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.

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.

Atomic-scale variability and control of III-V nanowire growth kinetics.

In the growth of nanoscale device structures, the ultimate goal is atomic-level precision. By growing III-V nanowires in a transmission electron microscope, we measured the local kinetics in situ as each atomic plane was added at the catalyst-nanowire growth interface by the vapor-liquid-solid process. During growth of gallium phosphide nanowires at typical V/III ratios, we found surprising fluctuations in growth rate, even under steady growth conditions. We correlated these fluctuations with the formation of twin defects in the nanowire, and found that these variations can be suppressed by switching to growth conditions with a low V/III ratio. We derive a growth model showing that this unexpected variation in local growth kinetics reflects the very different supply pathways of the V and III species. The model explains under which conditions the growth rate can be controlled precisely at the atomic level.

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.

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.

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.

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.

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.

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.

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.

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.

Sawtooth faceting in silicon nanowires.

We observe in situ the vapor-liquid-solid (VLS) growth of Si nanowires, in UHV-CVD using Au catalyst. The nanowire sidewalls exhibit periodic sawtooth faceting, reflecting an oscillatory growth process. We interpret the facet alternation as resulting from the interplay of the geometry and surface energies of the wire and liquid droplet. Such faceting may be present in any VLS growth system in which there are no stable orientations parallel to the growth direction. The sawtooth structure has important implications for electronic mobility and scattering in nanowire devices.

In situ reflection electron microscopy of Ge island nucleation on mesa structures.

We have used in situ electron microscopy to observe the nucleation of Ge islands on lithographically patterned Si(001) mesas. Images were obtained at video rate during chemical vapor deposition of Ge, using a reflection electron microscopy geometry that allows nucleation to be observed over large areas. By comparing the kinetics of nucleation and coarsening on substrates modified by different annealing conditions, we find that the final island arrangement depends on the nature of the mesa sidewalls, and we suggest that this may be due to changes in diffusion of Ge across the nonplanar surface.

Critical role of surface steps in the alloying of Ge on Si(001).

Using low-energy electron microscopy, we show that intermixing of Ge on Si(001) during growth is enhanced on stepped surfaces and is hindered on terraces where step flow does not occur. On large terraces we have identified a dramatic and unanticipated structural rearrangement that facilitates intermixing: Pairs of steps spontaneously form and migrate over the surface, leaving alloyed regions in their wake. The driving force for step formation is the entropy gain associated with the enhanced intermixing of Ge.

Influence of supersaturation on surface structure.

Using low-energy electron microscopy, we have investigated the influence of an external flux on the structure of the Si(111) surface during growth and etching at elevated temperatures. We find that varying the adatom supersaturation effectively changes the surface free energies of coexisting 7 x 7 and '1 x 1' regions of the surface. In response, the boundaries separating the phases adopt a new steady-state configuration. The measured configuration can be used to quantitatively determine the difference in free energy between the phases, Deltagamma. The change in Deltagamma provides a measure of the local supersaturation at the surface, and can be interpreted as a change in the phase-transition temperature.

Growth dynamics of pentacene thin films.

The recent demonstration of single-crystal organic optoelectronic devices has received widespread attention. But practical applications of such devices require the use of inexpensive organic films deposited on a wide variety of substrates. Unfortunately, the physical properties of these organic thin films do not compare favourably to those of single-crystal materials. Moreover, the basic physical principles governing organic thin-film growth and crystallization are not well understood. Here we report an in situ study of the evolution of pentacene thin films, utilizing the real-time imaging capabilities of photoelectron emission microscopy. By a combination of careful substrate preparation and surface energy control, we succeed in growing thin films with single-crystal grain sizes approaching 0.1 millimetre (a factor of 20-100 larger than previously achieved), which are large enough to fully contain a complete device. We find that organic thin-film growth closely mimics epitaxial growth of inorganic materials, and we expect that strategies and concepts developed for these inorganic systems will provide guidance for the further development and optimization of molecular thin-film devices.