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.

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.

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.

The influence of laser-induced nanosecond rise-time stress waves on the microstructure and surface chemical activity of single crystal Cu nanopillars.

An apparatus and test procedure for fabrication and loading of single crystal metal nanopillars under extremely high pressures (>1 GPa) and strain rates (>107 s-1), using laser-generated stress waves, are presented. Single-crystalline Cu pillars (∼1.20 µm in tall and ∼0.45 µm in diameter) prepared via focused ion beam milling of Cu(001) substrates are shock-loaded using this approach with the dilatational stress waves propagating along the [001] axis of the pillars. Transmission electron microscopy observations of shock-loaded pillars show that dislocation density decreases and that their orientation changes with increasing stress wave amplitude, indicative of dislocation motion. The shock-loaded pillars exhibit enhanced chemical reactivity when submerged in oil and isopropyl alcohol solutions, due likely to the exposure of clean surfaces via surface spallation and formation of surface steps and nanoscale facets through dislocation motion to the surface of the pillars, resulting in growth of thin oxide films on the surfaces of the pillars.

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.

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.

Formation of compositionally abrupt axial heterojunctions in silicon-germanium nanowires.

We have formed compositionally abrupt interfaces in silicon-germanium (Si-Ge) and Si-SiGe heterostructure nanowires by using solid aluminum-gold alloy catalyst particles rather than the conventional liquid semiconductor-metal eutectic droplets. We demonstrated single interfaces that are defect-free and close to atomically abrupt, as well as quantum dots (i.e., Ge layers tens of atomic planes thick) embedded within Si wires. Real-time imaging of growth kinetics reveals that a low solubility of Si and Ge in the solid particle accounts for the interfacial abruptness. Solid catalysts that can form functional group IV nanowire-based structures may yield an extended range of electronic applications.

In situ electron backscattered diffraction of individual GaAs nanowires.

We suggest and demonstrate that electron backscattered diffraction, a scanning electron microscope-based technique, can be used for non-destructive structural and morphological characterization of statistically significant number of nanowires in situ on their growth substrate. We obtain morphological, crystal phase, and crystal orientation information of individual GaAs nanowires in situ on the growth substrate GaAs(111) B. Our results, verified using transmission electron microscopy and selected area electron diffraction analyses of the same set of wires, indicate that most wires possess a wurtzite structure with a high density of thin structural defects aligned normal to the wire growth axis, while others grow defect-free with a zincblende structure. The demonstrated approach is general, applicable to other material systems, and is expected to provide important insights into the role of substrate structure on nanowire structure on nanowire crystallinity and growth orientation.

Kinetics of individual nucleation events observed in nanoscale vapor-liquid-solid growth.

We measured the nucleation and growth kinetics of solid silicon (Si) from liquid gold-silicon (AuSi) catalyst particles as the Si supersaturation increased, which is the first step of the vapor-liquid-solid growth of nanowires. Quantitative measurements agree well with a kinetic model, providing a unified picture of the growth process. Nucleation is heterogeneous, occurring consistently at the edge of the AuSi droplet, yet it is intrinsic and highly reproducible. We studied the critical supersaturation required for nucleation and found no observable size effects, even for systems down to 12 nanometers in diameter. For applications in nanoscale technology, the reproducibility is essential, heterogeneity promises greater control of nucleation, and the absence of strong size effects simplifies process design.

Germanium nanowire growth below the eutectic temperature.

Nanowires are conventionally assumed to grow via the vapor-liquid-solid process, in which material from the vapor is incorporated into the growing nanowire via a liquid catalyst, commonly a low-melting point eutectic alloy. However, nanowires have been observed to grow below the eutectic temperature, and the state of the catalyst remains controversial. Using in situ microscopy, we showed that, for the classic Ge/Au system, nanowire growth can occur below the eutectic temperature with either liquid or solid catalysts at the same temperature. We found, unexpectedly, that the catalyst state depends on the growth pressure and thermal history. We suggest that these phenomena may be due to kinetic enrichment of the eutectic alloy composition and expect these results to be relevant for other nanowire systems.

