Tribologija Tribology

A T O M I C - S C A L E F R I C T I O N
A N D S U P E R L U B R I C I T Y
STUDIED USING HIGH-RESOLUTION
FRICTIONAL FORCE MICROSCOPY
AT O M I C - S C A L E F R I C T I O N
A N D S U P E R L U B R I C I T Y
STUDIED USING HIGH-RESOLUTION
FRICTIONAL FORCE MICROSCOPY
PROEFSCHRIFT
TER VERKRIJGING VAN
DE GRAAD VAN DOCTOR AAN DE UNIVERSITEIT LEIDEN,
OP GEZAG VAN DE RECTOR MAGNIFICUS DR. D.D. BREIMER,
HOOGLERAAR IN DE FACULTEIT DER WISKUNDE EN
NATUURWETENSCHAPPEN EN DIE DER GENEESKUNDE,
VOLGENS BESLUIT VAN HET COLLEGE VOOR PROMOTIES
TE VERDEDIGEN OP DONDERDAG 13 MAART 2003
TE KLOKKE 14.15 UUR
DOOR
MARTIN DIENWIEBEL
GEBOREN TE LICH IN 1971
Promotor: Prof. dr. J.W.M. Frenken
Referent: Prof. dr. P.H. Kes
Overige leden: Prof. dr. S.P. Jarvis
dr. R. Bennewitz
dr. A. Fasolino
dr. ir. C. F. J. Flipse
Prof. dr. J. M. van Ruitenbeek
dr. ir. T. H. Oosterkamp
Cover Design: Hiroko Takei
Atomic-scale Friction and Superlubricity studied using High-Resolution Frictional
Force Microscopy
Martin Dienwiebel
ISBN 90-9016598-3
A digital version of this thesis can be downloaded from
http://www.physics.leidenuniv.nl
The work described in this thesis was performed at the FOM Institute for Atomic
and Molecular Physics (AMOLF), Kruislaan 407, 1098 SJ Amsterdam, the Kamer-
lingh Onnes Laboratory, Leiden University, Niels Bohrweg 2, 2333 CA Leiden, and
the Tokyo Institute of Technology, Department of Materials Science and Engineering,
4259 Nagatuta, Midori-Ku, Yokohama, 226, Japan. The work is part of the research
program of the Stichting voor Fundamenteel Onderzoek der Materie (FOM) and was
made possible by nancial support from the Nederlandse Organisatie voor Weten-
schappelijk Onderzoek (NWO).
This thesis is partly based on the following articles:
J.W.M. Frenken, M. Dienwiebel,J.A. Heimberg, T. Zijlstra, E. van der Drift, D.J. Spaan-
derman and E. de Kuyper, Towards the Ideal Nano-Friction Experiment, (Chapter 2),
In: Fundamentals of Tribology and Bridging the Gap between the Macro- and Mi-
cro/Nanoscales (B. Bhushan, ed.)( Nato Science Series Vol. 10, Kluwer Academic,
Dordrecht),137150 (2001).
T. Zijlstra, J.A. Heimberg, E. van der Drift, D. Glastra van Loon, M. Dienwiebel,
L.E.M. de Groot and J.W.M. Frenken, Fabrication of a novel scanning probe device
for quantitative nanotribology, (Chapter 3), Sensors and Actuators A: Physical 84,
1824 (2000).
M. Dienwiebel, J.A. Heimberg, T. Zijlstra, E. van der Drift, D.J. Spaanderman, E. de-
Kuyper and J.W.M. Frenken, A Novel Frictional Force Microscope with 3-Dimensional
Force Detection, (Chapter 4), In: Nanotribology: Critical Assessment and future Re-
search needs (S.M Hsu and Z.C. Ying, eds.)(Kluwer Academic, Boston) (2002).
M. Dienwiebel, J.A. Heimberg, T. Zijlstra, E. van der Drift, D.J. Spaanderman, E. de-
Kuyper, L. Crama, D. Glastra van Loon and J.W.M. Frenken, A High-Resolution
Frictional Force Microscope with Quantitative 3-Dimensional Sensitivity and Track-
ing,(Chapter 4), submitted to Rev. Sci. Instrum.
M. Dienwiebel, N. Pradeep, G.S. Verhoeven, J.A. Heimberg, H.W. Zandbergen and
J.W.M. Frenken, Why Graphite is a Good Solid Lubricant: an atomistic view (Chapter
5), submitted to Science.
M. Dienwiebel, N. Pradeep, G.S. Verhoeven, H.W. Zandbergen and J.W.M. Frenken,
Superlubricity of graphite (Chapter 5), submitted to Phys. Rev. B.
G.S. Verhoeven, M. Dienwiebel, and J.W.M. Frenken, A Tomlinson model for super-
lubricity of graphite (Chapter 6), submitted to Phys. Rev. B.
Other publications:
M. Kageshima, H. Jensenius, M. Dienwiebel, Y. Nakayama, H. Tokumoto, S.P. Jarvis
and T.H. Oosterkamp, Noncontact atomic force microscopy in liquid environment with
quartz tuning fork and carbon nanotube probe, Appl. Surf. Sci. 188, 440444 (2002).
