1.

-INTRODUCTION

Since the winning of the Nobel Prize in 1986 by Binning et al. thanks to its invention, the Atomic
Force Microscope (AFM) has been a powerful tool in all fields of science and a boost to the
development of nanotechnology as we know nowadays.The advantage of this technique comes from
the wide range of operation, having even the possibility to measure in insulator materials,
something imposible up to that date, when the furthest achievement in microscopy was the
Scanning Tunneling Microscopy (STM).
In this laboratory experiment, the basic operation of an AFM was understood and after a proper
calibration, the device was used to characterize the topology of the surface of diferent materials,
using two of its working modes (static mode and tapping mode). Furthermore, spectroscopy
measurements were carried out to obtain force-distance curves and compare with our theoretical
knowledge.
2-THEORETICAL BACKGROUND

2.2.-FORCES

Whereas STM uses a current of electrons through a surface (limiting its working to conductor
materials), AFM uses an actual force interaction for the measurement.
The probe of the microscope is placed very close to the material and it can feel diferent types of
interactions, that are to be referenced below:

Van der Waals

Van der Waals interaction describes atoms and molecules being atracted by respectively induced
dipole moments. Even in competely filled electronic orbitals, statistical fluctuations create temporal
dipoles in an atom that can polarize neighbor atoms. This results in a net attractive interaction that
can be described as r -6 .
However when the distance between atoms decreases further, a new interaction arises: Pauli
exclusion principle, that keeps the electrons from being in the same state and location. This
repulsive force can be approximately described as r -12 .

Bringing together the two interaction, the Lenard-Jones potential is obtained

A 12 B 6
V ( r )[( ) ( ) ]
r r

A sketch of the potential in arbitrary units can be see below

Figure 1: Lenard-Jones potential in arbitrary units

Capilar forces

Even in dry conditions, any surface is always covered by a film of water, that can vary its thickness
depending on the humidity. If the tip of the probe is close enough to the surface a meniscus can be
formed.
This meniscus contributes to the condensation of more water molecules, leading to the formation of
a water neck that pulls downwards the probe. This effect can completely dominate all the forces
in this range, so avoiding its appearance can be decisive in order to obtain good results.
Usually many AFM experiments are carried out in vacuum or in a liquid medium so this capillary
forces do not appear. Also, the shape of the tip could be a very important factor: blunt tips can
experience more capillar forces than sharp tips.

Figure 2: Water meniscus between sample and tip.

Image taken from [**]

Chemical bond

In case the tip comes really close to the surface, chemical bonds can be formed as the ones inside
the material to be studied. However, for this to happen, extraclean surfaces are needed.
Under ambient conditions the sample is covered with all sort of adsorbates that pasivate this effect,
so in the current experiment, chemical bonds can be neglected.

Friction forces

When two materials are put in contact and moved with respect to each other, friction forces start to
act, so it is natural to think that this iinteraction will play some role in our experiment.
Macroscopically, the well known Amonton's law gives a direct proportionallity between the friction
and normal load force, like

F fr = N

being the macroscopic coefficient of friction. According to this law, friction force is apparently
independent of the contact area between the bodies.
Nevertheless, this result fails when nanoscalar samples are considered. In this case, friction force
seems to be proportional to the number of atoms chemically interacting, i.e. to the contact surface.
This phenomena is still poorly understood [a]. Even a new kind of microscopy, the Friction Force
(FFM) was developed thanks to this property.

The advantage of our technique is that the contact surface can be idealy reduced up to one atom (the
very tip of the probe) and this effect can be considerably diminished.
Electromagnetic forces

At this scales, electrostatic forces can be described through electronics theory.

Let's remember that every material has its own 'work function' , i.e. the minimum necessary
energy for an electron to scape and thus, the energy difference between the Femi level and the
vacuum level.

When two diferent materials are separated (probe-sample) the only common level in the vacuum
one. Later, if the are brought together, electrons will be interchanged until Fermi levels are
equalised. The vacuum energy will be shifted between materials by , the difference in work
functions.

