Crystallographically Determined Etching and Its Relevance to the Metal-Assisted Catalytic Etching (MACE) of Silicon Powders

Metal-assisted catalytic etching (MACE) using Ag nanoparticles as catalysts and H2O2 as oxidant has been performed on single-crystal Si wafers, single-crystal electronics grade Si powders, and polycrystalline metallurgical grade Si powders. The temperature dependence of the etch kinetics has been measured over the range 5–37◦C. Etching is found to proceed preferentially in a h001i direction with an activation energy of ∼0.4 eV on substrates with (001), (110), and (111) orientations. A quantitative model to explain the preference for etching in the h001i direction is developed and found to be consistent with the measured activation energies. Etching of metallurgical grade powders produces particles, the surfaces of which are covered primarily with porous silicon (por-Si) in the form of interconnected ridges. Silicon nanowires (SiNW) and bundles of SiNW can be harvested from these porous particles by ultrasonic agitation. Analysis of the forces acting between the metal nanoparticle catalyst and the Si particle demonstrates that strongly attractive electrostatic and van der Waals interactions ensure that the metal nanoparticles remain in intimate contact with the Si particles throughout the etch process. These attractive forces draw the catalyst toward the interior of the particle and explain why the powder particles are etched equivalently on all the exposed faces

On the self-pinning character of synchro-Shockley dislocations in a Laves phase during strain rate cyclical compressions

Strain rate cyclical tests in compression, between 1350 and 1500 degrees C, have been employed to study the self-pinning character of thermally activated synchro-Shockley dislocations in the C15 Cr2Nb Laves phase. An average minimum effective (pinning) stress was calculated to be necessary for their propagation. The dislocation velocity cannot respond instantly to the strain rate changes and requires variations in the mobile dislocation density because the synchro-Shockleys can be pinned if the cooperating motion of their two Shockley components is hindered. (c) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved

The mechanical properties and the deformation microstructures of the C15 Laves phase Cr2Nb at high temperatures

Compression tests between 1250 and 1550 degrees C and 10(-5) and 5 x 10(-3) s(-1) and transmission electron microscopy have been employed to investigate the high temperature mechanical properties and the deformation mechanisms of the C15 Cr2Nb Laves phase. The stress-peaks in the compression curves during yielding were explained using a mechanism similar to strain aging combined with a low initial density of mobile dislocations. The primary deformation mechanism is slip by extended dislocations with Burgers vector 1/2 <110 >, whereas twinning is more frequent at 10(-4) s(-1). Schmid factor analysis indicated that twinning is more probable in grains oriented so as to have two co-planar twinning systems with high and comparable resolved shear stresses. Twinning produced very anisotropic microstructures. This may be due to synchroshear: a self-pinning mechanism which requires co-operative motion of zonal dislocations. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved

Hierarchical Porous Silicon and Porous Silicon Nanowires Produced with Regenerative Electroless Etching (ReEtching) and Metal Assisted Catalytic Etching (MACE)

ReEtching produces nanostructured silicon when a catalytic agent, e.g. dissolved V2O5, is used to facilitate etching between Si and H2O2. H2O2 regenerates dissolved V in a 5+ oxidation state, which initiates etching by injecting holes into the Si valence band. Independent control over the extent of reaction (controlled by the amount of H2O2 added) and the rate of reaction (controlled by the rate at which H2O2 is pumped into the etchant solution) allows us to porosify Si substrates of arbitrary size, shape and doping, including wafers, single-crystal powders, polycrystalline powders, metallurgical grade powder, Si nanowires, Si pillars and Si powders that have been textured with metal-assisted catalytic etching (MACE). Similarly, improved control over the nucleation and etching in MACE is achieved by pumped delivery of reagents. Nanowires are not produced directly by MACE of powders, rather they form when a porosified layers is cleaved by capillary forces or sonication

Low-Load Metal-Assisted Catalytic Etching Produces Scalable Porosity in Si Powders