Contents
1 Introduction 11
1.1 Nanotribology 12
1.1.1 Single-asperity experiments and continuum mechanics models 13
1.1.2 Friction Anisotropy 14
1.1.3 Atomic-scale friction experiments and simple atomistic models 15
1.1.4 Superlubricity 17
1.2 Scope of this thesis 19
2 The ideal nanotribology experiment 21
2.1 Introduction 22
2.2 Requirements 23
2.3 Traditional frictional force microscopy 24
2.4 Design of a novel force probe 25
3 Microfabrication of the Tribolever 33
3.1 Tribolever structure 34
3.2 Fabrication difculties 34
3.3 Fabrication process 36
3.4 Microfabrication results 39
3.5 Miniaturized Tribolever 42
3.6 Summary 43
4 Design and performance of a high-resolution frictional force microscope 45
4.1 Detection principle 46
4.2 The berhead 49
4.3 Electronics 50
4.4 Sample movement 52
4.5 Experimental setup and procedures 54
4.5.1 Calibration 54
4.5.2 Tip mounting 56
7
C O N T E N T S
4.5.3 Setup 57
4.6 Performance 59
5 Superlubricity of graphite 63
5.1 Introduction 64
5.1.1 Structure and mechanical properties of graphite 64
5.1.2 Tribological Properties 64
5.1.3 Nanotribological properties 66
5.2 Experimental 67
5.3 Results 69
5.3.1 Lateral force images 69
5.3.2 Friction versus load 72
5.3.3 Friction vs. sample rotation 77
5.3.4 A loose ake 81
5.3.5 Large-scale images on polycrystalline graphite 81
5.3.6 TEM analysis of the tip 84
5.3.7 Friction anisotropy 84
5.4 Discussion 87
5.5 Conclusions 89
6 Superlubricity in the Tomlinson model 91
6.1 Introduction 92
6.2 Model 93
6.3 Results 96
6.3.1 Symmetric contacts 96
6.3.2 Asymmetric contacts 98
6.4 Discussion 102
6.5 Conclusions 105
7 Towards the ideal friction experiment 107
7.1 Introduction 108
7.1.1 The need for ultra-high vacuum 108
7.1.2 Imaging the contact 108
7.2 Design of a miniaturized FFM for use in combination with HRTEM
or SEM 110
7.2.1 FFM/HRTEM berhead 113
8
C O N T E N T S
7.2.2 HRTEM-FFM assembly 114
7.2.3 HRTEM-FFM sample stage 115
7.3 Design of the UHV setup for FFM 116
7.3.1 UHV chamber 116
7.3.2 UHV-FFM stage 119
7.3.3 Mini-SEM 119
7.3.4 Field ion microscope 122
7.4 Summary 122
A Processing steps of the Tribolever fabrication 123
A.1 Overview 123
A.2 Processing 124
B FFM-TEM observations 129
B.1 Introduction 130
B.2 Experimental 130
B.3 Nanoscale wear of a gold surface 131
B.4 Summary 133
Summary 137
Samenvatting 139
Zusammenfassung 141
Nawoord 143
Curriculum Vitae 145
9
C O N T E N T S
10
I
Introduction

It is quite difcult to do quantitative experiments in friction, and
the laws of friction are still not analyzed very well, in spite of the enor-
mous engineering value of an accurate analysis. [...] At any rate, this
friction law is another of those semiempirical laws that are not thor-
oughly understood, and in view of all the work that has been done it is
surprising that more understanding of this phenomenon has not come
about. At present time, in fact, it is even impossible to estimate the co-
efcient of friction between two substances
R. P. Feynman, 1963 [1]
11
1. I N T R O D U C T I O N
Exactly forty years after Richard Feynman wrote his famous Lectures on Phy-
sics, the comment he made about our fundamental understanding of friction has lost
nothing of its timeliness. This is not to say that there has been no progress in the eld
of tribology and engineering. The name Tribology refers to the science and technol-
ogy of friction, lubrication and wear [2]. In every day life, this progress is illustrated
by the evolution of cars. Modern car engines do not need to be driven carefully for the
rst few thousand kilometers anymore because engine parts are machined better and
the engines are run in at the factory at optimal conditions to reduce initial wear. Also
oil change cycles have become longer over the last decades due to improved lubricants
and additives.
Over the centuries the phenomenon of friction has attracted both physicists and en-
gineers, as is beautifully illustrated in Duncan Dowsons book History of Tribol-
ogy [3], which covers the tribological progress of mankind from early prehistoric
toolmaking to the present (1997). The modern history of tribology since the indus-
trial revolution is characterized by the fact that technological advances have been
made mainly empirically in the eld of engineering. On the other hand, in the eld
of physics, for a long time friction research has lived a shadowy existence because the
processes that cause friction were considered to be too complex, thus too difcult to
measure. This has changed since the advent of new experimental techniques, such as
the frictional force microscope (FFM) [4], the surface forces apparatus (SFA) [5, 6],
and the quartz crystal microbalance (QCM) [7, 8]. Together with a fast progress in
atomic-scale surface science this has caused a renaissance of tribology on the nanome-
ter scale, or nanotribology. For the physicist, the wealth of phenomena encountered
when two surfaces slide over each other is no longer perceived to make friction inac-
cessible, and is now experienced as a great motivation.
1.1 Nanotribology
The classical friction laws, discovered by Leonardo da Vinci [9, 10] and rediscovered
by Guillaume Amontons [11] and Charles Augustin Coulomb [12], state that the fric-
tion force F
F
is proportional to the normal load F
N
and independent of the sliding
speed and the contact area of the sliding bodies i.e.,
F
F
= F
N
. (1.1)
is a proportionality factor that is commonly known as the coefcient of fric-
12
1.1 N A N O T R I B O L O G Y
tion. That the true contact area is a very small percentage of the apparent contact area
was recognized much later by Bowden and Tabor [13]. When two macroscopic bodies
are brought into contact, the roughness of their surfaces leads to the creation of a large
number of microcontacts or asperities. For the case of dry, wearless sliding, Bowden
and Tabor proposed that the friction force is directly proportional to the real area of
contact A,
F
F
= A, (1.2)
where is the shear strength of the contact. For randomly rough surfaces, A
increases proportional with normal load [14], in which case the classical friction law
is recovered from equation 1.2.
