NCCR Nanoscale Science

University of Basel

Scanning Probe Methods

(SPM)
Hans J. Hug1,2
1 Empa: Swiss Federal Laboratories for Material Testing and Research,

Laboratory for Nanoscale Materials Science

Überlandstrasse 129, CH-8600 Dübendorf, Switzerland
&
2 NCCR on Nanoscale Science, Department of Physics,

University of Basel, Klingelbergstrasse 82, CH-4056 Basel, Switzerland

Contents 1

1. General Introduction to Scanning Probe Microscopy.

Principles & Instrumentational Issues

2. Scanning Tunneling Microscopy (STM)

2.1. Principles of STM
2.2. STM Imaging of Semiconductors, Metals & Layered Materials
2.3. Scanning Tunneling Spectroscopy (STS)
2.3.1. Principle of STS
2.3.2. Spin Polarized Tunneling
2.3.4. Inelastic Tunneling
2.4. Manipulation by STM

3. Scanning Force Microscopy (SFM), Atomic Force Microscopy (AFM)

3.1. Introduction & Instrumentation
3.1.1. Force Sensors and their Properties
3.1.2. Deflection Sensors
3.1.3. relevant Forces
3.2. Contact Mode Scanning Force Microscopy
3.2.1. Principles of SFM in Contact
3.2.2. Examples of Dynamic Force Microscopy with Tip in Contact
3.2.3. Scanning Friction Force Microscopy
3.3. Intermittent contact and Peak Force Microscopy
Contents 2

3.4. non-contact AFM (ncAFM) or Dynamic Force Microscopy (DFM)

3.4.1. Principles and Instrumentation
3.4.2. Imaging with True Atomic Resolution
3.4.3. Kelvin Probe Force Microscopy
3.4.4. Magnetic Force Microscopy

4. Cantilever Sensors

5. Future Aspects
5.1. multi-dimensional Scanning Force Microscopy
5.2. Scanning Chemical Force Microscopy
3.5.1. Scanning Chemical Force Microscopy with X-rays
3.5.2. Scanning Chemical Force Microscopy with ToF-SIMS
5.3. Scanning Vector Magnetometry
5.4. Magnetic Resonance Force Microscopy, 3d Imaging of Viruses
 1.
General Introduction to
Scanning Probe Microscopy.

Principles & Instrumentational

Issues
The Scanning Probe Microscopy Family

Scanning Probe Microscopy (SPM)

• The starting point of SPM was the invention of the scanning tunneling microscope
(STM) by G. Binnig and H. Rohrer in 1982 [1,2] (Nobel prize in physics in 1986).

The family present family of scanning probe microscopes is based on a

variety of tip-sample interactions:

• The first and most important extension of the STM was the scanning force
microscope (SFM) or atomic force microscope (AFM), invented in 1986 by
Binnig, Quate, and Gerber [3].

• Most of the present scanning probe instrumentation is based on the AFM often
combined with other techniques mapping/controlling properties not accessible
by AFM.

Refs.: [1] G. Binnig and H. Rohrer et al. Helv. Phys. Acta 55, 726 (1982)
[2] G. Binnig and H. Rohrer et al. Phys. Rev. Lett. 50, 120 (1983)
[3] G. Binnig, C.F: Quate, CH. Gerber, Phys. Rev. Lett. 56, 930 (1986)
see also R. Wiesendanger and H.-J. Güntherodt, Vols. 20, 28, 29
Springer Series in Surface Science 1992, 1993, 1994 R. Colton et al., Wiley-VCM, Weinheim 1998
Basic Concepts of an STM
Basic setup of an STM (but
also any other type of SPM)
In an STM typically two signals are acquired, namely the z-coordinate (topography)
and the tunneling current, or more generally the measured tip sample interaction (error signal)
• tip-sample stability < 1pm in best instruments
➜ stiff, high resonance frequency instrument
➜ vibration isolation system
• tip can be scanned in x,y, z (tip-sample distance)
with pm precision
➜ piezo electric scanners
• tip-sample interaction (tunnel current)
is measured
➜ current amplifier for 1pA needed
➜ log I is used for the feedback
• PI-feedback adjusts z to keep log I constant
➜ maximum feedback speed depends on
resonance frequency of instrument and
bandwidth of current amplifier
• Computer controlled electronics is used for
scan-generation, feeback, data recording,
displaying and user GUI
• in other types of SPM other tip-surface
interactions are used to control the tip-sample
distance
Vibration Isolation

Note: Use multiple damping stages for optimal results !

Ref.: O. Züger, H.P. Ott, and U. Dürig, Rev. Sci. Instrum. 63 (1992) 5634
One & Two Stage Vibration Isolation

olation
n is
ibratio
a ge v
1-st

2-stage vibration isolation

Only the double vibration isolation stage can provide sufficient isolation @ the
resonance frequency of the microscope. Assume floor vibrations of 100nm (1000Hz).
Then the tip-sample vibration will be less than 10-3nm !
Piezo Electric Actuators

Since the piezo effect exhibited by natural materials (e.g. quartz) is very small, polycrystalline ferroelectric
ceramic materials such as barium titanate and lead zirconate titanate (PZT) with improved properties (e.g.
PZT-5H: d31=-2.62Å/V) have been developed. These ferroelectric ceramics become piezoelectric when
poled.

depolarized during after

ferroelectric polarization polarization
structure

E
E eletric field, L lengths, ΔL change in length
d31 transversal piezoelectric coefficient
L
Slip-Stick Piezomotoren
Mechanical Challenges Principle stick-slip piezo motor

• Approach & Positioning

• over distances of mm - cm
• with <100nm precision

• high stiffness & high resonance frequency of the SPM

Implementation of a piezo motor in a low temperature SFM

Pre-amplifier
R
IT from tip
_ Op.
Amp. U(IT) = IT * R
+
sample

Ubias typically 109 gain, i.e. IT = 1nA ➜ 1V @ output

PI(D) Feedback
P: proportional gain, I: integral gain, D: differential gain

SPM
signal
sensor

tip
setpoint
+ -
sample

z-piezo
signal
correction
signal

Feedback Setup:
1. experience / trial & error
2. Ziegler-Nichols procedure [1,2]:
- increase P-part until small oscillations of the current are observed.
- reduce P-part to 0.45Pkrit.
- measure oscillation period (Tkrit) and set I-part to 0.85Tkrit.
[1] J. Ziegler, N. Nichols: Trans. ASME 64, 759 (1942)
[2] H. Unbehauen: Regelungstechnik I (Friedr. Vieweg und Sohn, Braunschweig/ Wiesbaden, 1982)
Feedback - Signal and Error Signal
Si(111)-7x7, 10x10nm2

topography ∆z = 0.2nm IT = 0.5nA; ∆IT = 0.18nA; dz/dx derivative

„image“ „error signal“ „simulated error signal“
Note:
1. a feedback is like a low-pass filter, filtering away the high frequency signals.
The latter appear in the error signal.
2. Faster scanning or slower feedback generates larger errors.
3. maximum feedback speed is limited by the systems responce time.
4. Feedback errors look like the d/dx derivative of the image
Tunneling Tips
• Electrochemical etching:
• a 0.25mm tungsten wire is immersed in 1M acqueous solution of NaOH.
• the counterelectrode is a piece of stainless steel or platinum
• a positive voltage of 4-12V is applied to the wire.
• etching occurs at the liquid-air interface and a neck is formed
• the weight of the lower part of the wire pulls the neck and naturally fractures it.
• cutoff time after the tip has fractured is important parameter

600ns, with 32nm 140ms, with 58nm 640ms, with 100nm.

• cleaning in boiling water to remove residuals of NaOH.

• problem: formation of a surface oxide during etching, which has to be removed before tunneling.
• remove the oxide by resistive heating or electron bombardment

• Mechanical methods: cut PtIr wire with scissors !

• Field evaporation: in combination with FIM atomically sharp tips

• Controlled collision with surface

Influence of the Tip Geometry on Imaging Surface Features
Tip Shape Artifacts
Tip Shape Artifacts
Dependence of Image on Tip-Shape
The First STM by G. Binnig, H. Rohrer & Ch. Gerber (1981)

First Si(111) 7x7 image

The Nanosurf STM a simple STM for Students
 2.
Scanning Tunneling Microscopy
(STM)
2.1. Principles of STM
Tunneling: a quantum mechanical effect
1d tunneling junction
According to quantum mechanics, a
particle with an energy E can penetrate a
barrier ∅ > E. In the classically forbidden
region, the wave function ψ
decays exponentially

sample tip
where the barrier height Φ is in eV and z in
Angstrom. With a typical barrier height of Φ =
5eV , which corresponds to the work function of
gold, the tunneling current decays by an order
of magnitude when the vacuum gap is
changed by 0.1nm !

