NANO 703 Md Jamal Uddin

Spring 2015 03/30/2015

Assignment III
Nanoparticle Synthesis

Colloidal nanocrystals offer a variety of new properties which can be tuned by controlling their size, shape
and composition. These properties – such as, quantization of energy sub-bands, enormous surface to volume
ratio etc. – make them useful for numerous electronic, magnetic, photonic, and many other devices and
functional materials. Understanding the key points in colloidal nanocrystal synthesis will, thus, enable us to
exploit them to meet various novel functional requirements that will, in turn, create scope for different new
applications that we cannot even imagine. With more than two decades of work, scientists have successfully
developed a wide variety of methods to tailor the synthesis of colloidal nanocrystals such as –
co-precipitation in aqueous phase, using reverse micelles as templates, hydrothermal/solvothermal
synthesis and surfactant-controlled growth in a hot organic solvent. As much as work has been done on
developing the synthesis routes, very little progress have been made in understanding the key steps, such as
the effect of reaction kinetics on size and shape of the nanocrystals and the mechanism of the organic
surfactants binding and packing on the organic – inorganic interface. This review being summarized has
outlined a set concepts in understanding those key steps. With that, we can move onto the next stage of the
colloidal nanocrystal synthesis that will allow us to control and fabricate ever more complex structures with
exciting properties.

Regardless of the methods, synthesis system for colloidal nanocrystals consists of three components:
precursors, organic surfactants and solvents, and the end product is an inorganic core stabilized by a layer
of surface surfactants. The choice of precursors mainly determine the colloidal nanocrystal composition
whereas the surfactants along with other controlling parameters determine the size and shape of the
nanocrystal. One of the most important such controlling parameter is the reduction in melting temperature
that favors the growth of the nanocrystal and keeps the organic surfactants stable, which is in the range of
200 – 400 °C. Another important controlling parameter is the monomer (precursor) concentration which
controls the growth rate of the nanocrystals that determines the size as well as the size distribution of the
final colloidal nanocrystals. With the concept of size distribution focusing, it is found that optimal narrower
size distribution occurs if the monomer concentration is kept such that the average nanocrystal size present
is always slightly larger than the critical size. A rapid injection of precursor typically also helps focusing by
quick nucleation. However, delayed nucleation has also been proven to be helpful.

The adhesion energy with which the surfactant molecules adhere to the surface of the growing nanocrystals
also influences the size and the shape of the nanocrystals by a process called dynamic adhesion. During the
the growth of the nanocrystal, high-energy facets grow more quickly than low-energy facets. By selective
adhesion of the surfactants, it is possible to lower the growth rate of a particular facet – thus enable us to
kinetically control the shape of the nanocrystals. Sequential elimination of high-energy facets can lead to
intermediate-energy facets that also grows faster than the initial low-energy facets. This can lead to the
shapes with very complex patterns such as, arrow-shaped and zigzag-shaped nanocrystals. Complex shapes
can also form from the coalescence of faceted nanocrystals in such a way as to eliminate two high-energy
facets. Controlled branching of the nanocrystal is also possible with selective adhesion. With suitable agent,
the (111) facet in ZnS structure of a II-VI semiconductor can be converted into a (1000) facet of wurtzite
structure. This yields a crystalline inorganic structure of four rods at the tetrahedral angle, a so-called
tetrapod. Subsequent branching is also possible by kinetically driving the reaction again or by nucleation of
a second material.

As mentioned before, understanding the key points, specially the mechanism of surfactants' attachment to
the nanocrystal surface, can help us understand the process better and control the properties more directly.
To study and work on that mechanism, one has to study of nanocrystal growth kinetics, and monitor the
average size and shape in real-time. In-situ TEM offer exciting opportunities in this regard. With promising
development of the in-situ microscopy in recent years, it is now possible to precisely regulate the required
environment and monitor and analyze the data at the same time. This will, clearly, open the window of new
opportunities and possibilities.