Homogeneous Nucleation

S= (PV-PS)/PS is vapor supersaturation

If S = 0 and = 0 nucleation is impossible.
If, Pv > Ps, is negative and nucleation is possible.
Supersaturation is needed for Homogenous
nucleation.

PYL 116 Elements of Materials Processing, Dr. P. K. Muduli

Homogeneous Nucleation

Total free-energy change in forming

the nucleus :
4 3
= + 4 2
3
surface energy per unit area
PYL 116 Elements of Materials Processing, Dr. P. K. Muduli

Homogeneous Nucleation
Surface ~r2

Total energy change

4
= 3 + 4 2
3

Find r* from

=0

and =

16 3
3 2

if r < r* then the cluster is unstable

if r > r* then the cluster will grow =>Nucleation
r* is a critical radius for nuclei
PYL 116 Elements of Materials Processing, Dr. P. K. Muduli

Volume ~-r3

Homogeneous Nucleation
Examples
Liquid nickel can be supercooled by 250 K below TM (1453 C)
without solidification.
Pure water can be supercooled to as low as -42 C without being
frozen into ice.

PYL 116 Elements of Materials Processing, Dr. P. K. Muduli

Nucleation rate
How fast will the critical nucleus continue to grow ?

Nucleation rate is given by

A*

r*

N* = concentration of critical nuclei (nuclei/cm3)

A* = critical surface area of nuclei
= flux of atom impingement (atoms / cm2sec)

= 4

Density of nucleation sites

PYL 116 Elements of Materials Processing, Dr. P. K. Muduli

Growth Modes
Island

Layer by layer

Atoms or molecules in the deposit

are more strongly bound to
substrate than each other.
Example: Single-crystal epitaxial

growth of semiconductor films

Binding energy decreases with
thickness

Atoms or molecules in the deposit

are more strongly bound to each
other than to the substrate.
Example: Metal and semiconductor
films deposited on oxide substrates

PYL 116 Elements of Materials Processing, Dr. P. K. Muduli

Combination of the
two modes: Common
metal-metal and
metal-semiconductor

Surface energies
Atoms at free

surfaces are more energetic than atoms within

the underlying bulk - they make fewer bonds with surrounding
atoms and are thus less constrained.
There is a thermodynamic driving force to reduce the number
of dangling bonds at the surface through re-bonding between
atoms-leads to reduction of surface energy () per unit area.
Usually = 0.2 to 3 J/m2 , metals have higher surface energies
than oxides, alkali halides, sulfides, and organic substances.
Furthermore, the surface energy drops slightly with
temperature typically, d /dT = -0.05 mJ/m2-
usually is anisotropic, i.e. differently oriented surfaces have
different . fcc{111} has lowest

PYL 116 Elements of Materials Processing, Dr. P. K. Muduli

Heterogeneous nucleation
Homogeneous nucleation is rare.

Some CVD reactors where too highly supersaturated gases

rain "snow" down on substrates.

Heterogeneous nucleation
Simple qualitative model of film nucleation--quantitatively
inaccurate
Powerful connection to substrate temperature,
deposition rate, and critical film nucleus size.

PYL 116 Elements of Materials Processing, Dr. P. K. Muduli