Refs.: Theoretical: Frenkel: Phys. Rev. B 36, 1604 (1930) & Bardeen, J. PRL, vol. 6, no.2, pp.57-59, 1961
First experiments: R. Young, J. Ward, F. Scire: Phys. Rev. Lett. 27, 922 (1971)
First experiments: R. Young, J. Ward, F. Scire: Rev. Sci. Instr. 43(7), 999–1011 (1972)
First clear demonstration of vacuum tunneling: G. Binnig, H. Rohrer: Appl. Phys. Lett. 40, 178 (1982)
Tunneling: a quantum mechanical effect
sample tip sample & tip @ close distance
Uc
vacuum level t

s t s
Fermi level

z
applying a bias
electrons tunnel
Ub
• from sample to tip
t
(or vice versa if -Ub is applied)
s • out of filled states
• into empty states
tunnel current depends on
• distance z
• overlap of wave functions
z • density of filled and empty states
• ... „sligthly“ on temperature
Bardeen‘s tunnel current formalism [1]
Based on Bardeen, the tunneling current between two electrodes, separated by an insulator, is given by

Fermi function

ρs, ρt are the density of states of sample and tip. The tunneling matrix element M is given by

where ψt, ψt are the wave functions of the sample and of the tip. For low voltages the integral simplifies to

performing the integration in 1d (plane wave wave functions)

we obtain

[1] Bardeen, J. PRL, vol. 6, no.2, pp.57-59, 1961.

Operation Modes (imaging)
imaging:
• constant current mode, i.e. feedback adjusts z to keep IT constant
• constant height mode z = const. ➜ IT varies
in reality: IT ≈ constant, because z-feedback cannot adjust z infinitely fast
so in addition to the „topography“ image z(x,y) an „error signal“ image IT(x,y) exists.

Si(111)-7x7, 10x10nm2

topography ∆z = 0.2nm IT = 0.5nA; ∆IT = 0.18nA; dz/dx derivative

„image“ „error signal“ „simulated error signal“
Operation Modes (spectroscopy)
spectroscopy:
• barrier height measurements: because

• density of states mapping

neglecting the density of states in the tip (or assuming a flat density of states) we have

differentiation gives Example: W tip on Si(111)-7x7

How to measure derivatives with a lock-in amplifier
signal x low pass
filter
x signal, e.g.

reference
Ref phase

x low pass
filter
y

after multiplying:

sum frequency difference frequency

assuming the sum frequency is where as the difference frequency vanishes !

so after the low pass filter

and so the lock-in measures the amplitude and phase of a

signal in a bandwidth (given by the bandwidth of the
low pass filter) around the reference frequency
 2.2. STM Imaging of
Semiconductors, Metals & Layered Materials
Semiconductors

First Si(111) 7x7 image [1] First Si(100) 2x1 [2] and
STM @ various tip-sample potentials an GaAs

Ga As

Us = +1.9V Us = -1.9V

Refs.:[1] G. Binnig et al. PRL50 120 (1983)

[2] R. Feenstra Surf Sci. 181, 295 (1987) and PRL58 1192 (1987)
Metals
• first resolved by Binnig and Rohrer 1982 [1] (Au(110)-2x1 and Au(110)3x1 reconstructions)
• atomic resolution on a close-packed Au(111) by Hallmark et al. [2] in 1987
• today, a large number of clean metal surfaces could be resolved, such as
Cu(111), Cu(110), Cu(001), Pt(111), Pt(001), Ru(0001), Ni(001) and Ni(110)
• spacing between the atoms of the close-packed surfaces is 2-3Å.
• corrugation heights are found to be rather large of the order of tenths of Å
• corrugation in contradiction with results from He scattering (STM shows larger corrugations)
• contradiction explained by force induced variation of tip-sample distance

STM images of the Cu(111) surface in constant current mode. (left) Overview image with monatomic steps
(right) Atomic resolution on Cu(111). The spacing between the protrusions is 2.5Å.

Refs.:[1] G. Binnig et al. Rev. Mod. Phys. 56 615 (1987)

[2] V. M. Hallmark et al. PRL59 2879 (1987)
Superresolution on Metals
An impressive example of the resolution capabilities is given by Schmid et al. [1], where Pt-atoms
and Ni-atoms could be distinguished on a Pt25Ni75(111)-surface.

The best resolution was observed with small tunnel resistances of (50-300kOhms), which was
attributed to the interaction between adsorbates at the tunneling tip and the surface atoms.

D. Eigler (IBM Almaden Research Lab) calls these adsorbates “Behm amplifiers”. He often uses a
Xe-atom that is picked up by the tip. Such adsorbates are only weakly bound to the tip. The strong
force field between the tip and the sample leads to a modulation of the position of the adsorbate
within the tip-sample gap. This causes an enhancement of the corrugation and superresolution.

Refs.:[1] M. Schmid et al. PRL70 1141 (1993)

Layered Materials
• A number of layered materials, such as graphite or MoS2, could be resolved.
• Especially, graphite has attracted a lot of attention, because of the giant corrugation heights.
• transition metal dichalcogenides, such as 1T-TaS2 or 1T-TaSe2, with atomic structure and charge
density waves (CDW).
• A review of the STM work of layered materials with CDW has been published by
Coleman et al. [2]

Forces between tip and sample were attributed to play an important role [1].

Refs.:[1] Soler et al. PRL57 444 (1987)

[2] R.V. Colemann et al. Adv. Phys. 37 559 (1988)
2.3. Scanning Tunneling Spectroscopy (STS)
2.3.1. Principles of STS
Spectroscopic Modes

Scanning tunneling spectroscopy (STS) experiments are important to determine properties, such
as
• LDOS (density of states): vary voltage U
• barrier heights, vary distance z:

There exist a variety of spectroscopic modes, variation of one externally adjustable parameter
and measurement of tunneling current:
• voltage I(V) or dI/dV (often measured with lock-in amplifier)
• z-distance I(z), dI/dz (often measured with lock-in amplifier)

These curves can be either measured at a fixed lateral position or at various lateral positions
(xi,yi). A simple way to get spectroscopic information is to acquire several images at different
voltages or distances. Because of thermal drift this way is not ideal, but feasible. Alternatively, the
tip can be stopped at different positions (xi,yi), the voltage or distance is ramped, and then the tip
moves to the next position. In an ideal STS-experiment the tip DOS should be neglectable, which
seems to be not always the case.

Refs.:[1] Collma al. PRL50 120 (1983)

[2] R. Feenstra Surf Sci. 181, 295 (1987) and PRL58 1192 (1987)
Scanning Tunneling Spectroscopy on Carbon Nanotubes

a) Right hand side: Experimental STM image with atomic resolution of three single walled
carbon nanotubes (SWNT) with different chiralities. Left hand side: Atomic model
representation of the three SWNTs.
b) Ball-and-Stick model of a hydrogen chemisorption and a vacancy type defect on a (10,0)
semiconducting SWNT.
c) Upper panel: STM topography image of a (11,1) SWNT with two hydrogen-plasma induced
defect sites. Lower panel: Corresponding scanning tunneling spectroscopy (STS) line scan on
the dashed horizontal line in the topography image showing the band gap of the SWNT and
localized (spatially as well as energetically) states of the defect sites. The paired gap states of
the right defect is characteristic of a chemisorbed hydrogen-dimer [1,2].

