5.

Thin Film Growth Basics

Special Lecture on Nanofabrication, 2018 Spring, Han-Bo-Ram Lee

HBRL Research Group

Prof. Han-Bo-Ram Lee
Department of Materials Science and Engineering
Incheon National University, Korea

Growth of Thin Films

• Film deposition occurs through
-Nucleation
-Coalescence
-Continuous growth

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 Three Main Processes

Nucleation Coalescence Continuous growth

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Growth Modes

• Island or Volmer-Weber (VW) growth

: When atoms in clusters more strongly bond: metal, SC on oxide
• Layer or Frank-van der Merwe (FM) growth
: When atoms are more strongly bound to substrate: single crystal epitaxy
• Island-layer or Stranski-Krastonov (SK) growth
: Metal-metal, metal -semiconductor
Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr
 Surface to Volume Ratio
The percent of surface atoms vs Pd cluster size
• The ratio of surface atoms to interior atoms
changes dramatically if one successively divides a
macroscopic object into smaller parts.
• Cube of iron of 1cm3 → the percentage of surface
atoms ~ 10-5 %
• Cube of iron of 103 nm3 → the percentage of
surface atoms ~ 10 %

Variation of NaCl surface energy with particle size

Large surface energy → thermodynamically unstable

Stabilize nanostructures → need to understand surfaces of solids
Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Surface Energy I
• Atoms or molecules on a solid surface possess fewer nearest neighbors →
dangling or unsatisfied bonds exposed to the surface.
• Surface atom - interior atom < interior atom - interior atom due to inwardly
directed force
• The lattice constants of the entire solid particles show an appreciable reduction
with decreasing size
• Surface energy: the extra energy possessed by the surface atoms (surface free
energy or surface tension).

! ∂G $ G: Gibbs free energy

γ =# &
" ∂A %ni,T ,P A: surface area

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 Surface Energy II
• Surface atoms are moving toward interior
due to breaking bonds.
• Additional force to pull the surface atom
back to its original position ~ surface
energy
the number of broken bonds
1
γ = N bερa surface atomic density
2
bond strength
1 1 2 4ε
γ {100} = N bερa = ⋅ 4 ⋅ 2 ε = 2
2 2 a a
1 2 5ε
γ {110} = ⋅ 5 ⋅ ε =
2 2a 2 2a 2
1 2 2 3ε γ {100} > γ {110} > γ {111}
γ {111} = ⋅ 3⋅ 2 ⋅ ε =
2 3a 2 a2
http://www.energy.org
Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Minimization of Surface Energy

The lowest Gibbs free energy → material or system is stable
• Surface relaxation: the surface atoms or ions shift inwardly which occur more readily in
liquid phase than in solid surface due to rigid structure in solids
• Surface restructuring through combining surface dangling bonds into strained new
chemical bonds
• Surface adsorption through chemical or physical adsorption of terminal chemical
species onto the surface by forming chemical bonds or weak attraction forces such as
electrostatic or van der Waals forces
• Composition segregation or impurity enrichment on the surface through solid-state
diffusion.
Surface relaxation

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

 Homogeneous Nucleation
• If nucleus has spherical shape with radius, r
4 3
Δµ v = π r ΔGv
3
• Surface energy of nucleus
Δµ s = 4 π r 2γ
• Total change of chemical potential
4 3
ΔG = Δµ v + Δµ s = π r ΔGv + 4 π r 2γ
3
• r*: a critical size
• r > r* → stable
• r < r* → dissolved into the solution

dΔG γ 16 πγ
=0 → r* = −2 ΔG* = : energy barrier
dr ΔGv (3ΔGv )2
Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Heterogeneous Nucleation 1
• Heterogeneous nucleation: new phase forms on a surface of another material
• Similar to homogeneous nucleation, there is a decrease in the Gibbs free energy
and an increase in surface or interface energy surface change energy
volume change energy
ΔG = Δµ tv + Δµ ts
energy per
Δµ tv = Vsc Δµ v unit volume
nucleus volume
1
Vsc = π R 3 (2 − 3sin α + sin 3 α )
3
1
= π r 3 (2 − 3sin(90 − θ )+ sin 3 (90 − θ ))
3
1
= π r 3 (2 − 3cosθ + cos 3 θ )
3
1
Δµ tv = Vsc Δµ v = π r 3 (2 − 3cosθ + cos 3 θ )Δµ v = a3r 3Δµ v
3 1 3
a3 = π (2 − 3cosθ + cos θ )
Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr
3 http://nanomaterial.kr
 Heterogeneous Nucleation 2
surface areas of each interfaces
Δµ ts = Avf γ vf + A fsγ fs − Asvγ sv
Avf = 2 π Rh
= 2 π r 2 (1− cosθ )
A fs = π r 2 sin 2 θ
Asv = π r 2 sin 2 θ
Δµ ts = 2 π r 2 (1− cosθ )γ vf + π r 2 sin 2 θγ fs − π r 2 sin 2 θγ sv
= a1r 2γ vf + a2 r 2γ fs − a2 r 2γ sv
a1 = 2 π (1− cosθ )
a2 = π sin 2 θ
Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Heterogeneous Nucleation 3
ΔG = a3r 3Δµ v + a1r 2γ vf + a2 r 2γ fs − a2 r 2γ sv
γ sv = γ fs + γ vf cosθ

dΔG
=0 : maximum point in the volume energy and surface energy plot
dr
3a3r 2 Δµ v + 2a1rγ vf + 2a2 rγ fs − 2a2 rγ sv = 0

*
−2 ( a1γ vf + a2γ fs − a2γ sv )
r = : critical size of nucleus
3a3Δµ v
3

ΔG * =
4 ( 1 vf 2 fs 2 sv )
a γ + a rγ − a rγ
: critical energy barrier
27a 23Δµ v
Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr
 Heterogeneous Nucleation 4
• Critical size of nucleus and critical energy barrier with geometrical terms

2 πγ vf
*
# sin 2 θ cosθ + 2 cosθ − 2 &
r = $ 3
'
Δµ v % 2 − 3cos θ + cos θ (
" 16 πγ vf % " 2 − 3cosθ + cos 3 θ %
*
ΔG = # 2
&# &
$ 3(Δµ v ) '$ 4 '

wetting factor
16 πγ
ΔG* = : critical energy barrier of homogeneous nucleation
(3ΔGv )2
• Contact angle = 180 ° → wetting factor = 1 → the critical energy barrier is same as
that of homogeneous nucleation
• Contact angle < 180 ° → wetting factor ↓ → the energy barrier for heterogeneous

nucleation is always smaller than that of homogeneous nucleation → heterogeneous

nucleation is easier than homogeneous nucleation in most cases
• Contact angle = 0 ° → wetting factor = 0 → no energy barrier

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr

Growth Modes with Wettability

2 πγ vf
*
# sin 2 θ cosθ + 2 cosθ − 2 &
r = $ 3
'
Δµ v % 2 − 3cosθ + cos θ (
" 16 πγ vf % " 2 − 3cosθ + cos 3 θ %
*
ΔG = # 2
&# &
$ 3(Δµ v ) ' $ 4 '
• Island growth
γ sv < γ fs + γ vf
• Layer growth
γ sv = γ fs + γ vf

• Island-Layer growth

: Island-layer growth is a little more complicated and involves in situ developed stress

Prof. Han-Bo-Ram Lee hbrlee@incheon.ac.kr http://nanomaterial.kr