Laser-ablation studies of highly-oriented thin films of the electon-doped infinite-layer copper-oxide compounds Sr1 - xCuO2 are reported. We observe significant variations in film properties with substrate or buffer layer material. X-ray diffraction, atomic force microscopy (AFM), Rutherford back-scattering (RBS), and electrical resistivity were used to characterize the films. Films were deposited on strontium titanate (001) or on buffer layers of T′-phase copper oxides (Ln2CuO4 with Ln = Pr, Nd, Sm), Sr3FeNb2O9, and La1.8Y0.2CuO4 on SrTiO3 (001). The in-plane lattice constants of such buffer layers (a = 0.390-0.400 nm) should provide the bond tension required for electron doping. Extremely flat, epitaxial buffer layers with X-ray rocking curves as narrow as 0.08° were obtained from stoichiometric targets of Ln2CuO4; the other buffer layers yielded poor epitaxy. A linear dependence of infinite-layer c-axis plane spacing on substrate or buffer-layer in-plane a-axis lattice constant is observed.@en

Hydrogenography is an advanced combinatorial and standard method used for the search of new hydrogen-storage materials to synthesize bulk samples and to use volumetric or gravimetric techniques to follow their hydrogenation reaction. Hydrogenography, with a straightforward optical setup, makes it possible to monitor hydrogen absorption and desorption simultaneously on thousands of samples under exactly the same experimental conditions. Hydrogenography is much more than a monitoring technique, as it also provides a high-throughput method to measure quantitatively the key thermodynamic properties of hydride formation. The continuous change of optical transmission with hydrogen concentration was used to measure the pressure-concentration isotherms and determine the enthalpy of hydride formation. Hydrogenography is valuable for the search for catalytic caplayers promoting hydrogen uptake, electrode materials for batteries, and smart coatings for adaptive solar collectors.@en

The peculiar optical patterns observed in Mg2NiHx films during hydrogenation with their applicability as selective tunable absorbers were discussed. These films showed large change in reflection that yielded very low reflectance at different hydrogen contents. It was shown that these films are suitable as smart coatings due to their energy tunability, high reflectance contrast, and switching capabilities. It was observed that these films can be used as a switchable solar absorber in solar collectors as the film in this state emits only 16% of the 100°C blackbody radiation. It was found that.@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

We prepared epitaxial YH2 films on (111) CaF2 by pulsed laser deposition (PLD) from a metallic yttrium target. Without adding any reactive hydrogen, the dihydride is formed in situ due to the hydrogen evolving from the metallic target which contains ~7 at% H. Upon pulsed laser irradiation, the target acts as a pulsed source of both yttrium and hydrogen. The increased hydrogen content of the film as compared to the target is explained to be due to diffusion assisted preferential ablation of hydrogen. Due to this deposition process the hydrogen load on the deposition system is minimized, which is important in view of the fabrication of hydride/oxide stacks for all-solid-state switchable mirror devices. Furthermore, the preparation of both nanocrystalline and epitaxial YH2 films shows the versatility of the PLD process.@en

In-situ deposited YH2 films ranging from epitaxial to nanocrystalline were prepared by pulsed laser deposition (PLD). PLD has the advantage that the yttrium target acts as a hydrogen source. Comparing the switching behavior to that of MBE-grown, ex-situ loaded films, the PLD-films show a reduced optical and electrical contrast in switching, which is probably due to the formation of Y(OH)3. On the other hand, we found that in the nanocrystalline PLD-films the hysteresis in switching is absent. Moreover, these films have a smoother surface morphology. Both effects are important for the implementation of switchable rare earth hydride films in all-solid-state devices.@en

The optical properties, the switching kinetics and the lifetime of hydrogen switchable mirrors based on Mg-Ni alloys are determined with particular regard to the composition of the optically active metal-hydride layer in combination with the thickness of the catalytic capping layer. For this, a high-throughput experiment is introduced. The switching kinetics and the reversibility of switchable mirrors are strongly thickness dependent, though the details hinge on the fine structure of the clustered capping layer. Therefore, the kinetics is correlated with the surface structures of Pd on Mg y Ni 1-y as investigated by scanning tunneling microscopy. The results are explained by the so-called strong metal-support interaction (SMSI) state, characterized by a complete encapsulation of the capping layer clusters by oxidized species originating from the support. The SMSI-effect is less important with increasing Pd-layer thickness, and is suppressed by a good wetting of the Pd-clusters on the optically active film. This explains the critical thickness for the catalyzed hydrogen uptake observed in many switchable mirror systems. Moreover, the degradation of the kinetics during cycling is found to depend on the Pd-layer thickness and on the gas environment. Only films, covered with at least 15 nm Pd, show small degradation caused by the SMSI-effect. The SMSI-effect is partly reversible: after changing the gas environment from hydrogen to oxygen, the oxide on the Pd-clusters can be partly removed.@en

