Lift-off protocols for thin films for use in EXAFS experiments.

Lift-off protocols for thin films for improved extended X-ray absorption fine structure (EXAFS) measurements are presented. Using wet chemical etching of the substrate or the interlayer between the thin film and the substrate, stand-alone high-quality micrometer-thin films are obtained. Protocols for the single-crystalline semiconductors GeSi, InGaAs, InGaP, InP and GaAs, the amorphous semiconductors GaAs, GeSi and InP and the dielectric materials SiO2 and Si3N4 are presented. The removal of the substrate and the ability to stack the thin films yield benefits for EXAFS experiments in transmission as well as in fluorescence mode. Several cases are presented where this improved sample preparation procedure results in higher-quality EXAFS data compared with conventional sample preparation methods. This lift-off procedure can also be advantageous for other experimental techniques (e.g. small-angle X-ray scattering) that benefit from removing undesired contributions from the substrate.

Role of thermodynamics in the shape transformation of embedded metal nanoparticles induced by swift heavy-ion irradiation.

Swift heavy-ion irradiation of elemental metal nanoparticles (NPs) embedded in amorphous SiO(2) induces a spherical to rodlike shape transformation with the direction of NP elongation aligned to that of the incident ion. Large, once-spherical NPs become progressively more rodlike while small NPs below a critical diameter do not elongate but dissolve in the matrix. We examine this shape transformation for ten metals under a common irradiation condition to achieve mechanistic insight into the transformation process. Subtle differences are apparent including the saturation of the elongated NP width at a minimum sustainable, metal-specific value. Elongated NPs of lesser width are unstable and subject to vaporization. Furthermore, we demonstrate the elongation process is governed by the formation of a molten ion-track in amorphous SiO(2) such that upon saturation the elongated NP width never exceeds the molten ion-track diameter.

Temperature-dependent EXAFS analysis of embedded Pt nanocrystals.

The vibrational and thermal properties of embedded Pt nanocrystals (NCs) have been investigated with temperature-dependent extended x-ray absorption fine structure (EXAFS) spectroscopy. NCs of diameter 1.8-7.4 nm produced by ion implantation in amorphous SiO(2) were analysed over the temperature range 20-295 K. An increase in Einstein temperature (∼194 K) relative to that of a Pt standard (∼179 K) was evident for the smallest NCs while those larger than ∼2.0 nm exhibited values comparable to bulk material. Similarly, the thermal expansion of interatomic distances was lowest for small NCs. While the amorphous SiO(2) matrix restricted the thermal expansion of interatomic distances, it did not have a significant influence on the mean vibrational frequency of embedded Pt NCs. Instead, the latter was governed by finite-size effects or, specifically, capillary pressure.

Irradiation-Dependent Helium Gas Bubble Superlattice in Tungsten.

The implantation of noble gas atoms into metals at high gas concentrations can lead to the self-organization of nanobubbles into superlattices with symmetry similar to the metal host matrix. Here, we examine the influence of implantation parameters on the formation and structure of helium gas bubble superlattices within a tungsten host matrix to uncover mechanistic insight into the formation process. The determination of the size and symmetry of the gas bubbles was performed using a combination of small angle x-ray scattering and transmission electron microscopy. The former was demonstrated to be particularly useful in determining size and structure of the gas bubble superlattice as a function of irradiation conditions. Prior to the formation of a superlattice, we observe a persistent substructure characterized by inter-bubble spacings similar to those observable when the gas bubble superlattice has formed with very large ordering parameters. As the implantation fluence increases, the inter-bubble ordering parameter decreases, indicating improved ordering, until a superlattice is formed. Multiple implantation-specific differences were observed, including a temperature-dependent superlattice parameter that increases with increasing temperature and a flux-dependent superlattice parameter that decreases with increasing flux. The trends quantified here are in excellent agreement with our recent theoretical predictions for gas bubble superlattice formation and highlight that superlattice formation is strongly dependent on the diffusion of vacancy and implanted He atoms.

Fine structure in swift heavy ion tracks in amorphous SiO2.

We report on the observation of a fine structure in ion tracks in amorphous SiO2 using small angle x-ray scattering measurements. Tracks were generated by high energy ion irradiation with Au and Xe between 27 MeV and 1.43 GeV. In agreement with molecular dynamics simulations, the tracks consist of a core characterized by a significant density deficit compared to unirradiated material, surrounded by a high density shell. The structure is consistent with a frozen-in pressure wave originating from the center of the ion track as a result of a thermal spike.