The nanotribology approach to the fundamental processes of friction is to cre-
ate and investigate a single model asperity, with the idea that the behavior on a macro-
scopic scale naturally emerges from the statistical combination of the single-asperity
behavior. Such a prototype asperity can be the tip of an FFM touching a surface or the
contact formed in an SFA. The FFM is a variation of the well-known atomic force mi-
croscope [15], which makes use of a sharp tip, that is attached to a exible cantilever.
The cantilever twists, when a lateral force acts on the tip. The degree of twisting is usu-
ally measured with a light beam that is reecting from the cantilever (see also section
2.3). In the SFA, two curved, smooth mica sheets are brought into contact in a crossed
cylinder geometry. The friction force between the two sheets is measured by detecting
the extension or contraction of springs, connected to one of the two mica surfaces. In
addition, the contact area and separation can be measured by shining white light across
the contact and detecting the fringes of equal chromatic order (FECO) resulting from
multiple beam interference.
Several monographs have been published on nanotribology, of which we would like
to mention particularly the book by Bo Persson [16]. Also several review articles have
been published, which give a good overview over recent experimental and theoreti-
cal progress in nanotribology [1723]. In the following, we will briey review a few
selected studies to illustrate interesting new phenomena found in nanometer scale fric-
tion experiments.
1.1.1 Single-asperity experiments and continuum mechanics models
For a single asperity experiment, the friction force usually does not scale linearly with
the normal load, but follows a F
F
F
n
N
relation,where n < 1. A number of continuum
13
mechanics theories exist that describe the elastic deformation of two bodies under
load. The rst contact theory, which was formulated in 1881 by Heinrich Hertz [24],
describes the contact area of two elastic spheres with radii R
1
and R
2
. In the Hertz ap-
proximation the contact area scales with the normal load as F
1/3
N
and the friction force
scales as F
2/3
N
. The Johnson-Kendall-Roberts model (JKR) [25] also takes adhesive
forces inside the contact into account. The result is, that the friction force is non-zero
already at zero normal load. The Derjaguin-Muller-Toporov (DMT) model [26, 27]
includes not only adhesive forces but also attractive forces between those regions of
the two surfaces that are close to but outside of the contact. The Maugis-Dugdale (M-
D) theory [28] is a generalization of the above theories and includes the ingredients
of the Hertz, JKR and DMT models. All above models scale with the normal load
as F
2/3
N
. In FFM experiments, nearly all types of behavior have been observed exper-
imentally; JKR for a Pt tip sliding over mica [29], DMT for a tungsten carbide tip
sliding over diamond [30] and M-D for a silicon tip sliding over NbSe
2
[31]. In SFA
experiments, JKR behavior is commonly observed [32]. Recently, different friction
laws have been found by Wenning et al. [33] using a molecular dynamics (MD) simu-
lation. They observed F
F
F
0.63
N
for amorphous contacts and a linear dependence for
incommensurate and commensurate, crystalline contacts. A F
F
F
0.85
N
dependence
was found for incommensurate, boundary lubricated contacts, but was not regarded to
be universal.
1.1.2 Friction Anisotropy
Another interesting phenomenon, observed in single asperity experiments, is that of
friction anisotropy, where the friction depends on the sliding direction of the asper-
ity over the substrate lattice. Some authors use this term also for changes in friction
as a function of commensurability [34]. In this thesis, we will use the term friction
anisotropy strictly for the variation of friction with respect to the sliding direction and
not for a variation in the friction as function of commensurability (see section 1.1.4).
Bluhm et al. [35] observed that the frictional contrast on a triglycine sulfate (TGS)
surface depends on the sliding direction. The variation in friction was caused by an
alternating tilt of TGS molecules in two domains of the substrate. Overney et al. [36]
and others [3739] observed friction anisotropy on organic bilayer lms, caused by
different molecular alignments in the substrate as in the case of TGS. An extreme case
of anisotropy was reported by Sheehan and Lieber [40]. They observed that MoO
3
islands on a MoS
2
surface, that were manipulated using the tip of a FFM, could only
14
Figure 1.1: Two simple one-dimensional atomistic models. In the single-atom Tomlinson
model (a) an atom or a point-like tip, that is connected to a moving support by a spring with
stiffness k, is pulled through a periodic potential with periodicity a and corrugation V
0
. The sup-
port position is denoted with x
m
and the position of the atom with x
t
. In the Frenkel-Kontorova
model (b), the moving top solid is modelled by atoms that are connected by springs with stiffness
k. The springs are separated by a distance p and the periodicity of the potential is denoted with
q.
be moved along low-index directions of the substrate.
1.1.3 Atomic-scale friction experiments and simple atomistic models
The rst experiment that revealed atomic resolution of lateral forces was performed
by Mate et al. [4] using the tungsten tip of a modied scanning tunnelling micro-
scope (STM) sliding over a graphite surface. In this measurement, a saw-tooth pattern
in the lateral force with the lattice periodicity of the graphite surface was observed,
which could be explained by a stick-slip motion of the tip. Stick-slip motion was later
observed on many other materials, such as e.g. mica [41], MoS
2
[42], copper [43],
diamond [44, 45], and alkaline-halides (NaF, NaCl, KF, KCl, KBr) [4648].
