Structural Properties: Atomic Force Microscopy
R Hiesgen and J Haiber, University of Applied Sciences Esslingen, Esslingen, Germany
& 2009 Elsevier B.V. All rights reserved.
Principles of Atomic Force Microscopy:
An Introduction
With the development of the atomic force microscope
(AFM) in the year 1986 by Binnig, the disadvantage of
the previously invented scanning tunneling microscope
(STM), which needs an electrically conductive sample,
was overcome and the investigation of all kinds of ma-
terials was possible. With an AFM, the topography and
also profiles of almost any sample surface can be mea-
sured with a resolution down to the nanometer scale. The
instrument is based on its mechanical sensing of the
surface with a very fine tip and serves for imaging and
spectroscopic analysis of a variety of surface and material
properties with nanometer resolution.
This made the AFM a versatile instrument, especially,
not only for working on nanotechnological questions in
physics, chemistry, and biology but also applicable now
for material science. With an AFM, it is possible to di-
rectly image and, in addition, measure quantitatively the
three-dimensional (3D) structure of surfaces. Simul-
taneously, the mechanical, electronic, magnetic, and
chemical properties of the surface can be analyzed and
exhibited as an image with their lateral distribution on
the surface. The instrument can be used in ambient air, in
vacuum, and also in a liquid. The property of being used
in a liquid makes this technique quite desirable not only
for use in biology, where even living cells can be in-
vestigated in their natural liquid environment, but also
for use in electrochemistry. Here, the analysis of samples
in situ in an electrochemical cell under potentiostatic
control has been possible and surfaces during a chemical
reaction can be imaged.
The AFM belongs to the family of scanning probe
microscopes, where the image is not performed by optical
or electron-optical lenses as a whole involving a Fourier
transform, but is measured by scanning a fine probe point
by point over the surface, measuring the appropriate
signal, and subsequently exhibiting the measured data
points as an image. The image process is thereby based
on the interaction of probe and sample with different
types of forces (i.e., mechanical forces, electrostatic for-
ces, adhesion forces, magnetic forces, current) used in
different types of microscopy. Typically, the influence of
the probe on the surface is minimized as much as possible
in order not to change the sample, but it is also possible
to manipulate the surface by the tip. In addition to
the AFM (or scanning force microscopy (SFM)), the
most important techniques are STM, magnetic force
696
microscopy (MFM), and scanning near-field optical mi-
croscopy (SNOM or NSOM).
These techniques are characterized by a specially
designed small probe that allows for detecting the surface
properties of the sample with a high lateral and vertical
resolution. This benefit is to be attributed to the ex-
tremely short range of the particular interaction utilized
to image the sample, e.g., the fast decrease of the quan-
tum-mechanical electron tunneling probability with
distance (STM) or the short-range potential of inter-
atomic or intermolecular forces (AFM). In the case of
SNOM, it is the exponential decay of the optical near-
field – the so-called evanescent modes – that yields the
high resolution. These components of the radiation field
otherwise cannot be used in conventional (i.e., far-field)
light microscopy. Therefore, the lateral resolution which
follows Abbe’s theorem is restricted to 200–300 nm
(1 nm ¼ 109 m). With scanning probe microscopy, it can
be reduced significantly. The highest lateral resolution
has been reached by STM with 10 pm (1 pm ¼ 1012 m),
but with AFM also a resolution in the subnanometer
range has been demonstrated, typically the lateral reso-
lution is on the order of a few nanometers. The imaged
area has a length on the order of 0.1 mm to less than 1 nm.
The development of scanning probe microscopies has
been the prerequisite for the development of nano-
technology in the twentieth century.
Advantages of Atomic Force Microscopy
The advantages of AFM are as follows:
• nomeasurements
restriction of materials;
• resolution betterpossible in air, liquid, or vacuum;
• 3D measurement of surface
than 1 nm in all dimensions;
• and profiles and roughness;
• forces,
analysis of additional surface properties, i.e., friction
adhesion forces, hardness, conductivity, electric
fields, magnetic field, and chemical composition.
Disadvantages of Atomic Force Microscopy
The disadvantages of AFM are as follows:
• 150
the scanned area typically does not exceed 150 mm 
mm, and the maximum height is on the order of
micrometers;
• image quality strongly depends on probe geometry (as
in all probe microscopies); and
• the scanning speed is typically slow compared with
scanning electron microscopy (SEM).
 Measurement Methods | Structural Properties: Atomic Force Microscopy
Experimental Setup
A typical experimental setup for AFM measurements
includes the AFM instrument, consisting of a sample
holder positioned on a piezoelectric tube, the cantilever
system, and an optical unit for measuring the deflection
of the cantilever and electronics. For measurements in
liquid or electrolyte solution, a fluid cell containing the
sample is needed, which may be equipped with elec-
trodes for potential control. The whole system is often
positioned in a chamber for shielding the instrument
from noise and other annoying influences and, depending
on the analysis, for control of ambient conditions such
as surrounding gas atmosphere, temperature, or humidity.
The measured data are stored in a computer system,
which also controls the function of the instrument.
By using the software, the display of the measured data
as images or curves and the further evaluation of the
data are possible. A drawing of a typical setup is given
in Figure 1. Often it is necessary to isolate the instru-
ment from the influence of oscillation of the surround-
ing building by, for example, positioning the instrument
on a large mass or air-damped table or hanging it on
springs.
The AFM measuring system consists of a microscale
cantilever with a sharp tip (probe) at its end, which is
used to mechanically scan the specimen surface. The
cantilever is typically composed of silicon or silicon ni-
tride with a tip radius of curvature on the order of 10 nm.
When the tip is brought into proximity of a sample
surface, the forces between the tip and the sample lead to
a deflection of the cantilever according to Hooke’s law.
Depending on the situation, forces that are measured in
AFM include mechanical contact forces, van der Waals
forces, capillary forces, chemical bonding, electrostatic
forces, magnetic forces (e.g., Casimir forces and solvation
forces; see the section entitled ‘Magnetic Force Micro-
scopy’). The movement of the cantilever is sensed by on
optical-based feedback system (Figure 2).
A laser beam is directed onto the reflecting top side of
the cantilever tip. The movement of the reflected laser
beam on a split photodiode is dependent on the bending of
Environmental chamber
Fluid/
electrochemical cell
AFM
AFM control/
data aquisition Gas supply
Figure 1 Typical setup of an atomic force microscopy (AFM)
system.
697
the cantilever. On deflection from the cantilever, the re-
flected laser beam changes its position on the photodiode
array proportional to the deflection, but with a magnifi-
cation depending on the geometric proportions. The
position of the laser spot is sensed by the voltage differ-
ence between the split photodiode as long as the spot hits
both segments. For topographical measurements, a two-
segment photodiode is sufficient. With the exception of
atomically flat surfaces, the sample height has to be ad-
justed in order to avoid collisions of tip and sample. For
this purpose, the force and thereby the distance are kept
constant by keeping the deflection constant. This is per-
formed by a feedback mechanism that adjusts the sample
height accordingly. Traditionally, the sample is mounted
on a piezoelectric tube that can move the sample in the z
direction for maintaining a constant force and in the x and
y directions for scanning the sample. Alternatively, a ‘tri-
pod’ configuration of three piezo crystals may be used,
with each being responsible for scanning in the x, y, and z
directions, respectively. The resulting map of the area
represents the topography of the sample.
Atomic Force Microscopy Probes
Today, the tip-cantilever assembly typically is micro-
fabricated from silicon or silicon nitride (Si3N4). The
radius of curvature of these tips is about 5–10 nm. For
high resolution, imaging tips with a very high aspect ratio
are necessary. There are several techniques to micro-
fabricate sharper tips. One possibility is the sharpening of
the prefabricated tip with an ion beam or the growth of
nanotips by irradiation of the silicon tip with an electron
beam, generating electron polymerization layers from the
gas molecules in the electron beam chamber. For special
Split
Feedback
electronics
photodiode
V
Laser
Cantilever
Sample
Piezo driven
scan table
Figure 2 Principle of the optical feedback system for the force
regulation of an atomic force microscopy (AFM) tip. The
difference voltage of the split photodiode changes due to the
position of the reflected laser beam. The position of the spot
changes due to the bending of the cantilever.
698 Measurement Methods | Structural Properties: Atomic Force Microscopy
applications, specially prepared tips are needed. For
magnetic measurements, tips made from magnetic ma-
terials such as CoNi alloys are used. Conductivity
measurements need metal-coated (i.e., platinum, gold, or
aluminum) tips or highly doped silicon or diamond tips.
It is also possible to coat a tip with molecules to change
the chemical bonding and enhance a chemical or bio-
logical reaction (Figure 3).
Principal Imaging Techniques:
Topography
The AFM can be used in three different modes. The
imaging modes are often divided into static modes and
dynamic modes with an oscillating tip. The three main
modes of AFM operation that are currently in use are
contact mode (static), noncontact mode (dynamic), and
also the dynamic intermittent contact mode (tapping
mode). All measuring techniques can be sorted by the
following three systematic criteria (Figure 4):
(1) Imaging
J topographical
J spectroscopic
(2) Interaction
J contact mode
J noncontact mode
J intermittent mode
(3) Feedback regulation
J constant-height mode
J constant-force/amplitude mode
Figure 3 Scanning electron microscopy (SEM) image of atomic force microscopy (AFM) tip at the end of a cantilever.
Interactions Relevant for Atomic Force
Microscopy Imaging
The AFM uses the forces encountered by a probe tip
when it is in close proximity to a sample surface. There
are attractive and repulsive forces; the AFM is measuring
the total sum of all forces, which can be attractive or
repulsive, depending on the environment, the sample
properties, and the distance between the tip and the
surface. The typical applied force is on the order of
109 N (1 nN) (Figure 5).
Force-versus-Distance Curve
In addition to the topographic measurements, the AFM
can also provide information from the amount of force
acting on the cantilever as the probe tip is brought close
to a sample surface, indented into it, and afterward pulled
away. This technique can be used to measure the long-
range attractive or repulsive forces between the probe tip
and the sample surface, elucidating local chemical and
mechanical properties such as adhesion and elasticity,
and even the thickness of adsorbed molecular layers or
chemical bond rupture lengths.
Force-versus-distance curves (force curves) typically
show the deflection of the free end of the AFM cantilever
as the fixed end of the cantilever is brought vertically
toward and then away from the sample surface. Experi-
mentally, this is done by applying a triangle-wave voltage
pattern to the electrodes of the z-axis scanner. This
causes the scanner to expand and then contract in the
vertical direction, generating relative motion between the
cantilever and the sample. The deflection of the free end
 Measurement Methods | Structural Properties: Atomic Force Microscopy 699

