Convective crystal growth

Figure 1-11 Concentration profile for (a) crystal growth controlled by interface reaction (the concentration profile is flat and does not change with time), (b) diffusive crystal growth with t2 = 4fi and = 4t2 (the profile is an error function and propagates according to (c) convective crystal growth (the profile is an exponential function and does not change with time), and (d) crystal growth controlled by both interface reaction and diffusion (both the interface concentration and the length of the profile vary).

Supersaturation has been observed to affect contact nucleation, but the mechanism by which this occurs is not clear. There are data (19) that infer a direct relationship between contact nucleation and crystal growth. This relationship has been explained by showing that the effect of supersaturation on contact nucleation must consider the reduction in interfacial supersaturation due to the resistance to diffusion or convective mass transfer (20). 

These apparent restrictions in size and length of simulation time of the fully quantum-mechanical methods or molecular-dynamics methods with continuous degrees of freedom in real space are the basic reason why the direct simulation of lattice models of the Ising type or of solid-on-solid type is still the most popular technique to simulate crystal growth processes. Consequently, a substantial part of this article will deal with scientific problems on those time and length scales which are simultaneously accessible by the experimental STM methods on one hand and by Monte Carlo lattice simulations on the other hand. Even these methods, however, are too microscopic to incorporate the boundary conditions from the laboratory set-up into the models in a reahstic way. Therefore one uses phenomenological models of the phase-field or sharp-interface type, and finally even finite-element methods, to treat the diffusion transport and hydrodynamic convections which control a reahstic crystal growth process from the melt on an industrial scale. 

We have so far assumed that the atoms deposited from the vapor phase or from dilute solution strike randomly and balHstically on the crystal surface. However, the material to be crystallized would normally be transported through another medium. Even if this is achieved by hydrodynamic convection, it must nevertheless overcome the last displacement for incorporation by a random diffusion process. Therefore, diffusion of material (as well as of heat) is the most important transport mechanism during crystal growth. An exception, to some extent, is molecular beam epitaxy (MBE) (see [3,12-14] and [15-19]) where the atoms may arrive non-thermalized at supersonic speeds on the crystal surface. But again, after their deposition, surface diffusion then comes into play. 

In many crystal growth phenomena, transportation of material occurs not only via diffusion but also via hydrodynamic convection. We assume... 

L. Biihler, S. H. Davis. Flow induced changes of the morphological stability in directional solidification localized morphologies. J Crystal Growth 756 629, 1998 Y.-J. Chen, S. H. Davis, Directional solidification of a binary alloy into a cellular convective flow (unpublished). Applied Math Technical Report No. 9708, Northwestern University, Evanston, IL 60208. 

J. Holuigue, O. Bertrand, E. Arquis. Solutal convection in crystal growth effect of interface curvature on flow structuration in a three-dimensional cylindrical configuration. J Cryst Growth 180 591, 1997. 

M. C. Liang, C. W. Fan. Three-dimensional thermocapillary and buoyancy convections and interface shape in horizontal Bridgman crystal growth. J Cryst Growth 180 5% , 1997. 

Y.-S. Lee, C.-H. Chun. Experiments on the oscillatory convection of low Prandtl number hquid in Czochralski configuration for crystal growth with cusp magnetic field. J Cryst Growth 180 411, 1997. 

The linear instability theory of the behavior of a system near the bifurcation point can be successfully applied to many self-organization problems, such as thermal convection in hydrodynamics4 and crystal growth in solution.5 In these theories, various initial fluctuations play important roles. Occasionally the fluctuations arise from the thermal motion of atoms or molecules. If a system reaches an unstable mode over... 

The crystallization of the D-enantiomer is therefore considered to be induced by crystal growth on the surface of the seed crystal and at the same time initial breeding may play a role that causes small crystals near the seed crystal. The propagation of nucleation in distance from the seed may be caused by convective flow of the solution due to density difference during the crystal growth. 

The scope of kinetics includes (i) the rates and mechanisms of homogeneous chemical reactions (reactions that occur in one single phase, such as ionic and molecular reactions in aqueous solutions, radioactive decay, many reactions in silicate melts, and cation distribution reactions in minerals), (ii) diffusion (owing to random motion of particles) and convection (both are parts of mass transport diffusion is often referred to as kinetics and convection and other motions are often referred to as dynamics), and (iii) the kinetics of phase transformations and heterogeneous reactions (including nucleation, crystal growth, crystal dissolution, and bubble growth). 

Crystal growth rate may be constant, which could happen if temperature is decreasing or if there is convection. Smith et al. (1956) treated the problem of diffusion for constant crystal growth rate. In the interface-fixed reference frame, the diffusion equation in the melt is... 

Diffusive crystal growth at a fixed temperature would not result in a constant crystal growth rate (see below). However, under some specific conditions, such as continuous slow cooling, or in the presence of convection with diffusion across the boundary layer, time-independent growth rate may be achieved. Similarly, time-independent dissolution rate may also be achieved. 

For convective crystal dissolution, the dissolution rate is u = (p/p )bD/8. For diffusive crystal dissolution, the dissolution rate is u = diffusive boundary layer thickness as 5 = (Df), the diffusive crystal dissolution rate can be written as u = aD/5, where a is positively related to b through Equation 4-100. Therefore, mass-transfer-controlled crystal dissolution rates (and crystal growth rates, discussed below) are controlled by three parameters the diffusion coefficient D, the boundary layer thickness 5, and the compositional parameter b. The variation and magnitude of these parameters are summarized below. 

By the above definition, b is positive for crystal dissolution, and negative for crystal growth. During convective crystal dissolution, the dissolution rate u is directly proportional to b. During diffusive crystal dissolution, the dissolution rate is proportional to parameter a, which is positively related to b. Hence, for the dissolution of a given mineral in a melt, the size of parameter b is important. The numerator of b is proportional to the degree of undersaturation. If the initial melt is saturated, b = 0 and there is no crystal dissolution or growth. The denominator characterizes the concentration difference between the crystal and the saturated... 

Figure 3.3. Various features of diffusion and convection associated with crystal growth in solution (a) in a beaker and (b) around a crystal. The crystal is denoted by the shaded area. Shown are the diffusion boundary layer (db) the bulk diffusion (D) the convection due to thermal or gravity difference (T) Marangoni convection (M) buoyancy-driven convection (B) laminar flow, turbulent flow (F) Berg effect (be) smooth interface (S) rough interface (R) growth unit (g). The attachment and detachment of the solute (solid line) and the solvent (open line) are illustrated in (b).

K. Onuma, K. Tsukamoto, and I. Sunagawa, Effect of buoyancy driven convection upon the surface microtopographs of BalNOjjj and Cdl crystalsJ. Crystal Growth, 98,1989, 384-90... 

The presence of convection also affects crystal growth from the melt. Single crystals of Te-doped InSb were grown from flic melt on Sivlah. The crystals obtained in space were free of striations caused by convection-driven growth rate fluctuations that are normally seen on eanh. future space experiments will examine the grow th of electronic materials such as GaAs from a sululion subjected to an electric current. 

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