ChE 5535

Characterization of thin Films

Alexander Couzis
Motivation
Surface or interfacial properties determine
the extent of interaction of a material with
its surroundings.

It is very difficult to find materials that have
the right combination of bulk and surface
properties.
Objective
Determine New Ways for Controlling
Surface Properties of Materials.

Deliver Surface Functionality to a material
that would allow its use in new applications.
Surface Properties
Surface properties control processes such as :
Wettability
Adhesion
Adsorption
Biocompatability
Lubrication
Permeation
Colloidal Interactions and Stability
Catalytic Action
Technological Impact:
Printing Processes
Adhesion and sealing between coated
web material (Paper, Non-Wovens)
Flavor and aroma scavenging in food
packaging
Absorbency
Xerography
Pesticide and Herbiside Delivery
Microelectronics Packaging
Techniques for Modification of Surfaces
Coating Techniques:
Paints, Lacquers, Primers on Metal Surfaces
Sizing Agents on Paper or Non-wovens
Vapor Deposition Techniques
Surface Reactions:
Flame Treatment
Corona treatment
Plasma treatment
Chromic acid treatment
Grafting
Bulk Techniques
Blending of surface active compounds
Alloys
Water
Langmuir-Blodgett Transfer
t
t
Lateral
Pressure
Lateral
Pressure
Air
Experimental Method
Infrared spectrum
measurement
Calculation of A Calculation of c
ads
Water
Langmuir Film
t
t
Lateral
Pressure
Lateral
Pressure
Air
Preparation of Hydrophobic Surface by
OTS Deposition
Solvent Mixture :- Hexadecane:CHCl
3
:CCl
4
=80:8:12 (Volume)
OTS Concentration :- 2.0x10
-3
mol/lit
Solvents kept in 80-90% relative humidity for 48 hours to absorb water
TIME FOR HYDROLYSIS
INCUBATION TIME
SOLVENT
OTS
SUBSTRATE
OTS SOLUTION
TIME FOR DEPOSITION
DEPOSITION TIME
RINSE IN CHLOROFORM DRYING WITH NITROGEN
u
CONTACT ANGLE
MEASUREMENT
AFM
Layered Polyelectrolytes
Layered Polyeletrolytes
q
z
(
-1
)
Characterization Barriers
Typically thin film are deposited on opaque
substrates.
Often the films themselves are opaque.
Very wide range of refractive indices.
Thickness can range from a few ngstrms
to a fem micrometers.
Interaction of Materials and Light
Transmission

Reflection

Diffraction

Scattering
Spectral Range
Violet
Ultaviolet
Red
Infrared
-0.2
0
0.2
0.4
0.6
0.8
1
1.2
500 550 600 650 700 750
Data 1
B
nm
Gamma
Rays
X-Rays Ultraviolet
Infrared Microwave Radiowave
0.01
3 x 10
20
Hz
0.1
1

10
1240ev
10m
0.124 ev or 2850 cal/mol
1 cm
10cm
2.85 cal/mol
0.1cm
-1

Spin Alignments Molecular Transitions
Electronic
Transitions
Nuclear
Transitions
Tool Classification
Optical Techniques
Direct optical observation
Measurement of refractive index
Spectroscopic Techniques
Transmission
Reflection
Absorption
Scattering Techniques
Raman
Tool Classification
Diffraction Techniques
X-Ray
Neutron
Higher energy techniques
X-ray photoelectron spectroscopy
Neutron reflectivity
Electrochemical Techniques
Surface Potential
Gravimetric
Quartz crystal microbalance
Molecular Orbitals
Intermolecular Forces
ChE5570
Interaction Potentials
Typical Interaction Potentials of two
molecules have the form:
w(r)=
Cm
1
m
2
r
n
The corresponding force between these
two molecules is then given by:
F(r)=
dw(r)
dr
=n
Cm
1
m
2
r
n+1
Mies Interaction Pair Potential
w(r)=
A
r
n
+
B
r
m
Repulsive Term
Attractive Term
Classical Example of this form of an interaction potential
is the Lennard-Jones Potential:
w(r)=
A
r
6
+
B
r
12
Lennard-Jones Potential
In this description of a intermolecular potential the
attractive (negative) term is the Van der Waals
interaction potential.
Two species at equilibrium, r
e
, will be at a distance
from one another that results in a minimum of the
interaction potential:
dw(r)
dr
r=r
e
=0
Because F(r) is given by dw(r)/dr, the maximum force
occurs at a distance that satisfies d
2
w/dr
2
= 0.
Lennard-Jones Potential
w(r) = min when dw(r)/dr = 0 r = r
e
= (2B/A)
1/6