20 µm 5 µm
1326 nm 556 nm

0 nm 10 µm 0 nm
2.5 µm

0 µm 0 µm
0 µm 10 µm 20 µm 0 µm 2.5 µm 5 µm
(a) (b)

Figure 4 Topography of (a) a galvanic copper coating on silicon in contact mode and (b) bacillus subtilis on silicon imaged in
intermittent mode.

Tip far away

from surface
10−100 µm

Tip approaching Long-range interaction

surface Electrostatic forces
0.1−10 µm

Van der Waals forces

Adhesion
Tip close to Capillary forces (in humid environment)
surface Screened electrostatic forces (in aqueous solutions)
0−100 nm Chemical potential
Magnetic forces
Contact
Tip indenting sample Repulsive forces: elastic and inelastic
Deformation
Stiffness (Youngs modulus)
Viscoelastic response

Figure 5 Interaction forces between the atomic force microscopy (AFM) tip and the surface at different distances.

of the cantilever and subsequently the force acting on the
tip are measured as the z-axis scanner extends the can-
tilever toward the surface and then retracts it again.
Similar measurements can be made with oscillating
probe systems such as tapping mode and noncontact
AFM. Measurements of cantilever amplitude and/or
phase versus separation can provide more information on
the details of the distance-dependent forces acting above
the sample, for example, information on magnetic and
electric fields over surfaces, and also provide information
on the properties of sample surfaces, i.e., viscoelastic
properties or adhesion forces.
Anatomy of a force curve
A: The cantilever starts at a certain distance over the
surface not touching the sample. If there are long-
range attractive (or repulsive) forces acting on the
cantilever, it will deflect downward (or upward)
before making contact with the surface (Figure 6).
B: As the probe tip is brought very close to the sur-
face, it may jump into contact if there are sufficient
short-range attractive forces.
C: Once the tip is in contact with the surface (contact
regime), cantilever deflection will increase as the
fixed end of the cantilever is brought closer to
the sample. If the cantilever is sufficiently stiff, the
probe tip may indent into the surface at this point.
In this case, the slope or shape of the contact part
of the force curve can provide information about
the elasticity of the sample surface. The in-
dentation of the tip may be elastic or give rise to
plastic deformation of the sample.
D: After pushing the cantilever down up to a desired
force value, the process is reversed. As the cantilever
is withdrawn, adhesion or bonds formed during
contact with the surface may cause the cantilever to
adhere to the sample some distance past the initial
contact point on the approach curve (B).
700 Measurement Methods | Structural Properties: Atomic Force Microscopy

(a) (b)

(c) (d)

(e)

Figure 6 Bending of AFM cantilever at different stages of extension and retraction: (a) no forces, (b) tip jumps to surface, (c) tip is
forced into the surface, (d) tip is bent by adhesion forces during retracting, and (e) no forces.

E: A key measurement of the AFM force curve is the
point at which the adhesion is broken and the
cantilever comes free from the surface. This can be
used to measure the rupture force required to
break chemical bonds or the magnitude of adhesion
forces.
The force–distance curves can provide information on
the surface properties. In Figure 7, the case of an ideal
elastic sample is drawn. The horizontal line represents
the starting line before the tip is in contact with the
surface. The slope is linear, the force rising proportion-
ally to the distance traveled by the tip, and there is no
difference in the path of the curve during lowering and
retracting the tip, besides the final jump caused by an
adhesion force. At the end, the tip again reaches the
initial (zero) position. The different stages of tip move-
ment according to Figure 6 are marked.
In Figure 8, three main types of force–distance curves
are drawn. In Figure 8(a), the ideal case of a totally
elastic tip indentation is illustrated. In Figure 8(b), a
force–distance curve often measured on different types of
samples is shown. Here, in the contact regime the curve
is no longer linear, but has a smaller slope in the be-
ginning and ends with a steeper slope. This is caused by
elasto-plastic properties of the material or the rising
 Measurement Methods | Structural Properties: Atomic Force Microscopy 701

Cantilever deflection voltage (mV)

Retrace

Deflection (V) −120 Trace

−240
B
Indentation Jump to contact
depth A −360

C E Height (nm)
−480
0 3000 6000 9000
Adhesion
Z position (nm)
D
Figure 9 Force–distance curve of an applied contact force on a
Pt sample.
Figure 7 Force–distance curves at different stages.

Retracing
300

Cantilever deflection (nm)

Extending
Force Set point
200

100

0
(a) Distance −50
0 2000 4000 6000 8000
Z piezo (nm)

Figure 10 Force–distance curve on a polymer membrane

(Nafion). The deflection is converted into nanometer. The
crossing of the retraction and extension curves is due to an
artifact caused by the nonlinearity of the piezotubes.

