First-principles study of the α-Al2O3(0001)/Cu(111) interface

Adhesive energetics and interfacial electronic structures have been computed from first principles for the Cu/Al₂O₃ interface. Recent transmission electron microscopy results of Cu grown by molecular beam epitaxy on Al₂O₃(0001) were helpful in modelling the interfacial atomic structure. We found that Al₂O₃(0001) relaxation effects can lower the work of adhesion W _ad by over a factor of 3. Our computed W _ad value is in reasonably good agreement with experiment, being somewhat larger, as expected from our assumption of a coherent interface. One might begin to understand this metal/ceramic adhesion as a competition between Cu and Al for oxide formation, which is easily won by Al. However this simple picture is complicated by several indications of a significant metallic/covalent component to the Cu/Al₂O₃ adhesive bond.     

Discrete dislocation simulations of the development of a continuum plastic zone ahead of a stationary Mode III crack

We present results from discrete dislocation simulations showing the development of the plastic zone in front of a Mode III crack under constant load. We find that the equilibrated zone is circular, in agreement with continuum mechanics predictions of the elastic-perfectly plastic Mode III crack. The size of the equilibrated zone scales as the square of the applied load (K_III), also in agreement with the continuum results. The zone approaches saturation exponentially, with a time that scales as K_III²/σ_p³, where σ_p is the Peierls stress. These results delineate conditions under which the classical, continuum predictions of elastic-plastic fracture mechanics are applicable.     

H-transfer rates in ion-neutral complexes versus those in intact aliphatic ions

The relative rates of H-transfer between partners in ion-neutral complexes were compared with those in intramolecular rearrangements using results of first differential photoionization mass spectrometry measurements. Complex-mediated H-transfers are inferred to have rates of the same order as those for intramolecular hydrogen rearrangements, suggesting a similar range of motion of the reactive sites in both types of reactions. It is also concluded that at their fastest H-transfers take place between the partners in ion-neutral complexes within at most the time of several rotations of the partners in the complexes. Copyright 1999 John Wiley & Sons, Ltd.     

New high-energy luminescence bands from Co2+ in ZnSe

Three sharp absorption features in the energy range 2.36–2.55 eV have been detected in the transmission spectrum of Co-diffused ZnSe, and a number of luminescence transitions originating from the lowest of these states at 2.361 eV have been observed. Photoluminescence excitation spectra prove that these are high energy excited states of the Co²⁺_Zn impurity, a conclusion confirmed by comparison of measured and predicted luminescence energies. This represents the first identification of luminescence branching from a higher excited state of a transition metal ion in any semiconductor. The sharp, weakly phonon-coupled transitions involve either intra-impurity excitation or transitions from the impurity to localised states split off from a minimum in the conduction band. The implications of these observations for the mechanism of host-impurity energy transfer and for the nature of the excited state wavefunctions are discussed.     

Morphological instability and additive-induced stabilization in electrodeposition

Experiments show that electrodeposited (ED) films exhibit rough surfaces unless the electrochemical bath contains small quantities of molecular "additive" species. We develop a model for ED with additives which shows the suppression of the morphological instability by preferential additive accumulation near surface protrusions due to complex formation and additive codeposition, and subsequent growth site blocking. Linearly stable growth can be achieved over a wide range of deposition flux at sufficiently large additive bulk concentration. We predict the growth conditions necessary for level surfaces, in good agreement with experiments.     

Shear ordering in thin films of spherical block copolymer

We have investigated shear-induced alignment of a bilayer of spherical diblock copolymer micelles within thin films using molecular dynamics simulations at two different levels of coarse-graining. At the microscopic level, the copolymers are modeled as bead and spring chains with specific interaction potentials which produce strongly segregated spherical micelles. The simulations qualitatively reveal that long-range shear-induced ordering of hexagonally arranged micelles arises because of the tendency of micelles to pursue trajectories of minimum frictional resistance against micelles in the opposing layer. This influences their alignment in the direction of shear without them breaking apart and reforming within the time scale of the simulations. As observed in experiments, the ordering is shown to be very sensitive to the film thickness and shearing rates. To access larger lengths and longer time scales, we further coarse-grain our system to a mesoscopic level where an individual micelle is represented by a spherical particle, which interacts with other micelles through an effective potential obtained from the microscopic simulations. This approach enables us to follow the time evolution of global order from locally ordered domains. An exponentially fast growth of the orientational correlation length of the hexagonal pattern at early times, followed by a crossover to linear growth, is found in the presence of shear, in contrast to the much slower power-law scalings observed in experiments without shear.     

Systematic prediction of kinetically limited crystal growth morphologies

We develop a new, combined experimental and theoretical approach to make reliable predictions for the limiting case of surface reaction kinetics controlled growth. We solve the inverse problem of determining the growth velocity from observations of the evolution of the morphology of GaN islands grown by metalorganic chemical vapor deposition and make use of crystal symmetry and established theorems. We are able to predict the growth for both convex and concave surfaces, with faceted and curved features. We also give a general guideline for deducing growth velocities from experimental observations.     

Control of density fluctuations and electron transport in the reversed-field pinch

Contrary to what has been observed thus far collision-induced light scattering (CILS) can be completely polarized. This exceptional behavior characterizes the very far wing of the binary CILS spectrum by gaseous helium. This conclusion is drawn from an experimental study of the depolarization ratio of He (2) in a much extended, previously unexplored, spectral domain. Our analysis shows that this property, unique thus far, is mainly due to an almost perfect cancellation between polarization and exchange pair polarizability contributions to the depolarized spectrum, taking place at internuclear distances shorter than the atomic diameter.     

Momentum transport from nonlinear mode coupling of magnetic fluctuations

A cause of observed anomalous plasma momentum transport in a reversed-field pinch is determined experimentally. Magnetohydrodynamic theory predicts that nonlinear interactions involving triplets of tearing modes produce internal torques that redistribute momentum. Evidence for the nonlinear torque is acquired by detecting the correlation of momentum redistribution with the mode triplets, with the elimination of one of the modes in the triplet, and with the external driving of one of the modes.