Refs.: [1] G. Buchs, et al., Appl. Phys. Lett 90 (2007) 013104

[2] G. Buchs, et al., New J. of Physics 9 (2007) 275
2.3.2. Spin Polarized Tunneling
Spin Polarized Tunneling
in ferromagnetic metals:

split density of states for up and down spins

Select tip magnetization by:

• Fe-coated W tips: in plane (perpendicular to tip axis) –> in-plane component [1]
• FeGd coated W tips: perpendicular (along tip axis) –> perpendicular component [2]
• for samples with low coercivity use antiferromagnetic coatings (Cr) [3]
Fe-coated W tip: in-plane component FeGd coated W tips: perp. component

2 ML of Fe on W(110) crystal
Refs.: [1] M. Bode, et al. PRL81 4256 (1998) A. Kubetzka, et al. PRL88 057201 (2002)
[2] A. Kubetzka, et al. PRL88 057201 (2002)
[3] S. Heinze et. al. Science 288 1805 (2000) and A. Wachowiak,Science 298 577 (2002)
Note: other SPT-methods described in Meyer, Hug, Bennewitz „Scanning Probe Microscopy“ Springer ISBN 3-540-43180-2 (2004)
SP-STM: Revealing Magnetic Interactions from Single-Atom
Magnetization Curves
STM topograph colored with spin-pol. dI/dV map
Individual Co adatoms on the Pt(111) surface (blue)
and Co ML stripes (red and yellow) attached to the
step edges An external B can be applied perp. to
the sample surface to change the magnetization of
adatoms M, ML stripes M, or tip MT at different T.
The ML appears red when M ML is parallel to MT
and yellow when M ML is antiparallel to MT.
(Tunneling parameters are as follows: I = 0.8 nA, V =
0.3 V, modulation voltage Vmod = 20 mV, T = 0.3 K.)
Refs.: F. Meier et al., Science 320 (2008) 82
(A and B) Topographs of an area with several adatoms
colorized with the spin-pol. dI/dV map at B = −0.5 T
parallel to the tip magnetization MT (A)
and B = +0.5 T antiparallel to MT (B) (T = 0.3 K).
(C) M(B) curves from the same adatom taken at different
temperatures as indicated (dots). Reversal of MT is
corrected. (D) Magnetization curves of four adatoms at
0.3 K with fit curves and resulting Bsat of 99% saturation.
2.3.3. Inelastic Tunneling
Inelastic Tunneling
Schematic showing the emergence of
inelastic tunneling at the threshold for
vibrational excitation. The change in the
tunneling current due to vibrational excitation
is too small to be measured from the I–V
curve. While a change in the differential
conductance, dI/dV, can be seen for strong
modes, more often vibrational features
needs to be extracted from d2I/dV2. An
important characteristic of vibrational
inelastic electron tunneling spectroscopy is
the occurrence of a peak of the opposite sign
on the negative bias side. Lacking an
isotope shift analysis, the assignment of a
feature to vibrational excitation needs to be
confirmed by a corresponding feature with
the opposite polarity at the opposite bias.
This schematic depicts an increase in the
conductance, associated with a positive/
negative peak for positive/negative sample
bias. In contrast, electronic spectra arise
from elastic tunneling peaks are positive and
occur on either positive (unoccupied) states
or negative (occupied) states !

Ref.: W. Ho, J. Chem. Phys.117, 11033 (2002)

Vibrational Spectroscopy

56 Å x 56 Å STM topographical images and single-molecule vibrational spectra via STM-IETS

of three acetylene isotopes on Cu(001) at 8 K. The two protrusions bright in the image of each
isotope are due to the presence of the C–H and C–D bonds while the central depression dark is
attributed to the C–C bond. The C–H stretch is observed at 358 meV for C2H2 and the C–D
stretch is observed at 266 meV for C2D2. Small upshifts are found for the C–H and C–D stretches
of C2HD. The C2HD spectrum demonstrated for the first time single bond sensitivity with STM-
IETS.

Ref.: W. Ho, J. Chem. Phys.117, 11033 (2002)

Action Spectroscopy hopping @ U > 375mV: C(sp2)-H-stretch vibration
Propen (CH2=CH1-CH3) on Cu(211):
4 different states

switching chirality @ U = 500mV and I = 5nA

Ref.: M. Parschau et al., Angw. Chem. 48, 4065 (2009)

Action Spectroscopy - The Nanocar

action spectroscopy:
Here:
vibronic and electronic
excitation

M. Parschau and K.-H. Ernst et al., Nature 479 (2011)

2.4. Manipulation by STM
STM Manipulation of single Atoms

a) Vertical manipulation (transfer of the surface atom

to the tip and back to the sample):
The transfer of the adsorbate atom from the surface
to the tip, or vice versa, is achieved by approaching
the tip into contact or near-contact. The application
of voltage pulses can be used to set the direction.
Eigler [1] found that Xe atoms moved in the same
direction as the tunneling electrons, which was
related to heating-assisted electromigration.

b) Lateral manipulation mode (adsorbate is kept

adsorbed to the surface and moved laterally along
surface): The tip is moved to the initial point, the
set point is increased by about 2 orders of magnitude,
which corresponds to a decrease of the distance of several Angstrom. The tip forms a weak bond
with the adsorbate atom or molecule. The tip is then moved along the line of manipulation.
Typical threshold resistances to slide an adsorbate are 5MOhm for sliding Xe along rows of
Ni(110), 200kOhm for sliding CO along Pt(111) and 20kOhm to move Pt adatoms along Pt(111).

Ref.: [1] D. Eigler, E. Schweizer: Nature 344, 524 (1990)

STM Manipulation of single Atoms and Molecules

stick-slip motion
(pulling)

stick-slip motion
(pulling)

continuous motion
(pulling)

stick-slip motion
(pushing)

Ref.: [1] L. Bartels et al., Phys. Rev. Lett. 79, 697 (1997)
STM Manipulation of single Fe-Atoms on Cu(111)

Don Eigler, IBM Almaden Research Center

 3.
Scanning Force Microscopy
(SFM)
Atomic Force Microscopy
(AFM)
3.1. Introduction & Instrumentation
Force Effects in STM
Forces between tip and sample were attributed to play an important role [1].

Refs.:[1] Soler et al. PRL57 444 (1987)

[2] R.V. Colemann et al. Adv. Phys. 37 559 (1988)
The First AFM by G. Binnig, C. Quate and Ch.
Gerber (1986)
The First AFM by G. Binnig, C. Quate and Ch. Gerber (1986)

An AFM consists of:

• a 3d-scanner
(similar to that of an STM)
• a force sensor (cantilever)
• a deflection sensor
• in most cases a
sensor-cantilever
G. Binnig, C. Quate, Ch. Gerber, Phys. Rev. Lett. 56, 930 (1986) positioning unit
How to measure Forces

force sensor, cantilever determines:

• sensitivity,
F k • measurement bandwidth,
• instabilities, ...
the deflection sensor determines:
• flexural or torsional deflection, tip determines:
• sensitivity, • type of interaction force
• measurement bandwidth, • sensitivity,
• resolution, ...
Tip • may depend on outside parameters
note that
this is not
a simple spring interaction determines:
but • type of interaction force,
∂ F
is (e.g.) determined by • decay length of force,
overlap of orbitals, i.e. F or
• sensitivity,
chemical bonding • resolution, ...
∂ z
(quantum mechanical • may depend on outside parameters
exchange)

• forces of various physical nature that act simultaneously

• physics of the cantilever (particularly in dynamic mode)
• the need to adjust the force sensor to the cantilever
increased complexity of the instrumentation (hardware, electronics, software = measurement physics)
and (real, sample) physics !

• more complex than STM, but more versatile and a much higher challenge, so more fun ... but STM can still be done!
Cantilever modeled as driven damped oscillator
Amplitude of Cantilever Phase Loss of Cantilever relative to Excitation
0∘

on resonance the
cantilever lags
-90∘ 90o behind the
excitation

-180∘
Example of Measurement Physics: Dynamic Operation
cantilever resonance low Q, wide resonance: lock-in amplifier

in air
-> low quality factor of cantilever
-> excitation with fixed frequency
-> lock-in amplifier

high Q, narrow resonance: PLL

in vacuum
-> high quality factor
-> excitation on resonance
-> requires phase locked loop

57
AFM - SFM - or? - Possible Classification Schemes
1. operation mode bases schemes
measured cantilever property per imaged xy (z, other parameter) point:
a) Static Modes: (dc) deflection (flexural or torsional) of cantilever
b) Dynamic Modes: dynamic cantilever properties
i. oscillation amplitude, phase
ii. required drive amplitude, frequency shift
iii. overtones (harmonic & non-harmonic), intermodulation products

2. tip-sample interaction based schemes

a) physical nature of force
i. frictional forces (FFM),
ii. magnetic (MFM), electrostatic (EFM), contact potential (Kelvin)
iii. energy-loss: dissipation force microscopy
b) „mechanics“ of tip-sample interaction
i. contact mode
ii. pulsed force mode
iii. intermittent contact mode (tapping)
iv. non-contact mode

• be aware that you just measure forces or force gradients ...