Two simple ball and spring models are often used to analytically model atomic-
15
Figure 1.2: The Aubry transition in the Tomlinson model. The lateral force F
lat
= k(x
t

x
m
) vs. x
m
is plotted for < 1 (a), = 1 (b) and > 1. In panel (c) the dashed line shows
the inaccessible solution of equation 1.3, the solid lines show the physically meaningful paths
probed by an atom sliding from left to right and from right to left. The area in between the two
solid lines corresponds to the dissipated energy in one cycle (left-right plus right-left).
scale friction between two crystalline bodies. In the Tomlinson model [49], one atom
or a point-like tip is coupled by a spring to a moving support. This represents the slid-
ing top solid. The bottom solid is treated as a xed periodic potential energy surface
(g. 1.1a). In a second version of the Tomlinson model, the single atom is replaced
by an innite number of atoms, each connected by a separate spring to the support.
In the Frenkel-Kontorova (F-K) model the atoms are coupled to their neighbor atoms
by springs, and the coupling to other atoms in the top sliding surface (g. 1.1b) is
neglected. The simplest version is the one-dimensional static Tomlinson model of a
point-like contact (g. 1.1a). If the potential energy surface of the substrate has a sin-
gle Fourier component with amplitude V
0
, we can write the total force as
2
a
V
0
sin(
2
a
x
t
) = k(x
t
x
m
) (1.3)
where a is the periodicity of the potential energy surface and k is the stiffness
of the spring. x
t
and x
m
denote the tip and the support positions.
The relative strength of the spring with respect to the potential amplitude is
often characterized by a dimensionless parameter 2V
0
/ka. For a weak surface
potential and a stiff spring ( < 1) the upper solid slides continuously over the lower
surface and the average friction force is zero [50]. When exceeds unity, multiple
solutions exist to equation 1.3. The atom or the tip of the upper surface is sticking
at a metastable minimum position until the spring force is large enough to make the
atom rapidly slip to the next (meta)stable minimum. This leads to the stick-slip mo-
tion, which is commonly observed in FFM experiments and stick-slip motion, in turn,
16
implies energy dissipation. The transition to the onset of friction at = 1, due to the
breaking of analyticity, is called an Aubry transition [51]. Note, that this approach
implies the instantaneous, complete, and irretrievable dissipation involved in each slip
event. The Aubry transition is also observed in the one-dimensional F-Kmodel [51,52]
but static friction and the transition depend strongly on the ratio p/q of the lattice con-
stants of the top and bottom solid.
Consoli et al. showed, in the framework of an incommensurate dynamic F-K model
[53], that the onset of friction also depends on the velocity of the sliding chain of
atoms.
In the kinetic Tomlinson model, also the momentum and the damping are con-
sidered, leading to the following equation of motion
m x
t
x
t
k(x
t
x
m
) +
2
a
V
0
sin(
2
a
x
t
) = 0, (1.4)
where m is the effective mass of the sliding object and a phenomenological damping
factor. The values of m, k and determine the motion of the system immediately after
each slip event. When the system is not overdamped or critically damped ( =
2km),
each slip event will be followed by a damped oscillation. This situation even can result
in jumps over multiple lattice spacings if the spring is soft [54].
Gnecco et al. [55] have introduced a static Tomlinson model that includes the thermal
energy of the tip. This model predicts that the friction force increases logarithmically
with sliding velocity. The model also predicts a critical velocity v
c
at which the fric-
tion force becomes velocity independent [23]. The logarithmical dependence of the
friction force has been observed experimentally on the atomic scale for a silicon tip
sliding on NaCl [55].
In order to model lateral force maps measured with FFMs, Gyalog et al. [56] have
used a two-dimensional Tomlinson model. Similar models have been used later by
others [5760] to explain lateral force maps. Depending on the employed spring con-
stants, the atom in general will not only move in the pulling direction but also in the
perpendicular direction, leading to zig-zag stick-slip motion, which has been ob-
served experimentally, e.g. by Fujisawa et al. [61, 62] using a 2D-FFM.
1.1.4 Superlubricity
The term superlubricity was introduced in 1993 by Hirano and Shinjo [63]. It de-
scribes the effect that friction can vanish almost completely even when two crystalline
17
surfaces slide over each other in dry contact without wear. This was rst shown in a
quasistatic calculation by Hirano and Shinjo [64] for rigid crystals with fcc, bcc and
hcp symmetry and different orientations. In a later study they used a F-K model to
study the transition from kinetic friction to superlubricity in one and two dimensions.
In the one-dimensional case they found an Aubry transition from static friction to a
superlubric regime for a small interaction strength P and a high stiffness k of the upper
surface. This is equivalent to the Aubry transition at =1 in the one-dimensional F-K
and Tomlinson model. In the two-dimensional case they observed that the superlu-
bric regime can be reached for a much wider range of values of and they noted that
superlubricity should appear for any combination of at and clean metals when the
interaction potential is weak. They concluded that a way to tune the interaction poten-
tial experimentally, is to change the commensurability between the two surfaces.
This notion was conrmed by Srensen et al. [65] who studied the friction between a
at copper asperity and a copper surface in an MD simulation at T = 0. For the case
of a (111) terminated asperity sliding over a Cu(111) surface, atomic-scale stick-slip
motion was observed, when the two lattices were in perfect registry. When the asper-
ity was rotated 16.1
out of registry, the friction force vanished. However, for small

asperities, containing 55 atoms, an Aubry transition was observed at a positive nor-
mal load and a small friction force was observed. For larger asperities, containing
1919 atoms, superlubricity was observed also for the highest normal loads used in
the simulation. For a (100) terminated asperity that was sliding over a Cu(100) surface,
Srensen et al. observed adhesive wear and transfer of Cu atoms from the asperity to
the substrate. The wear was caused by slip along the {111}-planes inside the asperity,
leading to the creation of a dislocation network.