w(r
e
)
min
= w(r = (2B/A)
1/6
) = -A
2
/4B = -A/(2r
e
6
)
The ratio of the minimum total potential to the VDW potential is
then given by:
w(r
e
)
min
/w(r
e
)
VDW
= (-A/(2r
e
6
))/ (-A/r
e
6
) = 1/2
The interaction potential is zero for r that satisfies w(r
o
) = 0 :
r = r
o
= (B/A)
1/6
andthis means that r
e
/r
o
= 2
1/6
= 1.12
Lennard-Jones Potential
-4 10
-21
-2 10
-21
0
2 10
-21
4 10
-21
6 10
-21
2 3 4 5 6 7 8
B
I
n
t
e
r
m
o
l
e
c
u
l
a
r

P
o
t
e
n
t
i
a
l

(
J
)
Intermolecular Distance ()
r
e
= (2B/A)
1/6
r
o
= (B/A)
1/6
Repulsive
Attractive
Lenard-Jones Potential
The intermolecular force is maximum at r: dw
2
(r)/dr
2
= 0.
Substituting gives us r = r
s
= (26B/7A)
1/6

For realistic Lennard - Jones parameter values, A = 10
-77
J m
6

& B = 10
-134
J m
12
we can calculate a maximum attractive
force of
F
max
=1.89x10
-11
N
For the same values of A and B the minimum potential can
also be calculated: w
min
= -A
2
/4B = -2.5x10
-21
J = 0.61kT at T
= 298 K
Lennard-Jones Potential
-1 10
-10
0
1 10
-10
2 10
-10
3 10
-10
4 10
-10
5 10
-10
2 3 4 5 6 7 8
I
n
t
e
r
m
o
l
e
c
u
l
a
r

F
o
r
c
e

(
N
)
Intermolecular Distance ()
(26B/7A)
1/6
Repulsive
Attractive
Intermolecular Potential Between
Two Oxygen Molecules
Strong Intermolecular Forces
Covalent Bonds
Coulombic Interactions
Strengths of Covalent Bonds
Bond Type Strength
(kJ mole
-1
)
Bond Type Strength
(kJ mole
-1
)
CN
870 Si----O 370
C==O 690 C----C 360
C==C 600 C----O 340
O---H 460 N----O 200
C---H 430 F-----F 150
Coulomb Forces or Charge-Charge
Interactions
w(r)=
Q
1
Q
2
4tc
0
cr
=
z
1
z
2
e
2
4tc
0
cr
c is the relative permittivity or dielectric constant of the
medium and r is the distance between the two charges, z
i
is
the valency of each component, and when multiplied with
the elementary charge (e=1.602x10
-19
C) results in the
charge of each interacting species. The force is given by:
F=
dw(r)
dr
=
Q
1
Q
2
4tc
0
cr
2
=
z
1
z
2
e
2
4tc
0
cr
2
Coulomb Forces or Charge-
Charge Interactions
The electrical field at a distance r away from a charge Q
1
is then
defined by:
E
1
=
Q
1
4tc
0
cr
2
Vm
1
This field when acting on a second charge, Q
2
, at r, gives rise
to a force:
F=Q
2
E
1
=
Q
1
Q
2
4tc
0
cr
2
Coulomb Forces or Charge-
Charge Interactions
w(r)=
(1.60210
19
)
2
4t(8.85410
12
)(0.27610
9
)
=8.410
19
Joules
For a typical system, eg Na
+
Cl
-
, the interaction potential is:
The equilibrium separation is 2.76
For a temperature of 300 K this turns out to be equivalent of
200 kT per ion pair in vacuum, and this comparable to the
energies of a covalent bond.
Compare to VDW max potential of 0.61 kT
Interactions Involving Polar
Molecules
-5
0
5
10
2 4 6 8 10 12 14 16
I
n
t
e
r
a
c
t
i
o
n