(b)
(c)
Figure 8 Three main types of force–distance curves: (a) ideal
case of elastic material, (b) typical case of viscoelastic material,
and (c) typical artifact owing to nonlinear piezo elements.
influence of a harder layer beneath a softer surface, for
example, on very thin samples. From the hysteresis be-
tween the two curves, the work on the sample can be
calculated.
In Figure 8(c), the most often seen artifact is dem-
onstrated. The retracting curve is situated above the
curve measured during lowering of the tip, indicating a
smaller force during retraction. This artifact is caused by
a nonlinear behavior of the piezoelectric tubes.
Distance
In Figures 9 and 10, two measured force–distance
curves on platinum and on a polymer film (Nafion-112)
are shown. The artifact described above caused by the
nonlinear piezoelectric tubes can be clearly seen.
One of the first uses of force measurements was to
improve the quality of AFM images by monitoring and
Distance
minimizing the attractive forces between the tip and the
sample. Force measurements were also used to demon-
strate similarly reduced capillary forces for samples in
vacuum, in reduced humidity environments, or com-
pletely immersed in liquid. From mapping of force
measurements on a certain sample area, images on the
different forces, depending on the surface distance and
conditions, i.e., distribution of adhesion forces or stiffness
of the sample surface, can be displayed.
During elastic indentation of the tip into the sample,
the force acting on the AFM probe can be measured from
the slope of the curve using Hooke’s law for elastic
materials:
F ¼ k Dx ½1
702 Measurement Methods | Structural Properties: Atomic Force Microscopy
where F is the force acting on the tip, k is the spring
constant, typically given by the deliverer, and Dx is the
traveling distance of the tip.
From a calibration measurement, the sensitivity of the
specific cantilever has to be determined in order to
convert voltage into distance. From the slope of the
force–distance curve in Figure 11, a force of F ¼ 2.2 nN
during indentation was calculated.
Static Mode
The static mode AFM is almost always performed by
contacting tip and surface where repulsive forces dom-
inate the tip–sample interaction and the overall force is
repulsive. Consequently, this technique is typically called
contact mode. This mode is commonly used in the force
microscope. The force on the tip is repulsive with a mean
value of 109 N. This force is set by pushing the canti-
lever against the sample surface with a piezoelectric
positioning element. In contact mode AFM, the de-
flection of the cantilever is sensed and compared, in a
direct current (DC) feedback amplifier, to some desired
value of deflection. If the measured deflection is different
from the desired value, the feedback amplifier applies a
voltage to the piezo to raise or lower the sample relative
to the cantilever to restore the desired value of deflection.
By maintaining a constant deflection, the force between
the tip and the surface is kept constant during scanning.
The voltage that the feedback amplifier applies to the
piezo is a measure of the height of features on the sample
surface. It is displayed as a function of the lateral position
of the sample. A few instruments operate in ultrahigh
vacuum (UHV) but the majority operate in ambient at-
mosphere, or in liquids, i.e., in an electrochemical cell.
A large class of samples, including semiconductors and
insulators, can trap electrostatic charge (partially dissi-
pated and screened in liquid). This charge can contribute
to additional substantial attractive forces between the
probe and the sample. All of these forces combine to
define a minimum normal force that can be applied in a
well-defined manner by the probe to the sample. This
normal force creates a substantial frictional force as the
probe scans over the sample. In practice, it appears that
these frictional forces are far more destructive than the
normal force and can damage the sample, dull the can-
tilever probe, and distort the resulting data.
The effects can be reduced by minimizing tracking
force of the probe on the sample, but there are practical
limits to the magnitude of the force that can be con-
trolled by the user during operation in ambient en-
vironments. Under ambient conditions, sample surfaces
are covered by a 10–30 monolayer thick layer of adsorbed
gases consisting primarily of water vapor and nitrogen.
When the probe touches this contaminant layer, a me-
niscus forms and the cantilever is pulled by surface
tension toward the sample surface. The magnitude of the
force depends on the details of the probe geometry, but is
typically on the order of 100 nN. This meniscus force and
other attractive forces may be neutralized by operating
with the probe and with either a part or the entire sample
totally immersed in liquid. There are many advantages to
operate AFM with the sample and cantilever immersed
in a fluid. These advantages include the elimination of
capillary forces, the reduction of van der Waals forces,
and the ability to study technologically or biologically
important processes at liquid–solid interfaces. However,
there are also some disadvantages involved in working in
liquids. These range from nuisances such as leaks to more
fundamental problems such as sample damage on hy-
drated and vulnerable biological samples. In addition,
many samples such as semiconductor wafers cannot
practically be immersed in liquid.
The resolution is limited by the contact area and at
surface protrusions by the geometry of the tip. Me-
chanically stable samples such as metal, glass, and cer-
amics can be measured in this mode as the effort is
comparatively small. Sensitive surfaces may be disturbed
or damaged by the tip contact. Especially, the imaging of
particles is quite difficult as they are prone to be pushed
away.
Dynamic Mode
In the dynamic mode, the cantilever is externally oscil-
lated at or close to its resonance frequency (10–100 kHz,
applied by the z-piezo).
Noncontact Mode
Noncontact AFM is performed such that the tip–sample
interaction is in the attractive or van der Waals regime. In
order to perform measurements in this attractive force
region, the cantilever is oscillated with a low amplitude
(o5 nm) near its resonant frequency. For noncontact
AFM, the force is measured by comparing the frequency
and/or amplitude of the cantilever oscillation relative to
the driving signal. The tip performs a forced oscillation.
The oscillation amplitude, phase, and resonance fre-
quency of the tip are modified by the tip–sample inter-
action forces; these changes in oscillation with respect to
the external reference oscillation provide information on
the sample’s characteristics. The resonance frequency is
dependent on mass and spring constant of the cantilever.
The resonance frequency of a spring free of damping is
given by
rffiffiffi
1 k
fres ¼ ½2
2p m
where k is the spring constant of the cantilever and m the
mass of the cantilever.
 Measurement Methods | Structural Properties: Atomic Force Microscopy
AFM cantilevers generally have spring constants of
about 0.1 N m1. Forces between the sample and the tip
cause an energy loss and thereby a damping of the tip
oscillation. Depending on the amount of damping, the
frequency of the forced tip oscillation is changed and a
phase shift between generating and forced oscillation
occurs.
Schemes for dynamic mode operation include fre-
quency modulation and the more common amplitude
modulation. In frequency modulation, changes in the
oscillation frequency provide information about tip–
sample interactions: frequency can be measured with
very high sensitivity and thus the frequency modulation
mode allows for the use of very stiff cantilevers. Stiff
cantilevers provide stability very close to the surface and,
as a result, this technique was the first AFM technique to
provide true atomic resolution in UHV conditions.
Tapping Mode
Under ambient conditions, most samples develop a liquid
meniscus layer. It is difficult to keep the probe tip close
enough to the sample to detect short-range forces while
preventing the tip from sticking to the surface. The
tapping mode was developed to bypass this problem. This
technique allows high-resolution topographic imaging of
sample surfaces that are easily damaged, loosely held to
their substrate, or difficult to image by other AFM
techniques. Tapping mode overcomes problems associ-
ated with friction, adhesion, electrostatic forces, and
other difficulties in conventional AFM scanning methods
by alternately placing the tip in contact with the surface
to provide high resolution and then by lifting the tip off
the surface to avoid dragging the tip across the surface.
Tapping or intermittent contact mode is also done by
50 µm
25 µm
0 µm
0 µm 25 µm
Figure 11 Integrated electronic circuit: topography with height profile and roughness analysis.
703
oscillating the cantilever near its resonant frequency, but
the amplitude is significantly higher (420 nm). Now, the
tip touches the surface once during each oscillation such
that enough restoring force is provided by the cantilever
to detach the tip from the sample. During tapping mode
operation, the cantilever oscillation amplitude is main-
tained constant by a feedback loop. Thereby, only ver-
tically directed forces are present, and critical horizontal
forces that may disturb sensitive samples such as living
cells, polymers, liquids, or particles are minimized. The
choice of the amplitude regulates the maximal force. In
amplitude modulation, changes in the oscillation ampli-
tude or phase provide the feedback signal for imaging.
Changes in the phase of oscillation can be used to dis-
criminate between different types of materials on the
surface. Amplitude modulation can be operated either in
the noncontact or in the intermittent contact regime
(Figure 12).
Surface Morphology
Because the different measured data, especially the
sample height, are typically stored in a computer, they
can be analyzed with data analysis software. The stored
data combine the lateral coordinates with the measured
property, i.e., the height, or the adhesion, or the current.
The analysis of these data depends on the available
software. These images represent the topography of the
samples and morphological details, (e.g., steps or par-
ticles), can be observed, and their lateral and vertical
dimensions can be measured with very high resolution.
Height Profile and Roughness
As standard analysis with AFM, the 3D topography of the
sample surface can be displayed as an image; in addition,
1491nm
3
2 2 3
758.5
1
26
0 25 50 µm
Distance Height
1 10.02 µm 1163.98 nm
2 11.41µm 21.57 nm
3 4.66 µm 364.95 nm
Standard roughness
Ra: 412.87 nm
Rp: 812.70 nm
Rt: 1464.39 nm
50 µm Rtm: 864.51nm
704 Measurement Methods | Structural Properties: Atomic Force Microscopy

profiles at any line, providing very precise information on
height and width of structures on the surface, can be
drawn. Compared with a classical profilometer with a tip
curvature of about 1 mm, the resolution of the measure-
ment is much higher, typically in the range of nanometer.
In addition, the roughness data from a chosen area are
calculated by the software. This has become a standard
measurement for the analysis of surface quality in many
companies, for example, in semiconductor industry.
The following data can be typically derived from a
profile line or on an area:
• RR –– arithmetic
a mean roughness,
• R – maximum heightcompared
p profile height with mean value,
• RMS – standard deviation of theandmean roughness
t difference,
• value (Figure 12).
In Figure 13, the change of surface roughness of a silicon
wafer before and after plasma etching is shown as an
example (Table 1).
variety of additional physical and chemical properties of
the sample. All techniques can be sorted by one of the
above listed criteria. In the following, the main basic
techniques are described, but there is an infinite bunch of
variation in the AFM-based techniques used.
Lateral Force Microscopy or Friction Force
Measurement
The earlier discussion of the way in which the bending of
the cantilever is detected considered the use of a laser
and a split photodiode. As the cantilever is scanned over
the specimen surface (with the cantilever now scanning
with its long axis perpendicular to the fast-scan di-
rection), variations in friction between the tip and the
sample will cause the tip to slick/slip during its scan,
resulting in twisting of the cantilever, which is demon-
strated in Figure 5. These lateral forces (friction forces)
cause the cantilever to torque, and the reflected laser

Table 1 Surface roughness of a silicon wafer before and

Measurement of Additional Sample after plasma etching
Properties Nontreated surface Plasma etched surface
Ra 0.5 nm Ra 19.3 nm
RMS 0.62 nm RMS 24.5 nm
In addition to the basic measurement of surface topo-
Avg. height 17.65 nm Avg. height 53.7 nm
graphy, the AFM is a versatile instrument to investigate a

(a) (b) (c)

Figure 12 Three different technique for AFM measurements: (a) contact mode, (b) noncontact mode, and (c) intermittent mode.