In search of experimental evidence for superlubricity, Hirano et al. [34] showed that
frictional forces between mica sheets in contact in an SFA experiment were maximal
when the orientation of the mica sheets matched. Friction forces were a factor 4 lower
when the crystallographic directions of mica sheets were misoriented relative to each
other. In a consecutive experiment, Hirano et al. [66] claimed the observation of su-
perlubricity between a tungsten tip and a Si(001) in a scanning tunnelling microscope
(STM) experiment (see also section 5.4). Ko and Gellman measured the friction force
as function of the mist angle between two Ni(100) crystal surfaces using a UHV tri-
bometer [67]. They found a lower friction coefcient for 45
and 135
mist angles
than for other orientations, which was consistent with superlubricity. However, these
orientational variations were still observed even after adsorption of up to 20 mono-
18
1.2 S C O P E O F T H I S T H E S I S
layers of ethanol or sulfur. Therefore they concluded that the low friction in certain
directions was caused by easy shearing along the preferred slip planes in the bulk.
This explanation is consistent with the results found by Srensen [65], who concluded
that superlubricity between fcc metal surfaces should only be expected between (111)
surfaces. Recently, Falvo et al. [68, 69] manipulated carbon nanotubes (CNTs) on a
graphite surface using the tip of a FFM. They observed that the CNTs changed from
sliding to rolling motion, depending on the lattice mismatch between the tube and the
substrate. The rolling motion of the CNT in the case of a commensurate contact was
found to require a higher lateral force than the sliding motion of the CNT in the case
of an incommensurate contact.
Finally, we note that the concept of superlubricity only takes into account en-
ergy dissipation due to excitation of phonons. Other dissipative processes, such as
electronic friction or quantum friction [70], will not depend on the degree of
commensurability. Therefore even in the case of complete, phononic superlubricity,
the total friction force will not be identical to zero. The similarity of the term su-
perlubricity with similar terms such as superconductivity and superuidity is
therefore misleading. Nonetheless, under appropriate conditions, superlubricity might
cause a reduction of the friction force by two orders of magnitude or more.
1.2 Scope of this thesis
The objective of this thesis is to describe the development and performance of a new
instrument, with which quantitative measurements of friction processes can be per-
formed at the atomic and nanometer scale. As a rst application of our frictional force
microscope, we revisited the atomic scale friction of a tungsten tip sliding over a
graphite surface. To our surprise, the results show a strong signature of superlubricity,
which sheds new light on the extremely low friction forces found on graphite surfaces.
The outline of this thesis is as follows. In chapter 2, we formulate a list of require-
ments that serves as a roadmap for the development of a dedicated frictional force
microscope. We further present the design of a new friction force sensor that enables
one to simultaneously measure forces in three directions with very high sensitivity.
Chapter 3 describes the microfabrication of this novel force sensor. The complete fab-
rication recipe of the sensor is provided in appendix A. In chapter 4, we present
the design and performance of the complete FFM, that makes use of the special force
19
sensor. This rst version of the microscope operates in ambient conditions. In chapter
5 we present friction measurements on the atomic scale between two graphite sur-
faces. We show that the ultra-low friction forces found using the ambient version of
our FFM is caused by superlubricity. The data, shown in chapter 5 is further analyzed
in chapter 6, where we make use of a static Tomlinson model to describe the friction
between a thin sheet of graphite and a graphite substrate. A miniaturized version of
the FFM, that can be operated inside a transmission electron microscope (TEM), is
presented in chapter 7. A preliminary friction measurement inside a high-resolution
TEM is described briey in appendix B. In addition, chapter 7 introduces the design of
the ultra-high vacuum setup, which makes use of the miniaturized FFM. This second
version of the FFM will be combined with additional microcopy techniques, such as
eld ion microscopy (FIM) and scanning electron microscopy (SEM), to allow full
characterization and control of the sliding contact.
20
II
The ideal nanotribology experiment

In this chapter, we present a list of fundamental questions that
are at present of importance in nanotribology. The ideal nanofriction
experiment should be able to address these questions and demands a
number of technical specications to be met, which are not available
using commercial frictional force microscopes and force sensors. Based
on the technical specications we present the design of a novel force
sensor.
21
2. T H E I D E A L N A N O T R I B O L O G Y E X P E R I M E N T
2.1 Introduction
Although the eld of nanotribology has produced tremendous insight into energy dis-
sipation processes at the atomic scale, friction coefcients measured in nanotribolog-
ical experiments and macroscopic tribo-testing differ often by orders of magnitude.
Because of this, the usefulness of atomic-scale frictional force microscopy (FFM) ex-
periments is currently being debated [71]. Therefore, we should begin by considering
which FFM experiments need to be carried out, in order to establish the link with
macroscopic friction; in the framework of tribology, the interesting regime is certainly
not that of a single-atom contact, but rather that of contact areas ranging from a few
atoms to a few million atoms. The ideal experiment would be one in which we
record all three components of the force between two extended surfaces in which we
know and control where all the atoms are.
Some of the fundamental questions that can be addressed with such an exper-
iment are: (1) How does the friction force build up when the distance between the
surfaces is decreased? At which distance do we experience the onset of friction?
