the two NDs size and is lower than for bulk Mg. These hydrogen sorption features are discussed in the frame of a model that takes into account both interface energy and elastic strain energy in the constrained nanodots. The onset of plastic deformation, marked by a high pressure hysteresis between hydrogen absorption and desorption isotherms, limits the extent of hydride destabilization that can be achieved by elastic strain engineering.