Heterogeneous nucleation of diamond

We present theoretical study of the formation of diamond clusters on the non-diamond substrate. This phenomenon is modelled at the kinetic level and described by the Fokker-Planck-like equation governing the evolution of the distribution of newly-forming clusters. Incubation time of this process is calculated and compared with the experimental data.     

Heterogeneous crystal nucleation: the effect of lattice mismatch

A simple dynamical density functional theory is used to investigate freezing of an undercooled liquid in the presence of a crystalline substrate. We find that the adsorption of the crystalline phase on the substrate, the contact angle, and the height of the nucleation barrier are nonmonotonic functions of the lattice constant of the substrate. We show that the free-growth-limited model of particle-induced freezing by Greer et al. [Acta Mater. 48, 2823 (2000)] is valid for larger nanoparticles and a small anisotropy of the interface free energy. Faceting due to the small size of the foreign particle or a high anisotropy decouples free growth from the critical size of homogeneous nuclei.     

Heterogeneous nucleation in and out of pores

We study the nucleation of a new thermodynamic phase in pores and find that the nucleation often proceeds via two steps: nucleation of pore filling, and nucleation out of the pore. These two rates have opposing dependencies on pore size, resulting in a pore size at which the nucleation rate of the new phase is maximal. This finding is relevant to attempts to design and use porous media to crystallize proteins.     

Critical conditions for dislocation nucleation at surface steps

Dislocation nucleation at a surface step is analyzed based on a general variational boundary integral formulation of the Peierls–Nabarro dislocation model. By modelling the surface step as part of the surface of a three-dimensional crack, the free surface effect is taken into account by transferring the half space problem into an equivalent one in the infinite medium. The profiles of embryonic dislocations, corresponding to the relative displacements between the two adjacent atomic layers along the slip planes, are then rigorously solved through the variational boundary integral method. The critical conditions for dislocation nucleation are determined by solving the stress-dependent activation energies required to activate the embryonic dislocations from their stable to unstable saddle-point configurations. In particular, the effect of the step geometry, such as the height of the step, the dip angle of the slip plane and the inclined angle of the step surface on dislocation nucleation, is quantitatively ascertained. The results show that the atomic-scale surface step can rapidly reduce the critical stress required for dislocation nucleation from the surface by nearly an order of magnitude. The decrease in critical stress as a function of the height of the step is more significant for slip planes with smaller dip angles and surface steps with smaller inclined angles.     

Heterogeneous nucleation and depletion effect in nanowire growth

Recent experiments by Ross and co-workers proved the possibility of a mononuclear regime with heterogeneous nucleation as well as jerky growth in the vapor–liquid–solid (VLS) process for silicon nanowires. In this work, a theoretical model is presented which incorporates the effects of (i) a mononuclear regime with layer by layer growth, (i) heterogeneous nucleation of each new layer at the edge of a Au–Si droplet, (iii) drop of supersaturation after each successful nucleation and respective fast layer growth, (iv) time-dependent nucleation barrier during each new waiting period and (v) correlation between subsequent waiting periods (non-Markovian sequence of waiting periods).     

Heterogeneous hole nucleation in electron-charged 4He wetting films

4He wetting layers on Cs exhibit an unusually long-lived metastable state upon undercooling to temperatures well below the wetting temperature T(w) approximately 1.9 K. The decay of this state by homogeneous thermal nucleation of holes is disfavored by the incipient divergence of the free energy barrier separating the metastable thick film from the stable thin-film state. We propose that interface deformations ("dimples") created by electrons bound at the 4He liquid-vapor interface can be used as nuclei for the heterogeneous nucleation of holes. The size and excess free energy of the dimple can be tuned by an applied electric field E which allows the lifetime of the metastable film to be controlled.     

Modelling of kink nucleation and propagation along steps of finite length

A discrete model for kink nucleation and propagation along steps of finite length is developed. The step velocities were calculated as a function of the step length, the first order rate constants, k_s and k_K, for kink nucleation and propagation respectively, and a kink interaction parameter. The two limiting kinetic regimes of short and long steps as well as the intermediate transitional regime were considered. For very short steps, S² ? $\text{k}{}_{\mathrm{<mtext>K</mtext>}}\text{k}{}_{\mathrm{<mtext>s</mtext>}}$, the velocity varied directly with the number of sites S. Steps which met the criterion S² ? $\text{k}{}_{\mathrm{<mtext>K</mtext>}}\text{k}{}_{\mathrm{<mtext>s</mtext>}}$, were shown to have velocities on the order (2k_Kk_s)^{$\text{1}\text{2}$}, independent of step length. Step velocities were constant over large ranges of the kink interaction parameter. The steps were shown to be “sharp” for zero or attractive kink interaction, but with sufficiently large kink repulsion very diffuse steps could be formed. The density of kinks and numbers of kinks nucleated along an atom row were also calculated.     

