Synthesis of nanostructures in nanowires using sequential catalyst reactions.

Nanowire growth by the vapour-liquid-solid (VLS) process enables a high level of control over nanowire composition, diameter, growth direction, branching and kinking, periodic twinning, and crystal structure. The tremendous impact of VLS-grown nanowires is due to this structural versatility, generating applications ranging from solid-state lighting and single-photon sources to thermoelectric devices. Here, we show that the morphology of these nanostructures can be further tailored by using the liquid droplets that catalyse nanowire growth as a 'mixing bowl', in which growth materials are sequentially supplied to nucleate new phases. Growing within the liquid, these phases adopt the shape of faceted nanocrystals that are then incorporated into the nanowires by further growth. We demonstrate this concept by epitaxially incorporating metal-silicide nanocrystals into Si nanowires with defect-free interfaces, and discuss how this process can be generalized to create complex nanowire-based heterostructures.

The Role of Surface Passivation in Controlling Ge Nanowire Faceting.

In situ transmission electron microscopy observations of nanowire morphologies indicate that during Au-catalyzed Ge nanowire growth, Ge facets can rapidly form along the nanowire sidewalls when the source gas (here, digermane) flux is decreased or the temperature is increased. This sidewall faceting is accompanied by continuous catalyst loss as Au diffuses from the droplet to the wire surface. We suggest that high digermane flux and low temperatures promote effective surface passivation of Ge nanowires with H or other digermane fragments inhibiting diffusion and attachment of Au and Ge on the sidewalls. These results illustrate the essential roles of the precursor gas and substrate temperature in maintaining nanowire sidewall passivation, necessary to ensure the growth of straight, untapered, ⟨111⟩-oriented nanowires.

Au transport in catalyst coarsening and Si nanowire formation.

The motion of Au between AuSi liquid eutectic droplets, both before and during vapor-liquid-solid growth, is important in controlling tapering and diameter uniformity in Si nanowires. We measure the kinetics of coarsening of AuSi droplets on Si(001) and Si(111), quantifying the size evolution of droplets during annealing in ultrahigh vacuum using in situ transmission electron microscopy. For individual droplets, we show that coarsening kinetics are modified when disilane or oxygen is added: coarsening rates increase in the presence of disilane but decrease in oxygen. Matching droplet size measurements on Si(001) with coarsening models confirms that Au transport is driven by capillary forces and that the kinetic coefficients depend on the gas environment present. We suggest that the gas effects are qualitatively similar whether transport is attachment limited or diffusion limited. These results provide insight into manipulating nanowire morphologies for advanced device fabrication.

SnO2 anode surface passivation by atomic layer deposited HfO2 improves Li-ion battery performance.

For the first time, it is demonstrated that nanoscale HfO2 surface passivation layers formed by atomic layer deposition (ALD) significantly improve the performance of Li ion batteries with SnO2 -based anodes. Specifically, the measured battery capacity at a current density of 150 mAg(-1) after 100 cycles is 548 and 853 mAhg(-1) for the uncoated and HfO2 -coated anodes, respectively. Material analysis reveals that the HfO2 layers are amorphous in nature and conformably coat the SnO2 -based anodes. In addition, the analysis reveals that ALD HfO2 not only protects the SnO2 -based anodes from irreversible reactions with the electrolyte and buffers its volume change, but also chemically interacts with the SnO2 anodes to increase battery capacity, despite the fact that HfO2 is itself electrochemically inactive. The amorphous nature of HfO2 is an important factor in explaining its behavior, as it still allows sufficient Li diffusion for an efficient anode lithiation/delithiation process to occur, leading to higher battery capacity.

Jumping-catalyst dynamics in nanowire growth.

Nanowire growth is generally considered a steady-state process, but oscillatory phenomena are known to often play a fundamental role. Here we identify a natural sequence of distinct growth modes, in two of which the catalyst droplet jumps periodically on and off a crystal facet. The oscillatory modes result from a mismatch between catalyst size and wire diameter; they enable growth of straight smooth-sided wires even when the droplet is too small to span the wire tip. Jumping-catalyst growth modes are seen both in computer simulations of vapor-liquid-solid growth, and in movies of Si nanowire growth obtained by in situ microscopy. Our simulations also provide new insight into nanowire kinking.

Growth pathways in ultralow temperature Ge nucleation from Au.