• differentiate between
• instrumentation physics (how to measure) and
• physics of tip-sample interaction (what you measure)
58
Operation Modes in Force Microscopy
•Several modes of operation have been introduced in force microscopy, with a
variety of names describing their characteristic features.
3.1.1. Force Sensors & their Properties
Force Sensors - Cantilevers
There are some simple criteria to be considered, when cantilevers are fabricated:
• resonance frequency fR > 100Hz (building vibrations), > 10kHz (sound waves)
• high force sensitivity requires low spring constants (MFM:, 0.1 N/m, mRFM: 0.001 N/m)
• atomic resolution requires spring constant to be in range of atomic spring constants > 10N/m
• thermal vibrations of the cantilever < 0.1nm, i.e. k>0.4N/m @ 300K
It can be shown that only cantilevers of dimensions in the micrometer range fulfil these design
criteria. Generally, higher resonance frequencies require smaller cantilevers.

single cristalline silicon cantilevers high-aspect ratio tips ultrasharp tip tuning fork sensor

radius
>10µm < 3nm

force constant: 0.01 – 100 N/m

resonance frequency: 5 – 500 kHz
Team Nanotec GmbH, www.team-nanotec.de
Cantilever, a mass-loaded beam - Flexural theory
equation of motion E: elasticity module
ESi = 1.69e11 N/m2
y
I: area moment of inertia
: density
= 2330 kg/m3

general solution

dispersion relation

boundary conditions (free end - no tip-sample

and

inserting general solution in boundary conditions. Resulting 4 equations can only be

solved if characteristic equation

with
Rabe, Rev. Sci. Instrum., 67 (1996) 3281 & Refs. therein 62
Cantilever, a mass-loaded beam - Flexural theory - Results
solutions for non-harmonic resonances

cantilever force constant dynamic flexural force constants

static

and the deflection yn(x)

Rabe, Rev. Sci. Instrum., 67 (1996) 3281 & Refs. therein 63

Flexural theory of cantilever oscillation modes
torsional oscillation modes

GSi = 6.8e1010 N/m2

equidistant torsional modes

At higher frequencies the probability for the excitation of torsional modes increases compared to that of the flexural
modes, because the former are spaced equidistantly while the spacing of the latter increases.

torsional spring constant (for static (friction) measurements with tip-sample contact

tip with height h

Rabe, Rev. Sci. Instrum., 67 (1996) 3281 & Refs. therein 64

Cantilever oscillation modes: Experiment versus Theory
Thermal noise on two positions on conventional cantilever, experimental results
measure by our Fabry-Perot interferometer sensor: flexural modes torsional modes
tip base laser spot, 3µm diameter
cantilever, w = 32µm, laser spot off-axis to measure
L = 223µm, t = 5.17µm flexural and torsional modes

f1 f3 stiffness from fundamental mode

= 16,3590 N/m

oscillation mode calculation

f2 fT2

excellent agreement
fT1 f4
excellent agreement

comparison to theory (torsional modes)

note: f1 is fundamental mode, often denoted as f0

systematic error, presumably

cantilever width
65
Thermal noise of cantilevers for the nth mode
noise analysis based on harmonic oscillator model

\omega _n ^2

\Gamma _n =
with and dissipation term [kg/s]

with flat thermal noise spectrum that is related to the thermally excited cantilever amplitude as

integration performed over nth peak

Evaluation of the integral (for large quality factors) leads to

which has the units

For a measurement bandwidth B, this spectral density gives a minimum detectable force of

note: make sure that the native Qn is used here. Any quality factor that is changed with a non-stochastic feedback drive
circuitry must NOT be used !
Q-control does NOT change Fmin, n . Be aware of interferometer-induced cantilever heating/cooling phenomena

... and similarly and

minimally measurable force gradient minimally measurable

derived from D. Rugar et al., Appl. Phys. A 72 (2001) 3 note: this is what the PLL should be capable of doing
Thermal noise of cantilevers for the nth mode
For a measurement bandwidth B, this spectral density gives a minimum detectable force of

F_{min,\,n}

Force sensitivity for higher modes

minimally measurable changes of Q, if PLL drives cantilever at constant A

Force sensitivity for higher modes

derived from D. Rugar et al., Appl. Phys. A 72 (2001) 3, Grütter et al., Appl. Phys. Lett. 71 (1997) 279
Most force sensitive cantilevers
using and

we find

geometrical conditions for a sensitive cantilever:

• high Q
• small w
• long L
• thin t

D. Rugar et al., Appl. Phys. A 72 (2001) 3 68

 Quality factors of cantilevers
quality factor defined in terms of the energy loss per cycle

loss factors: and

• Qmount : energy dissipated through the mounting of the cantilever in the force microscope
• Qair : energy dissipated by viscous damping of oscillating cantilever
use vacuum
• Qsupport : energy dissipated from cantilever to support chip of cantilever
do not use too hard and too short cantilevers or torsional oscillators, do not coat across support
• QTED : energy loss by thermoelastic damping
• Qsurface : energy dissipated by cantilever surface losses
do not coat surface, be careful with reflective coatings
bake cantilevers in UHV @ 150C to remove H2O
bake cantilevers in UHV @ 800C to remove oxide or perform HF etch
• Qvol : energy dissipated in cantilever inside, can be neglected for single crystalline cantilevers

Support loss: analytical model long and thin is better

by Hao, Sensors Actuators A 109 (2003) 156

Thermoelastic loss: Any bending of the cantilever is with very low T & thin is better
related to temperature changes, and an irreversible
flow of heat driven by the generated temperature
gradients gives rise to TED. or with
See Lifshitz Phys. Rev. B61 (2000) 5600

Support loss: see Yasumura et al, J. small w and no additional coating is better
Microelectromech. Syst. 9 (2000 ) 117
thickness of surface layer property of surface layer

Damping by molecular flow: see Bianco et al J. Vac.

Sci. Technol. B 24 (2006) 1803 Qmolecular > 1012 below 10-8 mbar
Lübbe Meas. Sci. Technol. 21 (2010) 125501 69
Typical sensitivities for soft cantilevers

as sensitive as best
NEMS

Q can be increased
by more than 10, if
surface loss is
removed !

3E-06 950 46000 1.4 only pendulum setup

[1] H.J. Hug et al., MFM cantilevers

[2] K. Li, M. L. Roukes et al., Nature 2, 114 (2007)
[3] J. Yang, H.J. Hug et al., 86, 134101 (2005)
[4] for cantilevers [3] estimated from J. L. Yang, T. Ono, and M. Esashi, Appl. Phys. Lett. 77, 3860 (2000)
[5] typical for MRMFM cantilever see D. Ruger et. al. 70
Ultrasmall silicon cantilevers

collaboration between Uni Basel and IBM

J. Yang, H.J. Hug, et al., APL. 86 (2005) 134101-1

Typical sensitivities for hard cantilevers

100‘000 0.32

assumption based on first

experiments

Q up to 100‘000 at LT
sensitivity 2 x increased

• conventional cantilevers used for atomic resolution are 40 times more sensitive than tuning forks, but they
need to be operated under similar conditions!

• a cantilever with a similar stiffness is still 10 times more sensitive, and again 40 times more sensitive after
annealing.

However: tuning forks are successfully used for true atomic resolution imaging
3.1.2. Deflection Sensors
Deflection Sensors

Electron Tunneling: original concept, potentially sensitive, practically problematic

Beam Deflection: most widely used, robust, high sensitivity, not directly quantitative, requires calibration
Interferometry: best sensitivity, quantitative, uses limited space, complicated
Capacitance: sensor can be microfabricated, strong force from sensor, limited sensitivity
Piezoresistance: ideal for microfabrication & integration, limited sensitivity, heating of cantilever
Piezoelectric: mostly quartz tuning forks, good for true atomic resolution, limited sensitivity
Beam Deflection Principle

Animation: H.-R. Hidber, NCCR on Nanoscale Science University of Basel

A laser beam is reflected off the rear side of the cantilever. Angular deflections of the laser beam are measured
with a position sensitive detector (4-quadrant photo diode). The A-B-signal is proportional to the
normal force and the C-D-signal is proportional to the torsional force.
Beam Deflection Principle

Animation: H.-R. Hidber, NCCR on Nanoscale Science University of Basel

A laser beam is reflected off the rear side of the cantilever. Angular deflections of the laser beam are measured
with a position sensitive detector (4-quadrant photo diode). The A-B-signal is proportional to the
normal force and the C-D-signal is proportional to the torsional force.
Interferometer Optical Deflection Sensor
interferometer inside force microscope

laser diode fiber

2x2 coupler
4% reflection
@ fiber end
foto foto &
diode diode reflection
@ cantilever
amplifier amplifier
cantilever
signal reference signal

Inside the SFM only limited space is required. The fiber-cantilever distance is around 10um. A highly stable
laser power supply, stable (optically isolated) monomode laser diodes and temperature stabilization of the
laser is required to obtain maximal sensitivity. The fiber can usually be adjusted relative to the cantilever in
order to work at the point of maximum sensitivity.
Ref.: D. Rugar, H. Mamin, P. G¨uthner: Appl. Phys. Lett. 55, 2588 (1989)
A. Moser, H. J. Hug, Th. Jung, U. D. Schwarz, and H.-J. Güntherodt, Meas. Sci. Technol. 4, 769-775 (1993).
Interferometer Optical Deflection Sensor
inside force microscope