P
o
t
e
n
t
i
a
l

(
k
c
a
l
/
m
o
l
)
Interatomic Distance ( )
3.8186, -2.5253kcal/mol (1.755E-20 J)
Na
+
Cl
-

Ionic Crystals
For accurate determination of the lattice energy the Coulomb
energy of an ion with all the other ions in the lattice has to
be summed, and not only with the nearest neighbors.
In a NaCl crystal each Na
+
has 6 Cl
-

nearest neighbor at r=0.276nm, 12 Na
+

next nearest neighbors at (\2)r, and 8 Cl
-

more at (\3)r.
The total interaction potential is then:

i
=
e
2
4tc
0
r
6
12
2
+
8
3

6
2
+...



(

(
= 1.748
e
2
4tc
0
r
= 1.4610
18
J
The lattice cohesive energy: U = -N
0

i
= 880 kJ/mol
Born Energy of an Ion
When a single ion is in vacuum or in a medium, it still has an
electrostatic free energy, even though it is not interacting with
other ions. If in vacuum this energy is referred to as the self-
energy of the ion and if a medium it is the Born or solvation
energy of the ion.
The work done to increase the charge of a sphere of radius a by
gradually bringing charges from infinity to r = a is given by:
Q
1
=q and Q
2
=dq and r =o
dw=
qdq
4tc
0
co
And the total free energy is then:

i
= dw
}
=
qdq
4tc
0
co
0
Q
}
=
Q
2
8tc
0
co
=
ze ( )
2
8tc
0
co
Change of Medium
A
i
=
ze ( )
2
8tc
0
o
1
c
1

1
c
2



(

(
[J] =
=
28z
2
o
1
c
1

1
c
2



(

(
kT per ion at 300K
and
AG = N
o
A
i
=
69z
2
o
1
c
1

1
c2



(

(
kJ / mol
With a given in nanometers. Because moving from low
dielectric to high dielectric results in AG<0, the process in
favorable. The net energy gain of incorporating a monovalent
ion from air into water results is -1000 kJ/mol.
Solubility of ions in polar solvents
Polar Molecules


N

H

2

C

H

2

C

O

O

H

N

H

3

+

C

H

2

C

O

O

Glycine
Glycine in water
Most molecules carry no net
charge, but many possess an
electric dipole.
When a molecules shows a spatial
distribution of electron density they
possess a permanent dipole.
Dipole Moment
Unit of Dipole moment: 1 Debye 3.336x10
-30
C m
The dipole moment of two electrons (e = 1.602x10
-19
C)
separated by 1 is 1.6 x 10
-29
C m = 4.8 D
Permanent Dipoles only occur is asymmetric molecules:
They arise from the asymmetric displacement of electron
along covalent bonds.
The dipole moment of a molecule can be found by vectorial
summation of its component dipole moments: e.g. H
2
O
u
H2O
= 2 cos(1/2 u) u
OH
= 2 cos(52.25
o
) x 1.51 =1.85 D
u

Dipole Self-Energy
It is the sum of the Born energies to bring the two charges q
together minus the Coulomb interaction of bringing the two
charges together to form the dipole:

i
=
1
4tc
0
c
q
2
2o
+
q
2
2o

q
2
r



(

(
, with r = l = 2o

i
=
q
2
8tc
0
co
Ion-Dipole Interactions
Charge
Q=-ze
B
C
-q
+q
1/2 l
1/2 l
Dipole Moment
u=ql
w(r) =
Qq
4tc
0
c
1
AB

1
AC



(

(
with
AB= r
1
2
l cosu
|
\

|
.
|
2
+
1
2
l sin u
|
\

|
.
|
2



(

(
1/ 2
AC = r +
1
2
l cos u
|
\

|
.
|
2
+
1
2
l sin u
|
\

|
.
|
2



(

(
1/ 2
r
A
u
Ion-Dipole Interactions
At separation r much larger that the dipoles length AB and AC
simplify to: AB r - 1/2 l cosu, and AC r + 1/2 l cosu
w(r) = w(r, u) =
Qq
4tc
0
c
1
r
1
2
l cos u

