Chapter 8

f) Atomic Force Microscopy

(AFM)
 Atomic Force Microscopy
Important technique to investigate interfaces
Ancestor of all scanning techniques is STM (Scanning Tunnelling Microscopy), Binning und Rohrer Nobel prize 1986
Metal tip is moved over surface in a small distance, tunnelling current is measured
Typically current is maintained constant and distance is measured via piezoelectric levers.

Disadvantage of STM: limited to metallic / conducting surfaces.

 Can we measure force between tip and surface, rather than current?
 Atomic Force Microscopy

Yes, we can!
Force constant k of a 4 mm 1 mm piece of Al-foil is around 1 N/m,
while chemical bonds can be around 10 - 100 N/m.

 It is possible to measure force between tip and surface

 Initially, electrostatic or magnetic forces were measured, now
even van der Waals forces are accessible.
Initially, cantilevers were made of gold, now mostly
Si, SixNy oder SiO2, produced by photolithography,
size approximately100 m 1 m.

Tip: electrochemically etched wires with tips down

to 0.5 nm.
 Atomic Force Microscopy

Parts of an AFM :
• Sharp tip on sensitive cantilever
• Ability to measure small displacements of
the cantilever
• A system to monitor and control the
displacement (mostly optical methods).
• A mechanical system for moving the top on
the surface OR the surface below the tip.
• Imaging system
• Stability towards vibrations Displacement of the cantilever is monitored optically
via a split photodiode with four quadrants.
 Atomic Force Microscopy

4
4
3
2 1 0
3 1 0
6
2 5 6

0. tip far away from surface, no acting forces
1. tip approaches region of attractive interaction
2. Between points 2 and 4 the tip is in contact with
the surface. It exerts pressure and is bent upwards.
4. Cantilever is retracted, tip still interacts with
surface due to adhesive forces.
5. Elastic force becomes bigger than adhesion, tip
bounces back to original position.
6. Cycle is restarted
 Atomic Force Microscopy
To image a whole surface, the tip is moved over the sample (or the sample below the tip).
There are two possibilities, (a) Contact mode or (b) Tapping mode (non-contact mode).

Contact mode: Tip is moved maintaing distances betweenpoints „2“ and „4“, repulsive forces
act between surface and tip. Either the displacement of the cantilever is kept constant or the
force that acts on the tip.

Highly ordered graphite Polystyrene

 Atomic Force Microscopy
Tapping Mode: no contact to surface, distance between 10 – 100 nm. In this region van der Waals –
interactions can be measured.

Cantilever is forced to vibrate, frequencies around 100 kHz are

employed, corresponding to the resonance frequency of the
cantilever.

When an additional forces becomes active, the force constant

changes and thus the resonance frequency. An attractive force
reduces the force constant of the cantilever.

Properties to be measured: Change of frequency, amplitude or

phase between the driving force and the vibration.
 Chapter 9

Thermodynamics of Self Organisation

 Self Organisation

Spontaneous formation of mcroscopic structures and aggregates

 Association colloids, complex fluids, soft matter

 Examples: Tensides/amphiphilic molecules

Vesicles can store water molecules for 20 ms,

Na+ even for months.

1. What keeps these structures together?

2. How are they formed?
 Emulsions
Emulsion: Mixture between two unmiscible liquids, emulgator is required.

Oil in water: Micelle  Examples: mayonaise, milk, Crema (Espresso)

Water in oil: inverse micelles  Examples: Vinaigrette, butter

Often the emulgator decides the structure that is formed.

Emulgators: egg yolk (lecithin)

mustard

Further examples: cosmetics, body lotion

 Colloids
Tyndall-Effect: light scattering at interfaces, dependent on dilution

 Concentrated solution = white

 Diluted solution = blue

Systems that show Tyndall-effect are called colloids.

Stability?

Name Phasen Beispiel

Emulsion liquid/liquid

Suspension solid in liquid colored pigments,

(ink), wheat beer
Schaum gas in solid or liquid Whipped cream

Aerosol Solid or liquid in gas Cigarette smoke

 Aggregates
Questions:
• What keeps the structures together?  intermolecular forces
• How are the structures formed?  Can be answered using thermodynamics. Detailed know-
how on intermolecular interactions is not necessary.

