Helmut Uchida

Hydrogen Interaction with Defects in Nanocrystalline, Polycrystalline and Epitaxial Pd Films

Hydrogen interaction with defects and structural development of Pd films with various microstructures were investigated. Nanocrystalline, polycrystalline and epitaxial Pd films were prepared and electrochemically loaded with hydrogen. Structural changes of Pd films caused by absorbed hydrogen were studied by in-situ X-ray diffraction combined with acoustic emission and measurement of electromotorical force. Development of defects during hydrogen loading was investigated by positron annihilation spectroscopy. It was found that hydrogen firstly fills open volume defects existing already in the films and subsequently it occupies also interstitial sites in Pd lattice. Absorbed hydrogen causes volume expansion, which is strongly anisotropic in thin films. This introduces high stress into the films loaded with hydrogen. Acoustic emission measurements revealed that when hydrogen-induced stress achieves a certain critical level rearrangement of misfit dislocations takes place. The stress which grows with increasing hydrogen concentration can be further released by plastic deformation and also by detachment of the film from the substrate.

Hydrogen Interaction with Defects in ZnO

In the present work hydrothermally grown ZnO single crystals were electrochemically charged with hydrogen. The influence of hydrogen on ZnO microstructure was investigated by positron annihilation spectroscopy (PAS) combined with X-ray diffraction (XRD) using synchrotron radiation. Hydrogen concentration in the samples was determined by nuclear reaction analysis (NRA). It was found that a high concentration of hydrogen can be introduced into ZnO by electrochemical loading. At low concentrations, absorbed hydrogen causes elastic volume expansion of ZnO crystal. At higher concentration, hydrogen-induced stresses exceed the yield stress in ZnO and plastic deformation of the crystal takes place leading to formation of a defected subsurface layer in the crystals.

Anisotropy of Hydrogen Diffusivity in ZnO

Hydrogen absorption and diffusivity in high quality ZnO crystals were investigated in this work by X-ray diffraction combined with slow positron implantation spectroscopy and electrical resistometry. ZnO crystals were covered by a thin Pd over-layer and electrochemically charged with hydrogen. It was found that absorbed hydrogen causes plastic deformation in a sub-surface region. The depth profile of hydrogen concentration introduced into the crystal was determined by nuclear reaction analysis. Enhanced hydrogen concentration was found in the sub-surface region due to excess hydrogen atoms trapped at defects introduced by plastic deformation. Hydrogen diffusion in ZnO crystals with various orientations was studied by in-situ electrical resistometry. It was found that hydrogen diffusion in the c-direction is faster than hydrogen diffusion in the a-direction most probably due to open channels existing in the wurtzite structure along the c-axis.

Structural Studies of Nanocrystalline Thin Pd Films Electrochemically Doped with Hydrogen

Hydrogen absorption in Pd causes a significant volume expansion. In free-standing bulk Pd, the hydrogen-induced volume expansion is isotropic. However, the situation becomes more complicated in thin Pd films. Contrary to bulk samples, thin films are clamped to an elastically stiff substrate, which prevents in-plane expansion. Hence, the volume expansion of a thin film is strongly anisotropic because it expands in the out-of-plane direction only. Internal stresses introduced by absorbed hydrogen may become so high that detachment of a film from the substrate is energetically favorable and buckles of various morphologies are formed. In the present work, we studied hydrogen-induced buckling in a nanocrystalline thin Pd film deposited on a sapphire substrate. Slow positron implantation spectroscopy (SPIS) was employed as a principal tool for the characterization of defects and investigation of defect interactions with hydrogen. SPIS studies were combined with X-ray diffraction and direct observations of buckling by light microscopy. It was found that buckling of thin Pd film occurs at hydrogen concentrations xH > 0.1 and is accompanied by a strong increase of dislocation density.

Hydrogen-Induced Buckling of Pd Films Deposited on Various Substrates

A Pd-H system is a model system suitable for studying interactions of hydrogen with metals. In the present work, we studied hydrogen-induced buckling of thin Pd films deposited on various substrates with different bonding strengths (sapphire, glimmer) and also the effect of deposition temperature. Lattice expansion and phase transitions were investigated by X-ray diffraction of synchrotron radiation. The influence of the substrate and microstructure of the film on the buckling process and phase transformation to palladium hydride are discussed.