(2) How does the friction force depend on the contact area? (3) How does the fric-
tion force depend on the materials? Of course, the simplest model experiment would
be one in which the two surfaces in contact consist of the same material. Certain
unlubricated material couples are known to form sliding contacts that provide good
tribological properties, while other combinations lead to high friction coefcients and
excessive wear. The fundamental processes that cause these different behaviors still
lie in the dark. (4) How does the friction force depend on the relative crystallographic
orientation of the two surfaces? Single-atom contacts exhibit pronounced atomic-scale
stick-slip sliding motion. When two rigid lattices are sheared with the lattices rotated
out of registry, there should be a signicant cancellation of the individual contributions
to the friction force, leading to superlubricity. Of course, for larger contacts, this naive
picture should break down, as the two lattices are not perfectly rigid, and a network of
mist dislocations forms between the two. It is important to nd out whether superlu-
bricity exists, how it develops when the contact is made larger than just a few atoms,
and how it disappears when the contact area is increased further. (5) How does the
friction force in a multi-atom contact depend on contact pressure? (6) How does the
friction force depend on the sliding direction with respect to the crystal orientations
of the two surfaces? (7) How does the friction force depend on temperature? (8) How
22
2.2 R E Q U I R E M E N T S
does a (model) lubricant change the friction force? (9) How and why does the friction
force depend on sliding speed? (10) How and why does a contact age?
With quantitative experimental answers to these questions for ideal, fully controlled
contacts, very detailed comparisons can be made with microscopic theories and com-
puter simulations, in search for the energy dissipation mechanisms relevant on differ-
ent length scales.
2.2 Requirements
Based on the above ideas we can directly formulate the requirements that our ideal
instrument must meet: (1) First, we want to measure the lateral force in the sliding di-
rection as well as the component perpendicular to this direction with equal, and high
sensitivity. (2) The force sensing device should be stiff enough to withstand the high
force gradients normal to the contact, which otherwise lead to snap-to-contact. (3)
Next, we want full control over the contact area. In traditional FFMs, the contact area
is determined by the initial radius of the tip and the deformations caused by the forces
between the two surfaces (loading and adhesion forces). In our ideal experiment, we
want to control the contact area and the loading force independently. This means that
we need to go beyond the usual hemispherical tip shape. The tip should end in an
atomically at plane, i.e. a crystal facet, with a controllable radius. Here, it is of ut-
most importance that the two surfaces are well characterized and clean. (4) The facet,
formed by the end face of the tip, has to be oriented precisely parallel to the crystal
surface with which it is to be brought in contact. (5) To complicate matters further, we
want control over the precise crystallographic orientations of the two surfaces. This
means that we have to specify not only the crystallographic orientations of the surface
normal of the tip and the countersurface, but also their azimuthal orientations. (6) The
sliding direction has to be adjustable, independently of the azimuthal orientations of
tip and countersurface. (7) Of course, we want to have full freedom in the choice of the
materials of the two surfaces. (8) Measurements should be possible as a function of
temperature. (9) Finally, the instrument should allow us to add controlled overlayers
(model lubricants) on each of the two surfaces.
23
Figure 2.1: Model of a rectangular AFM cantilever. The motion of the cantilever is detected by
measuring the position of a light beam that is reected from the back side of the cantilever. Us-
ing a four-quadrant photodetector, normal motion and torsional motion can be simultaneously
monitored.
2.3 Traditional frictional force microscopy
Different techniques have been developed to detect the deection of an atomic force
microscope (AFM) cantilever. One of the most successful and widely used techniques
is optical beam deection, developed by Meyer and Amer [72]. In this method, an
optical beam is reected from the rear side of a cantilever onto a split photodiode (g.
2.1). Using a four-quadrant photodiode, vertical motion (normal to the surface) and
torsional motion of the cantilever can be simultaneously detected. The image obtained
by monitoring the vertical deection is commonly called the topographic AFM im-
age, while the image obtained by tracking the torsional motion of the cantilever has
come to be known as the FFM image.
Navely, this dual force measurement is trivial to implement but great difculty comes
24
2.4 D E S I G N O F A N O V E L F O R C E P R O B E
in performing quantitative measurements and in analyzing the data [57, 73, 74]. The
spring constants of AFM cantilevers are commonly deduced from their dimensions.
For the simplest case of a rectangular cantilever the spring constants in the x, z and
torsional directions can be calculated using classical mechanics textbook equations,
k
z
=
Ew
4
t
3
L
3
(2.1)
k
x
=
Et
4
w
3
L
3
(2.2)
k
=
Gwt
3
3La
2
. (2.3)
Here, E and G are the Youngs and the shear moduli, w, t and L are the width, thick-
ness, and length of the cantilever and a is the tip height, respectively. For widely used
V-shaped cantilevers the relations for the spring constants are more complicated [73].
The ratio between the torsional and normal spring constants can be on the order of
100, resulting in a relatively small frictional force signal. There is signicant coupling
between the normal and torsional responses of AFM cantilevers, making it difcult to
distinguish buckling from bending [75]. Small misalignments of the system produce
large errors in the FFM measurements. A true calibration of the cantilevers response
in the lateral direction is rarely performed and usually does not take into account the
dependence of the force signals on the location of the beam spot on the cantilever, and
on the precise tip position on the cantilever [74]. For cantilevers that are relatively stiff
in the lateral direction, the exibility of the tip, typically several tens of N/m, adds ex-
tra uncertainty to the total response of the system. Furthermore it is known, that high
values of the proportional and integral gain of the feedback loop inuence the mea-
sured lateral force to a great extent [76]. As we see, these traditional force probes fail
to meet several of the essential requirements that we formulated above. Our efforts to
build a new experimental setup therefore started by nding or constructing a suitable
force probe.
2.4 Design of a novel force probe
In the last 10 years, serious efforts have been made to produce force probes with
better lateral sensitivity. Using rectangular cantilevers as a starting point, a simple
way to improve the lateral sensitivity would be, to turn them simply by 90
and to
use cantilevers with a small width and a large thickness. This would result in reduced
25
Figure 2.2: Two examples of complex structures that have been designed for lateral force
detection. (a) shows a meandering structure that was designed to have low spring constants in
the x-, y- and z-directions. Reprinted from [77] c 1992, with permission from Elsevier Science.
