Suppression of Phase Transformation in Nb-H Thin Films below Switchover Thickness

Hydrogen uptake in metal-hydrogen (M-H) nanosized systems (e.g., thin films, clusters) is both a fundamental and a technologically relevant topic, which is becoming more important due to the recent developments of hydrogen sensors, purification membranes, and hydrogen storage solutions. It was recently shown that hydrogen (H) absorption in nanosized systems adhered to rigid substrates can lead to ultrahigh mechanical stress in the GPa range. About -10 GPa (compressive) stress were reported for hydrogen loaded niobium (Nb) thin films. Such high stresses can be achieved when conventional stress-release channels are closed, e.g., by reducing the system size. In this paper, we demonstrate that the high stress can be used to strongly modify the system's thermodynamics. In particular, a complete suppression of the phase transformation is achieved by reducing the film thickness below a switchover value d_so. Combined in situ scanning tunneling microscopy (STM) and in situ X-ray diffraction (XRD) measurements serve to determine the switchover thickness of epitaxial Nb/Al₂O₃ films in the thickness range from 55 to 5 nm. A switchover thickness d_so = 9 ± 1 nm is found at T = 294 K. This result is supported by complementary methods such as electromotive force (EMF), electrical resistance, and mechanical stress measurements in combination with theoretical modeling.