Asymmetric diffusion at the interfaces in multilayers

Nanoscale diffusion at the interfaces in multilayers plays a vital role in controlling their physical properties for a variety of applications. In the present work depth-dependent interdiffusion in a Si/Fe/Si trilayer has been studied with sub-nanometer depth resolution, using x ray standing waves. High depth-selectivity of the present technique allows one to measure diffusion at the two interfaces of Fe namely, Fe-on-Si and Si-on-Fe, independently, yielding an intriguing result that Fe diffusivity at the two interfaces is not symmetric. It is faster at the Fe-on-Si interface. While the values of activation energy at the two interfaces are comparable, the main difference is found in the pre-exponent factor suggesting different mechanisms of diffusion at the two interfaces. This apparently counter-intuitive result has been understood in terms of an asymmetric structure of the interfaces as revealed by depth selective conversion electron Mossbauer spectroscopy. A difference in the surface free energies of Fe and Si can lead to such differences in the structure of the two interfaces.Comment: 4 pages, 5 figure

Point defects in silicon after zinc diffusion - a deep level transient spectroscopy and spreading-resistance profiling study

We present results from spreading-resistance profiling and deep level transient spectroscopy on Si after Zn diffusion at 1294 K. Concentration profiles of substitutional in dislocation-free and highly dislocated Si are described by a diffusion mechanism involving interstitial-substitutional exchange. Additional annealing at 873 K following quenching from the diffusion temperature is required in the case of dislocation-free Si to electrically activate . The formation of complexes of with unwanted impurities upon quenching is discussed. Additional Ni diffusion experiments as well as total energy calculations suggest that Ni is a likely candidate for the passivation of Zns. From total energy calculations we find that the formation of complexes involving Zn and Ni depends on the position of the Fermi level. This explains differences in results from spreading-resistance profiling and deep level transient spectroscopy on near-intrinsic and p-type Si, respectively

Pressure dependence of diffusion in simple glasses and supercooled liquids

Using molecular dynamics simulation, we have calculated the pressure dependence of the diffusion constant in a binary Lennard-Jones Glass. We observe four temperature regimes. The apparent activation volume drops from high values in the hot liquid to a plateau value. Near the critical temperature of the mode coupling theory it rises steeply, but in the glassy state we find again small values, similar to the ones in the liquid. The peak of the activation volume at the critical temperature is in agreement with the prediction of mode coupling theory

Ab-initio molecular dynamics simulation of hydrogen diffusion in α\alpha-iron

First-principles atomistic molecular dynamics simulation in the micro-canonical and canonical ensembles has been used to study the diffusion of interstitial hydrogen in $\alpha$-iron. Hydrogen to Iron ratios between $\theta=1/16 and 1/2 have been considered by locating interstitial hydrogen atoms at random positions in a$2 \times 2 \times 2$ supercell. We find that the average optimum absorption site and the barrier for diffusion depend on the concentration of interestitials. Iron Debye temperature decreases monotonically for increasing concentration of interstitial hydrogen, proving that iron-iron interatomic potential is significantly weakened in the presence of a large number of diffusing hydrogen atoms

Influence of the Ion Coordination Number on Cation Exchange Reactions with Copper Telluride Nanocrystals

Cu2-xTe nanocubes were used as starting seeds to access metal telluride nanocrystals by cation exchanges at room temperature. The coordination number of the entering cations was found to play an important role in dictating the reaction pathways. The exchanges with tetrahedrally coordinated cations (i.e. with coordination number 4), such as Cd2+ or Hg2+, yielded monocrystalline CdTe or HgTe nanocrystals with Cu2-xTe/CdTe or Cu2-xTe/HgTe Janus-like heterostructures as intermediates. The formation of Janus-like architectures was attributed to the high diffusion rate of the relatively small tetrahedrally coordinated cations, which could rapidly diffuse in the Cu2-xTe NCs and nucleate the CdTe (or HgTe) phase in a preferred region of the host structure. Also, with both Cd2+ and Hg2+ ions the exchange led to wurtzite CdTe and HgTe phases rather than the more stable zinc-blende ones, indicating that the anion framework of the starting Cu2- xTe particles could be more easily deformed to match the anion framework of the metastable wurtzite structures. As hexagonal HgTe had never been reported to date, this represents another case of metastable new phases that can only be accessed by cation exchange. On the other hand, the exchanges involving octahedrally coordinated ions (i.e. with coordination number 6), such as Pb2+ or Sn2+, yielded rock-salt polycrystalline PbTe or SnTe nanocrystals with Cu2-xTe@PbTe or Cu2-xTe@SnTe core@shell architectures at the early stages of the exchange process. In this case, the octahedrally coordinated ions are probably too large to diffuse easily through the Cu2-xTe structure: their limited diffusion rate restricts their initial reaction to the surface of the nanocrystals, where cation exchange is initiated unselectively, leading to core@shell architectures.Comment: 11 pages, 7 figures in J. Am. Chem. Soc, 13 May 201