1
r +
1
2
l cos u





(

(
(
(
=
=
Qq
4tc
0
c
l cos u
r
2

1
4
l
2
co
2
su





(

(
(
(
=
Qucos u
4tc
0
cr
2
=
ze ( )ucos u
4tc
0
cr
2
w(r, u) = uE(r)cos u
Ion-Dipole Interactions
If u is 0
o
then interaction energy is negative and thus there is
attraction, is the dipole points towards the charge, ie. u is 180
o

then the interaction is repulsive.
Ion dipole interaction dictate the interactions of ions in solvents.
Ions in Polar Solvents
In a solvent like water the electrostatic interactions are
reduced by a factor of 80. Still they are strong enough for
these interactions to be significant.

WHAT DOES THIS INTERACTION MEAN ??????
+ion
+
?
Ions in Polar Solvents
This process cannot involve any energy gain by bringing one
solvent molecule close to a ion, because that would require
that one solvent molecule depart from the vicinity of the ion.
SO where is the gain ?
+
ORDER ING IS WHAT GIVES
ONE THE ENERGY GAIN
Near cations u =0 is favored
Near anions u=180 is favored
Number of water molecules that
are bound is known as the
hydration number
Dipole-Dipole Interactions
When two polar molecules are close to one another
there is dipole-dipole interactions, analogous to the
interactions of two magnets.
u
2

u
1


w r, u
1
, u
2
, ( ) =
u
1
u
2
2 cosu
1
cos u
2
sin u
1
sin u
2
cos
| |
4tc
0
cr
3
Maximum interaction occurs when the two dipoles are
lying flat and are in line:
w r, 0, 0, ( ) =
2u
1
u
2
4tc
0
cr
3
Rotating Dipoles and Angle
Averaged Potentials
At large separation distances or in high c (angle
dependence of interaction falls below kT), dipoles can
now rotate more or less freely.
Even though the angle averaged potential over all space
should be zero, it is not.
Orientations with lower energy (more negative) are
favores [Boltzman weighting factor]
Rotating Dipoles and Angle
Averaged Potentials
e
w r ( )/ kT
=
e
w r,O ( )/ kT
dO
}
dO
}
= e
w r,O ( )/ kT
, dO= sin udud
and so dO
}
= d sin udu = 4t
0
t
}
0
2t
}
And so in general one can write
e
w r ( )/ kT
= e
w r,O ( )/kT
=
1
4t
d e
w r,u,
( )
/kT
sin udu
0
t
}
0
2t
}
Bottom Line
For charge-dipole interactions:
w r ( ) ~
Q
2
u
2
6 4tc
0
c
( )
2
kTr
4
for kT >
Qu
4tc
0
cr
2
w r ( ) ~
u
1
2
u
2
2
3 4tc
0
c
( )
2
kTr
6
for kT >
u
1
u
2
4tc
0
cr
3
For Dipole-Dipole interactions:
Entropic Effects
A = U TS = U+ T
cA
cT
|
\

|
.
|
but
T
cA
cT
|
\

|
.
| = A
A = U A =
1
2
U
So half the total energy is absorbed internally during the
interaction.
Since A < 0 the entropic contribution is negative and so the
interaction is associated with a loss in entropy.
Entropic Effects
Dielectric constant is temperature dependent (for water not for
organic solvents) and as such it introduces an entropic
component to the interaction potential even if it does have an
explicit temperature dependence.
For the Born energy, A=Q
2
/8tc
0
c a, and the Coulomb energy
is A=Q
1
Q
2
/ 4tc
0
c a we find that:
TS = T
cA
cT
|
\

|
.
| =
Q
2
8tc
0
ca
T
c
cc
cT
|
\

|
.
| = A
T
c
cc
cT
|
\

|
.
|
For water T/c c/T = -1.36 at 25
o
C
Interactions Involving
Polarization of Molecules
Polarizability is defined according to the strength of the
induced dipole moment that a molecule acquires when
in a field of strength of E:
u
ind
=o E
+e
-e

