Colossal injection of catalyst atoms into silicon nanowires.

The incorporation of impurities during the growth of nanowires from the vapour phase alters their basic properties substantially, and this process is critical in an extended range of emerging nanometre-scale technologies. In particular, achieving precise control of the behaviour of group III and group V dopants has been a crucial step in the development of silicon (Si) nanowire-based devices. Recently it has been demonstrated that the use of aluminium (Al) as a growth catalyst, instead of the usual gold, also yields an effective p-type doping, thereby enabling a novel and efficient route to functionalizing Si nanowires. Besides the technological implications, this self-doping implies the detachment of Al from the catalyst and its injection into the growing nanowire, involving atomic-scale processes that are crucial for the fundamental understanding of the catalytic assembly of nanowires. Here we present an atomic-level, quantitative study of this phenomenon of catalyst dissolution by three-dimensional atom-by-atom mapping of individual Al-catalysed Si nanowires using highly focused ultraviolet-laser-assisted atom-probe tomography. Although the observed incorporation of the catalyst atoms into nanowires exceeds by orders of magnitude the equilibrium solid solubility and solid-solution concentrations in known non-equilibrium processes, the Al impurities are found to be homogeneously distributed in the nanowire and do not form precipitates or clusters. As well as the anticipated effect on the electrical properties, this kinetics-driven colossal injection also has direct implications for nanowire morphology. We discuss the observed strong deviation from equilibrium using a model of solute trapping at step edges, and identify the key growth parameters behind this phenomenon on the basis of a kinetic model of step-flow growth of nanowires. The control of this phenomenon provides opportunities to create a new class of nanoscale devices by precisely tailoring the shape and composition of metal-catalysed nanowires.

Organic crystal lattices in the axial filament of silica spicules of Demospongiae.

The skeletal system of Demospongiae consists of siliceous spicules, which are composed of an axial channel containing an organic axial filament (AF) surrounded by a compact layer of hydrated amorphous silica. Here we report the ultrastructural investigations of the AF of siliceous spicules from two Demospongiae: Suberites domuncula and Tethya aurantium. Electron microscopy, electron diffraction and elemental mapping analyses on both longitudinal and transversal cross-sections yield that spicules's AF consist of a three-dimensional crystal lattice of six-fold symmetry. Its structure, which is the result of a biological growth process, is a crystalline assembly characterized by a lattice of organic cages (periodicity in the range of 6nm) filled with enzymatically-produced silica. In general, the six-fold lattice symmetry is reflected by the morphology of the AF, which is characterized by six-fold facets. This seems to be the result of a lattice energy minimization process similar to the situation found during the growth of inorganic crystals. Our structural exploitation of three-dimensional organic lattices generated by biological systems is expected to contribute for explaining the relation between axial filament's ultrastructure and spicule's ultimate morphology.

Electron microscope analyses of the bio-silica basal spicule from the Monorhaphis chuni sponge.

We report on a structural analysis of several basal spicules of the deep-sea silica sponge Monorhaphis chuni by electron microscope techniques supported by a precise focused ion beam (FIB) target preparation. To get a deeper understanding of the spicules length growth, we concentrated our investigation onto the apical segments of two selected spicules with apparently different growth states and studied in detail permanent and temporary growth structures in the central compact silica axial cylinder (AC) as well as the structure of the organic axial filament (AF) in its center. The new findings concern the following morphology features: (i) at the tip we could identify thin silica layers, which overgrow as a tongue-like feature the front face of the AC and completely fuse during the subsequent growth state. This basically differs from the radial growth of the surrounding lamellar zone of the spicules made of alternating silica lamellae and organic interlayers. (ii) A newly detected disturbed cylindrical zone in the central region of the AC (diameter about 30 µm) contains vertical and horizontal cavities, channels and agglomerates, which can be interpreted as permanent leftover of a formerly open axial channel, later filled by silica. (iii) The AF consists of a three-dimensional crystal-like arrangement of organic molecules and amorphous silica surrounding these molecules. Similar to an inorganic crystal, this encased protein crystal is typified by crystallographic directions, lattice planes and surface steps. The 〈001〉 growth direction is especially favored, thereby scaffolding the axial cylinders growth and consequently the spicules' morphology.