Definition: N is the number of aggregated species (N=2: dimer, N=3: trimer etc.),
xN is mol fraction of the N-mer.

X
N
N  X 1  X 2  X 3  ...  1

Equilibrium: chemical potential of all species 1 X2 1 X

  10  kT ln X 1   20  kT ln  30  kT ln 3  ...
has to be equal. 2 2 3 3

Note that energy per aggregate is 𝜇 (𝑡𝑜𝑡𝑎𝑙) = 𝑁 𝜇°

1 X
In general:    N0  kT ln N  Constant
N N
Aggregates

Definition of parameters
 Aggregates

Reaction rate for association from monomer v Ass  k Ass  X 1N

XN
v Diss  k Diss 
…and the dimer dissociation N
k Ass
Equilibrium constant K K
k Diss

K in thermodyn. expression for

equilibrium between monomer and K  e  N   N  1  / kT   e 2 2  1  / kT 
dimer

Solve equation for mole fraction of dimer,

normalize to X1 as reference state (all mole

X 2  2 X 1  e 1  2   / kT  
2

fractions relative zu X1)

Assumption: Chemical potential is equal for all N  equations only hold, when Concentration decreases with N.
 Aggregates
Thus, a requirement for the formation of aggregates N is a different chemical potential for
the different N-meres.

(a) µN° decreases steadily with increasing N

(b) µN° exhibits a minimum at a certain size of N

Important factors:
 Interaction between molecules
 Shape of the aggregates: rods,chains, disks, spheres….
 Aggregates
Standard shapes of aggregates:
 chains
 disks
 spheres
 Chains

Binding energy has to be on the same order of magnitude than thermal energy.

Stabilising Helmholtz-energy A of the aggregates compared to the monomer:

 ~ a  kT mit a>1

- Energy gain/profit is proportional to chain length

- Terminal units have only one bond to a neighbour and contribute only half the energy of the central
units, terminal sites have to be subtracted

- Energy gain/profit N   N  ( N  1)  a  kT

 1
- For large N, factor 1/N accounts for terminal sites  N0  1  a  kT
 N

- Starting from the solid, there is an energy increase. a  kT

 N0   0 
The larger N, the smaller this increase N
 Disks
Number of monomers ist proportional to area N ~   R2

Number of edge binding sites is proportional to NR ~ R

circumference,

 Number of edge sites scales as square root of total

monomer number. Expression for chem. potential has to be
modified:

2  V    Line
1/ 2
a  kT
  
0
N
0
 1 a With volume V and line tension Line with unit N
N 2 kT

Interaction parameter a is not identical for the different geometries!

line tension is equivalent to surface tension in 2D systems

Additional interaction possible due to charges (Tenside), not considered here.

 Spheres/Droplets
Number of monomers ist proportional to volume N ~ R3

Number of missing binding sites on the surface is N ~ R2

proportional to surface area
1
So with increasing monomer number, the number of N 3

surface sites increases as

a  kT
 N0  0  1
Chemical potential starting from solid N 3

4  R 2   s with surface tension s and molecular radius R

Interaction parameter a a
kT

- surface tension is related to intermolecular forces

- System dependent, here aggregate/water.   kT
 N0  0 
- General expression for chemical potential: NP

with interaction parameter a and shape parameter P

 Aggregation
Why do aggregates form?  Consider previous expression


X N  N X 1  e  1    N   / kT  
N

 N  X 1  e 
N Approximation for small differences in , interaction small
compared to  of monomers.

There is a maximum size for X1 :  X 1 critical  ea

Addition of monomer beyond this point HAS to lead to aggregate formation

Independent of aggregate shape, but dependent on intermolecular interaction and thus parameter a.
Strong interaction with large a results in a smalll X1(critical).

critical micelle concentration, CMC

Aggregation

Typical concentration dependence for

aggregate-forming molecules
 Determination of CMC
- When ions contribute: Conductivity measurments
- Spectroscopy: molecules inside micelles exhibit absorption spectrum that is different
from the non-interacting molecules.

