Atomic Resolution in Situ Imaging of a Double-Bilayer Multistep Growth Mode in Gallium Nitride Nanowires.

We study the growth of GaN nanowires from liquid Au-Ga catalysts using environmental transmission electron microscopy. GaN wires grow in either ⟨112̅0⟩ or ⟨11̅00⟩ directions, by the addition of {11̅00} double bilayers via step flow with multiple steps. Step-train growth is not typically seen with liquid catalysts, and we suggest that it results from low step mobility related to the unusual double-height step structure. The results here illustrate the surprising dynamics of catalytic GaN wire growth at the nanoscale and highlight striking differences between the growth of GaN and other III-V semiconductor nanowires.

Stable Self-Catalyzed Growth of III-V Nanowires.

Nanowire growth has generally relied on an initial particle of a catalyst such as Au to define the wire diameter and stabilize the growth. Self-catalyzed growth of III-V nanowires avoids the need for a foreign element, with the nanowire growing from the vapor via a droplet of the native group-III liquid. However, as suggested by Gibbs' phase rule, the absence of third element has a destabilizing effect. Here we analyze this system theoretically, finding that growth can be dynamically stable at pressures far above the equilibrium vapor pressure. Steady-state growth occurs via kinetic self-regulation of the droplet volume and wire diameter. In particular, for a given temperature and source-gas pressures there is a unique stable wire diameter and droplet volume, both of which decrease with increasing V/III ratio. We also examine the evolution of the droplet size and wire diameter toward the steady state as the wire grows and discuss implications for structural control.

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.

Strain-driven mound formation of substrate under epitaxial nanoparticles.

We observe the growth of crystalline SiC nanoparticles on Si(001) at 900 °C using in situ electron microscopy. Following nucleation and growth of the SiC, there is a massive migration of Si, forming a crystalline Si mound underneath each nanoparticle that lifts it 4-5 nm above the initial growth surface. The volume of the Si mounds is roughly five to seven times the volume of the SiC nanoparticles. We propose that relaxation of strain drives the mound formation. This new mechanism for relieving interfacial strain, which involves a dramatic restructuring of the substrate, is in striking contrast to the familiar scenario in which only the deposited material restructures to relieve strain.

Wetting transition for carbon nanotube arrays under metal contacts.

Structural arrays with nanoscale spacing arise in many device concepts. Carbon nanotube transistors are an extreme example, where a practical technology will require arrays of parallel nanotubes with spacing of order 10 nm or less. We show that with decreasing pitch there is a first-order transition, from a robust structure in which the metal wets the substrate between tubes, to a poorly wetting structure in which the metal rides atop the nanotube array without touching the substrate. The latter is analogous to the superhydrophobic "lotus leaf effect." There is a sharp minimum in the delamination energy of metal contacts at the transition pitch. We discuss implications for contact resistance and possible mitigation strategies.

Carbon nanotube deformation and collapse under metal contacts.

In carbon nanotube transistors, typically part of the nanotube is covered by a metal contact. This covered region plays an important role due to the significant electron transfer length. Here we predict that capillary and van der Waals forces cause the nanotube to deform or even collapse under the metal. Nanotubes are known to collapse when their diameters are above some critical value around 4 nm. Under the metal, we find that spontaneous collapse occurs for diameters down to ∼ 1.5-1.6 nm, close to the range used in high-performance transistors. Even at smaller diameters, we find surprisingly large deformations that could significantly affect the electronic structure.

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.

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.

Schottky-to-Ohmic crossover in carbon nanotube transistor contacts.

For carbon nanotube transistors, as for graphene, the electrical contacts are a key factor limiting device performance. We calculate the device characteristics as a function of nanotube diameter and metal work function. Although the on-state current varies continuously, the transfer characteristics reveal a relatively abrupt crossover from Schottky to Ohmic contacts. We find that typical high-performance devices fall surprisingly close to the crossover. Therefore, tunneling plays an important role even in this regime, so that current fails to saturate with gate voltage as was expected due to "source exhaustion."

Origin of quantum ring formation during droplet epitaxy.

Droplet epitaxy of GaAs is studied in real time using in situ surface electron microscopy. The resulting movies motivate a theoretical model for quantum ring formation which can explain the origin of nanoscale features such as double rings observed under a variety of experimental conditions. Inner rings correspond to GaAs deposition at the droplet edge, while outer rings result from the reaction of Ga and As atoms diffusing along the surface. The observed variety of morphologies primarily reflects relative changes in the outer rings with temperature and As flux.

Multiplicity of steady modes of nanowire growth.