Device integration on flexible or low-cost substrates has driven interest in the low-temperature growth of semiconductor nanostructures. Using in situ electron microscopy, we examine the Au-catalyzed growth of crystalline Ge at temperatures as low as 150 °C. For this materials system, the model for low temperature growth of nanowires, we find three distinct reaction pathways. The lowest temperature reactions are distinguished by the absence of any purely liquid state. From measurements of reaction rates and parameters such as supersaturation, we explain the sequence of pathways as arising from a kinetic competition between the imposed time scale for Ge addition and the inherent time scale for Ge nucleation. This enables an understanding of the conditions under which catalytic Ge growth can occur at very low temperatures, with implications for nanostructure formation on temperature-sensitive substrates.

Evidence for a new tumour suppressor locus (DBM) in human B-cell neoplasia telomeric to the retinoblastoma gene.

Roughly 25% of human B-cell chronic lymphocytic leukaemias (CLL) are characterized by a chromosomal lesion involving 13q14. This region contains the retinoblastoma gene (RB1). We have used a variety of techniques to determine whether RB1 or some other locus is the critical region in 11 cases of low grade B-cell malignancy (mainly CLL), all with deletions or translocations involving 13q14. In all cases, except the one with minimal disease, there was deletion or a structural lesion in the region of D13S25, with at least 4 cases showing homozygous disruption. We conclude that D13S25 lies close to a tumour suppressor locus whose inactivation contributes to the initiation or progression of low grade B-cell malignancy. This locus is located at least 530 kilobases telomeric to RB1.

Atomic-scale transport in epitaxial graphene.

The high carrier mobility of graphene is key to its applications, and understanding the factors that limit mobility is essential for future devices. Yet, despite significant progress, mobilities in excess of the 2×10(5) cm(2) V(-1) s(-1) demonstrated in free-standing graphene films have not been duplicated in conventional graphene devices fabricated on substrates. Understanding the origins of this degradation is perhaps the main challenge facing graphene device research. Experiments that probe carrier scattering in devices are often indirect, relying on the predictions of a specific model for scattering, such as random charged impurities in the substrate. Here, we describe model-independent, atomic-scale transport measurements that show that scattering at two key defects--surface steps and changes in layer thickness--seriously degrades transport in epitaxial graphene films on SiC. These measurements demonstrate the strong impact of atomic-scale substrate features on graphene performance.

The influence of the surface migration of gold on the growth of silicon nanowires.

Interest in nanowires continues to grow, fuelled in part by applications in nanotechnology. The ability to engineer nanowire properties makes them especially promising in nanoelectronics. Most silicon nanowires are grown using the vapour-liquid-solid (VLS) mechanism, in which the nanowire grows from a gold/silicon catalyst droplet during silicon chemical vapour deposition. Despite over 40 years of study, many aspects of VLS growth are not well understood. For example, in the conventional picture the catalyst droplet does not change during growth, and the nanowire sidewalls consist of clean silicon facets. Here we demonstrate that these assumptions are false for silicon nanowires grown on Si(111) under conditions where all of the experimental parameters (surface structure, gas cleanliness, and background contaminants) are carefully controlled. We show that gold diffusion during growth determines the length, shape, and sidewall properties of the nanowires. Gold from the catalyst droplets wets the nanowire sidewalls, eventually consuming the droplets and terminating VLS growth. Gold diffusion from the smaller droplets to the larger ones (Ostwald ripening) leads to nanowire diameters that change during growth. These results show that the silicon nanowire growth is fundamentally limited by gold diffusion: smooth, arbitrarily long nanowires cannot be grown without eliminating gold migration.

Control of structure and spin texture in the van der Waals layered magnet CrSBr.

Controlling magnetism at nanometer length scales is essential for realizing high-performance spintronic, magneto-electric and topological devices and creating on-demand spin Hamiltonians probing fundamental concepts in physics. Van der Waals (vdW)-bonded layered magnets offer exceptional opportunities for such spin texture engineering. Here, we demonstrate nanoscale structural control in the layered magnet CrSBr with the potential to create spin patterns without the environmental sensitivity that has hindered such manipulations in other vdW magnets. We drive a local phase transformation using an electron beam that moves atoms and exchanges bond directions, effectively creating regions that have vertical vdW layers embedded within the initial horizontally vdW bonded exfoliated flakes. We calculate that the newly formed two-dimensional structure is ferromagnetically ordered in-plane with an energy gap in the visible spectrum, and weak antiferromagnetism between the planes, suggesting possibilities for creating spin textures and quantum magnetic phases.

Geometrical frustration in nanowire growth.

