▪ Abstract Obtaining a good atomistic description of diffusion dynamics in materials has been a daunting task owing to the time-scale limitations of the molecular dynamics method. We discuss promising new methods, derived from transition state theory, for accelerating molecular dynamics simulations of these infrequent-event processes. These methods, hyperdynamics, parallel replica dynamics, temperature-accelerated dynamics, and on-the-fly kinetic Monte Carlo, can reach simulation times several orders of magnitude longer than direct molecular dynamics while retaining full atomistic detail. Most applications so far have involved surface diffusion and growth, but it is clear that these methods can address a wide range of materials problems.

The energetics of nanoclusters is investigated for five different metals (Ag, Cu, Au, Pd, and Pt) by means of quenched molecular dynamics simulations. Results are obtained for two different semiempirical potentials. Three different structural motifs are considered: icosahedra (Ih), decahedra (Dh), and truncated octahedra (TO). The crossover sizes among structural motifs are directly calculated, considering cluster up to sizes $\text{N≃40\hspace{0.05em}000.}$ For all the systems considered, it is found that icosahedra are favored at small sizes, decahedra at intermediate sizes, and truncated octahedra at large sizes. However, the crossover sizes depend strongly on the metal: in Cu, the icosahedral interval is rather large, and it is followed by a very wide decahedral window; on the contrary, in Au, the icosahedral interval is practically absent, and the decahedral window is narrow. The other metals display intermediate behaviors, Ag being close to Cu, and Pd and Pt being close to Au. A simple criterion, which is based on the ratio between the bulk modulus and the cohesive energy per atom, is developed to account for the differences among the metals.

We present a molecular-dynamics simulation of self-diffusion on the (110) surfaces of Cu, Ag, and Au. The metals are modeled by semiempirical potentials developed in the framework of the second-moment approximation to the tight-binding model. The energy barriers for the relevant diffusion processes are calculated by quenched molecular dynamics and compared with the available data in literature, obtaining a good agreement. The occurrence of long jumps is investigated in detail, showing that the three metals behave quite differently with this respect: long jumps are practically absent in Au and frequent in Cu. The effect of the specific features of the potential-energy surface and of the energy dissipation to the substrate on the probability of long jumps is investigated. The Arrhenius behavior of the jump rate is discussed, and deviations are found at high temperatures. Concerning correlated jump-exchange processes and double exchanges, we find that they are common in Cu even at rather low temperatures, whereas they are never observed in Au, Ag showing an intermediate behavior.

By high resolution scanning tunneling microscopy, we investigate the morphological transition from pyramid to dome islands during the growth of Ge on Si(001). We show that pyramids grow from top to bottom and that, from a critical size on, incomplete facets are formed. We demonstrate that the bunching of the steps delimiting these facets evolves into the steeper dome facets. Based on first principles and Tersoff-potential calculations, we develop a microscopic model for the onset of the morphological transition, able to reproduce closely the experimentally observed behavior.

The commonly accepted Stranski-Krastanow model, according to which island formation occurs on top of a wetting layer (WL) of a certain thickness, predicts for the morphological evolution an increasing island aspect ratio with volume. We report on an apparent violation of this thermodynamic understanding of island growth with deposition. In order to investigate the actual onset of three-dimensional islanding and the critical WL thickness in the Ge/Si(001) system, a key issue is controlling the Ge deposition with extremely high resolution [0.025 monolayer (ML)]. Atomic force microscopy and photoluminescence measurements on samples covering the deposition range 1.75–6.1 ML, taken along a Ge deposition gradient on 4 in. Si substrates and at different growth temperatures $\left(T_{\text{g}}\right)$, surprisingly reveal that for $T_{\text{g}}>675°\text{C}$ steeper multifaceted domes apparently nucleate prior to shallow {105}-faceted pyramids, in a narrow commonly overlooked deposition range. The puzzling experimental findings are explained by a quantitative modeling of the total energy with deposition. We accurately matched ab initio calculations of layer and surface energies to finite-element method simulations of the elastic energy in islands, in order to compare the thermodynamic stability of different island shapes with respect to an increasing WL thickness. Close agreement between modeling and experiments is found, pointing out that the sizeable progressive lowering of the surface energy in the first few MLs of the WL reverts the common understanding of the SK growth onset. Strong similarities between islanding in SiGe and III/V systems are highlighted.

Self-assembled Ge wires with a height of only 3 unit cells and a length of up to 2 micrometers were grown on Si(001) by means of a catalyst-free method based on molecular beam epitaxy. The wires grow horizontally along either the [100] or the [010] direction. On atomically flat surfaces, they exhibit a highly uniform, triangular cross section. A simple thermodynamic model accounts for the existence of a preferential base width for longitudinal expansion, in quantitative agreement with the experimental findings. Despite the absence of intentional doping, the first transistor-type devices made from single wires show low-resistive electrical contacts and single-hole transport at sub-Kelvin temperatures. In view of their exceptionally small and self-defined cross section, these Ge wires hold promise for the realization of hole systems with exotic properties and provide a new development route for silicon-based nanoelectronics.