4% reflection
@ fiber end
&
reflection
@ cantilever
λ/2
cantilever

Note:
• WP1 and WP2 are the most sensitive operation points
• the w-Piezo (piezo to control fiber-to-cantilever distance) is used to move fiber to one of
these operation points
• then a feedback keeps fiber at this position
• small cantilever deflections can now be detected
Ref.: D. Rugar, H. Mamin, P. G¨uthner: Appl. Phys. Lett. 55, 2588 (1989)
A. Moser, H. J. Hug, Th. Jung, U. D. Schwarz, and H.-J. Güntherodt, Meas. Sci. Technol. 4, 769-775 (1993).
3.1.3. relevant Forces
Relevant Forces tip

typical long-range forces (> 1nm):

• van der Waals
• electrostatic, magnetic, Casimir

> 1nm
forces in liquids:
• hydrophobic / hydrophilic forces
• steric forces
sample
• solvation forces
tip

typical short-range forces

(contact / near contact):
• short-range repulsive forces
(Pauli exclusion) or ionic repulsion forces
• short-range chemical binding forces

sample

• When the tip is in contact with the sample, a large, repulsive tip-sample force may
occur to the tip apex due to the possibly large long-ranged attractice forces !!!
• So zero cantilever deflection does not mean that the tip apex force is zero !!!
Refs.:
J. Israelachvili
Intermolecular and Surface Forces with Applications to Colloidal and Biological Systems, Academic Press (1985)
D. Tabor
Gases, liquids and solids, Cambridge University Press (1979)
Short-Range Forces
• due to overlap of electron wave functions and from the repulsion of the ion cores.
• can be both attractive:
• attractive when the overlap of electron waves reduces the total energy.
These situations are comparable to molecular binding.
• around 0.5 - 1 nN per interacting atom at tip-sample distances typical for STM operation.
• decay length of the order of atomic units, i.e. 0.05 nm for metallic adhesion, but around
0.2 nm for covalent bonding.
• true atomic resolution AFM operates with these forces
• or repulsive:
• repulsive when strong electron wave overlap (Pauli exclusion principle). These forces are
directly connected to the total electron density.
• The ionic repulsion acts for small distances, where the screening of the ion cores by the
electrons falls away.
• usual contact AFM operates with these forces.

• Model potentials like the Lennard-Jones or the Morse potential are used to describe the
short-range forces.

• However, their application is essentially limited to the pairwise interaction of atoms.

• For covalent bonds non-pair potentials may be more useful, i.e. Stillinger-Weber for Si
• The displacement of atoms by the action of the short-range force has to be taken into
account.
Van der Waals Forces
Dipole-dipole forces between non-permanent dipoles (dispersion forces).
• These act between dipoles that arise from fluctuations and dipoles induced in their electric field.
• They are always present and attract even chemically inert noble gas atoms.
• When the distance between molecules is larger than the way light can travel during the
characteristic lifetime of the fluctuations, the dispersion forces are weakened. This effect is called
retardation.
• The van der Waals force at short distances decay like:
F = 1/r6, beyond r > 5 nm this power law reduces to F = 1/r7.

Because the range of van der Waals forces is limited, the tip-sample geometry of the force
microscope can be well approximated as a sphere approaching a semi-infinite body. For this
configuration, the van der Waals force is

where H denotes the Hamaker constant, R the tip radius, and D the distance between tip and
sample surface.

• The value of the Hamaker constant H is of the order of 10-19 J. For materials with high dielectric
constant like metals it is about a factor of ten higher than for insulators.
• For a tip of radius R = 30 nm, the van der Waals force in vacuum at a distance of D = 0.5 nm is
of the order of FvdW = 2 nN.
• The van der Waals force can also be determined for more complex tip-sample geometries like a
half-sphere at the end of a truncated cone.
Van der Waals Forces
• are attractive in vacuum and in most cases
• Lifshits theory predicts that the force is proportional to (ε1-ε3)(ε2-ε3) and (n12-n32)(n22- n23),
where ε and n are dielectric constant and refractive index of tip (1), sample (2), and medium (3) in
between.
• medium with ε and n close to the respective values of tip and sample will greatly reduce van der
Waals forces.
• immersing liquid can lead to a negative Hamaker constant and to repulsive van der Waals forces.
• repulsive van der Waals Forces in liquids are used to stabilize suspensions of (nano)particles
• repulsive van der Waals Forces have also been used for the first AFM experiments showing true
atomic resolution [1]

[1] F. Ohnesorge and G. Binnig, Science 260, 1451 (1993)

Electrostatic Forces
• The strength and distance dependence of electrostatic forces obey Coulombs law.
• Charges can easily be trapped at sample surfaces in the course of surface preparation, for
example by sample cleavage or by UHV techniques like ion sputtering.
• contact electrification can charge tip and sample after their contact is broken. Even in air such
charge can persist for hours particularly on polymers, in vacuum for days.
• Charges on the surface attract conductive tips. The method to determine the force is to
calculate the interaction between the charges and their mirror image in the tip.
• neutral but polar surfaces interact with a conductive tip via image forces. Likewise, a polar
group at the tip apex causes an attractive force towards a conductive sample.
• Electrostatic forces also act between conductive tips and conductive samples when they are
on a different potential. If one considers the system tip-sample as a capacitor with the
distance dependent capacitance C, the force is given by

where Ubias is the bias voltage and Ucpd is the contact potential difference due to different
work functions.
• zero bias voltage normally does not correspond to a minimal electrostatic force but that the
contact potential difference has to be compensated.
• the work function is very sensitive to perturbations at of the surface. The irregular shape of a
the tip gives rise to patch charges, which can not be completely compensated by a bias
voltage.
• For tip radius R = 20 nm at a tip-sample distance of z = 0.5 nm and Ubias - Ucpd = 1 V the
electrostatic force is about Fel = 0.5 nN.
Contact Potential
Band alignment under zero sample bias.
Ucpd
The Fermi levels match, no net tunnel or
contact current is flowing.

A contact potential Ucpd is established

Quadratic dependence of measured force (or here frequency shift) on tip-sample bias
Magnetic Forces
• The forces that act on magnetic dipoles located in a magnetic field are called magnetic forces.
• In force microscopy experiments the magnetic dipoles are usually contained in the ferromagnetic
material on/of the tip of the cantilever and the magnetic sample.
• A field is produced by a ferromagnetic sample or a current distribution located in close proximity
of the tip. The current distribution may be the one of a current carrying device or be present in a
superconductor.

• The force on the tip is then given by the derivative of the magnetostatic energy.

• Note that the z-derivative of the stray field is inside the integral expression. Thus when the inte-
gration is performed along a long slab like tip (see figure), the integration along the z-axis will
lead to an expression for the force that is proportional to
the stray field times the magnetic charge at the lower tip
end (plus the stray field times the magnetic charge at the upper tip end – however for a long
tip this part can be neglected).

Attention:
• the magnetic force is rather proportional to the stray field (and NOT to the derivative
• of the stray field as documented in many
• manuals of SPMs and publications !!!)
Capillary Forces
• microcontacts act as nuclei of condensation.
• In air, water vapor plays the dominant role.
• If the radius of curvature of the microcontact is below a certain critical radius (approximately
equal to the Kelvin radius) a meniscus will be formed.
• The Kelvin radius is given by

where γ is the surface tension, R the gas constant, T the temperature, V the molar volume and pS
the saturation vapor pressure.
• The surface tension of water is γ = 0.074 N/m at T = 20 C which gives the parameter γV/RT =
0.54 nm. Therefore we obtain for p/ps = 0.9 a Kelvin radius of 100 nm.
• In Scanning Force Microscopy, typical tips having radii of less than 100 nm are possible nuclei of
condensation. If a meniscus is formed an additional capillary force acts on the tip. A simple
estimation is given by:

• where R is the radius of curvature, Θ the contact angle, D the distance between tip and sample
and φ the angle of the meniscus. The maximum force is given by Fmax =4πRγ cosΘ .
• For a tip radius of 100 nm we obtain a force Fmax=9.3·10-8N, which is significantly stronger than
the corresponding van der Waals force.
• Typical force vs. distance curves in ambient conditions reveal forces of the order of 10-8-10-7N,
which mainly originates from capillary forces.
• These adhesion forces limit the minimum force which acts on the outermost tip region, and have
to be equilibrated by the repulsive force in this small contact region. Consequently, capillary
forces can determine the size of the contact and play an essential role in force microscopy
measurements in air.
Capillary forces

Fmax = 4 π R γ cos(Θ)

R
γ (H2O) = 0.074N/m R=100nm
Contact angle foir hydrophilic surfaces Θ ≈ 0°

⇒ Fmax = 90nN
 3.2. Contact Mode
Scanning Force Microscopy
3.2.1. Principles of SFM in Contact
Snap to Contact
critical tip-sample distance tip in contact with sample multi-atom tip-sample
contact

tip

tip
tip
snap-in

sample surface sample surface sample surface

tip snaps to surface @ critical
tip-sample distance due to
attractive van der Waals force.
attractive van der Waals force
acting on tip are compensated
by local repulsive force at the
tip apex.
large repulsive force at tip
apex leads to re-ordering
of atoms at the tip apex. A
multi-atom contact is formed.
The imaging of single atoms
and atomic defects is not
possible under this condition.