10 µm 5 µm
193 nm
54 nm

0nm 0 nm
5µm 2.5 µm

0µm 0 µm
0µm 5 µm 10 µm 0 µm 2.5 µm 5 µm

Figure 13 Topography image of silicon wafer: left, nontreated surface; right, plasma etched surface.
 Measurement Methods | Structural Properties: Atomic Force Microscopy
Figure 14 Principle of the lateral force microscopy (LFM) measurement: twisting of the cantilever owing to enhanced friction forces on
the tip shifts the reflected laser beam in the horizontal direction, which can be detected by a four-segment photodiode (in the middle).
beam on the photodiode to additionally move in a di-
rection perpendicular to the basic movement. Lateral
force microscopy (LFM) therefore uses a four-segment
(or quadrant) photodiode to enable measurement of the
torsion of the cantilever as well. The measurement is
performed in contact mode. During scanning the tip over
the surface, the additional torsion of the tip is monitored.
Thereby, areas on the sample acting with different lateral
forces on the tip can be registered and displayed as an
image. Different surface materials can thereby be dis-
tinguished, which may give information on surface ma-
terial composition or surface layers (Figure 14).
Conductivity
With the use of a conducting AFM tip, the measurement
of electronic properties of the sample in addition to the
topographical data is possible. For the measurement of
electrostatic forces, only a thin metallic coating of the tip
is necessary, as the current flow is small. With the use of
an oscillating tip, the measurement of local potential
including photovoltage, electrical fields, and capacitance
of the sample is possible.
The measurement of larger currents, for example, the
analysis of sample conductivity, makes the use of AFM
tips with a sufficiently low resistance necessary.
Capacity
By using a vibrating conductive tip in a certain defined
distance over the surface, the capacitance and, under
suitable conditions, the work function of the surface can
be measured and displayed as an image.
Electrochemical AFM
The electrochemical AFM (EC-AFM) has a high im-
portance for battery research. A big advantage of AFM is,
705
to some extent, the independence of the measurement
from the environment. It is possible to measure under
high humidity or when fully immersed in liquid. Per-
forming the AFM in an electrolyte or in an electro-
chemical cell can provide information on the structure of
surfaces at the solid–liquid interface under different
potential and on the change of surfaces during an elec-
trochemical reaction. With EC-AFM, the structure of the
interface can be measured in situ and has provided im-
mense information on the structure of overlayers, i.e., the
carbon monoxide adsorption on platinum single-crystal
surfaces, or the growth of metal films.
Ionic Conductivity
In a humid environment, the measurement of proton
conductivity, for example, of a solid-state electrolyte such
as Nafion, is possible. In this case, electrochemical re-
actions require Nafion and, take place on both sides of
the sample, for example, a polymer electrolyte mem-
brane. At the membrane bottom side, which is connected
to a metallic electrode, an electrochemical reaction
(water splitting) provides protons, which can pass
through the ion-conductive membrane channels. At the
other side of the membrane, which has no extended
electrode, the protons are consumed at the platinum-
coated AFM tip by another electrochemical reaction,
thereby closing the current circle. The visualization of
the ionic active areas on the surface of Nafion mem-
branes, as used in PEM fuel cells, under controlled hu-
midity has been demonstrated with a resolution on the
order of 10 nm (Figures 15 (a) and 15(b)).
Magnetic Force Microscopy
Magnetic force microscopy is used for the investigation
of the local magnetic force from the stray magnetic fields.
This technique is widely applied in the development of
706 Measurement Methods | Structural Properties: Atomic Force Microscopy

A Cathode: O2 + 4H+ + 4e− 2H2O 0.8 V

Pt-AFM tip
U

Membrane

1.55 V
Electrode
Anode: 2H2O O2 + 4H+ + 4e−

(a)

Current Topography
pA m
Z: 255.4 Z: 83.2 n
Y:

Y:
3.0

3.0
µm

µm
µm µm
X: 3.0 X: 3.0

(b)

Figure 15 (a) Schematic drawing of the experimental setup: the electrochemical reactions at the lower electrode of the single-side-
coated membrane and the Pt-coated atomic force microscopy (AFM) tip on the other membrane side drive a proton current through the
solid electrolyte membrane, which is measured by the AFM and (b) surface topography (right) and ionic conductive areas (left) on the
same areas measured on a Nafion-112 membrane at 52% humidity.

mass storage media for computers. The measurement is 0 µm

performed in noncontact mode. The AFM probe is
coated with a ferromagnetic layer. The complete meas-
urement includes two steps: first, the height profile of the
image line is measured and stored; second, the tip follows
this height profile, thereby keeping a constant distance to
the surface (do100 nm). Depending on the local field
strength, the tip is bound toward or away from the surface
1.25 µm
(Figure 16).

