Hydrogenography is a new optical thin film combinatorial method that follows hydrogenation and determines its associated thermodynamic properties. Due to clamping to the substrate, stresses generated in thin films are larger than in bulk. This must be taken into account for a comparison between these two types of systems. In this article, we follow the microstructure, surface morphology and in-plane stress changes of thin polycrystalline PdHx films upon several hydrogen ab/desorption cycles and correlate them to the evolution in shape and hysteresis of pressure-optical transmission isotherms (PTIs) recorded by hydrogenography. The in-plane stress in the first instance is relaxed inhomogeneously by buckling, and a more complete, homogeneous relaxation is only reached after the creation of a buckle-and-crack network that is the two-dimensional analogue of bulk decrepitated grains. This sequence of changes is clearly visible in the PTIs, demonstrating another useful facet of hydrogenography for characterizing metal-hydrogen systems.@en

For many hydrogen related applications it is preferred to use optical hydrogen sensors above electrical systems. Optical sensors reduce the risk of ignition by spark formation and are less sensitive to electrical interference. Currently palladium and palladium alloys are used for most hydrogen sensors since they are well known for their hydrogen dissociation and absorption properties at relatively low temperatures. The disadvantages of palladium in sensors are the low optical response upon hydrogen loading, the cross sensitivity for oxygen and carbon, the limited detection range and the formation of micro-cracks after some hydrogen absorption/desorption cycles. In contrast to Pd, we find that the use of magnesium or rear earth bases metal-hydrides in optical hydrogen sensors allow tuning of the detection levels over a broad pressure range, while maintaining a high optical response. We demonstrate a stable detection layer for detecting hydrogen below 10% of the lower explosion limit in an oxygen rich environment. This detection layer is deposited at the bare end of a glass fiber as a micro-mirror and is covered with a thin layer of palladium. The palladium layer promotes the hydrogen uptake at room temperature and acts as a hydrogen selective membrane. To protect the sensor for a long time in air a final layer of a hydrophobic fluorine based coating is applied. Such a sensor can be used for example as safety detector in automotive applications. We find that this type of fiber optic hydrogen sensor is also suitable for hydrogen detection in liquids. As example we demonstrate a sensor for detecting a broad range of concentrations in transformer oil. Such a sensor can signal a warning when sparks inside a high voltage power transformer decompose the transformer oil over a long period.@en

We report on the implementation of Pd-capped chemo-chromic metal hydrides as a sensing layer in fiber optic hydrogen detectors. Due to the change in optical properties of Mg-based alloys on hydrogen absorption, a drop in reflectance by a factor of 10 is demonstrated at hydrogen levels down to 15% of the lower explosion limit. The switching takes place in only a few seconds. Comparing Mg-Ni and Mg-Ti based alloys, we find that the latter has superior optical and switching properties. Using a 50 nm thick Mg70Ti30 film capped with a 30 nm Pd catalytic layer as the sensing layer, we report on the sensitivity of the fiber optic detector for hydrogen both in argon and oxygen, the temperature behavior and the reversibility.@en

Pd-capped gasochromic metal hydrides can be used as sensing layer in fiber optic hydrogen detectors. Using a sensing layer consisting of a 50 nm thick Mg70Ti30 film capped with a 30 nm Pd catalytic layer we demonstrate a drop in reflectance by a factor of 10, at hydrogen levels down to 10% of the lower flammability limit. The switching takes place within a few seconds, depending on the actual amount of hydrogen in the vicinity of the detector. We report on the sensitivity of the fiber optic detector for hydrogen, both in argon and oxygen rich environments. We further show that the sensing behavior in oxygen rich gas mixtures and in normal air can be improved by adding silver to the catalytic Pd cap layer.@en