Improving accuracy and precision of strain analysis by energy-filtered nanobeam electron diffraction.

This article deals with uncertainty in the analysis of strain in silicon nanoscale structures and devices using nanobeam electron diffraction (NBED). Specimen and instrument related errors and instabilities and their effects on NBED analysis are addressed using a nanopatterned ultrathin strained silicon layer directly on oxide as a model system. We demonstrate that zero-loss filtering significantly improves the NBED precision by decreasing the diffuse background in the diffraction patterns. To minimize the systematic deviations the acquired data were verified through a reliability test and then calibrated. Furthermore, the effect of strain relaxation by specimen preparation using a FIB is estimated by comparing profiles, which were acquired by analyzing slices of strained structures in a 220-nm-thick region of the sample (invasive preparation) and the entire strained nanostructures, which are embedded in a thicker region of the same sample (noninvasive preparation). Together with the random deviation, the corresponding systematic shift results in a total deviation of ∼1 × 10(-3) for NBED analyses, which is employed to estimate the measurement uncertainty in the thinner sample region. In contrast, the strain in the thick sample region is not affected by the preparation; the systematic shift reduces to a minimum, which improves the total deviation by ∼50%.

Nano-channels in the spider fang for the transport of Zn ions to cross-link His-rich proteins pre-deposited in the cuticle matrix.

We identify the presence of multiple vascular channels within the spider fang. These channels seem to serve the transport of zinc to the tip of the fang to cross-link the protein matrix by binding to histidine residues. According to amino acid and elemental analysis of fangs extracted shortly after ecdysis, His-rich proteins are deposited before Zn is incorporated into the cuticle. Microscopic and spectroscopic investigations in the electron microscope and synchrotron radiation experiments suggest that Zn ions are transported through these channels in a liable (yet unidentified) form, and then form stable complexes upon His binding. The resulting cross-linking through the Zn-His complexes is conferring hardness to the fang. Our observations of nano-channels serving the Zn-transport within the His-rich protein matrix of the fibre reinforced spider fang may also support recent bio-inspired attempts to design artificial polymeric vascular materials for self-healing and in-situ curing.

Weyl Semimetals as Hydrogen Evolution Catalysts.

The search for highly efficient and low-cost catalysts is one of the main driving forces in catalytic chemistry. Current strategies for the catalyst design focus on increasing the number and activity of local catalytic sites, such as the edge sites of molybdenum disulfides in the hydrogen evolution reaction (HER). Here, the study proposes and demonstrates a different principle that goes beyond local site optimization by utilizing topological electronic states to spur catalytic activity. For HER, excellent catalysts have been found among the transition-metal monopnictides-NbP, TaP, NbAs, and TaAs-which are recently discovered to be topological Weyl semimetals. Here the study shows that the combination of robust topological surface states and large room temperature carrier mobility, both of which originate from bulk Dirac bands of the Weyl semimetal, is a recipe for high activity HER catalysts. This approach has the potential to go beyond graphene based composite photocatalysts where graphene simply provides a high mobility medium without any active catalytic sites that have been found in these topological materials. Thus, the work provides a guiding principle for the discovery of novel catalysts from the emerging field of topological materials.

A perfectly periodic three-dimensional protein/silica mesoporous structure produced by an organism.

The discovery of perfectly ordered 3D mesoporous protein/silica structure in the axial filament of the marine sponge Monorhaphis chuni is reported. The structure belongs to body-centered tetragonal symmetry system (a=9.88 nm, c=10.83 nm) and comprises interconnecting lattices of protein and silica, templated by the self-assembled, enzymatically active protein-silicatein, whose primary function is the precipitation of silica.