Molecular Forces
Recent progress in AFM technology has allowed the
measurement of inter- and intra-molecular forces at the
level of individual molecules. The mechanical manipu-
lation of single polymer chains immobilized on solid
substrates has become possible in solution, as they are
spanned and stretched between the tip of an AFM can-
tilever and the substrate surface. The technique for
measuring single-molecular binding forces, for example,
in proteins or polymers, is in some respect similar to the
measurement of force–distance curves. The interesting
molecules are covalently bound to a sample holder and
to the AFM tip. This can be done by using special
2.5 µm
0 µm 1.25 µm 2.5 µm
Figure 16 Magnetic force microscopic image of the highly
ordered nickel nanowire array with a pitch of 100 nm embedded in
the alumina matrix in the demagnetized state, showing the
magnetic polarization of the pillars alternately ‘up’ (white) and
‘down’ (black). Reproduced with permission from Nielsch K,
Wehrspohn RB, Barthel J, et al. (2002) High density hexagonal
Nickel nano wire array. Journal of Magnetism and Magnetic
Materials 249: 234–240.
 Measurement Methods | Structural Properties: Atomic Force Microscopy
molecules as a kind of glue. By retracting the tip, the
molecules are stretched and the force applied to the
molecule increases with distance. Because proteins are
specifically folded by binding forces of hydrogen bridges
or even weaker forces, the molecule has to be first
completely unfolded in steps until the covalent bond is
broken under a certain force. During the experiment, a
force–distance curve is measured and the unfolding
processes as well as the breaking of the molecular bonds
can be recognized as saw-like features.
This investigation on polymer chains far from their
maximum entropy configurations has stimulated the re-
finement of existing polymer theories.
From the measured force–distance curves, quantita-
tive information can be obtained about the elasticity of
single macromolecules in solution, on conformational
transitions along the chains, the mechanical stability of
chemical bonds, and about the secondary structures, as
well as on the desorption of individual polymer mol-
ecules from solid substrates.
Phase Imaging
The intermittent mode AFM was developed as a method
to achieve high resolution without inducing destructive
frictional forces both in air and fluid. Tapping mode is a
key advance in AFM. With the intermittent mode tech-
nique, the very soft and fragile samples can be imaged
successfully. Also, incorporated with phase imaging, the
tapping mode AFM can be used to analyze the com-
ponents of the sample.
In phase imaging, the phase lag of the cantilever os-
cillation, relative to the signal sent to the cantilever’s
piezo driver, is simultaneously monitored and recorded
by the SPM controller. The phase lag is very sensitive to
variations in material properties such as adhesion and
viscoelasticity. Sensitive samples such as living cells,
polymers, liquids, particles, have to be mea-
sured in the dynamic mode in order not to disturb or
destroy the surface. The phase can be recorded at the
working frequency or also at a second resonance fre-
quency of the tip with the advantage of a higher sensi-
tivity toward material properties.
Pulsed Force Mode
The AFM is used not only for imaging but also for
measuring surface properties, i.e., the viscoelastic prop-
erties of the surface or current–voltage curve, at a defined
surface site. It is also possible to obtain spectroscopic
information at each data point on an area and display the
lateral distribution of the values as an image.
The pulsed froce mode (PFM) mode is a material-
selective technique for the identification of different
707
materials or ultrathin surface layers, according to dif-
ferences in adhesion forces and/or surface stiffness. The
stiffness measured here is different from the classical
hardness values (Vickers, Brinell, etc.) and mirrors a
dynamic interaction force between the AFM tip and the
sample surface. Similar to the noncontact intermittent
mode, the tip has contact with the sample once during an
oscillation. However, the movement of the cantilever is
controlled by the AFM electronic at all the time. The
different measuring intervals are illustrated in Figure 17.
The cantilever oscillation is forced by a sine wave with a
frequency of some a few kilohertzs. During one period,
the tip has contact with the surface and is held above the
surface. In time interval A the tip is pressed against
the surface, in time interval B the tip retracts from the
surface but keeps the contact, and in time interval C the
contact is lost and the tip is oscillating with its resonance
frequency (B100 kHz). From the difference between
base line and adhesion force, an adhesion force image is
calculated; simultaneously, an image of the surface
stiffness is calculated from the difference between
the force at the working point and the maximum force.
Both images can be measured and displayed simul-
taneously to the topography, thereby allowing identifi-
cation of different material properties at different areas
(Figure 18).
Figure 18 provides the three simultaneously
measured images from the same area of a silicon wafer
coated with a carbonic acid: (a) topography, (b) adhesion
forces, and (c) stiffness. The height differences in the
Fmax Cantilever Fmax
Cantilever deflection
oscillation
Wp
Slope:
Adhesion
stiffness
c a b c a
Time
Figure 17 Schematic drawing of the cantilever movement with
time in pulsed force mode (PFM) mode: in time interval (a), the tip
performs one forced sine wave toward (indentation) and away
from the surface, and the stiffness is calculated from the slope of
the curve; in time interval (b), the adhesion force is measured
upon the delayed break of contact; and in time interval (c), the tip
performs a free damped oscillation.
708 Measurement Methods | Structural Properties: Atomic Force Microscopy
Topography
5µm
5 µm
5.02 µm
0 µm 2.5 µm
2.5 µm
0 µm 0 µm
0µm 2.5 µm 5 µm
Figure 18 Pulsed force mode (PFM) images of topography, adhesion forces, and surface stiffness measured in PFM mode on silicon,
partly covered by a 2-nm-thick monolayer of carbonic acid.
topography image show an upper as well as a lower
flat surface. The height differences measure 2 nm and can
be attributed to a one molecular layer of the carbonic
acid. From the topography image alone, the identity
of the upper and lower layers is unclear. With the add-
itional information from the adhesion and stiffness
measurements, the upper layer can be identified as the
carbonic acid layer, which partly covers the surface of
silicon.
Chemical Force Microscopy
Chemical force microscopy (CFM) combines LFM with
treatments of the tip to customize its interaction with the
sample.
The CFM enables the chemical imaging of a surface
in addition to its topography. Here, in one specific way
chemically modified tips are used working in different
liquid media that allow only one specific interaction with
the surface. The measuring probe is coated uniformly
with one chemical group with a high density, for ex-
ample, –OH, –CH3, –CF3, –NH2, or –COOH. Because of
the choice of water, buffered media, or solvent as media
for imaging, it can be assured that only one specific
interaction is active between the probe and the surface.
The strength of the interaction varies along the surface
and gives information on the density of active substances,
which can be displayed as an image. The technique used
is the PFM, where stiffness, adhesion, and magnitude of
interaction force can be measured simultaneously for
each data point.
Artifacts
The evaluation and interpretation of the measured data
and images typically needs further analysis as there are a
variety of disturbances that may influence the data.
There are artifacts caused by the system and by the
environment.
Adhesion Stiffness
100%
0µm 2.5 µm 5 µm 0µm 2.5 µm 5 µm
System Inherent Artifacts
A basic problem with all nanoprobe methods using a real
probe with certain dimensions is that the measured data
do not show the real surface but the convolution of the
geometry of the tip with structures on the sample. This
problem becomes serious in some cases where the di-
mensions of probe and sample structure have comparable
size or the latter are even smaller. In this case, the tip is
imaged by the surface features and it is impossible to get
a true image of the surface. Because of the convolution
with the probe, for example, the diameter of small par-
ticles on the surfaces can easily be measured too large.
This problem becomes even worse with higher surface
roughness. Therefore, the tip has to have a high aspect
ratio (quotient of width and length), which means that it
has to be very narrow and long. Limits are only set by
stability aspects (Figure 19).
In Figure 20, the effect of convolution of tip and
surface feature is demonstrated. In the upper part, the
influence of a small aspect ratio on the image of a step is
demonstrated: the step is smeared out. In the bottom part
with a high aspect ratio, the step can be imaged much
better, although a vertical step is always imaged with a
slope. The highest possible slope is limited by the apex
angle of the tip. Height measurements are insensitive to
the tip geometry.
Hysteresis of the piezo elements
Atomic force microscopy images can be affected by
hysteresis of the piezoelectric material and cross-talk
between the (x, y, z) axes that may require software en-
hancement and filtering. Such filtering could ‘flatten’ out
real topographical features. However, newer AFM tech-
niques use real-time correction software or closed-loop
scanners, which practically eliminate these problems.
Some AFM techniques also use separated orthogonal
scanners (as opposed to a single tube), which also serve to
eliminate cross-talk problems (cf. Figure 12).
 Measurement Methods | Structural Properties: Atomic Force Microscopy 709

Environmental Disturbances imaging. The relatively slow rate of scanning during

AFM imaging often leads to influences of thermal drift in
Thermal drift
the image, making the AFM less suited for measuring
Because of thermal expansion between the probe and the
accurate distances between structures on the image.
cantilever, a displacement of the tip position during
However, several fast-acting designs were suggested to
scanning may lead to a deformation of the image. This
increase microscope scanning productivity including
problem becomes more serious for high-resolution
what is being termed video-AFM (reasonable quality
images are being obtained with video AFM at video rate
faster than the average SEM). To eliminate image dis-
W tortions induced by thermal drift, several methods were
also proposed.

Vibrations
Vibrations are caused by the building or by footfall
sound. For isolation purposes, the AFM system can be
placed on air-damped tables or actively, by piezoelectric
elements, on damped tables. In addition, the acoustic
sound may disturb the measurements, especially if its
L frequency comes close to the resonance frequency of the
cantilever. To avoid this problem, the AFM can be placed
in noise protection boxes. Another possibility may be,
under certain conditions, working in vacuum.

Interference
In the case of a highly reflecting sample surface, the
reflected laser beam may cause inference stripes with the
light reflected from the photodiode. These interference
d
stripes are visible in the image in addition to the height
Aspect ratio =L/W
profile and have a direction vertical to the actual scan-
Figure 19 Definition of the aspect ratio of a probe. ning direction.

