Nucleation and Growth of Nanosystems

Nucleation and growth

The growth of nanocrystals in solution involves two important processes, the nucleation followed by the growth of the nanocrystals (Rao et al., 2007). Nucleation is the phenomenon of initiation of formation of the first nanocrystals in solution. It involves the appearance of very small particles or nuclei of the new phase which are capable of growing. There are two types of nucleation 1) Homogenous-nuclei form simultaneously and uniformly throughout the solution. 2) Heterogeneous-nuclei form preferentially at structural inhomogeneities like container surface, insoluble impurities etc. During growth the nuclei increase in size

Nucleation and Growth

Nucleation (Cont.)
Nucleation is the creation of nuclei upon which growth can occur. Nucleation plays an important role in controlling the properties of the final product, size distribution and nature of the phase. Nano particles need strong nucleation and slow growth. Highly monodisperse nanoparticles are formed if the processes of nucleation and growth can be successfully separated. The distance among nucleation sites has to be bigger than diffusion length.

Nucleation (Cont.)
Nucleation is the process by which atoms (or ions) that are free in solution come together to produce a thermodynamically stable cluster. The cluster must exceed a specific size (the critical size). Once the critical size is exceeded, the cluster is capable of further growth. If the nucleus is smaller than the critical size, spontaneous dissolution can occur (Tojo et al., 2006). LaMer et al. (1950) have studied extensively nucleation and growth in sulfur solutions, from which they developed an understanding of the mechanism for the formation of colloids or nanocrystals from a homogeneous medium.

LaMers Diagram (Concentration vs Time)

In the first step, the concentration increases continuously with increasing time. As the concentration reaches the critical super saturation value, nucleation occurs. This leads to a decrease of the concentration. Between the concentrations C max and C min the nucleation occurs. Later, the decrease of the concentration is due to the growth of the particles by diffusion. This growth occurs until the concentration reaches the solubility value. Nucleation occurs in the first part of the reaction and later only growth of the particles occurs. If this model is followed, the size of the particles will increase continuously with the concentration of the precursor or a minimum in the variation of the size with the concentration can also be expected. This stems from the fact that the number of nuclei is constant and the increase of concentration leads to an increase of the size of the particles (Destree et al., 2006).

Tuning of the size of nanoparticles

Tuning of the size of nanoparticles can be achieved by control over nucleation and growth rates, as illustrated in Scheme. Fast nucleation provides a high concentration of nuclei, ultimately yielding smaller nanocrystals, whereas slow nucleation provides a low concentration of seeds consuming the same amount of precursors, thus resulting in larger particles.

Schematic representation of the synthesis of nanocrystals.

Nanoparticles: From Theory to Application. Edited by Gunter Schmid (2004)

Aspects of Nanoparticle Growth in Solution

Arrested Precipitation Precipitation under starving conditions: a large number of nucleation centers are formed by vigorous mixing of the reactant solutions. If concentration growth is kept small, nuclei growth is stopped due to lack of material.

Particles had to be protected from Ostwald ripening by stabilizers

Oswald Ripening The growth mechanism where small particles dissolve, and are consumed by larger particles. As a result the average nanoparticle size increases with time and the particle concentration decreases. As particles increase in size, solubility decreases.

Stabilization of Nanoclusters Against Aggregation

1. Electrostatic stabilization Adsorption of ions to the surface. + - - -- + + + + Creates an electrical double layer -- d+ d d+ - - d+ d d+ - -+- + + + + which results in a Coulombic d d d d -- --+ repulsion force between individual + - - - --- - + particles

2. Steric Stabilization Surrounding the metal center by layers of material that are sterically bulky, called capping agents Examples: polymers, surfactants, etc

Tuning of the shape of nanoparticles

Growth mechanism of gold nanorods

Synthesis of gold nanoparticles of different shapes

General idea is the same as the growth of gold nanorods (seed-mediated method) Slightly change the conditions when growing nanorods (concentration of different reactants) Cubes, hexagon, triangle, tetropods, branched

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Gold nanoparticles. Scale bar=100nm