(b) shows a cantilever that consist of a combination of rectangular beams for lateral force
detection and a V-shaped cantilever for normal force detection. Piezoresistive readout is used
to monitor the cantilevers deection. Reprinted with permission from T. Kenny [78]. c 1998,
American Institute of Physics.
spring constants in one lateral direction and a high spring constant in the z direction
(equations 2.1 and 2.2). This approach was has been pushed to the extreme by Stowe
et al. [79]. Using a cantilever that was oriented perpendicular to the surface, they could
achieve a lateral force resolution of 5.6 attonewtons (5.6 10
18
N/
Hz). The lateral

spring constant of this cantilever (k
lateral
= 6.5 10
6
N/m, k
normal
> 1000N/m) was
so low that the cantilever would snap into contact 60nm away from the surface, when
it would have been mounted parallel to the sample surface. In a geometry, where the
cantilever is mounted parallel to the surface, the width of a cantilever is limited by
the size of the tip and optical detection of the cantilevers deection is not feasible
because the cantilevers endpoint is very close to the sample unless the spot size of the
light beamis smaller than the height of the cantilver. Piezoresistive detection, however,
would be possible (gure 2.2) but is usually about an order of magnitude less sensitive
26
than optical detection.
A more practical approach is to modify commercial cantilevers using focused
ion beam (FIB) methods [80]. It has been demonstrated, that by cutting a hinge into a
rectangular cantilever, the lateral spring constant in the x-direction could be reduced
by roughly an order of magnitude to 118N/m. However, the normal spring constant
was reduced as well, to 16.4N/m.
By cutting a more complex H-shape into a rectangular cantilever, a lateral spring
constant of 20N/m was obtained with a normal stiffness of 126N/m [80]. The draw-
back of the FIB method is, that it can be used only to modify single cantilevers one by
one, so that reproducible results are difcult to obtain. In addition, modifying a single
cantilever is extremely time consuming. Cantilevers with more complex geometries,
that were optimized to measure lateral forces with higher sensitivity, have been fabri-
cated using lithography and micromachining techniques [77, 78, 81, 82]. For example,
Buser et al. have designed a meandering cantilever with low spring constants in the
X-, Y-, and Z-direction.
In spite of the improvements, none of the above designs provides low and symmetric
spring constants in both lateral directions x and y, in combination with a normal stiff-
ness in z.
To obtain symmetric spring constants, the geometry of the force probe should
of course be symmetric in the X- and Y-directions. Ideally, one would like to place
four equal springs around the scanning tip of the cantilever as depicted in gure 2.3a.
This cannot be achieved by using four straight rectangular beams as the springs,
as this structure would be completely inexible. Therefore we introduced a 90
bend
in each beam to provide the required exibility in the lateral plane (g. 2.3b). As
we discussed above, it is not trivial to measure the displacement of the cantilever
in the plane parallel to the sample surface by optical means. Therefore we placed a
detection pyramid at the center of the cantilever. Using this pyramid as a set of four
mirrors, we can detect the displacement of the pyramid with the use of four glass-ber
interferometers, which are placed symmetrically around the pyramid, under an angle
with the plane of the sample surface. This is the basic design of our new force probe
(gure 2.4) that we called the Tribolever
1
In order to test the principle of our new design and to choose suitable dimen-
sions of the four legs for a sensor made out of silicon, we have used nite element
1. Tribolever R is a registered trademark of Interface Physics Group, Leiden University.
27
Figure 2.3: Design of a cantilever that is symmetric in two lateral directions (X and Y). The
idea is to place four equal springs around a central scanning tip (a). Using rectangular legs
with a 90
bend we precisely create such a symmetric geometry. By choosing high aspect ratio
legs, we can create a device with lowlateral spring constants but with high normal and torsional
spring constants (b).
analysis (FEA) [83].
Figure 2.5a shows the calculated spring constants as a function of the width of
the four legs. For the FEA we used legs with lenght L = 450m and height t = 10m
(for comparison with the thickness of simple beam cantilevers we will denote the
height with t). We used the following material properties for silicon: Youngs modulus,
E = 1.69 10
11
N/m
2
, Poissons ratio s = 0.333 and density = 2330kg/m
3
. For our
ideal experiment the lateral spring constants should be signicantly lower than the
normal spring constants, which means that the width of the legs should stay well below
the cross-over point in gure 2.5a , which for 10m-high legs, is 7.4m. The smallest
width that can be achieved by our microfabrication methods is about 1m (for details
see chapter 3). This forms a lower limit for the lateral spring constants of 0.3N/m.
Figure 2.5b shows a FEA calculation as a function of the thickness, while the width
was kept constant at 5m. The microfabrication process allows a maximum height of
about 2025m, which would lead to a normal spring constant in the order of a few
hundreds to one thousand N/m.
Table 2.6 shows a comparison of our calculated results to those of a traditional
AFM diving board cantilever. The Tribolever data in this table were calculated for
the actual dimensions of our prototype sensor of w = 1.4m and t = 10.6m Si legs,
which will be discussed later. The torsional spring constant (
) for AFM cantilevers

governs the lateral response for a traditional FFM, as discussed earlier.