The hydrogenation of metallic Mg2 Ni films was shown to proceed via a self-organized double layering of transparent Mg2 NiH4 and metallic Mg2 NiH0.3. For stoichiometries departing from Mg2 Ni we conclude from optical reflection, transmission and electrical measurements that the hydrogenation process involves two competing effects: (i) the nucleation of the initial Mg2 NiH4 layer near the substrate and the ensuing growth of this layer and (ii) the slow random nucleation of the same phase within the remaining part of the film. Which process dominates depends critically on the stoichiometry of the parent metal alloy.@en

The reflection and transmission spectra of Pd capped Mgy Ti1 - y thin films (y = 0.7, 0.8 and 0.9) are measured in the 0.5-5.5 eV energy range, both in the as-prepared and hydrogenated states. Upon hydrogenation these films switch reversibly from a shiny metallic state into a "black" absorbing one. The composition and thicknesses can be tailored to achieve high solar absorptance and low thermal emittance in the hydrogenated state. The combination of these two characteristics is interesting for the application of this material as switchable absorber in solar collectors. The use of a Mgy Ti1 - y switchable absorber in solar collectors allows to lower the stagnation temperature from 180 to 80 °C. The collector efficiency is affected only minimally.@en

A novel optical technique to measure catalytic activity for hydrogen sorption is presented. The catalytic activity of the noble metals of Pd, Ni, Cu and Ag is studied as function of pressure and temperature. The uptake rate is limited by chemisorption as deduced by modelling kinetics. An empirical relation between uptake rate and the measured activation energy is given. The catalytic activity of NbOx is studied as a function of the oxygen concentration determined from electron spectroscopy. The measured activation energy depends strongly on the oxygen concentration and reaches a minimum of 0.6 eV at the highest oxygen content (x=2.5, i.e. Nb2O5). Pure Nb does not display a significant catalytic efect.@en

The engineering of pure and metal alloy catalysts for hydrogen absorption is needed to improve the kinetics of hydrogen-related devices. We introduce a new route to search for alloys that can yield superior catalytic behavior for hydrogen absorption, using an optical technique to measure the catalytic activity for hydrogen sorption of thin films. The catalytic activity of the noble metals Pd, Ni, Cu, Ag, Pt, and Au is studied as a function of hydrogen pressure and temperature. The rate-limiting step is identified by the pressure dependence and the normal isotope effect for hydrogen absorption. The measured rates and activation energies are correlated to such physical properties as activation barrier for dissociation and heat of solution. The observed compensation effect is explained in the framework of interplay between surface and bulk processes. From the experimentally derived model, a guiding principle for the search for catalysts promoting hydrogen absorption is drawn.@en

A new method has been developed to synthesize compact yttriumtrihydride by making use of a thin film technique. For electrical measurements yttrium films of typically 500 nm thickness are covered under UHV conditions by a 5 nm thick palladium overlayer which consists of electrically disconnected islands. Loading of these films with hydrogen up to the trihydride phase can then be done ex-situ in a reasonably short time (around 20-40 h) by applying gas pressures of about 60 × 105 Pa. For a thicker Pd layer (above 20 nm) this time can be considerably shorter (t ∼ 125 s). The film morphology stays intact during the loading process although the film thickness increases by approximately 11% and the crystal structure changes from h.c.p. to f.c.c. and back to h.c.p. These samples are, therefore, very well suited for an investigation of the remarkable electrical and optical properties of trihydrides, as recently reported by Huiberts et al. (Nature, 380, 1996, 231). In this article we give evidence for the island structure of the palladium overlayer and make a comparison of a number of physical properties of yttrium and its related hydrides as thin films with literature values for the same material in bulk form. These properties include lattice parameters for the different hydride phases, electrical resistivity for yttrium and its dihydride and Hall coefficient for yttrium. The characteristics of the yttriumhydride thin films are very similar to those of bulk material. Furthermore, we performed concentration measurements and resistivity measurements during hydrogen loading. It is shown that the resistivity rises three orders of magnitude when yttrium is loaded up to the trihydride phase at 60 × 105 Pa.@en

YBa2Cu3O7-δ films on SrTiO3 are characterized by a network of anti-phase boundaries (APB's), protruding from the interface to the film surface. We propose that the island morphology of these films is to a large extent determined by this network. At APB-outcrops deep trenches form which separate the growth islands. At the cross-section of three APB's deep holes are formed. It is found that the growth island size can be increased by increasing the substrate temperature or the oxygen pressure during growth.@en

Investigating the epitaxial nature of YBa2Cu3O7-δ films on NdGaO3 (001) by Rutherford backscattering (RBS) and X-ray diffraction (XRD) texture measurements we find that the films are almost single crystalline, in the sense that the a, b and c axes are uniquely defined with respect to those of NdGaO3. The crystalline perfection is, however, not reflected in the electrical properties of the films. Although we measure a Tc of 89.7 K, we did not observe the expected anisotropy in the resistivity. We interpret this to be due to Ga diffusion from the substrate into the film, which effectively blocks the chain conductivity.@en