Idealized nanowire geometries assume stable sidewalls at right angles to the growth front. Here we report growth simulations that include a mix of nonorthogonal facet orientations, as for Au-catalyzed Si. We compare these with in situ microscopy observations, finding striking correspondences. In both experiments and simulations, there are distinct growth modes that accommodate the lack of right angles in different ways--one through sawtooth-textured sidewalls, the other through a growth front at an angle to the growth axis. Small changes in conditions can reversibly switch the growth between modes. The fundamental differences between these modes have important implications for control of nanowire growth.

Periodically changing morphology of the growth interface in Si, Ge, and GaP nanowires.

Nanowire growth in the standard <111> direction is assumed to occur at a planar catalyst-nanowire interface, but recent reports contradict this picture. Here we show that a nonplanar growth interface is, in fact, a general phenomenon. Both III-V and group IV nanowires show a distinct region at the trijunction with a different orientation whose size oscillates during growth, synchronized with step flow. We develop an explicit model for this structure that agrees well with experiment and shows that the oscillations provide a direct visualization of catalyst supersaturation. We discuss the implications for wire growth and structure.

In situ observations of endotaxial growth of CoSi2 nanowires on Si(110) using ultrahigh vacuum transmission electron microscopy.

We report in situ observations of the growth of endotaxial CoSi(2) nanowires on Si(110) using an ultrahigh vacuum transmission electron microscope with a miniature electron-beam deposition system located above the pole-piece of the objective lens. Metal deposition at 750-850 °C results in formation of coherently strained silicide nanowires with a fixed length/width (L/W) aspect ratio that depends strongly on temperature. Both dimensions evolve with time as L, W ∼ t(1/3). To explain this behavior, we propose a fixed-shape growth mode based on thermally activated facet-dependent reactions. A second growth mode is also observed at 850 °C, with dimensions that evolve as L ∼ t and W ∼ constant. This mode is accompanied by formation of an array of dislocations. We expect that other endotaxial nanowire systems will follow coherently strained growth modes with similar geometrical constraints, as well as dislocated growth modes with different growth kinetics.

Structure, growth kinetics, and ledge flow during vapor-solid-solid growth of copper-catalyzed silicon nanowires.

We use real-time observations of the growth of copper-catalyzed silicon nanowires to determine the nanowire growth mechanism directly and to quantify the growth kinetics of individual wires. Nanowires were grown in a transmission electron microscope using chemical vapor deposition on a copper-coated Si substrate. We show that the initial reaction is the formation of a silicide, eta'-Cu(3)Si, and that this solid silicide remains on the wire tips during growth so that growth is by the vapor-solid-solid mechanism. Individual wire directions and growth rates are related to the details of orientation relation and catalyst shape, leading to a rich morphology compared to vapor-liquid-solid grown nanowires. Furthermore, growth occurs by ledge propagation at the silicide/silicon interface, and the ledge propagation kinetics suggest that the solubility of precursor atoms in the catalyst is small, which is relevant to the fabrication of abrupt heterojunctions in nanowires.

Step-flow kinetics in nanowire growth.

Nanowire growth occurs by step flow at the wire-catalyst interface, with strikingly different step-flow kinetics for solid versus liquid catalysts. Here we report quantitative in situ measurements of step flow together with a kinetic model that reproduces the behavior. This allows us to identify the key parameters controlling step-flow growth, evaluate changes in the catalyst composition during growth, and identify the most favorable conditions for growing abrupt heterojunctions in nanowires.

An off-normal fibre-like texture in thin films on single-crystal substrates.

In the context of materials science, texture describes the statistical distribution of grain orientations. It is an important characteristic of the microstructure of polycrystalline films, determining various electrical, magnetic and mechanical properties. Three types of texture component are usually distinguished in thin films: random texture, when grains have no preferred orientation; fibre texture, for which one crystallographic axis of the film is parallel to the substrate normal, while there is a rotational degree of freedom around the fibre axis; and epitaxial alignment (or in-plane texture) on single-crystal substrates, where an in-plane alignment fixes all three axes of the grain with respect to the substrate. Here we report a fourth type of texture--which we call axiotaxy--identified from complex but symmetrical patterns of lines on diffraction pole figures for thin films formed by solid-state reactions. The texture is characterized by the alignment of planes in the film and substrate that share the same d-spacing. This preferred alignment of planes across the interface manifests itself as a fibre texture lying off-normal to the sample surface, with the fibre axis perpendicular to certain planes in the substrate. This texture forms because it results in an interface, which is periodic in one dimension, preserved independently of interfacial curvature. This new type of preferred orientation may be the dominant type of texture for a wide class of materials and crystal structures.