This electron interchange and the appearance of a potential leads to the formation of an electric
field, E /d, that will be responsible of the attraction force.

To undestand the magnetic contribution the surface must be pictured as a mesh of magnetic
domains. The tip can be treated as a charge (monopole) moving over this surface.
Obviously the tip will feel the attraction or repulsion from the magnetic field created by the
domains and the cantilever will bend upwars or downwards.
This effect is used in magnetic microscopes but in our particular case of study, in which the only
interest is the topography of the sample, magnetic interactions can introduce the so-called 'artifacts'.
Objectively, the effect of the cantilever moving up and down because of the topography is the same
as if it moves because of the magnetism so eventually an image with false "textures" can be
obtained.

Contact force

One of the effects that will be exploited in laboratory is the actual mechanical contact between the
tip and the sample, forcing it and leading to the appearance of an adhesive force.
Simplifying the model at most, the tip can be treated as a spring that after the contact with the
surface will feel a linear repulsive interaction described by Hooke's Law

F rep=k z

for z<0 and F=0 otherwise.

This ansatz is the basic principle for the Contact mode and will be revisited later in the section
Spectroscopy.
2.3.-STRUCTURE OF A MICROSCOPE

Knowledge of the basic structure of the AFM will help understand its functioning.

As mentioned before, the most important part of the device is the so-called 'cantilever'.The
cantilever is a single piece of Silicon usually, obtained after etching processes in a waffle. It
consists of a rod (~200m) ending in a sharp point: the tip.
The tip will be the part of the device closer to the sample, the one that will suffer every of the
atomic interactions explained above. Several types of tips can be found commercially, and the main
difference between them lies on their shape.
As the tips feels the forces, repulsions and attractions the cantilever bends up and
down following its movement and this (cantilever bending) is the signal to be
processed to obtain the desired topology.

The deflection of the cantilever is registered thanks to the optical part of the set
up. A laser beam is continuosly pointed to the cantilever and reflected
(sometimes with a system of mirrors, as in our case) to a photodiode array.
The back of the cantilevers are normally covered with a reflective metal coating
for this purpose.
Usual photodiodes for this purpose are divided in two or four quadrants, and
detecting the position of the incident beam gives enough information to calculate
the position on the cantilever in every moment (x,y and z directions) and with
that, the topology of the sample.

**Pictures taken from 'Bruker AFM' Probes and accesories Catalog (2013) -->

Having control over the cantilever movement is also important to scan the desired
zone of the sample (x-y movement) or to control the applied force and maintain a
constant load or constant deflection (z-movement) as it is done in the contact
mode of operation. For that purpose, the cantilever is directly attached to piezoelectric elements.

Figure 3: Schematic structure of the AFM. Image taken

from [***]
Piezoelectricity is a property present in some crystalline materials such as quartz, with the ability to
generate electrical current under mechanical stress and viceversa. In other words, we can make a
piezoelectric element somehow deform or change its size applying an external voltage.
The feedback system of the AFM device is able to vary this voltages for piezo's and thus control the
cantilever motion. The easiest way to create a tridimensional movement is to have three piezo
elements, one for every spacial direction.

2.4.-MEASURING MODES

Depending on which kind of material is to be studied and what type of interactions are expected, an
Atomic Force Microscope can be operated in diferent modi. In this section three methods shall be
reviewed: contact mode, tapping (dynamical) mode and no-contact (flying) mode. At the end, a
brief explanation of the Spectroscopy mode is added, in order to understand the last measurements
done in laboratory.

2.4.1.-STATIC MODES

As mentioned in Forces section, the contact between tip and surface implies the appearance of an
elastic force that, in first approximation can be studied with Hooke's law (FORMULA ABOVE).
In the static modes, also called 'contact modes', the cantilever moves mainly because of the
mechanical contact then (as well as for the other explained forces). Two general methods can be
distinguished: equiforce and variable deflection mode.

