UNIT NAME: Fundamentals of Nanoscience and Nanotechnology

LECTURE 3: 29-09-2023

Properties of Nanomaterials
What determines Property Change?

a) Size effects- RECAP Lecture 2 on 22-09-2023

Size effects constitute a peculiar and fascinating aspect of nanomaterials. The
effects determined by size pertain to the evolution of structural,
thermodynamic, electronic, spectroscopic, electromagnetic, and chemical
features of these finite systems with changing sizes.
The properties of a material depend on the type of motion its electrons can
execute, which depends on the space available for them. Thus, the properties
of a material are characterized by a specific “length scale”, usually on the nm
dimension. If the physical size of the material is reduced below this length
scale, its properties change and become sensitive to size and shape.
Variation of Au NPs with size. Melting temperature versus size for CdS
nanocrystals

Melting point decreases with size (gold) Optical properties vary with size (gold)

b) Quantum confinement effects:

In any material, substantial variation of fundamental electrical and optical
properties with reduced size will be observed when the energy spacing between
the electronic levels exceeds the thermal energy (kT).
In small nanocrystals, the electronic energy levels are not continuous asin the
bulk but are discrete (finite density of states), because of the confinement of the
electronic wavefunction to the physical dimensions of the particles. This
phenomenon is called quantum confinement and therefore nanocrystals are also
referred to as quantum dots (QDs).
Moreover, nanocrystals possess a high surface area and a large fractionof the
atoms in a nanocrystal are on its surface. Since this fraction depends largely on
the size of the particle (30% for a 1-nm crystal, 15%
for a 10-nm crystal), it can give rise to size effects in the chemical andphysical
properties of the nanocrystal.
Below: Electronic energy level spacing of sodium as a function of the particle
diameter.

A plot of the average electronic energy level spacing (Kubo gap, δ) of sodium as
a function of the particle diameter. Also shown is the percentage of Na atoms
at the surface as a function of particle diameter.
In summary: Quantum effects
The overall behavior of bulk crystalline materials changes when the dimensions
are reduced to the nanoscale.
• For 0-D nanomaterials, where all the dimensions are at the nanoscale,
an electron is confined in 3-D space. No electron delocalization (freedom
to move) occurs.
• For 1 -D nanomaterials, electron confinement occurs in 2 -D,
• For 1 -D nanomaterials, electron confinement occurs in 2 -D, whereas
delocalization takes place along the long axis of the nanowire/rod/tube.
• In the case of 2-D nanomaterials, the conduction electrons will be
confined across the thickness but delocalized in the plane of the sheet.
3. Electronic band theory
• For individual atoms there exist discrete energy levels that may be
occupied by electrons, arranged into shells and subshells. Shells are
designated by integers (1, 2, 3, etc.), and subshells by letters (s, p, d,
and f). For each of the s, p, d, and f subshells, there exist, respectively,
one, three, five, and seven states. The electrons in most atoms fill just
the states having the lowest energies, two electrons of opposite spin
per state, in accordance with the Pauli Exclusion Principle. The
electron configuration of an isolated atomrepresents the arrangement
of the electrons within the allowed states.

• A solid may be thought of as consisting of a large number, say, N,of

atoms initially separated from one another, which are subsequently
brought together and bonded to form the ordered atomic arrangement
found in the crystalline material. At relatively large separation
distances, each atom is independent of all the others and will have the
atomic energy levels and electron configuration as if isolated. However,
as the atoms come within close proximity of one another, electrons are
acted upon, or perturbed, by the electrons and nuclei of adjacent
atoms. This influence is such that each distinct atomic state may split
into a series of closely spaced electron states in the solid, to form what
istermed an electron energy band.

Li molecule and Li solid (bulk)

Electronic Bands in metallic Lithium (MO=Molecular Orbital)

Electronic bands in Na metal

NB: Fermi level: in an orbital band electronic structure, it is the highest

occupied electronic level.
(a) The electron band structure found in metals such as copper, in which
there are available electron states above and adjacent to filled states, in
the same band. (b) The electron band structure of metals such as
magnesium, wherein there is an
overlap of filled and empty outer bands. (c) The electron band structure is
characteristic of insulators; the filled valence band is separated from the
empty conduction band by a relatively large band gap (>2 eV). (d) The
electron band structure found in the semiconductors is the same as
for insulators except that the band gap is relatively narrow (<2 eV).

ENERGY LEVELS IN METALLIC AND SEMICONDUCTOR NANOPARTICLES

(Assignment Hint):

• Density of states in metal (A) and semiconductor (B) nanocrystals.

In each case, the density of states is discrete at the band edges.
The Fermi level is in the center of a band in a metal, and so kT
will exceed the level spacing even at low temperatures and small
sizes.

• Nevertheless, metal nanoparticles of very small size can exhibit

insulating properties. In contrast, in semiconductors, the Fermi
level lies between two bands, so that the relevant level spacing
remains large even at large sizes. The band gap increases in
smaller semiconductor nanocrystals.

Definition. Density of states: The density of states is defined as the

number of available states in a given interval of energy at each energy
level. (Available to be occupied by electrons).

In Summary: Electrons Confinement:

• For 0-D nanomaterials the electrons are fully confined.

• For 3-D nanomaterials the electrons are fully delocalized.
• In 1-D and 2-D nanomaterials, electron confinement and
delocalization coexist.
• The effect of confinement on the resulting energy states can be
 calculated by quantum mechanics, as the “particle in the box”
problem. An electron is considered to exist inside of an infinitely
deep potential well (region of negative energies), from which it
cannot escape and is confined by the dimensions of the
nanostructure. i.e.

Energies

where h¯ ≡ h/2π, h is Planck’s constant, m is the mass of the electron, L

is the width (confinement) of the infinitely deep potential well, and nx,
ny, and nz are the principal quantum numbers in the three dimensions
x, y, and z.

The smaller the dimensions of the nanostructure (smaller L), the wider
is the separation between the energy levels, leading to a spectrum of
discreet energies.