Using scanning probe microscopy we observe a growth mode transition in pulsed laser deposited (PLD) YBa2Cu3O7-δ films. By increasing the background oxygen pressure the generally observed 2D-nucleation and growth mode transforms into a spiral growth mode. Keeping the oxygen pressure at increased levels and reducing the target-sub strate distance, the growth spirals disappear and 2D-nucleation and growth becomes the dominant growth mode again. We attribute the growth mode transition to a change in surface diffusivity of ∼ 2 orders of magnitude. Our experiments confirm that in PLD surface kinetics is strongly linked to plume dynamics.@en

Rutherford backscattering (RBS) ion channeling measurements and X-ray diffraction experiments are performed to study the epitaxial nature of as-deposited yttrium on CaF2〈111〉 substrates and the effect of hydrogenation on the crystalline quality. The RBS and X-ray results clearly demonstrate the unique epitaxial relation between as-deposited films and the substrate, which is preserved upon loading with hydrogen. X-Ray diffraction reveals: (i) a remarkably large lattice expansion in the direction normal to the substrate, which decreases with increasing film thickness; and (ii) an in-plane compression of the lattice. This peculiar result is related to the difference in thermal expansion coefficients of film and substrate. RBS ion channeling measurements reveal a thickness dependence of the mismatch-induced stresses. As expected, the stresses relax with increasing distance from the film/substrate interface, but surprisingly, even with films as thick as 400 nm considerable dechanneling is still observed at the film surface. Film quality, i.e. the film/substrate mismatch as well as the induced stresses and their relaxation, are discussed in relation to atomic force microscopy (AFM) results on these epitaxial films.@en

Recently, threading dislocations were identified as the origin of the high critical currents in YBa2Cu3O7-δ films [Nature (Lond.) 399 (1999) 439]. As these dislocations originate at the substrate-film interface, the termination of the (100) SrTiO3 substrate is expected to influence both the nucleation and the dislocation formation in YBa2Cu3O7-δ (123) films. To investigate this substrate-film interaction, we developed a new ex situ method to prepare SrO-terminated substrates in addition to the well-known TiO2 termination. It is shown that: (i) preferential precipitation occurs when depositing submonolayer 123 films on SrO-terminated SrTiO3 and (ii) such precipitates are absent on the TiO2 termination. It appears that the substrate termination determines both the starting and terminating layer of the 123 phase. Similar effects are observed in submonolayer thick films with cation stoichiometries of 122, 124 and 133. When growing several 123 monolayers on SrO-terminated substrates, no precipitates are formed. Instead, to incorporate the off stoichiometry, defects are introduced. Surprisingly, the density of threading dislocations does not depend on the substrate termination.@en

The catalytic activity of niobium oxide for hydrogen absorption is determined using an optical indicator technique to measure hydrogen sorption kinetics. The catalytic activity of NbOx is studied as a function of the oxygen concentration determined from electron spectroscopy. STM measurements display a clustered NbOx surface, disproving a diffusion-controlled kinetics. The catalytic effect results from dissociation of hydrogen by niobium oxide. The measured activation energy depends strongly on the oxygen concentration and reaches a minimum of 0.6 eV at the highest oxygen content (x=2.5, i.e., Nb2O5). Pure Nb does not display a catalytic effect. Oxide surfaces with a high concentration of artificial oxygen vacancies are less catalytically active.@en

At low fluences, the [Sr]/[Ti] ratio of laser deposited SrTiO3 films appears to be a function of the laser fluence. The deviation from stoichiometry is remarkably constant in time. From an analysis of both the composition of the film and the irradiated target, we deduce a volume-diffusion-assisted preferential ablation process. At high fluences (above 1.3 J/cm2), stoichiometric SrTiO3 films are obtained. This is not due to a change in ablation mechanism, but follows from the fact that at 1.3 J/cm2 the calculated diffusion length of Sr within the irradiated target, becomes of the order of the ablation rate per shot.@en

The kinetics of the metal-insulator transition in polycrystalline, Pd-capped YHx switchable mirrors upon hydrogenation is investigated. Using the accompanying optical transition, we study switching of matrix-like samples with many (∼200) combinations of Pd and Y layer thicknesses. We find that: (i) With increasing Y thickness dY, the switching time τ increases for any constant Pd thickness dPd. (ii) With increasing dPd, there are three regimes. In regime I, it is impossible to switch a device. This can mainly be related to Pd-Y compound formation consuming all Pd within the UHV system, followed by surface oxidation in air. In regimes II and III switching is possible, but only in regime III does Pd form a closed cap layer. The Pd thickness needed for a closed cap layer depends on dY. (iii) An oxide buffer layer hinders Pd-Y interdiffusion, so that a thinner Pd cap layer is needed for switching than in the case without buffer layer. This is interesting for potential applications since it yields a higher optical transmission in the open state of the device.@en