Relaxation dynamics of saturated and unsaturated oriented lipid bilayers.

We present experimental measurements and analysis of the dynamics and the phase behaviour of saturated DMPC and unsaturated DOPC oriented multi-lamellar bilayers. Elastic and inelastic neutron scattering were used to directly probe the dynamical processes of these membrane systems on time and length scales relevant to the internal and localized motion of lipid monomers. Mobility in this regime can be informative in elucidating the local interactions responsible for material properties of these fluid lipid systems. DMPC and DOPC are structurally similar in terms of their membrane hydrophobic thickness; however, they exhibit different mechanical properties in terms of both elastic compressibility and bending moduli. The analyses suggest that the constraint imposed by the double bonds in DOPC acyl chains restricts atomic motion in both liquid and gel phases compared to DMPC. We discuss applications of molecular dynamics to further elucidate the atomic details of the dynamical processes. Such an understanding may suggest how membrane properties can be tuned using a variety of different lipid species.

Phase-field crystal model with a vapor phase.

Phase-field crystal (PFC) models are able to resolve atomic length scale features of materials during temporal evolution over diffusive time scales. Traditional PFC models contain solid and liquid phases, however many important materials processing phenomena involve a vapor phase as well. In this work, we add a vapor phase to an existing PFC model and show realistic interfacial phenomena near the triple point temperature. For example, the PFC model exhibits density oscillations at liquid-vapor interfaces that compare favorably to data available for interfaces in metallic systems from both experiment and molecular-dynamics simulations. We also quantify the anisotropic solid-vapor surface energy for a two-dimensional PFC hexagonal crystal and find well-defined step energies from measurements on the faceted interfaces. Additionally, the strain field beneath a stepped interface is characterized and shown to qualitatively reproduce predictions from continuum models, simulations, and experimental data. Finally, we examine the dynamic case of step-flow growth of a crystal into a supersaturated vapor phase. The ability to model such a wide range of surface and bulk defects makes this PFC model a useful tool to study processing techniques such as chemical vapor deposition or vapor-liquid-solid growth of nanowires.

Identification of an intrinsic source of doping inhomogeneity in vapor-liquid-solid-grown nanowires.

The vapor-liquid-solid (VLS) process of semiconductor nanowire growth is an attractive approach to low-dimensional materials and heterostructures because it provides a mechanism to modulate, in situ, nanowire composition and doping, but the ultimate limits on doping control are ultimately dictated by the growth process itself. Under widely used conditions for the chemical vapor deposition growth of Si and Ge nanowires from a Au catalyst droplet, we find that dopants incorporated from the liquid are not uniformly distributed. Specifically, atom probe tomographic analysis revealed up to 100-fold enhancements in dopant concentration near the VLS trijunction in both B-doped Si and P-doped Ge nanowires. We hypothesize that radial and azimuthal inhomogeneities arise from a faceted liquid-solid interface present during nanowire growth, and we present a simple model to account for the distribution. As the same segregation behavior was observed in two distinct semiconductors with different dopants, the observed inhomogeneity is likely to be present in other VLS grown nanowires.

Direct measurement of dopant distribution in an individual vapour-liquid-solid nanowire.

Semiconductor nanowires show promise for many device applications, but controlled doping with electronic and magnetic impurities remains an important challenge. Limitations on dopant incorporation have been identified in nanocrystals, raising concerns about the prospects for doping nanostructures. Progress has been hindered by the lack of a method to quantify the dopant distribution in single nanostructures. Recently, we showed that atom probe tomography can be used to determine the composition of isolated nanowires. Here, we report the first direct measurements of dopant concentrations in arbitrary regions of individual nanowires. We find that differences in precursor decomposition rates between the liquid catalyst and solid nanowire surface give rise to a heavily doped shell surrounding an underdoped core. We also present a thermodynamic model that relates liquid and solid compositions to dopant fluxes.

Phase equilibrium and nucleation in VLS-grown nanowires.

Phase diagrams accounting for capillarity and surface stress in VLS-grown nanowires have been calculated, and linearized forms for the compositions of the solid and liquid are given. The solid-vapor interfacial energy causes a significant depression of the liquidus, and the impurity concentration in the wire decreases with decreasing wire diameter. Nucleation calculations give upper bounds on the nucleation temperature and liquid supersaturation during growth that are consistent with measurements in the Au-Ge system.