AFM tip
Resulting image

Scanning direction

Figure 20 Influence of the tip geometry on the resulting image line for a tip with large opening angle (above) and small opening angle
(bottom). In the case of a large angle, the convolution leads to a significant change in the slope of the measured image line.
710 Measurement Methods | Structural Properties: Atomic Force Microscopy
Static charging
This is a problem observed on nonmetallic samples and a
nonconducting AFM probe, especially during magnetic
force measurements. Charges collected during scanning
by the tip cannot flow away and cause electrostatic forces.
In this case, the use of a thin conducting layer on tip and
sample and the earthing of both sides on the same po-
tential may be necessary.
Application of Atomic Force Microscopy
for Batteries
Atomic force microscopy is a commonly used technique
in battery research. Especially, for the development of
novel materials relevant for lithium batteries and lithium-
ion batteries and, to a less extent, lead–acid batteries,
many investigations using a variety of techniques are
available and have proven to be of benefit for the
understanding of the nanoscopic material properties. One
advantage of the use of surface-sensitive methods is that
the performance of the cathodes is, to a large extent,
surface film controlled. Hence, aging of lithium-ion bat-
teries relates mostly to surface phenomena that increase
the electrodes’ impedance, especially at elevated tem-
peratures. In addition, because batteries are electro-
chemical devices, the investigation can make use of the
advantage of the AFM technique to investigate the sample
in humid environment or liquid electrolyte (also aprotic
electrolytes) and/or under potential control. Thereby,
structural changes of the surface are directly visible and
measurable and can be attributed to changes in the ex-
perimental conditions such as potential, temperature, or
concentration of electrolyte and additives (Figure 21).
This approach is useful to clarify the microscopic
reasons for macroscopic properties such as capacity or
aging processes. Another application is the investigation
of the sample surface during or after a preparation pro-
cess to collect information on surface structure, rough-
ness, or sample thickness. With high-resolution AFM,
also the growth of nanostructures on the surface as well
as nanoscopic structure details of layers or surfaces has
been measured.
Typically, most investigations are performed in com-
bination with other methods, i.e., electrochemical char-
acterizations, other surface-sensitive probes, as well as
spectroscopy.
Lithium-Based Batteries
Lithium batteries are primary batteries that have lithium
metal or lithium compounds as an anode. The most
common type of lithium cell used in consumer appli-
cations uses metallic lithium as anode and manganese
dioxide as cathode, with a salt of lithium dissolved in an
600
400
200
0
0 200 400 600
nm
Figure 21 Atomic force microscopy (AFM) micrograph of
Li1.4Mn2O4 film. Reproduced with permission from Das S, Fachini
IR, Majumdera S, and Katiyar RS (2006) Structural and
electrochemical properties of nanocrystalline LixMn2O4 thin film
cathodes (x ¼ 1.0–1.4). Journal of Power Sources 158: 518–523.
organic solvent. Depending on the design and chemical
compounds used, lithium cells can produce voltages from
1.5 V to about 3 V, twice the voltage of an ordinary zinc–
carbon battery or alkaline cell. Because of the high re-
activity of elementary lithium with water or humid air,
solely aprotic or solid electrolytes are used. There are
many different approaches, which differ in cathode,
electrolyte, separator, and anode material. The lithium-
ion battery is a secondary battery and is rechargeable.
Recent developments include lithium polymer and lith-
ium titanate batteries.
The active cathode material is composed of graphite.
The anode is typically composed of a lithium-based
metal oxide such as lithium cobalt oxide (LiCoO2) and
lithium nickel oxide (LiNiO2), or spinels such as lithium
manganese oxide (LiMn2O4). The electrolyte has to be
free of water (H2O o20 ppm) and is typically composed
of ethylene carbonate (EC) and propylene carbonate
(PC) with a low viscosity, such as alkyl carbonate/ether
and lithium salts. During charging, lithium ions are
intercalated into the graphite layers, and during
decharging, they are released and they flow back to the
metal oxide. The existence of a passivation layer on top
of the graphite that is permeable for the lithium ions but
not for the electrolyte molecules is crucial for the
function and safety of the device. Intercalation of elec-
trolyte molecules into the graphite causes an irreversible
aging of the cathode.
Critical subjects that are highly important to the field
of lithium-ion batteries relate to the capacity, especially
 Measurement Methods | Structural Properties: Atomic Force Microscopy 711

at elevated temperatures, and to aging processes. In this
respect, established as well as novel materials are under
investigation. These are listed in the following with the
older materials appearing first:
Cathode:
 Graphite (intercalation of Li)
 Nanocrystalline, amorphous silicon (intercalation
of Li)
Electrolyte:
 Salts, i.e., LiPF6 in water-free aprotic solvents
 Polymer from poly(vinylidene fluoride) (PVDF)
Anode:
 Spinels, i.e., LiCoO2, LiNiO2, LiNi1–xCoxO2, or
LiMn2O4
 Li4Ti5O12
 LiFePO4
Surface morphology
In situ electrochemical SFM was used as a main ana-
lytical tool for the investigation of surface morphology
changes of graphite during charging and discharging and
ion–solvent interactions in various nonaqueous electro-
lyte solutions.
The surface morphology of anode, cathode, and solid
electrolyte interphase (SEI) components from a variety of
materials has been investigated by AFM and EC-AFM.
Examples
Composite graphite electrodes were studied by in situ
AFM working in EC-dimethyl carbonate (EC-DMC)
and EC-PC solutions of lithium bis(oxalato)borate
(LiBOB), lithium hexafluorophosphate (LiPF6), and
lithium perchlorate (LiClO4) in an attempt to follow any
pronounced morphological changes in the graphite par-
ticles owing to the surface film formation in the course of
the first cathodic polarization and during lithium in-
sertion and desertion processes. Figure 22 gives AFM
images obtained in situ from composite graphite elec-
trodes at open-circuit voltage (B3 V) and after polar-
ization to 0.3 V (Li/Li þ ) in 1 mol L1 LiBOB and
1 mol L1 LiPF6 solutions. They show morphological
changes owing to cathodic polarization of both electrodes
connected with the formation of surface films. A rougher
surface film was formed in the case of a LiPF6 solution.
More examples of different studies for determination
of surface morphology and on the development of novel
measuring techniques are given in (Table 2).
Lead–Acid Battery
The lead–acid battery is one of the oldest battery types
but owing to its ability to supply high surge currents, it is
still widespread, for example, in cars. Each cell contains
(in the charged state) electrodes of lead metal (Pb) and
lead(IV) oxide (PbO2) in an electrolyte of about 37%
w/w (5.99 mol L1) sulfuric acid (H2SO4). In the dis-
charged state, both electrodes turn into lead(II) sulfate
(PbSO4) and the electrolyte loses its dissolved sulfuric
acid and becomes primarily water. Because the battery is
working in liquid environment with sulfuric acid as
electrolyte, the use of in situ AFM is possible to directly
study the microscopic surface processes during charging
and discharging of the battery as well as to study aging
processes.
The in situ EC-AFM was mainly used to study the
reaction of a lead electrode in sulfuric acid electrolyte,
when the reaction corresponding to what occurs at the

LiPF4 LiBOB

1800 1800
0 0
0 0
0
500 0
1000 500
1000 1000
OCP 1000
1500
1500

1800 1800
0.3 V
0 0
0 0
0 0
500 500
1000 1000
1000 1000
1500 1500

Figure 22 Atomic force microscopy images (2 mm  2 mm) of composite graphite electrodes obtained in situ in 1 mol L1 LiBOB and
1 mol L1 LiPF6 solution in ethylene carbonate:propylene carbonate 2:3 at open-circuit potential and after polarization to 0.3 V
(vs Li/Li þ ). Reproduced with permission from Larush-Asraf L, Biton M, Teller H, Zinigrad E, and Aurbach D (2007) On the
electrochemical and thermal behavior of lithium bis(oxalato)borate (LiBOB) solutions. Journal of Power Sources 174(2): 400–407.
712 Measurement Methods | Structural Properties: Atomic Force Microscopy