Contact Radius:
• in atmosphere: 2-10nm @ 1nN < F < 100nN
• in UHV: 1-4nm @ 0.1nN < F < 10nN
Force versus Distance Curves

Long-range contributions have

force gradients like
dF/dz » 1-10 N/m.
Spring constants of
k ≈ 0.01-1 N/m provokes “jump-
into-contact” when
k < dF/dz.
Adhesion causes hysteresis in
force vs. distance curves.

92
Unzipping Bacteriorhodopsin

Oesterhelt et al. Science 2000

Low Force Imaging of Soft Biological Material in
Buffer Solution
Imaging Biological Functionality:
Opening and Closing of Pores
pH 3

Schindler & Rosenbusch, 1978

3 Å X-ray AFM: pH 7 pH 7, -200 mV

Cowan et al., Nature 1992 Müller & Engel, J Mol Biol 1999
Pseudo Atomic Resolution

• contact AFM on NaF(001)

• observation of atomic lattice
(Moirée-effect)
• step width approximately 1nm
indication of tip radius
• single atoms or atomic defects not visible

1nm
3.2.2. Examples of Dynamic Force Microscopy
with Tip in Contact
Force Modulation Scanning Force Microscopy

Imaging Local Stiffness

Piezo-response Force Microscopy (PFM)
Static AFM configuration Lateral Polarization

Lock-in In-phase
Frequency Oscillation Ref Amplifier
Generator

Lateral Normal Polarization

Deflection

Laser
Normal Lock-in In-phase
Deflection Ref Amplifier

Cantilever
Topography
Sample
x
Scan
Generator y Feedback z
Scanner Setpoint Control
3.2.3. Scanning Friction Force Microscopy
Friction Contrast

Material-specific contrast in Friction Force Microscopy. friction on NaCl(100)

Topography (a) and lateral force (b) recorded on a mixed
Langmuir-Blodgett film (C21H43COO -/C9F19C2H4OCC2H4COO -)

Circular areas of
hydrocarbon molecules
are surrounded by
fluorocarbon molecules.
Within the hydrocarbon
islands, material has
been removed by the
action of the tip (low
scanning velocity, high
load).

Ref.: E. Meyer et al. Thin Solid Films 220, 132 (1992)

Atomistic Simulation of the Tip-Sample Interaction:
Observaton of Tip-internal Motions

keff = 1N/m keff = 1.6N/m

U. Wyder et al. , JVST B 25,1547 (2007)

Atomic stick-slip as a function of normal
force: Observation of „Superlubricity“

Stick-slip η>1 η<1 “Superlubricity”

Experiment Theory

⇒Transition to minimum dissipation state

Ref.: A. Socoliuc, R. Bennewitz, E. Gnecco and E. Meyer, Phys. Rev. Lett. 92, 134301 (2004)
Controlling Friction by Actuation of
Nanometer-Sized Contacts

A. Socoliuc, E. Gnecco, S. Maier, O. Pfeiffer, A. Baratoff, R. Bennewitz, E. Meyer, Science 313, 207 (2006)
3.3. Intermittent Contact Mode
and Peak Force Microscopy
Advantages of the Intermittent Contact Mode

Intermittent contact mode is good for

• works best in air (not vacuum)
• measurement of topography on soft samples
• measurement of loose particles adsorbed on surfaces
• topography Measurement on samples with high friction
• topography on samples with vertical features
is easy to use and robust !

but: • the cantilever oscillation can be strongly non-harmonic, i.e. bent resonance
curves with instabilities
• stable operation is obtained at high amplitudes and with hard cantilevers
• but the highest phase contast is obtained close to the critical points
Intermittant Contact Mode
Tapping Mode Phase reveals Local Stiffness
Peak Force Tapping – Force Monitor

• Force curves are displayed in the Force Monitor and are useful for monitoring feedback conditions.

• The Vertical axis displays the Vertical Deflection data from the photo detector. The axis is labeled
Force and the units are always in Volts for ScanAsyst.

• The horizontal axis can be in terms of nm of z piezo position or time.

Peak Force Setpoint Peak Force Setpoint

Pull-off ringing

Retract (red on Force vs. Z

Approach (blue plot)
on Force vs. Z
plot)
PeakForce QNM
• Based on PeakForce Tapping mode

• Every tap on the surface produces additionally a force curve, which is extracted

• Force-curves are acquired more than 1000x faster than in standard force distance spectroscopy

• Obtain quantitative material properties by force curve analysis at every pixel.

Peak Force Setpoint

Z Drive (~2KHz)

Derjaguin-Muller-Toporov (DMT) model and E1,E2 are the elastic moduli and ν1,ν2 the Poisson's ratios associated with each
body.

in contact:
Hertz Theory
New Applications – Li Battery

Characterizing Lithium battery cathode material (L333-glue)

Only possible with PeakForce TUNA

Sample courtesy of Dr. Battaglia, LBL

• Correlation revealed: less conductive, higher Young’s modulus, higher adhesion

• Enabling material assignments and characterization of dispersion.
 Force during trench measurements

Tip

Z Z

Sample Sample

• With the same tip sample distance, van der Waals forces increase a lot due to the
contribution from the side wall

• Capillary force also proportional to effective tip radius and can be 10-20 times larger
inside the trench
 Real Advantages

• ScanAsyst can image samples that are

extremely challenging or impossible
with conventional TappingMode™

• Deep, narrow trenches and pits are

very difficult for TappingMode because
the geometry excessively damps the
tapping oscillation, preventing the tip
from reaching the bottom.

• Because ScanAsyst is based on direct

imaging force control, it is immune to
these effects.

Deep (~65 nm), narrow (~50 nm) trenches are difficult to image with TappingMode due to
excessive damping of the probe oscillation. But here ScanAsyst easily reaches the bottom
of the trenches. Scan size 1 µm on a Dimension Icon.
 3.4. non-contact AFM (ncAFM)
or Dynamic Force Microscopy (DFM)
3.4.1. Principles and Instrumentation
Principle of Dynamic Force Microscopy
with Atomic Resolution

cantilever-sample First demonstration of true atomic resolution:

distance ~ 10 nm
F.J. Giessibl, , Science 267, 68 (1995),
oscillation S. Kitamura et al.,
~ 9.5 nm Jpn. J. Appl. Phys., 34, L145 (1995)
H. Ueyama et al.,
Jpn. J. Appl. Phys., 34, L1086 (1995)
sample

feedback system
FM Detection:
T.R. Albrecht et al., J. Appl. Phys. 69, 668 (1991)
minimal describe an FM demondulation technique for
tip-sample fast measurement of frequency shift.
distance:
tip U. Dürig et al., J. Appl. Phys. 82, 3641 (1997),
Incipient 0.2 - 1nm Ch. Loppacher et al., Appl. Phys. A66, 215 (1998)
chemical - adjust frequency of oscillation circuit to keep
bond phase between excitation and cantilever oscillation
constant (phase locked loop)
- keep cantilever oscillation amplitude constant, i.e.
cantilever excitation signal is proportional to
surface of sample energy dissipation
- conservative and non-conservative interactions
can be separated
frequency shift, ∆f
Modeling dynamic AFM
q(t) q‘(t)
with

with d+2A A
cantilever

from 1st order perturbation theory d+A 0

d -A
which is justified for larger A, because d
0
sample
for A = 5nm

from this follows

For small amplitudes, the frequency shift is a very simple function of the tip-sample forces:
• it is proportional to the tip-sample force gradient kts .
• for large amplitudes, the frequency shift is given by the rather complicated equations (see above).
• with integration by parts, the complicated formula transform into a very simple expression

with

Giessibl, Rev. Mod. Phys. 75 (2003) 949 118

Modeling dynamic AFM
For small amplitudes, the frequency shift is a very simple function of the tip-sample forces:
• it is proportional to the tip-sample force gradient kts .
• for large amplitudes, the frequency shift is given by the rather complicated equations (see above).
• with integration by parts, the complicated formula transform into a very simple expression

with

relevant issues
• large amplitudes reduce <kts>; cantilever does not snap
• large amplitudes reduce signal, but improve noise
• large amplitudes suppresses non-harmonic terms and
higher harmonics
• large A:

• large A allows renormalization

• large amplitudes increase contribution of long-range force

compared to short-range force

• ideal amplitude corresponds to interaction length of force

• ideal amplitude maximizes higher harmonics generation

• small amplitude: frequency shift no longer depends on A,

but becomes proportional to kts

Giessibl, Rev. Mod. Phys. 75 (2003) 949 119

Large vs. small oscillation amplitude

large  thermal  noise low  detection  sensitivity

Detection  sensitivity

Thermal  noise

Amplitude  comparable  to  range  of  interaction  is  optimal!