The recently discovered low-load metal-assisted catalytic etching (LL-MACE) creates nanostructured Si with controllable and variable characteristics that distinguish this technique from the conventional high-load variant. LL-MACE employs 150 times less metal catalyst and produces porous Si instead of Si nanowires. In this work, we demonstrate that some of the features of LL-MACE cannot be explained by the present understanding of MACE. With mechanistic insight derived from extensive experimentation, it is demonstrated that (1) the method allows the use of not only Ag, Pd, Pt, and Au as metal catalysts but also Cu and (2) judicious combinations of process parameters such as the type of metal, Si doping levels, and etching temperatures facilitate control over yield (0.065−88%), pore size (3−100 nm), specific surface area (20−310 m2·g−1), and specific pore volume (0.05−1.05 cm3·g−1). The porous structure of the product depends on the space-charge layer, which is controlled by the Si doping and the chemical identity of the deposited metal. The porous structure was also dependent on the dynamic structure of the deposited metal. A distinctive comet-like structure of metal nanoparticles was observed after etching with Cu, Ag, Pd, and, in some cases, Pt; this structure consisted of 10−50 nm main particles surrounded by smaller (\u3c5 nm) nanoparticles. With good scalability and precise control of structural properties, LL-MACE facilitates Si applications in photovoltaics, energy storage, biomedicine, and water purification

Noncontact Material Testing Using Low-Energy Optical Generation and Detection of Acoustic Pulses

We will discuss preliminary results on the use of a low-energy laser and a sensitive laser interferometer for noncontact material testing of metals and nonmetals. There have been numerous reports [1–12] on the use of lasers to generate acoustic signals, but this is the first use of a relatively low-energy tunable laser source and improved interferometer to measure acoustic waveforms in both metals and nonmetals [13]. The use of a laser interferometer for the noncontact detection of acoustic pulses has also been reported previously [14–20], but we now report the use of a sensitive “non-Michelson” interferometer with increased signal-to-noise capabilities. The combination of these features allows noncontact, low-energy optical generation and optical detection in a variety of materials, in potentially hostile environments, and provides accurate accoustic waveforms which can be used to characterize specimens. These results, therefore, begin to demonstrate the feasibility of a portable (entirely) optical system for the nondestructive evaluation of materials

Orientational and translational ordering of sub-monolayer films of passivated multiply-twinned gold clusters

The influence of the substrate on the translational and orientational ordering in sub-monolayer films of passivated multiply-twinned gold clusters has been investigated using high resolution and dark field transmission electron microscopy. Although clear differences were observed in the degree of translational ordering on amorphous carbon and etched silicon substrates, there was no corresponding variation in the crystallographic orientation of the nanocrystal cores. The results demonstrate that the orientation of passivated clusters with multiply-twinned cores is effectively random with respect to both the superlattice and the substrate

Crystallographically Determined Etching and Its Relevance to the Metal-Assisted Catalytic Etching (MACE) of Silicon Powders

Metal-assisted catalytic etching (MACE) using Ag nanoparticles as catalysts and H2O2 as oxidant has been performed on single-crystal Si wafers, single-crystal electronics grade Si powders, and polycrystalline metallurgical grade Si powders. The temperature dependence of the etch kinetics has been measured over the range 5–37°C. Etching is found to proceed preferentially in a 〈001〉 direction with an activation energy of ~0.4 eV on substrates with (001), (110), and (111) orientations. A quantitative model to explain the preference for etching in the 〈001〉 direction is developed and found to be consistent with the measured activation energies. Etching of metallurgical grade powders produces particles, the surfaces of which are covered primarily with porous silicon (por-Si) in the form of interconnected ridges. Silicon nanowires (SiNW) and bundles of SiNW can be harvested from these porous particles by ultrasonic agitation. Analysis of the forces acting between the metal nanoparticle catalyst and the Si particle demonstrates that strongly attractive electrostatic and van der Waals interactions ensure that the metal nanoparticles remain in intimate contact with the Si particles throughout the etch process. These attractive forces draw the catalyst toward the interior of the particle and explain why the powder particles are etched equivalently on all the exposed faces