l
E
E
+e
-e
u
ind
= o
0
E = le
F
ext
= eE
F
int
=
e
2
4tc
0
R
2
sin u ~
e
2
l
4tc
0
R
3
~
e
4tc
0
R
3
u
ind
u
ind
= 4tc
0
R
3
E = o
0
E
o
0
= 4tc
0
R
3
Polarizability of Polar Molecules
Consider a freely rotating dipolar molecule
+
E
u
ind
= ucosue
uE cosu
kT
=
u
2
E
kT
cos
2
u =
u
2
3kT
E, uE <<kT
Since the induced dipole is proportional to the electrical field, the
factor u
2
/(3kT)is an additional contribution to the molecular
polarizability, and is known as orientational polarizability
o
orient
=
u
2
3kT
E
and
o =o
0
+
u
2
3kT
E (Debye Langevin Equation)
In low enough T, or high E
the molecules dipole will
align totally with the field
Interaction Between Ion and
Uncharged Molecule
+
-
Cation
Anion
q
q
Development of
Attractive force
E
r
=
2u
ind
4tc
0
cr
3
=
2oE
4tc
0
cr
3
=
2o ze ( )
4tc
0
c
( )
2
r
5

attractive force is: F = ze ( )E

r
=
2o ze ( )
2
4tc
0
c
( )
2
r
4
=
1
2
oE
2
The energy is half what is expected
of an ion and a s similarly aligned
permanent dipole:
w r ( ) = uE = oE
2
Net Ion-Induced Dipole
Intercation
w r ( ) =
ze ( )
2
o
2 4tc
0
c
( )
2
r
4
=
ze ( )
2
2 4tc
0
c
( )
2
r
4
o
0
+
u
2
3kT
|
\

|
.
|
Dipole-Induced Dipole
Interactions
E =
u 1+3cos
2
u
( )
1/ 2
4tc
0
cr
3

w r, u
( )
=
1
2
o
0
E
2
=
u
2
o
0
1+3cos
2
u
( )
2 4tc
0
c
( )
2
r
6
Averaging over all angles:
w r ( ) =
u
2
o
0
2 4tc
0
c
( )
2
r
6
Debye Interaction or Induction Interaction
w r ( ) =
u
1
2
o
02
+u
2
2
o
01
| |
2 4tc
0
c
( )
2
r
6
Van Der Waals Forces
(I) Origin
Force acting between all atoms and molecules,
similar to gravitational forces-----> London Forces
or Dispersion forces
Play a significant role is phenomena such as
adhesion, surface tension, wetting, etc.
Can be effective in ranges greated than 10nm or down to
interatomic spacings.
Can be attractive or repulsive, no simple power law.
Dispersion Forces tend to align molecules
Non-additivity
Quantum Mechanical Nature of
VanDer Waals Forces
+
-
F =
e
2
4tc
0
o
0
= 2hv, hv = 2.2 10
18
J
Bohr Radius o
0

Simply solving gives us the value
of this first radius: 0.053nm
A Bohr atom has no permanent dipole moment, but at any
given moment an instanteneous dipole exists that is equal to:
u = a
0
e
Londons Equation
w r ( ) =
u
2
o
0
4tc
0
( )
2
r
6
=
a
0
e
( )
2
o
0
4tc
0
( )
2
r
6
'
w r
( )
~
o
0
2
hv
4tc
0
( )
2
r
6
similar to London Equation
( )
w r ( ) =
C
disp
r
6
=
3
4
o
0
2
hv
4tc
0
( )
2
r
6
=
3
4
o
0
2
I
4tc
0
( )
2
r
6
and for dissimilar molecules
w r ( ) =
3
2
o
01
o
02
4tc
0
( )
2
r
6
hv
1
v
2
v
1
+ v
2
( )
=
3
2
o
01
o
02
4tc
0
( )
2
r
6
I
1
I
2
I
1
+ I
2
( )
Magnitude of Dispersion Forces
w(r=a)=10
-21
J=1kT