Heterogeneous nucleation and growth of CdSe on magnetite seed nanocrystals: The influence of ligand and morphology

The heterogeneous nucleation and growth of CdSe domains on the Fe₃O₄ seed nanocrystals are hard to be controlled because of significant lattice mismatch between Fe₃O₄ and CdSe nanocrystals. Current study exploits the choice of surface ligand and crystal morphology for Fe₃O₄ seed to investigate ways to overcome the energy barrier imposed by the lattice mismatch for the promotion and control of subsequent growth of CdSe nanocrystals on seeded crystals. Results indicate that the growth of CdSe domains on seed nanocrystals not only depends on the affinity of ligands toward seed nanocrystals, but also is affected by the seed ligands in a similar way to synthesizing individual second-domain nanocrystals. Furthermore, preferential growth of CdSe domains on the corner of cubic seeds are observed, and cubic Fe₃O₄ nanocrystals are favored for the heterogeneous nucleation of CdSe as opposed to spherical ones. A three-stage growth model (heterostructures formation, the adsorption of Se and the heterogeneous nucleation and growth) is proposed, where choice of ligands, geometry features, such as surface curvature and defects are found to have significant impact to overcome energy barrier from lattice mismatch.     

Oxidation of CO on Pt and Pd: I. Theory

The kinetics of CO oxidation on the metals Pt and Pd have been analyzed theoretically within the framework of a model that incorporates both the Eley-Rideal and Langmuir-Hinshelwood mechanisms. The model takes into account the dissociative adsorption of oxygen on adjacent vacant surface sites. Exact solutions to the differential equations describing the model have been obtained for (a) the steady-state characterized by constant temperature and pressure, and (b) a quasi-equilibrium state in which one of the reactant gas phase pressures is modulated with frequency ω.     

Heterogeneous nucleation of martensite on precipitates and the martensitic-transformation kinetics in shape memory alloys

The formation of martensite in an elastic stress field near a disk-shaped coherent precipitate is discussed in terms of the theory of diffuse martensitic transformations. The heterogeneous martensite nucleation on precipitates is found to increase the characteristic martensitic-transformation temperature, which increases linearly with the volume density of precipitates. The theoretical results are illustrated quantitatively using the example of the B2 → R phase transition in titanium nickelide alloys.     

Chemisorption of indium on (111) silicon substrates: I. Adsorption and nucleation by mass-spectrometric technique

The adsorption and nucleation of indium on clean (111) silicon surfaces are studied by a UHV molecular beam mass-spectrometric technique. The thermal accommodation of the adatoms on the surface is complete. At very low surface coverages θ, an adsorption energy of $\text{57}\text{kcal}\text{mole}$ and a preexponential term τ₀ of the Frenkel relation equal to 8 × 10^?13 s are found from transient response measurements. The isosteric heat of adsorption E_a varies very slowly with θ, E_a is equal to $\text{59}\text{kcal}\text{mole}$ for θ ～ 10^?3 and $\text{57}\text{kcal}\text{mole}$ for θ = 0.9. The nucleation occurs without supersaturation in an adsorbed layer near a monolayer.     

Heterogeneous nucleation and growth of silver nanoparticles on unmodified polystyrene spheres by in situ reduction

The in situ reduction growth of Ag nanoparticles (NPs) on unmodified polystyrene (PS) spheres is investigated via controlling Ag nucleation and growth rates by continuous dripping addition of reductant solution in the absence of surfactants. The sub-micro PS spheres were coated by a uniform coverage of Ag NPs with several shapes like elongated islands, spherical particles, and particle aggregates. The reaction temperature and reductant concentration are demonstrated to influence the crystal structure, distribution, and stability of the Ag NPs on the PS substrates. The heterogeneous nucleation and growth of Ag NPs on PS spheres are found to depend on the inhibition of in-solution reduction and homogeneous nucleation.     

Heterogeneous nucleation and microstructure formation in colloidal model systems with various interactions

Recent studies of crystal nucleation and further microstructure formation in colloidal model systems are reviewed. Homogeneous as well as different heterogeneous nucleation scenarios will be discussed. We focus on the crystallization process of one component colloidal model systems with hard sphere like interaction, long range electrostatic interaction and depletion force induced attractive interaction. Heterogeneous crystallization on flat and smooth substrates, on structured substrates, induced by different kind of seed particles as well as inoculation adding a larger amount of seeds will be presented.