Real time observation of GeSi/Si(001) island shrinkage due to surface alloying during Si capping.

The Si capping of Ge/Si(001) islands was observed by in situ time-resolved transmission electron microscopy. During the initial stages of the Si deposition, islands were observed not only to flatten but also to shrink in volume. This unexpected shrinkage is explained by taking into account the intermixing of the deposited Si with the wetting layer and a consequently induced diffusion of Ge from the islands into the wetting layer. A model of the capping process which takes into account Ge diffusion is presented which is in good agreement with the experimental data.

Sublimation of atomic layers from a chromium surface.

We employ low-energy electron microscopy to study the kinetics of thermal etching, or sublimation, of Cr(001) at approximately 1100 K. Atomic layers are removed from the surface by spontaneous nucleation and growth of two-dimensional vacancy islands, by rotation of spiral steps, and by island decay. The growth rates of vacancy islands and the rotation frequencies of double spirals are measured as a function of temperature, and the results are correlated with activation barriers of surface processes. Mass transport between the surface and bulk is shown to be unimportant.

Diameter-independent kinetics in the vapor-liquid-solid growth of Si nanowires.

We examine individual Si nanowires grown by the vapor-liquid-solid mechanism, using real-time in situ ultra high vacuum transmission electron microscopy. By directly observing Au-catalyzed growth of Si wires from disilane, we show that the growth rate is independent of wire diameter, contrary to the expected behavior. Our measurements show that the unique rate-limiting step here is the irreversible, kinetically limited, dissociative adsorption of disilane directly on the catalyst surface. We also identify a novel dependence of growth rate on wire taper.

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.

Dislocation-driven surface dynamics on solids.

Dislocations are line defects that bound plastically deformed regions in crystalline solids. Dislocations terminating on the surface of materials can strongly influence nanostructural and interfacial stability, mechanical properties, chemical reactions, transport phenomena, and other surface processes. While most theoretical and experimental studies have focused on dislocation motion in bulk solids under applied stress and step formation due to dislocations at surfaces during crystal growth, very little is known about the effects of dislocations on surface dynamics and morphological evolution. Here we investigate the near-equilibrium dynamics of surface-terminated dislocations using low-energy electron microscopy. We observe, in real time, the thermally driven nucleation and shape-preserving growth of spiral steps rotating at constant temperature-dependent angular velocities around cores of dislocations terminating on the (111) surface of TiN in the absence of applied external stress or net mass change. We attribute this phenomenon to point-defect migration from the bulk to the surface along dislocation lines. Our results demonstrate that dislocation-mediated surface roughening can occur even in the absence of deposition or evaporation, and provide fundamental insights into mechanisms controlling nanostructural stability.

Size-dependent detachment-limited decay kinetics of two-dimensional TiN islands on TiN(111).

In situ high-temperature (T(a)=1050-1250 K) scanning tunneling microscopy was used to determine the coarsening and decay kinetics of two-dimensional TiN adatom and vacancy islands on atomically smooth TiN(111) terraces. We report the first observation of an abrupt decrease in decay rates, irrespective of T(a), of adatom islands with areas less than a critical value of 1600 A(2). However, no decay rate transition was observed for vacancy islands. We attribute the size-dependent island decay behavior, which is consistent with detachment-limited kinetics, to anisotropic attachment and detachment barriers.

Absolute TiN(111) step energies from analysis of anisotropic island shape fluctuations.

In situ high-temperature (1165-1248 K) scanning tunneling microscopy was used to measure fluctuations around the equilibrium shape of two-dimensional vacancy islands on TiN(111) terraces. From the equilibrium shape, the ratio of the two <110> step energies was found to be 0.72 +/- 0.02. Combining this with the results of an exact approach for analysis of shape fluctuations, applicable to highly anisotropic islands, we obtain absolute values for step energies and step stiffnesses as a function of orientation.