David Llewellyn

Structural perturbations within Ge nanocrystals in silica

Extended x-ray absorption fine structure (EXAFS) spectroscopy was used to identify structural perturbations in Ge nanocrystals produced in silica by ion implantation and annealing. Although the nanocrystals retained tetrahedral coordination, both the short- and medium-range orders were perturbed relative to bulk crystalline material. Equivalently, the nanocrystal interatomic distance distribution deviated from that of bulk crystalline Ge, exhibiting enhanced structural disorder of both Gaussian and non-Gaussian forms in the first, second, and third nearest-neighbor shells. The relative influences of nanocrystal size, bonding distortions, multiple phases, and a matrix-induced compression were considered.

Structural characterization of Cu nanocrystals formed in SiO2 by high-energy ion-beam synthesis

Cu nanocrystals (NCs) were produced by multiple high-energy ion implantations into 5‐μm-thick amorphous silica (SiO2) at liquid-nitrogen temperature. The Cu-rich SiO2 films were subsequently annealed to reduce irradiation-induced damage and promote NC formation. The NC size distribution and structure were studied utilizing a combination of Rutherford backscattering spectroscopy, x-ray diffraction, cross-sectional transmission electron microscopy, and extended x-ray-absorption fine-structure (EXAFS) spectroscopy. We present results derived from all four techniques, focussing on EXAFS measurements to study the local atomic structure surrounding Cu atoms, and comparing NC samples with bulk standards. Using a unique sample preparation method, we drastically improve the signal-to-noise ratio to extract high-quality EXAFS data to enable the determination of a non-Gaussian bond length distribution via the third-order cumulant. We quantify subtle concentration- and annealing-temperature-dependent changes in the C...

Amorphization of embedded Cu nanocrystals by ion irradiation

While bulk crystalline elemental metals cannot be amorphized by ion irradiation in the absence of chemical impurities, the authors demonstrate that finite-size effects enable the amorphization of embedded Cu nanocrystals. The authors form and compare the atomic-scale structure of the polycrystalline, nanocrystalline, and amorphous phases, present an explanation for the extreme sensitivity to irradiation exhibited by nanocrystals, and show that low-temperature annealing is sufficient to return amorphized material to the crystalline form.

Pt nanocrystals formed by ion implantation: a defect-mediated nucleation process

The influence of ion irradiation of SiO2 on the size of metal nanocrystals (NCs) formed by ion implantation has been investigated. Thin SiO2 films were irradiated with high-energy Ge ions then implanted with Pt ions. Without Ge irradiation, the largest Pt NCs were observed beyond the Pt projected range. With irradiation, Ge-induced structural modification of the SiO2 layer yielded a decrease in Pt NC size with increasing Ge fluence at such depths. A defect-mediated NC nucleation mechanism is proposed and a simple yet effective means of modifying and controlling the Pt NC size is demonstrated.

Analytical electron microscopy in clays and other phyllosilicates; loss of elements from a 90-nm stationary beam of 300-keV electrons

Diffusion of alkali and low-atomic-number elements during the microbeam analysis of some silicates by analytical electron microscopy (AEM) has been known for some time. Our repeated analyses at 300 kV of kaolinite, halloysite, smectite, biotite, muscovite and pyrophyllite, however, showed differential loss (relative to Si) of not only alkali elements (such as K, Na, Mg) and low-atomic-number elements (such as Al) but also higher-atomic-number elements (such as Fe, Ti). For AEM of these phyllosilicates, a Philips EM430/EDAX facility with a tungsten filament was used to provide a current of 0.3 nA in a stationary beam of nominal diameter 90 nm. The loss of Al in kaolin minerals during analysis is particularly severe. Kaolin crystals can be damaged by the electron irradiation over several seconds, making it the most sensitive clay to the electron beam; in general, relative phyllosilicate stabilities are kaolin < smectite < pyrophyllite < mica. A clear dependence of element loss on crystallographic orientation has been observed for layer silicates in our study; a greater element loss occurred when the plane of the specimen foil was perpendicular to the basal planes of the phyllosilicate crystals than when the foil was parallel to the basal planes. Lower beam current, larger beam diameter and thicker specimens all reduce the loss of elements. The initial stage of irradiation produces highest rates of element loss and the rate of loss can be fitted by an exponential decay law. The analyses at low temperature of phyllosilicates showed that element loss remains serious in our analytical conditions. Since the element loss appears to be instrument- and method-dependent, one should use closely related, well-characterized phyllosilicates as compositional standards to calibrate any AEM instrument that is to be used to analyze unknown phyllosilicates, and the standards and unknowns should be analyzed under identical conditions.

