Zero Dimensional systems

PG Elective

Dr. S De

 The ultimate zero dimensional (0D) structure is the atom

We are actually interested in quasi 0D structures
These are materials whose size is very small in all three dimensions
(x,y,z)

As a piece of a given material gets smaller and smaller, eventually

its properties begin to deviate from the bulk
How small is small?
It depends on what property we are considering. For example, the
melting temperature might begin to change from that of the bulk a given
particle size. However the ionization potential may begin to change at a
completely different size.

 As a general rule of thumb, we can consider

particles that have size <100nm in all directions to
be quasi 0D.

Au Nanoparticle

However, this is just a rule of thumb. A particle

of size 90nm, made up of atoms of a given element,
may have some properties that are identical to those
of the bulk.
There are many different types of quasi 0D
structures

1 nm
CdSe nanoparticle

We will look at some examples

o Nano-particles
Metallic and semiconducting

o Molecular nanostructures

C60

Nanoparticles
Nanoparticles are just very small particles of known materials such
as aluminium, gold or CdSe
They have been studied intensely for the last 3 decades or so
However they have been used by mankind for thousands of years,
without people having any idea what they were.
example is the Lycurgus Cup (4thC AD)

The Lycurgus Cup is unusual in that the

reflected light colour (green) is different
to the colour of transmitted light (red).

How do we make these things??

Nanoparticles have been studied for ~25 years. By now, there are
many ways of making them: Some common examples
Mechanical
Ball Milling

Thermal routes
Thermolysis

Attritional milling

Wet Chemistry

Gas phase synthesis

Sol gel

Laser ablation

Liquid phase chemistry

Chemical / physical vapour

Colloid chemistry

synthesis
You all know about these Methods

Silver Nano
particles

TEM Images of few

Nanoparticles

HW1.

For a sodium nanoparticle of size 60 nm

a) Find out number of atoms in the nanoparticle
b) fraction of atoms on the surface, Fs.

Dws for sodium is 0.4 nm

Geometric structure
A nanocluster is a nanometer sized particle made up of
equal subunits.
These subunits can be atoms of a single element,
molecules or even combinations of atoms of several
elements in subunits with equal stoichiometries (alloys,
etc.)
E.g.: Nan, (SF6)n, (H2O)n, (Cu3Au)n, (TiO2) etc
The properties of nanoclusters are solely guided by the
number of subunits they contain.

Usually the crystal structure of a large nanocluster is the

same as the bulk structure of the material with somewhat
different lattice parameters
E.g. Cu clusters tend to have an FCC structure (Wulff
polyhedra).

Some exceptions do, however, occur. Smaller clusters of

Cu (e.g. Cu55, Cu147, . . . ) have perfect icosahedral
structures.
- structural magic numbers: occur when an exact amount
of atoms is needed for a specific structure

As I Said in last class

We can think as a nanoparticle as a cluster of atoms all of

which are attracted to each other. This is the liquid drop
model.
The Liquid drop model is a crude approximation that works
for relatively big particles.
However it says nothing about the crystal structure of the
nanoparticles.

We need to consider this to more fully understand

Nanoparticles
We will focus on nanoparticles made from elements that
form metals in the bulk.

Metal nanoparticles
Most metals form close packed lattices in the bulk eg
Face Centred Cubic (FCC)
Ag, Al, Au, Co, Cu, Pb, Pt, Rh
Hexagonal Close Packed (HCP)
Mg, Nd, Os, Re, Ru, Y, Zn
We will focus on FCC
The FCC unit cell has ___ atoms

This means
The nano-particle likes to have atomic planes on its surface
These planes have different surface energies
The total energy associated with the surface is given by

where i represents each type of atomic plane

A general tendency of the clusters is to form structures where the
total surface energy is minimized for a given volume
the exact structure then depends on the surface energies related to
the specific crystal facets of the material.
This means we would expect atomic planes with high surface
energy to account for a small fraction of the surface and vice versa

Thus the shape of a nano-particle depends on the crystal structure

and the surface energies of the atomic planes (and hence the
element)
This means the shape is independent of the nano-particle size

However this is not true for very small nano-particles

The shape can only be size independent if we model the
nanoparticles as made from a continuum
However for small nano-particles, the facet size will be of the same
order as the atomic size
This means the discrete nature of the atoms will effect the shape

3 - Face Centered Cubc

Crystal Structure

Atoms are all same.

29

 Most,

in fact form the 12 vertex polyhedron, the

icosahedron. A smaller number form the decahedron.

There is one big difference between this and the 1D square

well
In the 1D case each level takes only 2 electrons
Here we can have a level described by the quantum numbers:
nx=1 ny=2 and nz=3
There is also a level with the quantum numbers: nx=3 ny=2 and
nz=1
These levels have the same energy!!!!
Thus we can have energy levels with more than 2 electrons

The levels are degenerate!!!!!

The jellium model has successfully been used in the theoretical

modelling of nanoclusters. The jellium model envisions a cluster of
atoms as a single large atom, where the distribution of ionic cores is
replaced by a constant positive background, the so called jellium
density, and only valence electrons are treated explicitly.

HW

Use the Brus equation to find how much bigger is a 1nm

nanoparticles bandgap compared to the bulk.(take r=10).
Assume me*~3me and mh*~2me