Example:  
Absolute  value  of  resolution  depends  on: k=2000N/m,  f0=  1.6MHz,  Q=100  000
 probe  specifications  (f0,  k,  Q)   Ath=  1440fm  @300K
Ath=  170fm  @4.2K
 detector  sensitivity
Required  sensitivity  of  detector  @1kHz  BW:
Anoise<  50fm  @300K
Anoise<  6fm  @4.2K

S.  Kawai  and  H.  Kawakatsu.  APL  88,  133103  (2006)

Issues with controlling dynamic AFM
distance feedback issues:
1. measured signal(z) must be monotonous; note that this is NOT the case for small A
2. further note that (attractive) short-range force may not exist at all sample locations
3. slope of signal(z) changes
4. at closer distances, the overall z-feedback speed increases. The z-feedback may start to oscillate.
5. PLL instabilities at small A

how to overcome these issues:

1. make measured signal(z) remains monotonous
- check feedback direction (does frequency decrease when going closer? note the opposite is true for tunnel current)
- note that this is NOT the case for small A, so use larger A to average differently such that long range attractive
part of potential dominates
- use blunter tip, this is to generate sufficient van der Waals background force for feedback operation
2. further note that (attractive) short-range force may not exist at all sample locations
- use larger A to average differently such that long range attractive part of potential dominates
- use blunter tip, this is to generate sufficient van der Waals background force for feedback operation
3. slope of signal(z) changes
- make sure this does not happen using frequency-versus-distance curves
- use correct feedback sign
4. at closer distances, the overall z-feedback speed increases. The z-feedback may start to oscillate.
- watch for signs of feedback oscillations: - avoid them
- carefully reduce P,I of z-feedback when approaching to keep overall z-feedback speed constant
- smarter feedback (local log ... needs to be implemented in software)
5. PLL instabilities
- do not use silicon tips at small A, to avoid stochastic energy dissipation events; use metal tips
- use sufficiently high dynamic reserve
- work @ larger tip-sample distances or use bimodal operation
6. hands-on-practice

H.J. Hug 121

3.4.2. Imaging with True Atomic Resolution
ncAFM with True Atomic Resolution
Dynamic Operation
distance of cantilever to surface and oscillation
amplitude adjusted to obtain less than 1nm
minimal tip-sample distance at lower turning point
Animation: H.-R. Hidber,
NCCR on Nanoscale Science
University of Basel
View from the oscillating tip
during a large fraction of the oscillation period only
the long-ranged van der Waals force is acting on
the tip. Only at the lower turning point a chemical
interaction between the tip apex atom and a surface
atom may occur.
Atomic Resolution on Si(111)-7x7

1nm

measurement parameters
∆f = -31Hz, scan speed 0.6nm/s
Cantilever: cL = 28.6 N/m, 200
150

z [pm]
f0 = 155 719.3 Hz, Q = 370‘000
temperature: 7.2K 100
50
0
0 1 2 3 4 5
cross section [nm]

• height difference between inequivalent adatoms due to small differences in reactivity

M. A. Lantz and H.J. Hug et al., Phys. Rev. Lett. 84, 2642 (2000)
K. D. Brommer, et al., Phys. Rev. Lett. 68, 1355 (1992) &
I. Stich, et al., Phys. Rev. Lett. 68, 1351 (1992).
Site Specific Forces
0

0
frequency shift. [Hz]
@ Corner
Hole vdW force

force [nN]
-40
-1

short-range force
@ Adatom -2
-80 total force

-3
2 4 6 8 10 12 14 2 4 6 8 10 12 14
tip-sample distance [Å] tip-sample distance [Å]

conversion from df(z) to F(z) [1]

235pm

absolute distance to sample from Si-Si bond-length: 235pm !

atomic resolution imaging @ F= -0.4nN and 4.5A tip-sample distance !

[1] U. Dürig, APL. 75, 433 (1999) and APL 76, 1203 (2000) and other inversion methods ...
[2] Lantz and Hug et al., Science 291, 2580 (2001)
ncAFM and Atom Manipulation
Vertical atom manipulation Dissipation
Oyabu et al., PRL 90, 176102-1 (2003) Oyabu et al., PRL 96, 106101 (2006)

Lateral atom manipulation

Sugimoto et al., Nature 146, (2005)
Imaging Molecules
Imaging the chemical structure of
molecules with atomic resolution was
achieved by probing the short-range
chemical forces via noncontact atomic
force microscopy (NC-AFM). Our low-
temperature STM/AFM is based on a qPlus
sensor design [1] and is operated in an
ultrahigh vacuum at a temperature of 5 K.

The key step to achieving atomic resolution

on molecules is the functionalization of the
microscope’s tip apex with suitable,
atomically well-defined terminations, such
as CO molecules (see schematic image).
In this case, atomic manipulation
techniques are essential for the controlled
buildup of the tip used for AFM imaging.

Density functional theory (DFT)

calculations are performed to elucidate the
physical origin of the observed atomic
contrast. The calculations reveal that the
Pauli repulsion is the source of the atomic
resolution, whereas van der Waals and
electrostatic forces only add a diffuse
attractive background [2].
References
[1] F. J. Giessibl, Appl. Phys. Lett. 76, 1470 (2000).
[2] L. Gross, F. Mohn, N. Moll, P. Liljeroth, G. Meyer, Science 325, 1110 (2009).
3.4.3. Kelvin Probe Force Microscopy
Contact Potential
Band alignment under zero sample bias.
Ucpd
The Fermi levels match, no net tunnel or
contact current is flowing.

A contact potential Ucpd is established

Quadratic dependence of measured force or here frequency shift on tip-sample bias

Kelvin Probe Microscopy

Vdc=0 if Ucpd=Utip-sample
Error of
Kelvin
Frequency Oscillation Ref Signal
Generator Lock-in Feedback z
In more sophisticated setups the input
Amplifier Control Contact
of the Kelvin Lock-in can be driven by:
- the frequency shift signal Potential
Setpoint = 0 or Kelvin
- by the phase Normal
- etc Signal
Deflection
ac-Signal
Ucpd

Normal
Deflection
Laser „dc“-Signal

-
Utip-sample
Summation Cantilever
+
Sample Feedback z
Control Topography
Setpoint
x
Scanner
Scan
y
Generator
Surface Potential on a CD-RW

Height 5µm scan Potential

Courtesy: Yasudo Ichikawa, Toyo Corporation

©2006 Veeco Instruments Inc.
3.4.4. Magnetic Force Microscopy
Basics about Magnetic Force Microscopy

MFM maps the stray magnetic field (not Msample)

→ measures through non-magnetic top layers (protection layers)
→ information depth depends on source of field, i.e.
magnetization, sensitivity of instrument, size of domains
→ sees hidden interfaces
→ works on polycristalline, medium rough samples (e.g. technical materials)

Environments
→ ambient air, vacuum, UHV
→ various temperatures & magnetic fields

MFM is a Scanning Force Microscope with a magnetic tip

→ the MFM has a tip that can also measure
topography → correlation with magnetism
→ resolution 10nm and potential for < 5 nm
→ quantitative (for inhomogeneous fields)
(as quantitative as any other scanning field sensor)
→ non-destructive ?
MFM Sensitivity Limit
single crystalline silicon cantilevers minimal measurable force derivative

k: force constant, ω0: free resonance

Q: quality factor, T: temperature, A: amplitude
magnetic
layer

radius sensitivity > 15 times higher in vacuum

< 3nm
force constant: ∼ 0.3 N/m
res. frequency: ∼ 50 kHz

Typical MFM high resolution MFM SEMPA

@ HGST, San Jose (2003) hr-MFM (2003) Hitachi CRL, Dr. T. Kohashi

Resolution:
white domains
with 10nm diameter
are visible.
Improved tips
can go below 10nm.