Table 2 Examples of atomic force microscopy (AFM) studies on different components for Li-based batteries
Examples of studies using AFM at components for Li-based batteries
AFM has been performed
During the formation of a passivation film (solid electrolyte interphase, SEI) at the surface of the negative electrode of full LiCoO2/
graphite lithium-ion cells using LiPF6 (1 M) in carbonate solvents as electrolyte, the formation of a passivation layer what appears to be
crystallites at the lithium/poly(ethylene oxide)-lithium triflate electrolyte interface.
On a LiCoO2 thin film cathodes, prepared by RF magnetron sputtering and post-annealing, and a difference of micro-structural evolution
after post-annealing was observed, which related to the thin film properties.
On amorphous lithium ion conductor films, prepared by pulsed laser deposition (PLD), for the determination of the nominal composition
of 0.6(Li4SiO4-0.4(Li3VO4)) for a good amorphous thin film.
On spinel-based (LiMn2O4, Li4Ti5O12) foil electrodes with combined additive of graphite, carbon black and polyvinyl difluoride compacted
by a magnetic pulsed laser.
Nanocrystalline lithium manganate thin films (LixMn2O4; x ¼ 1.0–1.4).
On Lithium iron phosphate (LiFePO4) thin film electrodes, prepared by pulsed laser deposition (PLD), the film annealed at 773 K (773 K-
film) consisted of small grains with 50 nm in thickness, and the grain size increased with an increase of annealing temperature.
To measure the thickness of thin-film electrodes of LiNi0.8Co0.2O2, deposited by pulsed laser ablation.
Of the basal plane of highly oriented pyrolytic graphite (HOPG), before and after cyclic voltammetry in 1 mol dm3 LiClO4 dissolved in
ethylene carbonate (EC), EC þ diethyl carbonate (DEC), and EC þ dimethyl carbonate (DMC) to clarify the effects of co-solvents in EC-
based solutions on surface film formation on graphite negative electrodes in lithium-ion cells.
Of the interfacial phenomena between graphite (mesocarbon-microbeads (MCMB)) electrode and organic electrolyte solution.
The nucleation and growth mechanism for the electropolymerization of aniline was investigated at higher potentials on highly oriented
pyrolytic graphite.
Of performances and morphology of the lead foam.
To measure the step height change during the intercalation/de-intercalation of Li þ into the graphene layers of highly oriented pyrolytic
graphite (HOPG).
Of the microstructure and morphology of Si thin films, deposited on stainless steel substrates that act as current collectors using the
pulsed laser deposition (PLD) technique.
Of the growth of nano-size particles are deposited in LiPF6 solutions at the boundaries of the V2O5 grains, thus slowing the insertion of
lithium ions into the layered matrix, while in the presence of the ClO4 anions, there were only negligible changes in the morphology,
leading to intercalation of lithium ions only.
Of influence of substrate temperature on the growth of V2O5 films, prepared by the pulsed laser deposition technique, in order to
understand the growth mechanism.
An in situ electrochemical atomic force microscopy (EC-AFM) cell was developed to study surface and dimensional changes of
individual LixCoO2 crystals during lithium de-intercalation.
Discrete Li2CO3 particles having 50–250 nm in diameter and 5–15 nm in height were observed on the surface of stoichiometric LiCoO2
crystals and they were shown to gradually dissolve into the LiPF6-containing electrolyte. The dimensional change of individual
LixCoO2 crystals along the chex axis was monitored in situ during lithium de-intercalation.
Development of novel techniques
Current-sensing atomic force microscopy was used for imaging the cathode surface which revealed that the cathode of a pouch-type
lithium-ion cell, with graphite anode and LiNi0.8Co0.15Al0.05O2 cathode. The surface electronic conductance diminished significantly in
the tested cells. Loss of contact of active material particles with the carbon matrix and thin film formation via electrolyte decomposition
not only led to LiNi0.8Co0.15Al0.05O2 particle isolation and contributed to cathode interfacial charge-transfer impedance but also
accounted for the observed cell power and capacity loss.
Surface morphology in 3.5  3.5 mm2 area of spinel LiMn2O4, which is a typical cathode material for Li ion secondary batteries, is studied
using an AFM with a conductive probe. Negative bias voltage is applied to the probe to attract Li þ ions toward LiMn2O4 surface during
the AFM observation. Before applying the voltage (0 V), the whole LiMn2O4 surface is covered with scale-shaped grains. Under the
negative voltage of 5.5 V, electric current abruptly increases, indicating Li þ ionic conduction. Simultaneously, part of the scale-shaped
grains expand and flatten.
A thin-film solid-state battery was prepared with a vanadium pentoxide cathode and a lithium phosphate electrolyte and studied in situ by
ultrahigh vacuum scanning tunneling microscope/atomic force microscopy (STM/AFM). Orientation of the (001) plane of V2O5 parallel
to the substrate was detected via observation of the periodicity of 11.770.5 Å, which is consistent with the unit cell spacing in the [100]
direction. Conductance of the battery was studied locally with the probe tip of the STM/AFM in the regime of mechanical contact with a
constant repulsive force. Lateral variation of contact conductance from 0.4 to 2.2 nA was detected as a function of position of the tip in
contact with the cathode. The device revealed an extremely high current density of 1 A cm1(2) due to the low thickness of the
electrolyte and the cathode and the concentration of electric field under the scanning probe microscope tip. Transformation of cathode
structure due to Li ion intercalation was observed in real time.
The volume changes of continuous and patterned films of crystalline Al, crystalline Sn, amorphous Si (a-Si), and a-Si0.64Sn0.36 as they
reversibly react with Li. Although these materials all undergo large volume expansions, the amorphous phases undergo reversible
shape and volume changes, the crystalline materials do not.
In situ atomic force microscopy measurements of patterned amorphous Sn–Co–C sputtered films reacting with Li in an electrochemical
cell have been made. Prismatic-shaped patches of Sn0.34Co0.19C0.47 were found to undergo reversible volume expansion of 17575%
[(Vfinal  Vinitial)/Vinitial] without fracture.
(Continued )
 Measurement Methods | Structural Properties: Atomic Force Microscopy 713

Table 2 Continued
Examples of studies using AFM at components for Li-based batteries
AFM analyses prove that after storage at room temperature for a month, PEO–LiTFSI forms large dendrites while only a small amount of
tiny crystals can be observed in the PEO–LiTFSI–ZnO(PEGME) film. In contrast, ZnO(Ac) particles agglomerate around the PEO–
LiTFSI dendrites and separate from the original phase. This direct observation on the micromorphology of the SPE films after long-
term storage elucidates why the PEO–LiTFSI–ZnO(PEGME) electrolyte is much more stable than its counterparts.
For thickness measurements without a reference in situ AFM roughness measurements have been performed on alloy film electrodes
on rigid substrates as they react with lithium electrochemically. The addition (or removal) of lithium to (or from) the alloy causes the
latter to expand (or contract) reversibly in the direction perpendicular to the substrate and, in principle, the change in the overall height
of these materials is directly proportional to the change in roughness.
In situ AFM observation of the basal plane of highly oriented pyrolytic graphite was performed during cyclic voltammetry at a slow scan
rate of 0.5 mV s1 in 1 mol dm3 LiClO4 dissolved in a mixture of ethylene carbonate and diethyl carbonate. In the potential range 1.0–
0.8 V, atomically flat areas of 1 or 2 nm height (hill-like structures) and large swellings of 15–20 nm height (blisters) appeared on the
surface. These two features were formed by the intercalation of solvated lithium ions and their decomposition beneath the surface,
respectively, and may have a role in suppressing further solvent co-intercalation. At potentials more negative than 0.65 V, particle-like
precipitates appeared on the basal plane surface. After the first cycle, the thickness of the precipitate layer was 40 nm, and increased
to 70 nm after the second cycle. The precipitates were considered to be mainly organic compounds that are formed by the
decomposition of solvent molecules, and they have an important role in suppressing further solvent decomposition on the basal plane.
The surface morphology changes on polyaniline films as well as polyaniline (PANI)-LiNi0.5La0.02Fe1.98O4 nanocomposites was
investigated by in-situ AFM and the surface morphology changes and surface roughening occurring during doping and de-doping
cyles was investigated under different conditions and with different additives.

PicoSPM1 controller
HZ-3000

PicoScan 2100
Automatic
polarization
system

RE CE WE
0:01

Air
inlet

WE
RE CE

Electrolyte
HgIHg2So4

inlet

Sample Pb
(WE)
Electrolyte

Figure 23 Schematic representation of experimental equipment. Reproduced with permission from Vermesan H, Hirai N, Shiota M,
and Tanaka T (2004) Effect of barium sulfate and strontium sulfate on charging and discharging of the negative electrode in a lead–acid
battery. Journal of Power Sources 133: 52–58.

negative electrode of a lead–acid battery took place.
It is possible to obtain continuous in situ images of the
surface morphology during cyclic voltammetry (CV).
These AFM images dynamically show the surface
morphology change during the oxidation/reduction
cycle. As a result, it was confirmed that lead sulfate
crystals began to deposit from the moment the reduction
potential is applied and the reduction transient shows a
sharp peak shape at the same time. On the contrary, the
dissolution of lead sulfate crystals is delayed from
the moment the oxidation potential is applied. The
quick deposition of lead sulfate crystals occurs after
714 Measurement Methods | Structural Properties: Atomic Force Microscopy

−1194 mV −1021mV −1012 mV

a b c

Scanning direction
BaSO4

Scanning direction

Scanning direction
−1024 mV
Rest potential
PbSO4

1 µm 1µm 1µm
−1200 mV −1026 mV −1007 mV
(i) (ii) (iii)
−992 mV −983 mV −906 mV
d e f

Scanning direction
Scanning direction

Scanning direction

1µm 1 µm 1 µm
−997 mV −988 mV −901 mV
(a) (iv) (v) (vi)

−900 mV −1200 mV
a b 3:27 c
Scanning direction

Scanning direction

Scanning direction

−1200 mV
t (m:s) 0:00

PbSO4
1 µm 1 µm 1 µm
3:02
−905 mV −1197 mV
(i) (ii) (iii)
3:31 d 4:24 e 4:27 f
Scanning direction

Scanning direction
Scanning direction

1 µm 1 µm 1 µm
3:56 3:59 4:53
(b) (iv) (v) (vi)