For nanowire growth by the vapor-liquid-solid process, we examine whether there is a unique steady-state growth morphology. Applying a continuum model for faceted nanowire evolution to a model crystal structure, we enumerate the possible growth morphologies and calculate their dynamical stability. We find that even for a single set of experimental conditions there can be multiple distinct modes of steady-state growth. The actual growth mode occurring in experiment thus depends on the initial conditions and growth history. Relevant experiments are discussed.

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.

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.

Phonon-mediated interlayer conductance in twisted graphene bilayers.

Conduction between graphene layers is suppressed by momentum conservation whenever the layer stacking has a rotation. Here we show that phonon scattering plays a crucial role in facilitating interlayer conduction. The resulting dependence on orientation is radically different than previously expected, and far more favorable for device applications. At low temperatures, we predict diode-like current-voltage characteristics due to a phonon bottleneck. Simple scaling relationships give a good description of the conductance as a function of temperature, doping, rotation angle, and bias voltage, reflecting the dominant role of the interlayer beating phonon mode.

Deformation and scattering in graphene over substrate steps.

The electrical properties of graphene depend sensitively on the substrate. For example, recent measurements of epitaxial graphene on SiC show resistance arising from steps on the substrate. Here we calculate the deformation of graphene at substrate steps, and the resulting electrical resistance, over a wide range of step heights. The elastic deformations contribute only a very small resistance at the step. However, for graphene on SiC(0001) there is strong substrate-induced doping, and this is substantially reduced on the lower side of the step where graphene pulls away from the substrate. The resulting resistance explains the experimental measurements.

Metastable crystalline AuGe catalysts formed during isothermal germanium nanowire growth.

We observe the formation of metastable AuGe phases without quenching, during strictly isothermal nucleation and growth of Ge nanowires, using video-rate lattice-resolved environmental transmission electron microscopy. We explain the unexpected formation of these phases through a novel pathway involving changes in composition rather than temperature. The metastable catalyst has important implications for nanowire growth, and more broadly, the isothermal process provides both a new approach to growing and studying metastable phases, and a new perspective on their formation.

Anomalous smoothing preceding island formation during growth on patterned substrates.

We show that on suitably pit-patterned Si(001), deposition of just a few atomic layers of Ge can trigger a far larger flow of Si into the pits. This surprising effect results in anomalous smoothing of the substrate preceding island formation in the pits. We show that the effect naturally arises in continuum simulations of growth, and we identify its physical origin in the composition dependence of the surface diffusivity. Our interpretation suggests that anomalous smoothing is likely to also occur in other technologically relevant heteroepitaxial systems.

Elementary processes in nanowire growth.

We propose that many of the complex morpho-logical phenomena observed during nanowire growth arise from the interplay of just three elementary processes: facet growth, droplet statics, and the introduction of new facets. We incorporate these processes into an explicit model for the vapor-liquid-solid growth of fully faceted nanowires. In numerical simulations with this model, different conditions can lead to either growth of a free-standing wire or lateral growth where the catalyst droplet crawls along the surface. An external perturbation can cause the wire to kink into a different direction. Different growth conditions can also change the shape of the growth tip. All of these phenomena have been observed, and the model behavior is consistent with the experimental observations.

Conductance through multilayer graphene films.

The ballistic conductance through junctions between multilayer graphene films and several different metals is studied using ab initio calculations within the local density approximation. The system consists of films of up to four graphene layers (Bernal stacking) between metallic electrodes, assuming reasonable metal-graphene epitaxial relationships. For some metals, the conductance decays exponentially with increasing number of layers, while for others the conductance saturates with film thickness. This difference in asymptotic behavior stems from the crystal momentum (mis)match between the bulk Fermi-level states in the electrode and those in the film. In contrast, for sufficiently thin films the bonding between the metal and the adjacent graphene layer dominates, giving a metal dependence for graphene similar to that seen experimentally for single-wall carbon nanotubes. Among the metals considered here, we find Pd to be the best for electrodes to films with up to 4 graphene layers.

Nonlinear screening in multilayer graphene systems.

Electrostatic screening in multilayer graphene is highly nonlinear due to the vanishing density of states at the Fermi level. Using a discrete model we study the charge screening normal to the layers. Our model shows a strong charge and temperature dependence and has a simple continuum limit at T=0 for undoped systems. Doped systems can exhibit more complex behavior due to minority-carrier screening. Most importantly we find that the screening length can vary more than an order of magnitude depending on the experimental conditions, reconciling the large range of screening lengths reported in previous experiments. This has important consequences for technological applications of multilayer graphene used in electrodes or transistor channels.