Lattice diffusion and surface segregation of B during growth of SiGe heterostructures by molecular beam epitaxy: effect of Ge concentration and biaxial stress

Si1-xGex/Si1-yGey/Si(100) heterostructures grown by Molecular Beam Epitaxy (MBE) were used in order to study B surface segregation during growth and B lattice diffusion. Ge concentration and stress effects were separated. Analysis of B segregation during growth shows that: i) for layers in epitaxy on (100)Si), B segregation decreases with increasing Ge concentration, i.e. with increased compressive stress, ii) for unstressed layers, B segregation increases with Ge concentration, iii) at constant Ge concentration, B segregation increases for layers in tension and decreases for layers in compression. The contrasting behaviors observed as a function of Ge concentration in compressively stressed and unstressed layers can be explained by an increase of the equilibrium segregation driving force induced by Ge additions and an increase of near-surface diffusion in compressively stressed layers. Analysis of lattice diffusion shows that: i) in unstressed layers, B lattice diffusion coefficient decreases with increasing Ge concentration, ii) at constant Ge concentration, the diffusion coefficient of B decreases with compressive biaxial stress and increases with tensile biaxial stress, iii) the volume of activation of B diffusion () is positive for biaxial stress while it is negative in the case of hydrostatic pressure. This confirms that under a biaxial stress the activation volume is reduced to the relaxation volume

Interacting Random Walkers and Non-Equilibrium Fluctuations

We introduce a model of interacting Random Walk, whose hopping amplitude depends on the number of walkers/particles on the link. The mesoscopic counterpart of such a microscopic dynamics is a diffusing system whose diffusivity depends on the particle density. A non-equilibrium stationary flux can be induced by suitable boundary conditions, and we show indeed that it is mesoscopically described by a Fourier equation with a density dependent diffusivity. A simple mean-field description predicts a critical diffusivity if the hopping amplitude vanishes for a certain walker density. Actually, we evidence that, even if the density equals this pseudo-critical value, the system does not present any criticality but only a dynamical slowing down. This property is confirmed by the fact that, in spite of interaction, the particle distribution at equilibrium is simply described in terms of a product of Poissonians. For mesoscopic systems with a stationary flux, a very effect of interaction among particles consists in the amplification of fluctuations, which is especially relevant close to the pseudo-critical density. This agrees with analogous results obtained for Ising models, clarifying that larger fluctuations are induced by the dynamical slowing down and not by a genuine criticality. The consistency of this amplification effect with altered coloured noise in time series is also proved.Comment: 8 pages, 7 figure

Self-organized transient facilitated atomic transport in Pt/Al(111)

During the course of atomic transport in a host material, impurity atoms need to surmount an energy barrier driven by thermodynamic bias or at ultra-low temperatures by quantum tunneling. In the present article we demonstrate using atomistic simulations that at ultra-low temperature transient inter-layer atomic transport is also possible without tunneling when the Pt/Al(111) impurity/host system self-organizes itself spontaneously into an intermixed configuration. No such extremely fast athermal concerted process has been reported before at ultra low temperatures. The outlined novel transient atomic exchange mechanism could be of general validity. We find that the source of ultra-low temperature heavy particle barrier crossing is intrinsic and no external bias is necessary for atomic intermixing and surface alloying in Pt/Al although the dynamic barrier height is few eV. The mechanism is driven by the local thermalization of the Al(111) surface in a self-organized manner arranged spontaneously by the system without any external stimulus. The core of the short lived thermalized region reaches the local temperature of $\sim 1000$ K (including few tens of Al atoms) while the average temperature of the simulation cell is $\sim 3$ K. The transient facilitated intermixing process also takes place with repulsive impurity-host interaction potential leading to negative atomic mobility hence the atomic injection is largely independent of the strength of the impurity-surface interaction. We predict that similar exotic behaviour is possible in other materials as well.Comment: 12 pages, 8 figures, full paper at: http://www.mfa.kfki.hu/~sule/papers/ptonal.pdf . J. Chem. Phys. (2008), in pres