Understanding the influence of relevant parameters on
the kinetics
of nanocrystal formation, from reaction and nucleation to the final
stages of growth in a homogeneous medium, is crucial in the design
and synthesis of nanoparticles of desired dimension. ZnO is chosen
as a model system to study spherical nanoparticle formation in solution,
using a combination of experiments and mathematical modeling. Stable
dispersions of ZnO nanocrystals were synthesized in alcoholic solvents
at various temperatures, while size-selection between ∼1.5
and ∼5 nm diameters were achieved by a rapid-quenching to 253
K, with simultaneous use of a capping agent. A priori time-scale calculation
of the rate processes involving different elementary events, in conjunction
with nanoparticle microscopy and spectroscopic data on particle diameter,
has led to an underlying three-stage mechanism for nanoparticle formation.
These sequential stages consist of: (I) nucleation of ZnO nanocrystal
and growth by molecular diffusion, (II) interparticle coagulative-growth
via oriented attachment (OA), and, finally, (III) interparticle growth
by Ostwald ripening (OR). Predictions of our mathematical model based
on the above mechanism compare favorably with experimental trends
on temporal evolution of mean particle diameter, for different alcoholic
solvents at various temperatures in the range of 273–353 K.
Solvents of lower carbon chain-length and lower temperature independently
reduce the rates of both OA and OR facilitating particles of smaller
diameter, thereby justifying methanol as the optimum solvent of choice
to size-select ZnO nanoparticles in the strong-confinement regime.
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