In the equiforce mode, a constant deflection for the cantilever is kept during the measuring. To
respond correctly to the topography changes, a PID feedback system (Proportional-Integral-
Derivative) imust correct the force applied in every point to keep the same bending state of the
cantilever. The signal processed then is the change in applied load, that can be understood as the
topography.

The counterpart of the previous method is the variable deflection mode. In this case, applied force
is constant and the cantilever swings following changes in the surface of the sample. This
movement is registered thanks to the optical system of the AFM, as mentioned before.

One of the disadvantages of contact modes is that the tip tends to push away small particles that
there could be in the surface of the sample, so the obtained image can get blurry or with lost of
information. It can be even a destructive procedure for delicate samples.

2.4.2.-TAPPING MODE

In this case, the cantilever is excited with an oscillation of frequency close to its resonance
frequency. *NAOMIIIII* WHY CLOSE AND NOT AT THE RESONANCE FREQ.?? The
excitation (frequency and amplitude) are kept constant during the measurement.
For this mode, the elastic constant of the cantilever is a decisive factor. As can be read in the
original article by Binning in 1986 we need the maximum deflection for a given force. This
requires a spring that is as soft as possible. At the same time a stiff spring with high resonant
frequency is necessary in order to minimize the sensitivity to vibrational noise from the building"
[b].
The resonance frequency for such a system comes described by

f 0=
1

2 m0
k

To make the spring softer the constant k must be minimized and to get a high resonance frequency,
the quotient k/m must be conserved, so the mass must be very small too.
Nowadays, nanofabrication allows to create really light cantilevers with any desired resonance
frequency.

The observed magnitudes in this case are the changes in phase or amplitude, that the feedback
system has to correct. To have an example, if the tip hits the surface in one of the vibrational cycles,
the frequency and amplitude of the movement can decrease considerably, and then the z-piezo must
compensate this by increasing the excitation.

2.4.3.-FLYING MODE

The basic principle is the same as in the tapping mode (vibration of the cantilever, record of the
changes in amplitude or phase due to the interactions), but in this case the tip is held a few tens of
nanometers over the surface.
One of the advantages of this method is to avoid damaging the surface of the sample as happens in
the contact mode, so it is a good way to obtain images of biological samples, for instance.
Furthermore, at that distance only long rage order forces, as van der Waals are detected. It is also a
good procedure to make electrostatic and magnetic measurements.
2.4.4.-SPECTROSCOPY Force vs Distance Curves

Besides imaging, another interesting use for AFM is the Force Spectroscopy. The procedure for the
measuring, based inf the Hooke's Law again, goes as follows:

The tip of the probe is approached to the surface of the sample, while no change in force is recorded
(A). At a given height the tip starts to be attracted by the interaction forces and at some point it
snaps in contact with the surface.
While the applied load increases, the cantilever bends downwards- the tip meanwhile is stuck in the
sample and doesn't move (B). After reaching a predefined value, the device tries to snap back the tip
from the material.
While retracting, adhesion forces are still present and hold the tip on to the sample. The cantilever
will bend upwards (C) and only when the applied elastic force of the cantilever is over the adhesive
force an abrupt jump back of the tip can be seen (D).

Figure 4: Ideal force-distance curve, with the steps explained above

Studying this difference between trace and retrace curves with the help of Hooke's Law, adhesive
forces can be calculated.

REFERENCES

[a] Y. MO, K. T. TURNER and Izabela SZLUFARSKA (2009), Friction laws at the nanoscale,
Nature, 457.
[b] G. BINNING and C. F. QUATE (1986), Atomic Force Microscope, Physical Review Letters,
56(9).

[**] TSENG, Ampere A. (2011), Tip Based nanofabrication , Chapter ' Double Layer Local Anodic
Oxidation Using Atomic Force Microscopy', pp 91-127.

[***] Our laboratory protokol!! Can we reference that??