MgHx thin films are grown by activated reactive evaporation in a Molecular Beam Epitaxy system fitted with an atomic hydrogen source. During deposition the electrical and optical properties are measured in-situ. The structural properties are determined ex-situ by Atomic Force Microscopy. These measurements confirm the growth of the MgH2 phase, however the presence of 10 vol.% of metallic Mg cannot be prevented. The metallic Mg grains cause an optical absorption edge at 2.0 eV, which has a completely different origin than the observed band gap of MgH2 at 5.6 eV. The observed optical spectra can be modelled using an effective medium theory. The Mg hydride films are electrically insulating despite the presence of metallic Mg particles. Upon re-hydrogenation of a de-hydrogenated in-situ grown MgHx thin film, the absorption edge at 2.0 eV disappears and the resistivity decreases to values normally observed for ex-situ hydrogenated films.@en

In order to develop optical fiber hydrogen sensors, thin film materials with a high optical contrast between the metallic and hydrided states are needed. Magnesium exhibits such a contrast but cannot be easily hydrogenated at room temperature. However, thin films of Pd-doped Mg (MgPdy with 0.023 ≤ y ≤ 0.125) prepared by magnetron dc sputtering can easily be hydrided at room temperature and 0.5 bar H2 within a few minutes. The rate of first hydrogenation increases linearly with increasing Pd concentration. Hydrogenation induces high variations of transmission (ΔT up to 20%) and reflection (ΔR up to 70%) of light (0.5 eV ≤ℏω≤6.0 eV corresponding to 2500 nm≥λ ≥ 210 nm). The optical properties can be understood by considering Pd as a deep donor in semiconducting MgH2.@en

Mg2NiH4 thin films have been prepared by activated reactive evaporation in a molecular beam epitaxy system equipped with an atomic hydrogen source. The optical reflection spectra and the resistivity of the films are measured in situ during deposition. In situ grown Mg2NiH 4 appears to be stable in vacuum due to the fact that the dehydrogenation of the Mg2NiH4 phase is kinetically blocked. Hydrogen desorption only takes place when a Pd cap layer is added. The optical band gap of the in situ deposited Mg2NiH4 hydride, 1.75 eV, is in good agreement with that of Mg2NiH4 which has been formed ex situ by hydrogenation of metallic Pd capped Mg2Ni films. The microstructure of these in situ grown films is characterized by a homogeneous layer with very small grain sizes. This microstructure suppresses the preferred hydride nucleation at the film/substrate interface which was found in as-grown Mg2Ni thin films that are hydrogenated after deposition.@en

Hydrogenography, an optical high-throughput combinatorial technique to find hydrogen storage materials, has so far been applied only to materials undergoing a metal-to-semiconductor transition during hydrogenation. We show here that this technique works equally well for metallic hydrides. Additionally, we find that the thermodynamic data obtained optically on thin Pd-H films agree very well with Pd-H bulk data. This confirms that hydrogenography is a valuable general method to determine the relevant parameters for hydrogen storage in metal hydrides.@en

The optical switching from shiny metallic to "black" absorbing states of 30 nm Mg2Ni/50 nm TM/10 nm Pd (TM = Ti, V, Cr, Mn, Fe, Co, Ni, Pd) trilayer thin films upon hydrogenation is used to determine the hydrogen absorption/desorption kinetics at moderate H2 pressure and room temperature. A strong correlation is observed between these kinetics and the enthalpies of solution of H in TM. A diffusion model based on chemical potentials of hydrogen in metals has been developed that agrees qualitatively with the experimental data, both from kinetics and hydrogen concentration profile points of view. The influences of the solution enthalpy and the diffusion coefficient of H in TM and that of the TM layer thickness are discussed with respect to this model. Finally, we conclude with potential applications of these trilayers, from optical hydrogen detection to reinvestigation of diffusion coefficients of H in TM.@en

A triple layer thin film (30 nm Mg2Ni/100 nm Ti/10 nm Pd sputtered on glass) switches reversibly from a shiny metallic to a "black" state upon exposure to moderate hydrogen pressure (≈5.103 Pa). This black state resembles that obtained in thick Mg2NiHx layers and has the great advantage of being stable and easily controlled. Both the reversible high optical contrast (R reflective/Rblack ≈ 10 in the red wavelength range) and the fast kinetics of hydrogen absorption and desorption make this material interesting for applications as optical hydrogen sensors.@en