Figure 24 (a) Oxidation of negative electrode with BaSO4 as additive: (i) image of initial BaSO4 on lead surface at the beginning of
oxidation (discharge), (ii) point where potential reaches rest potential, (iii)–(v) formation and growth of PbSO4 crystals, and (vi) end of
oxidation. (b) Reduction of negative electrode with BaSO4 as additive: (i) image of BaSO4 crystals at the beginning of reduction phase,
(ii) image of the crystal immediately after potential reaches  1200 mV, (iii) beginning of dissolution of PbSO4 crystals about 3 min after
potential reaches  1200 mV, (iv) process of dissolution of lead sulfate, (v) end of dissolution of lead sulfate, after less than 1 min from
the beginning of dissolution formation and growth of PbSO4 crystals, and (vi) image of the surface after reduction. Seed crystals of
BaSO4 are dragged with PbSO4 into H2SO4 solution. Reproduced with permission from Vermesan H, Hirai N, Shiota M, and Tanaka T
(2004) Effect of barium sulfate and strontium sulfate on charging and discharging of the negative electrode in a lead–acid battery.
Journal of Power Sources 133: 52–58.
 Measurement Methods | Structural Properties: Atomic Force Microscopy
Figure 25 Current image of an electrode on an MEA prepared with the dry spraying technique at the DLR, Institute for Technical
Thermodynamics, Stuttgart, Germany. The electrode is composed of 70% Pt/C and 30% Nafion, loading is 0.3 mg cm2, image size
3  3 mm2, relative humidity 30%, and the conductive area measures 91% of the image. Hiesgen R, Wehl I, and Friedrich KA,
unpublished results.
supersaturation phenomena at the oxidation peak on CV,
and the slow dissolving of the lead sulfate crystals occurs
after the reduction peak; the crystal size becomes smaller
when the potential sweeping rate is high or the electro-
lyte concentration is high. When lignin is added, the
density of lead sulfate crystals formed on the lead elec-
trode after anodic oxidation decreases and the crystal size
becomes larger. Furthermore, the addition of lignin
delays dissolution of lead sulfate crystals during cathodic
reduction at room temperature (RT). The AFM in-
vestigation of surface morphology reveals a uniform
deposition of lead sulfate crystals after oxidation of the
electrode.
Examples
The use of EC-AFM allows examination of the intimate
phenomena that occur on the surface of the lead elec-
trodes using barium sulfate (BaSO4) or strontium sulfate
(SrSO4) as additives in the electrolyte. With this tech-
nique, it has become possible to see how the sulfate
crystals are formed on the surface, how they grow, and
how they appear. In these respects, AFM assists in the
understanding of the complex processes that occur at the
electrode–electrolyte interface in a lead–acid battery.
In Figure 23, the schematic drawing of an in situ ex-
periment is shown. The electrochemical cell comprised a
lead working electrode, a PbO2 counterelectrode, and a
Hg/Hg2SO4 reference electrode. The images have been
715
Platinum
Carbon support
performed with a gold-coated silicon nitride cantilever. In
Figures 24(a) and 24(b), series of AFM images demon-
strate the surface changes during oxidation and reduction,
respectively, with the addition of BaSO4 as additive in the
electrolyte.
The EC-AFM measurement leads to the following
results:
• the
Inorganic additives such as BaSO or SrSO promote
4
precipitation of lead sulfate (PbSO ) on lead
4
4
electrodes.
• During discharge, PbSO4 is formed very rapidly on
SrSO4 crystals and is very difficult to dissolve during
the charge process.
• PbSO4 crystallizes on BaSO4 or SrSO4 seeds and the
surrounding regions remain free of PbSO4 crystals,
thereby preventing coating of the active mass.
Atomic Force Microscopy
Characterization of Fuel Cell Components
Atomic force microscopy is a versatile instrument also for
the analysis of the different components of PEM fuel
cells. Measurement of the surface topography stays back
behind the analysis of the material contrast of hydro-
philic and hydrophobic regions. Different experimental
approaches exhibit the extension of ionic regions on one
716 Measurement Methods | Structural Properties: Atomic Force Microscopy

side. Measurement of the ionic current through the Dx traveling distance of the tip
membrane gives the percentage of active ionic regions Abbreviations and Acronyms
contributing to the current flow. For description of the 3D three-dimensional
applications concerning an ionic conducting membrane, AFM atomic force microscope, atomic force
see Fuel Cells – Proton-Exchange Membrane Fuel microscopy
Cells: Membranes: Spatially Resolved Measurements. An CFM chemical force microscopy
example of characterization of fuel cell electrodes is CV cyclic voltammetry
given in the following. DC direct current
DEC diethyl carbonate
DMC dimethyl carbonate
AFM on Fuel Cell Electrodes
EC ethylene carbonate
By using an EC-AFM in the experimental setup shown EC-AFM electrochemical atomic force
in Figure 15, the electrode on a complete membrane– microscopy
electrode assembly (MEA) can be analyzed. A voltage is HOPG highly oriented pyrolytic graphite
applied between the lower electrode and the conductive LFM lateral force microscopy
AFM tip. The electronic conducting parts such as plat- MCMB mesocarbon-microbeads
inum catalyst particles and carbon support are always MEA membrane–electrode assembly
conductive, and in humid environment the ionic con- MFM magnetic force microscopy
ducting Nafion is also contributing to the current. The NSOM near-field scanning optical microscopy
current images measured simultaneously with the topo- OCP open circuit potential
graphy of the electrode reveal the surface structure of the PANI polyaniline
different components in more detail as can be seen in PC propylene carbonate
(Figure 25). PEM proton-exchange membrane
PEO polyethylene oxide
PFM pulsed force mode
Concluding Remarks
PLD pulsed laser deposition
PVDF poly(vinylidene fluoride)
The technique of AFM, especially if performed in situ in
RT room temperature
the electrochemical cell, is a widely used analytical tool
SEI solid electrolyte interphase
in battery research. By giving an insight into the micro-
SEM scanning electron microscopy
scopic world, it serves well in providing a deeper
SFM scanning force microscopy
understanding of the processes involved in charging,
SNOM scanning near-field optical microscopy
decharging, and aging. Thereby, a base for a further de-
STM scanning tunneling microscopy
velopment of novel materials is given. The technique is
UHV ultrahigh vacuum
quite versatile and can be tailor-made to analyze a
number of properties on the microscopic level.

See also: Electrolytes: Gel; Ionic Liquids; Non-Aqueous;

Nomenclature Overview; Polymer; Solid: Protons; History:
Symbols and Units Electrochemistry; Fuel Cells; Primary Batteries;
d distance to the surface Secondary Batteries; Secondary Batteries – Lithium
f frequency Rechargeable Systems – Lithium-Ion: Positive
F force Electrode: Nanostructured Transition Metal Oxides.
Fmax maximum force
fres resonance frequency
k spring constant Further Reading
L length
Besenhard JO (1998) Handbook of Battery Materials. Weinheim:
m mass Wiley-VCH.
Ra roughness on an area Das S, Fachini IR, Majumdera S, and Katiyar RS (2006) Structural
RMS standard deviation of the mean and electrochemical properties of nanocrystalline LixMn2O4
thin film cathodes (x ¼ 1.0–1.4). Journal of Power Sources 158:
roughness value 518–523.
Rp profile height compared to mean value David LD and Reddy TB (eds.) (2002) Handbook of Batteries, 3rd edn.
Rt maximum height difference New York: McGraw-Hill.
Jossen A and Weydanz W (2006) Moderne Akkumulatoren richtig
V voltage einsetzen. http://www.elektroauto.tipp.de
 Measurement Methods | Structural Properties: Atomic Force Microscopy
Larush-Asraf L, Biton M, Teller H, Zinigrad E, and Aurbach D (2007) On
the electrochemical and thermal behavior of lithium
bis(oxalato)borate (LiBOB) solutions. Journal of Power Sources
174 (2): 400–407.
Nielsch K, Wehrspohn RB, Barthel J, et al. (2002) High density
hexagonal nickel nano wire array. Journal of Magnetism and
Magnetic Materials 249: 234--240.
Parkinson B (1997) Procedures in Scanning Probe Microscopies.
Cambridge: John Wiley & Sons Ltd.
Seizo Morita S and Wiesendanger R (2002) Noncontact Atomic Force
Microscopy (NanoScience and Technology). Berlin: Ernst Meyer,
Springer.
Trueb IF and Rüetsch P (1998) Batterien und Akkumulatoren – Mobile
Energiequellen für heute und morgen. Berlin: Springer.
Vermesan H, Hirai N, Shiota M, and Tanaka T (2004) Effect of barium
sulfate and strontium sulfate on charging and discharging of the
717
negative electrode in a lead–acid battery. Journal of Power Sources
133: 52--58.
Wiesendanger R (1994) Scanning Probe Microscopy and
Spectroscopy – Methods and Applications. Cambridge: Cambridge
University Press.
Wiesendanger R (1998) Scanning Probe Microscopy: Analytical
Methods (Nanoscience and Technology). Berlin: Springer.
Wiesendanger R and Güntherodt HJ (eds.) (1995a) Scanning Tunneling
Microscopy II, 2nd edn. Berlin: Springer.
Wiesendanger R and Güntherodt HJ (eds.) (1995b) Scanning Tunneling
Microscopy III: Theory of STM and Related Scanning Probe
Methods, Springer Series in Surface Sciences. Berlin: Springer.
Wiesendanger R, Guntherodt HJ, and Workman P (1994) Scanning
Tunneling Microscopy I: General Principles and Applications to Clean
and Adsorbate-Covered Surfaces, Springer Series in Surface
Sciences. Berlin: Springer.