Nanoscale

materials as intermediate between Atomic and

Bulk Ma6er

Dr. Ashutosh Pandey

Chemistry Department
MNNIT Allahabad
 Nanoscale materials and quantum mechanics

•  Nanoscale materials frequently show behaviour which is intermediate between that of a

macroscopic solid and that of an atomic or molecular system. Consider for instance the
case of an inorganic crystal composed of few atoms. Its properties will be different from
those of a single atom and also from a bulk solid. The number of atoms on the crystal’s
surface is a significant fraction of the total number of atoms., and therefore will have a
large influence on the overall properties of the crystal.
•  A fundamental aspect of quantum mechanics is the particle- wave duality, introduced by
De Broglie ,according to which any particle can be associated with a matter wave whose
wavelength is inversely proportional to the particle‘s linear momentum. Whenever the
size of a physical system becomes comparable to the wavelength of the particle that
interact with such a system the behavior of the is best described by the rules of quantum
mechanics .All the information we need about the particle is obtained by solving its
Schrodinger equation. The solutions of this equation represent the possible physical
states in which the system can be found. Fortunately, quantum mechanics is not
required to describe the movement of objects in the macroscopic world. The wavelength
associated with a macroscopic object is in fact much smaller than the object’s size, and
therefore such systems can be explained by classical mechanics.
 Quantum confinement
•  In bulk inorganic semiconductor, conduction band electrons and valence band
holes are free to move through out the crystal, and their motion can be described
satisfactorily by a linear combination of plane waves whose wavelength is generally
of the order of nanometers. This means that whenever the size of the semiconductor
solid becomes comparable to these wave lengths, a free carrier confined in this
space will behave as a particle in a potential box. The solutions of Schrodinger
wave equation in such case are standing waves confined in a potential well., and the
energies associated with two distinct wavefunctions are different and discontinuous.
This means that the system exhibits a discrete energy level spectrum. Transitions
between any two levels are seen as discrete peaks in the optical spectra. The system
is called as quantum confined. The main point here is that in order to rationalize the
physical properties of nano materials such as electrical & thermal conductivity,
absorption and emission spectra, we need to first determine their energy level
structure.
 Two Approaches

•  A. Start from a bulk solid, and study the evolution of the band
structure as its dimensions shrink down to few nanometers.

•  B. Start from the individual electronic states of single isolated

atoms and then study how the energy levels evolve as atoms
come closer and start interacting with each other.
 From Atoms to Molecules and quantum dots

•  In atoms electrons reside in orbitals with an associated discrete energy level.

•  In molecules electrons are shared between atoms and no longer belong to single atom
and belong to molecular orbitals. Using the same principle, it is possible to derive the
electronic structure of more complex systems such as large molecules or atomic clusters.
When combining atoms to form a molecule , we start from discrete energy levels of
atomic orbitals and still we end by getting discrete levels of MOs.
•  When the size of the system is very large then above theories don’t work. However, if
the system is crystalline solid then periodic combinations of AOs (Bloch functions) are
used. As opposed to the case of atoms and molecules , the energy structure of a solid no
longer consists of discrete energy levels, but rather of broad energy bands. Every band
can be filled only with a limited no. of electrons.
•  For very small crystals (nano) we can imagine that the electronic structure is in between
discrete levels of atoms and band of the solid. In fact energy levels are discrete, their
density is much larger and their spacing is much smaller than that of atoms or molecules.
Because of the discrete levels they are called QDs. Highest occupied AOs interact to
form valence band of nanocrystals and the lowest unoccupied AOs combine to make
conduction band. The energy gap between the two is called BAND GAP of the
nanocrystal.
 Quantum dots as markers

•  During the last decade quantum dots like CdSe and CdSe/ZnS (core/
shell or cap structure) (i.e. semiconductor nanocrystals) have been
found to be more robust than organic fluorophores for biolabeling.
•  The need of ZnS capping is that the exciton photogenerated in the
core (CdSe) is prevented from spreading over the enKre parKcle, and
by this it is forced to recombine while spaKally confined to the core
and mostly accompanied by enhanced luminescence.
•  Due to their size tunable emission properKes and a broad absorpKon
spectrum the quantum dots can at once be excited for almost all the
possible emission colors and unlike organic dyes they do not undergo
significant photobleaching.
 Colloidal quantum dots
–  Colloidal quantum dots (fluorescent nanocrystals) are semiconductor
nanocrystals with size dependent fluorescence properKes. Because of
their reduced tendency to photobleach, colloidal quantum dots are
interesKng fluorescence probes for all types of labeling studies.

•  These nanocrystals which are synthesized in hydrophobic
media can be made hydrophilic by several methods, which
rely on the exchange of the hydrophobic surfactant coaKngs
with ligand molecules that carry on one end funcKonal groups
which are reacKve towards the nanocrystal surface, and
hydrophilic groups on the other end, which ensure water
solubility.
 Diameter about 3 - 10 nm
Different properKes depending on material and size:

CdSe/ZnS
•  Semiconductors: core/shell nanocrystals
•  Different colors 1.4
depending on 1.2

parKcle size 1.0

•  Fluorescent label 0.8

0.6

0.4

0.2
for biological applications 0.0
and artificial nanostructures 450 500 550 600 650 700 750