Keto-isomer forms H-bonds in aqueous solution

Enol-isomer with intramolecular H-bond is more stable inside micelles
Micelle formation is associated with a red-shift of bands in the UV/Vis-spectrum
 Aggregation
When does aggregation stop?

 During aggregation, system gains cohesion, but change in entropy S is negative

 Large aggregates are enthalpically favored, small ones entropically

Spheres and disks often continue to aggregate, until phase separation starts (hydrocarbons in water).
In tensides on the other hand there is often a minimum in  at a certain aggregate size, for example due to electrostatic
effects (repulsion of polar heads).

What do aggregates do, when they face repulsive forces at increasing monomer concentration?
Change of shape: spheres  cylinders  disks  stacks. Interaction for spheres
 4 r 2 
 

 A for phase transfer
 X 1 critical  e

a  kT
Alkanes dissolve in water until CMC is reached, at concen- e 
Surface tension enters
trations above CMC phase separation sets in

Methane = sphere with R=0.2 nm, hydrocarb./H2O= s  50 mJm-2 at 20 °C 2.510-20 J bzw. 15 kJMol-1 and a=6

Experimental value (chapter 7b):  PT G  14.5 kJ  Mol  Good match

 Ostwald Ripening
Laplace-pressure
• Previously for droplets and bubbles
• can also determined for particles

2  s
P 
R

• Small particles have larger , more

monomers dissociate compared to large
particles
• monomers diffuse to larger particles and
associate with them, Laplace pressure is
smaller

large particles grow at the cost of small ones, because surface tension decreases
with size of the aggregate.
 Ostwald Ripening
Examples: Crystal growth, re-crystallisation of water in ice cream, coagulation of emulsions

Kinetics:
- Oswald-ripening depends on rate of diffusion.
- Increases at high T and low 
- Becomes faster at high particle densities and high
solubility
- Increases, when surface tension is high
- Growth can be monitored via Tyndall-effect or via STM Two 300 nm x 300 nm STM images, separated
in time by 20000 s, showing island ripening of
Cu on Cu(001) at 343K

J. B. Hannon et al, Phys. Rev. Lett. 1997, 19, 2506

 Aggregation
Typical size distribution of aggregates, defined
by average aggregation number M=<N> and
polydispersivity (standard deviation) .

Typical size distribution for disks and spheres:

- Still many monomers at the CMC
- Mol fraction of small aggregates decreases
rapidly.
- Pronounced maximum at a certain value of N

Chains: Often polydisperse distribution with a

maximum.
 Interactions between Particles and Interfaces
Interactions between all bodies can be calculated, as long as we can assume additive behaviour.

Difficult for macroscopic bodies.

Simple relation for interaction with two bodies (nanoparticles, macromolecules, interfaces), dependence on
the geometry of the bodies and the Hamaker-constant A.

 = particle density of material,

C= van der Waals constant, depends on interaction

Hamaker-constant has units of energy, depends on polarisability  of the compounds.

Similar values for different

compounds!
 Hamaker-Constants

1
𝐴~𝛼 , 𝑉 𝜌~ 𝐴~𝐶 𝜌 ~ 𝛼 𝜌 ~𝑉 ≈ 𝑐𝑜𝑛𝑠𝑡
𝑉 𝑉

Hamaker-Constants scatter around 10-19 J. If this value is used for unknown

compounds/materials, the interaction depends exclusively on the geometry of the system.
Hamaker-Konstante

Simple expressions for interactions

between macroscopic bodies and/or
nanoparticles allow to estimate the
interaction.

Examaple:

Interaction of two spheres, R=10 mm

distance r=10 nm.

A  R1 R2 
w(r )    
6r  R1  R2 

With 𝐴 = 1 10 𝐽  w10-14 J,
 2106 kT at 298 K
 Summary & Conclusion

We have…..

• derived expression for fundamental intermolecular interactions, arranged accordingto their

distance dependence
• described experimental methods to derive properties relevant for intermolecular
interactions
• described more complicated interactions like H-bonds, hydrophobic interactions, -,
cation- interactions and halogen bonding in terms of more fundamental concepts
• received a superficial view on interactions with surfaces
• seen how intermolecular interactions determine e.g. protein structure or adhesion
• derived fundamental expressions to describe aggregation