Trapping of Pd, Au, and Cu by implantation-induced nanocavities and dislocations in Si

The gettering of metallic impurities by nanocavities formed in Si is a topic of both scientific importance and technological significance. Metallic precipitates observed in the regions where nanocavities were formed have been considered the result of the metal filling the nanocavities, either as elemental metal or a silicide phase. However, our transmission electron microscopy observations demonstrate that many of these precipitates are concentrated along dislocations, rather than randomly distributed as expected for precipitates formed by the filling of nanocavities. Consequently, the gettering contribution of dislocations in the lattice caused by nanocavity formation must be considered. For Pd, dislocations are the preferred sites for the precipitation of the metal silicide. We compare results of gettering by nanocavities and dislocations for Pd, Au, and Cu to determine which structure is the dominant influence for the formation of precipitates of these metals and/or their silicides.

Instability of nanocavities in amorphous silicon

This letter demonstrates that, whereas nanocavities are quite stable in crystalline Si (c-Si), they are unstable in amorphous Si (a-Si). This behavior is illustrated by introducing a band of nanocavities into c-Si by H implantation, followed by annealing at 850 °C. Amorphization of the c-Si surrounding the nanocavities led to their disappearance. Transmission electron microscopy, Rutherford backscattering, and channeling and time resolved (optical) reflectivity were used to provide details of the cavity instability process by studying the amorphous Si after implantation and subsequent crystallization. Two possible reasons are suggested for the instability of nanocavities in a-Si.

Gettering of Pd to implantation-induced nanocavities in Si

The authors thank the Australian Research Council for their financial support. G.deM.A. acknowledges the Brazilian agency CNPq ~Conselho Nacional de Desenvolvimento Cienti´fico e Tecnolo´gico! for a postdoctoral fellowship.

Implantation and annealing of Cu in InP for electrical isolation: microstructural characterisation

The formation of metallic precipitates to produce embedded Schottky barriers within a conductive layer has been investigated as a potentially new form of implantation-induced isolation. Accordingly, Cu-implanted InP has been characterised with Rutherford backscattering spectrometry, transmission electron microscopy and secondary ion mass spectrometry as functions of implantation and annealing temperatures. Substrates implanted at room temperature were amorphised, resulting in greater post-anneal disorder in the form of microtwins and dislocations. However, annealing-induced Cu diffusion was reduced in such samples as attributed to gettering at end-of-range disorder. Additional defect centres, potentially Cu-based precipitates, were also observed. Further to the structural characterisation presented herein, complementary electrical measurements are necessary to deduce the appropriate combination of residual disorder and precipitate concentration to yield electrical compensation. This will ultimately determine the viability of this isolation technology for producing extremely resistive substrates for very high frequency devices.

Solid‐phase epitaxial growth of amorphized GaAs: The influence of microscopic nonstoichiometry

The solid‐phase epitaxial growth of amorphized GaAs has been characterized with a variety of techniques to investigate the influence of microscopic nonstoichiometry on the onset of twinning and subsequent interfacial nonplanarity. Nonstoichiometry on a local, microscopic scale (or equivalently, chemical disorder) can result from the statistical nature of the ion recoiling and stopping processes. For the present study, microscopic nonstoichiometry was produced by implanting samples with equal doses of both Ga and As ions. The onset of twinning and subsequent interfacial nonplanarity were not correlated with the energy deposited in vacancy production – the latter considered a first estimate of relative differences in microscopic nonstoichiometry between samples. Such observations are potentially indicative of the saturation of microscopic nonstoichiometry over the given dose range.