Etched ion tracks in amorphous SiO2 characterized by small angle x-ray scattering: influence of ion energy and etching conditions.

Small angle x-ray scattering was used to study the morphology of conical structures formed in thin films of amorphous SiO2. Samples were irradiated with 1.1 GeV Au ions at the GSI UNILAC in Darmstadt, Germany, and with 185, 89 and 54 MeV Au ions at the Heavy Ion Accelerator Facility at ANU in Canberra, Australia. The irradiated material was subsequently etched in HF using two different etchant concentrations over a series of etch times to reveal conically shaped etched channels of various sizes. Synchrotron based SAXS measurements were used to characterize both the radial and axial ion track etch rates with unprecedented precision. The results show that the ion energy has a significant effect on the morphology of the etched channels, and that at short etch times resulting in very small cones, the increased etching rate of the damaged region in the radial direction with respect to the ion trajectory is significant.

Nanoscale density variations induced by high energy heavy ions in amorphous silicon nitride and silicon dioxide.

The cylindrical nanoscale density variations resulting from the interaction of 185 MeV and 2.2 GeV Au ions with 1.0 µm thick amorphous SiN x :H and SiO x :H layers are determined using small angle x-ray scattering measurements. The resulting density profiles resembles an under-dense core surrounded by an over-dense shell with a smooth transition between the two regions, consistent with molecular-dynamics simulations. For amorphous SiN x :H, the density variations show a radius of 4.2 nm with a relative density change three times larger than the value determined for amorphous SiO x :H, with a radius of 5.5 nm. Complementary infrared spectroscopy measurements exhibit a damage cross-section comparable to the core dimensions. The morphology of the density variations results from freezing in the local viscous flow arising from the non-uniform temperature profile in the radial direction of the ion path. The concomitant drop in viscosity mediated by the thermal conductivity appears to be the main driving force rather than the presence of a density anomaly.

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.

SAXS investigations of the morphology of swift heavy ion tracks in α-quartz.

The morphology of swift heavy ion tracks in crystalline α-quartz was investigated using small angle x-ray scattering (SAXS), molecular dynamics (MD) simulations and transmission electron microscopy. Tracks were generated by irradiation with heavy ions with energies between 27 MeV and 2.2 GeV. The analysis of the SAXS data indicates a density change of the tracks of ~2 ± 1% compared to the surrounding quartz matrix for all irradiation conditions. The track radii only show a weak dependence on the electronic energy loss at values above 17 keV nm(-1), in contrast to values previously reported from Rutherford backscattering spectrometry measurements and expectations from the inelastic thermal spike model. The MD simulations are in good agreement at low energy losses, yet predict larger radii than SAXS at high ion energies. The observed discrepancies are discussed with respect to the formation of a defective halo around an amorphous track core, the existence of high stresses and/or the possible presence of a boiling phase in quartz predicted by the inelastic thermal spike model.

Tracks and voids in amorphous Ge induced by swift heavy-ion irradiation.

Ion tracks formed in amorphous Ge by swift heavy-ion irradiation have been identified with experiment and modeling to yield unambiguous evidence of tracks in an amorphous semiconductor. Their underdense core and overdense shell result from quenched-in radially outward material flow. Following a solid-to-liquid phase transformation, the volume contraction necessary to accommodate the high-density molten phase produces voids, potentially the precursors to porosity, along the ion direction. Their bow-tie shape, reproduced by simulation, results from radially inward resolidification.

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.

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.

Large melting-point hysteresis of Ge nanocrystals embedded in SiO2.

The melting behavior of Ge nanocrystals embedded within SiO2 is evaluated using in situ transmission electron microscopy. The observed melting-point hysteresis is large (+/-17%) and nearly symmetric about the bulk melting point. This hysteresis is modeled successfully using classical nucleation theory without the need to invoke epitaxy.