Determination of size effects during the phase transition of a nanoscale Au-Si eutectic.

The phase diagram of a nanoscale system can be substantially different than in the bulk, but quantitative measurements have proven elusive. Here we use in situ microscopy to observe a phase transition in a nanoscale system, together with a simple quantitative model to extract the size effects from these measurements. We expose a Au particle to disilane gas, and observe the transition from a two-phase Au + AuSi system to single-phase AuSi. Size effects are evident in the nonlinear disappearance of the solid Au. Our analysis shows a substantial shift in the liquidus line, and a discontinuous change in the liquid composition at the transition. It also lets us estimate the liquid-solid interfacial free energy.

Genome complexity in acute lymphoblastic leukemia is revealed by array-based comparative genomic hybridization.

Chromosomal abnormalities are important for the classification and risk stratification of patients with acute lymphoblastic leukemia (ALL). However, approximately 30% of childhood and 50% of adult patients lack abnormalities with clinical relevance. Here, we describe the use of array-based comparative genomic hybridization (aCGH) to identify copy number alterations (CNA) in 58 ALL patients. CNA were identified in 83% of cases, and most frequently involved chromosomes 21 (n=42), 9 (n=21), 6 (n=16), 12 (n=11), 15 (n=11), 8 (n=10) and 17 (n=10). Deletions of 6q (del(6q)) were heterogeneous in size, in agreement with previous data, demonstrating the sensitivity of aCGH to measure CNA. Although 9p deletions showed considerable variability in both the extent and location, all encompassed the CDKN2A locus. Six patients showed del(12p), with a common region encompassing the ETV6 gene. Complex CNA were observed involving chromosomes 6 (n=2), 15 (n=2) and 21 (n=11) with multiple regions of loss and gain along each chromosome. Chromosome 21 CNA shared a common region of gain, with associated subtelomeric deletions. Other recurrent findings included dim(13q), dim(16q) and enh(17q). This is the first report of genome-wide detection of CNA in ALL patients using aCGH, and it has demonstrated a higher level of karyotype complexity than anticipated from conventional cytogenetic analysis.

Deletion of chromosome 13 detected by conventional cytogenetics is a critical prognostic factor in myeloma.

In myeloma, the prognostic impact of different strategies used to detect chromosome 13 deletion (Delta13) remains controversial. To address this, we compared conventional cytogenetics and interphase fluorescence in situ hybridization (iFISH) in a large multicenter study (n=794). The ability to obtain abnormal metaphases was associated with a poor prognosis, which was worse if Delta13, p53 deletion or t(4;14) was present, but only Delta13 remained significant on multivariate analysis. Patients with Delta13, by either cytogenetics or iFISH, had a poor prognosis. However, when cases with Delta13 detectable by both cytogenetics and iFISH were separated from those detected by iFISH only, the poor prognosis of iFISH-detectable Delta13 disappeared; their outcome matched that of patients with no detectable Delta13 (P=0.115). Addition of ploidy status to iFISH-Delta13 did not affect the prognostic value of the test. Indeed both cytogenetics and iFISH Delta13 divided both hyperdiploidy and nonhyperdiploidy into two groups with similar prognoses, indicating that the poor prognosis of ploidy is entirely due to its association with Delta13. We conclude that Delta13 detected by metaphase analysis is a critical prognostic factor in myeloma. Absence of Delta13, even in those patients yielding only normal or no metaphases, is associated with a relatively good prognosis.

In situ study of the growth kinetics of individual island electrodeposition of copper.

The growth kinetics for individual islands during electrodeposition of copper have been studied using in situ transmission electron microscopy. We show that for sufficiently large overpotentials, the growth kinetics approach the rate laws expected for diffusion-limited growth of hemispherical islands, characterized by two distinct regimes. At short times, the island growth exponent is 0.5 as expected for diffusion-limited growth of uncoupled hemispherical islands, while at longer times, the growth exponent approaches 1/6 as expected for planar diffusion to the growing islands. These results provide the first direct measurements of the growth of individual islands during electrochemical deposition. However, quantitative comparison with rate laws shows that the island radii are smaller than predicted and the island densities are much larger than predicted, and we suggest that this is related to adatom formation and surface diffusion, processes which are not included in conventional growth models.