PART-II

Introduction to Nanoparticles and

Nanostructures
 Definition of Nanoparticle
• A structure with at least 1 dimension less
than 1 µm.
• Examples:
– Sphere-like particles
• Ag nanoparticles, buckyballs
– Rod-like particles
• Si & Ni nanowires
– Tube-like particles
• Carbon nanotubes
• TiO2 nanotubes
 Size is a Material Property?

The gold we know: The gold we are discovering:

Material properties don’t Material properties (such as optical

change with size Absorption, shown here) change with the
- resistivity size of the gold nanoparticle.
- melting point
- optical absorption
 Unique Characteristics of Nanoparticles
• Large surface to volume ratio.

• High percentage of atoms/molecules on the surface

• Surface forces are very important, while bulk forces are not as
important.

• Metal nanoparticles have unique light scattering properties

and exhibit plasmon resonance.

• Semiconductor nanoparticles may exhibit confined energy

states in their electronic band structure (e.g., quantum dots).

• Can have unique chemical and physical properties.

• Same size scale as many biological structures

 Examples of Unusual Properties
• Lowered phase transition temps
• Increased mechanical strength
• Different optical properties
• Altered electrical conductivity
• Magnetic properties
• Self-purification and self-perfection
 Physical Properties of Nanoparticles

• Physical properties of nanoparticles are

dependent on:
– Size
– Shape (spheres, rods, platelets, etc.)
– Composition
– Crystal Structure (FCC, BCC, etc.)
– Surface ligands or capping agents
– The medium in which they are dispersed
 Size
# of atoms
• Molecules, nanoparticles, and 1
Molecules
bulk materials can be 10

distinguished by the number

102
of atoms comprising each
type of material. 103
Nanoparticles
• Note: these are very 104
approximate numbers!
105

106
Bulk

Poole, C., Owens, F. Introduction to Nanotechnology. Wiley, New Jersey. 2003

 Size
• Nanoparticles exhibit unique properties due to their
high surface area to volume ratio.
• A spherical particle has a diameter (D) of 100nm.
– Calculate the volume (V) and surface area (SA)

4 3 πD3 SA = 4 πr 2 = πD2
V = πr =
3 6 SA = π(100 × 10-9 )2
π(100 × 10-9 )3 SA = 3.141× 10-14 m2
V=
6
V = 5.24x10-22 m3
 Surface Area:Volume Ratio
• This gives an approximate surface area to volume ratio of
>107:1 which is significantly larger than a macro sized particle.

• As the surface area to volume ratio increases so does the

percentage of atoms at the surface and surface forces become
more dominant.

• Generally accepted material properties are derived from the

bulk, where the percentage of atoms at the surface is
miniscule. These properties change at the nanoscale.
 Size
Some example calculations for volume and surface area of nanoparticles.
These calculations use nm as unit of length.

Nanoparticle Nanoparticle Volume Surface Area SA:Vol Ratio

Diameter (nm) Diameter (um) (nm3) (nm2) (nm2/nm3)
1 0.001 0.524 3.14 6
10 0.01 524 314 0.6
100 0.1 523598 31416 0.06
1000 1 5.24E+08 3.14E+06 0.006
10000 10 5.24E+11 3.14E+08 0.0006
100000 100 5.24E+14 3.14E+10 0.00006
1000000 1000 5.24E+17 3.14E+12 0.000006
Surface Area:Volume Ratio

In this graph:
SA = nm2
Vol = nm3

SA:Vol Ratio = nm2/nm3

The ratio increases

dramatically when the
nanoparticle diameter drops
below about 100 nm
 Size
• As the percentage of atoms at the surface increases, the
mechanical, optical, electrical, chemical, and magnetic
properties change.
– For example optical properties (color) of gold and silver change, when
the spatial dimensions are reduced and the concentration is changed.
 Size
Melting point as a function of particle size
• Nanoparticles have a lower melting point than their bulk counterparts

Melting point of gold nanoparticles as a

function of size.

Source: Ph. Buffat and J-P. Borel, Phys. Rev. A 13,

2287–2298 (1976)
 Melting point versus Shape

• Particles: May sinter together at lower than expected

temperature.
• Rods: Can melt and form spherical droplets if heated
too high.
• Films: Thin films can form pin-holes. Continued
heating can lead to de-wetting behavior and island
formation.
 Crystal Structure
• Most solids are crystalline with their atoms arranged in a
regular manner.
• This arrangement of atoms impacts the functionality of the
material.
• Some solids have this order presented over a long range as in
a crystal.

• Amorphous materials such as glass and wax lack long range

order, but they can have a limited short range order, defined
as the local environment that each atom experiences.
 Crystal Structure
• The spatial arrangement of atoms in a crystal lattice
is described by its unit cell.
• The unit cell is the smallest possible volume that
displays the full symmetry of the crystal.
• Many materials have a “preferred” unit cell.
 Crystal Structure
• In 3 dimensions, unit cells are defined by 3 lattice
constants and 3 angles.
• This leads to 14 Bravais lattices, each having
characteristic restrictions on the lattice constants,
angles, and centering of atoms in the unit cell.

c
a
 Crystal Structures
For cubic unit cells, there are three centering types:

Simple Cubic Body Centered Cubic Face Centered Cubic

(SC) (BCC) (FCC)
 Size & Crystal Structure
• Most metals in the solid form close packed lattices
• Ag, Al, Cu, Co, Pb, Pt, Rh are Face Centered Cubic
(FCC)
• Mg, Nd, Os, Re, Ru, Y, Zn are Hexagonal Close Packed
(HCP)
• Cr, Li, Sr can form Body Centered Cubic (BCC) as well
as (FCC) and (HCP) depending upon formation energy
 Size & Crystal Structure
• How does crystal structure impact nanoparticles?
• Nanoparticles have a “structural magic number”, that is, the
optimum number of atoms that leads to a stable configuration
while maintaining a specific structure.
• Structural magic number = minimum volume and maximum
density configuration
• If the crystal structure is known, then the number of atoms per
particle can be calculated.

Poole, C., Owens, F. Introduction to Nanotechnology. Wiley, New Jersey. 2003

Close-Packed Magic Number
Clusters

• Magic Number = Cluster has a complete, regular outer geometry

• Formed by successively packing layers around a single metal atom.
• Number of atoms (y) in shell (n): y = 10n2 + 2 (n = 1,2,3…)
• Maximum number of nearest neighbors (metal-metal hcp packing)
• Decreasing percentage of surface atoms as cluster grows
J. D. Aiken III, R. G. Finke, J. Mol. Catal. 1999, 145, 1
 Size & Crystal Structure
• For n layers, the number of atoms N in an
approximately spherical FCC nanoparticle is
given by the following formula:

N = 1/3[10n3 – 15n2 + 11n - 3]

• The number of atoms on the surface Nsurf

NSurf = 10n2 – 20n +12

Size & Crystal Structure
Example Calculations:

How many atoms (N) are in

idealized Au NP’s with the
following diameters?

5 nm Au NP:
With 9 shells, n = 9 and
NP diameter = 17d = 4.896 nm
N = 1/3[10n3 – 15n2 + 11n - 3]
N = 2057

Other Approximate Values

10 nm = 17,900
20 nm = 137,000
30 nm = 482,000
40 nm = 1.1 million
50 nm = 2.2 million
Poole, C., Owens, F. Introduction to Nanotechnology. Wiley, New Jersey. 2003