1µm
200nm 1µm
200nm 1µm
200nm
MFM Image Formation ➜ Transfer-Function Theory
• The force on the MFM tip at position frequency shift proportional to force derivative:

• qtip depends on the spatial

wavelength of the field
+

>10µm radius +

< 3nm +
+
qtip
+
++

• Description with 2D Fourier:

• Fourier transformed:

proportional to

canting of cantilever & oscillation amplitude considered

transfer-function including tip-transfer-function

H.J.Hug et al., J. Appl. Phys. 83 (1998) 5609, P.J.A. van Schendel et al., J. Appl. Phys. 88 (2000) 435
Calibration of the MFM tip
F-layer data magnetization pattern

calculation of tip-transfer function circular averaging

FFT( )
= FFT( )
FFT( )

test of circularly averaged tip transfer function

FFT( ) ⋅FFT( )= FFT( )

✔
the numerics of the calibration procedure is ok!
PPMS-AFM: 2K < T < 400K; B up to 7T
0 Oe 2500 Oe

3500 Oe 4500 Oe

+
Sample courtesy of J. Ahner, Seagate, USA

Vortices in superconducting Nb

H.J. Hug and S. Vranjkovic www.nanoscan.ch

Van der Waals Forces and their Contribution
to the MFM Signal (in constant-average-height imaging)
Δf vs. tip-sample distance curve
Influence of topography

van der Waals force

Variable local tip-sample distance:

 fluctuation of local vdW force.

Topographical features become visible

in the MFM image.

Real topography image

Separation of Topography and Magnetism
Measure with opposite magnetization states of tip

- +

= =

500 nm 500 nm

magnetic signal topographical perturbation

4. Cantilever Sensors
Cantilever based Sensors

bi-metallic dynamic static

Heat Source Resonance frequency- Cantilever Bending

shift

Heat Drain

Calorimeter Microscale Surface Tension

Pico-Joule Pico-Gramm Atto-Mol

Important: Functionalization of Cantilever Surface.

 Cantilever Sensor Principle
Detection of Molecular Interactions using Cantilever Arrays

• Silicon cantilevers are coated with a

chemically sensitive layer

• Selective binding of target molecules leads

to bending of the cantilever and changes
its resonance frequency

• Optical beam-deflection allows to measure

the tiny deflections.

• This method allows the sensitive and label-

free detection of e.g. DNA, proteines,
microorganisms or chemical substances
Cantisens® Research

www.concentris.com Supported by
Cantilever based chemical Nose

Quantitative Analysis
Principle

Neuronal Network Analysis

5. Future Aspects
 5.1. multi-dimensional
Scanning Force Microscopy
AFM in UHV Today
Cantilever-AFM
• needs extra force sensor
• atomic resolution on many systems
• cantilevers typically 40N/m, 300kHz
• high force sensitivity (measurement of
small magnetic or electrostatic forces
possible)
• mostly large oscillation amplitudes
• lower sensitivity for short-range forces
• higher and multi-mode operation
• in-principle vertical and lateral forces
• simultaneous AFM and (bad) STM
• bandwidth up to 3MHz in best systems
• (mostly) sharp Si tips:
• inherently instable
• dissipation of energy by tip instabilities
Tuning Fork AFM
• every STM can be converted to a TF-AFM
• atomic resolution on many systems
• quartz with typically 1600N/m, 30kHz
• relatively poor force sensitivity, e.g. very bad
MFM.
• mostly small oscillation amplitudes
• higher sensitivity for short-range forces
• only fundamental mode operation
• forces can only be measured along ONE
direction
• simultaneous AFM and (good) STM
• very slow, very limited bandwidth
• (mostly) blunt metal tips:
• inherently stable
• dissipation of energy difficult to measure,
because of poor sensitivity
147
AFM in UHV - Challenges toward Ultimate AFM
measure forces simultaneously in multiple directions
• while manipulating of single atoms and molecules
• mapping surface potentials, local reactivity
• measure quantum pressure
• magnetic exchange interactions
measure tip-sample force or bonding energy @ each image point
• measure 3d force/energy map in single scan
• intelligent feedback working. e.g. working on local bonding energy
• evaluate force curves at each xy-position from non-harmonic distortions or inter-modulation
measure force and do (state-of-the art) STM simultaneously
• inelastic tunneling / spin flip tunneling
• mapping of atomic/molecular vibrations/instabilities by AFM
ultimate force sensitivity
• UHV preparation of ultrasmall cantilevers
• ultimate MFM, EFM (single spin level)
• Casimir forces
• atomic charge distributions
• cantilever cooling to quantum limit

AFM beyond state-of-the art

• will make new physics and surface chemistry accessible
• ongoing technology transfer to industry 148
Fabry-Perot Interferometer with fm/sqrt(Hz) Sensitivity
Signal 3 lenses Cantilever with micron-sized
Fiber Cantilever reflective coating
PD

Laser

˦˥˨
diode 20µm
Core: 5 µm Step
Beam
splitter PD
Reference
Lens surface, R~90% Chip
thermal noise data (flexural modes) (torsional modes)

Patent : P. Frederix and H. J. Hug, PCT/IB/02/03253,

5.2. Scanning Chemical Force Microscopy
5.2.1. Scanning Chemical Force Microscopy
with X-rays
The Setup: a confocal arrangement of a SPM and a STXM

NanoXAS can be operated as a classical

Scanning Probe Microscope (SPM):
Scanner range 40µm x 40µm x 6µm

and as a classical Scanning Transmission

X-Ray Microscope (STXM) resolution:
~ 40nm, energy range ~270-1800eV
or
As a combined SPM ⊕ STXM
In UHV
STXM
14 Piezo step-motors / 1 closed-loop fine scanner, (40 x 40 x 6 µm)
4 Position Sensitive Detectors (PSD) / 1 optical encoder

SPM
Polymer Blend imaged at different x-ray Energies
Materials: poly(3-hexylthiophene) (P3HT) and polystyrol (PS)

N. Pilet et al. Nanotechnology 23, 475708 (2012)

153
Polymer Blend imaged with
Electron (surface) & Photo (bulk) Detector

Polymer blend: F8BT/PFB STXM 285eV (PFB)

e- detection
(channeltron)

F8BT = Poly[(9,9-di-n- 10 um x 10 um ph. detection

octylfluorenyl-2,7-diyl)-alt- (photo diode)
(benzo[2,1,3]thiadiazol-4,8-diyl)]

PFB = poly(9, 9 '-dioctylfluorene-co-bis-
N,N '-(4-butylphenyl)-bis-N,N '-
phenyl-1,4-phenylenediamine
B. Watts et el (2012) @ x07da PolLux
Magnetic Domains imaged by MFM and XMCD
5.2.1. Scanning Chemical Force Microscopy
combination with ToF-SIMS
Time-of-Flight Scanning Ion Mass Spectrometry (ToF-SIMS)

Detection of secondary ions

high sensitivity ppm – ppb range

detect all elements & Si, 29Si, 30Si,

isotopes

organic and inorganic Molecules &

chem. information -fragments, atoms,
clusters

small information depth first 1-3 at. layers

lateral resolution ~ 100 nm
depth resolution ~ 1 nm
high mass resolution > 16,000
high mass range up to 10,000 u
parallel mass detection

157
Surface Spectroscopy: Mass Resolution
3D retrospective analysis: LCD Switch

© Ion-Tof GmbH
Concept of combining SFM & ToF-SIMS for the in-situ measurement of
direct 3D chemical information
... after 4 Years of Development

3D NanoChemicope instrument:
IONTOF

♥
inside

NanoScan
@ IONTOF laboratories
… inside the 3D NanoChemicope instrument

ToF-SIMS meas. position

SFM measurement position • bearing-free 5 axis XYZRT stage for ToF-SIMS

and SFM operation
• Fast & precise displacement between ToF-
SIMS and SFM measurement positions

• 40s for 23cm distance,

< 0.5um accuracy
• Fast coarse
positioning (6mm/s)
• 20nm positioning
precision
… inside the 3D NanoChemicope instrument: the 5-axis stage
… inside the 3D NanoChemicope instrument: operation
5.4. Magnetic Resonance Force Microscopy:
3d Imaging of Viruses ...