Heterogeneous nucleation

 Homogeneous nucleation is rare.

 Some CVD reactors where too highly supersaturated gases

rain "snow" down on substrates.

Capillarity theory of 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

 Capillarity theory of heterogeneous nucleation
(𝑣)
Assume nuclei
are spherical
caps 𝜽 is called wetting
angle

(𝑠)

Young's equation
𝛾𝑠𝑣 =𝛾𝑓𝑠 +𝛾𝑓𝑣 𝑐𝑜𝑠𝜃

𝜃 = 𝐶𝑜𝑠 −1 (𝛾𝑠𝑣 − 𝛾𝑓𝑠 )/𝛾𝑓𝑣

-depends solely on the surface properties of the involved materials.

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

 Growth Modes
Layer by layer

• Atoms or molecules in the deposit • Atoms or molecules in the deposit • Combination of the
are more strongly bound to are more strongly bound to each two modes: Common
substrate than each other. other than to the substrate. • metal-metal and
• Example: Single-crystal epitaxial • Example: Metal and semiconductor metal-semiconductor
growth of semiconductor films films deposited on oxide substrates
(𝛾𝑠𝑣 > 𝛾𝑓𝑠 + 𝛾𝑓𝑣 ),
• The deposit "wets" the substrate • 𝜃>0
and 𝜃~0
(𝛾𝑠𝑣 ≥ 𝛾𝑓𝑠 + 𝛾𝑓𝑣 ), (𝛾𝑠𝑣 <𝛾𝑓𝑠 + 𝛾𝑓𝑣 ),
PYL 116 Elements of Materials Processing, Dr. P. K. Muduli
 Capillarity theory of heterogeneous nucleation
(𝑣)
Assume nuclei
are spherical
caps 𝜃 is called wetting
angle

(𝑠)

Surface area of Nucleus =𝑎1 𝑟 2 𝑎1 = 2𝜋(1 − 𝑐𝑜𝑠𝜃)

Contact area of Film =𝑎2 𝑟 2 𝑎2 = 𝜋 sin2 𝜃
2−3𝑐𝑜𝑠𝜃+cos3 𝜃 Substrate-vapor
Volume of nucleus =𝑎3 𝑟3 𝑎3 = 𝜋 interface is lost by
3
Formation of nucleus
So total free energy change on the formation of cluster is
Δ𝐺 = 𝑎3 𝑟 3 Δ𝐺𝑣 + 𝑎1 𝑟 2 𝛾𝑣𝑓 + 𝑎2 𝑟 2 𝛾𝑓𝑠 −𝑎2 𝑟 2 𝛾𝑠𝑣

Negative Positive
PYL 116 Elements of Materials Processing, Dr. P. K. Muduli
 Capillarity theory
𝑑Δ𝐺
Find r* from =0
𝑑𝑟

2(𝛾𝑓𝑣 𝑎1 + 𝑎2 𝛾𝑓𝑠 − 𝑎2 𝛾𝑠𝑣 )

𝑟∗ =−
3𝑎3 Δ𝐺𝑉
3
∗
4 𝑎1 𝛾𝑓𝑣 + 𝑎2 𝛾𝑓𝑠 − 𝑎2 𝛾𝑠𝑣
Δ𝐺 =
27𝑎32 Δ𝐺𝑣 2
After substitution of the geometric constants, it is easily shown that

3
∗
16𝜋𝛾 𝑓𝑣 2 − 3𝑐𝑜𝑠𝜃 + cos3 𝜃 For homogeneous nucleation we had
Δ𝐺 = 16𝜋𝛾 3 2𝛾
3 Δ𝐺𝑣 2 4 ∗ ∗ =−
Δ𝐺 = and 𝑟
3 Δ𝐺𝑣 2 Δ𝐺𝑉

• When 𝜃 = 0, the film wets the substrate then Δ𝐺 ∗ =0, i.e., no barrier to
nucleation
• When 𝜃 = 𝜋, the film dewetts the substrate then Δ𝐺 ∗ is maximum, same as
homogenous nucleation.
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 = 𝑁 ∗ 𝐴∗ ω

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

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

−Δ𝐺 ∗
𝑁∗ = 𝑛𝑠 𝑒 𝑘𝑇 𝐴∗ = 4𝜋 𝑟 ∗ 2

Density of nucleation sites

−Δ𝐺 ∗
𝑁 = 𝑛𝑠 𝑒 𝑘𝑇 4𝜋 𝑟∗ 2ω
PYL 116 Elements of Materials Processing, Dr. P. K. Muduli