28
Figure 2.4: Model of the Tribolever used in the nite element analysis. Lateral and normal
forces acting on the scanning tip are measured via the displacement of the central pyramid,
which is detected by four laser interferometers reecting from the pyramids faces. The leg
geometry has been optimized to be sensitive for lateral forces while providing relatively high
normal and torsional stiffness. Panel (a) shows the back side of the Tribolever with the detection
pyramid pointing up. Also shown are the four glass bers that are guiding light on the pyramid
and collecting the reected light. Panel (b) shows a zoom-in at the central part of the front side
with a scanning tip pointing up.
Calculated lateral spring constants k
x
= k
y
for Tribolevers are signicantly lower
than those for simple beams. It is important to note that although the lateral spring
constant (k
y
), which causes buckling of AFM cantilevers, is small compared to
,
this component of the lateral force is extremely difcult to extract from the verti-
cal response and is therefore usually not measured in traditional AFMs. In addition
to making the spring constants ideal for frictional force microscopy, the Tribolever
design also minimizes the coupling between the three orthogonal directions. The cou-
pling of the the lateral response on vertical motion is in the order of 10
5
%. This
is due to the torque introduced by the scanning tip. Besides the leg geometry, other
considerations have played an important role in the overall design. For example, at the
front side of the central detection block (gure 2.4b) the tip is sticking out. In order to
allow measurements for a range of tip materials (requirement 7), the tip should be a
completely separate entity, to be placed at the center of the Tribolever.
The design of the Tribolever forms the rst step towards the ideal nanotribology ex-
29
Figure 2.5: (a) Spring constants of the Tribolever as function of the width of the legs for a
xed height of 10m, calculated using nite element analysis: the open circles show the values
for the lateral spring constants and square points are for the Z spring constant. The dashed
line represents a cubic t for the lateral spring constant and the solid line is a linear t for
the Z spring constant, according to equations 2.1 and 2.2 for the spring constants of a simple
rectagular beam. However, the value for the effective Youngs modulus E
e f f
= 9.33 10
12
N/m
2
30
Figure 2.5: continued obtained from the cubic t differs signicantly from the value of E for
silicon from literature, which demonstrates that the response of the Tribolever differs signi-
cantly from that of a simple beam and emphasizes the importance of the nite element analysis
prior to the microfabrication. (b) Spring constants of the Tribolever as function of the height of
the legs for a xed width of 5m.
Dimensions [m] Length, L Width, w Thickness, t Tip Height, a
simple beam cantilever 450 47 2.1 15
Tribolever 351 1.4 10.6 50
Spring constants [N/m] k
x
k
y
k
z

simple beam cantilever 4.03 101.1 0.2 71.6

Tribolever 1.48 1.48 25.8 136
Tribolever (hole joints) 0.93 0.93 25.8 136
Figure 2.6: Comparison between the mechanical characteristics of a traditional AFM can-
tilever and a Tribolever with and without hole joints. Torsional spring constants are for torques
along the x-axis. All dimensions are in m. See schematic gures for denitions of simple beam
and Tribolever dimensions. Values of silicon constants used in the calculation are Youngs
modulus, E=1.69 10
11
N/m
2
, Poissons ratio, s=0.333, and density, = 2330kg/m
3
.
periment. During the following chapters, we will stay enroute towards the ideal ex-
periment. A discussion of the silicon microfabrication of the Tribolever will be given
in chapter 3. In chapter 4 we will then describe the technical details, the operation and
performance of our ambient-condition friction force microscope that makes use of the
Tribolever. Chapter 7 introduces the design of a new ultra-high vacuum setup that will
meet all requirements that we formulated at the beginning of this chapter.
31
32
III
Microfabrication of the Tribolever

This chapter describes the fabrication process of the Tribolever.
Because of the complexity of the structure of the Tribolever device, a
special etching scheme needed to be developed, that combines different
etching techniques. The etching process development and the fabrica-
tion of a prototype were performed at the Delft Institute of Microelec-
tronics and Submicron Technology (DIMES) [84].
The chapter is organized as follows. First, we will discuss problems in
the fabrication and describe in short the process that solves these prob-
lems. Then results of the fabrication of a rst prototype are presented.
Finally, we will turn our attention to the fabrication process of a smaller,
second generation device.
33
3. M I C R O F A B R I C A T I O N O F T H E T R I B O L E V E R
Figure 3.1: Schematic drawing of the Tribolever device. The prototype chip (10mm8mm)
includes two force sensors, each with its own set of kinematic mounts.
3.1 Tribolever structure
The aim of the microfabrication described in this chapter was to produce an all-silicon
force sensor, with a shape and dimensions according to those discussed in chapter 2
(gs. 2.4 and 2.6). Furthermore, the sensor was produced with a central hole, such that
tips can be placed in the sensor relatively easily. Finally, the microfabrication also in-
cludes provisions for reliable and reproducible mounting of the sensors in the friction
force microscope.
The rst prototype sensors have been realized on 1080.525mm
3
chips that each
include two Tribolevers and a set of kinematic mount structures to ensure that the chip
can be mounted in the FFM with high reproducibility (gure 3.1). The dimensions of
the prototype chip were too large for the nal UHV version of the microscope, since it
inhibited the combination of the FFMwith high-resolution electron microscopy (chap-
ter 7). Therefore in a second fabrication run the layout of the chip was changed such
that its dimensions could be greatly reduced (520.525mm
3
).
3.2 Fabrication difculties
Before describing the actual fabrication process, we briey list some of the fabrication
difculties, arising from the special shape of our force sensor. At the front side two
34
3.2 F A B R I C A T I O N D I F F I C U L T I E S
Figure 3.2: Processing scheme of the central Tribolever part: (a) pattern overview, (b)
anisotropic etch of the leg and cross pattern, (c) all-sided thermal oxidation, (d) optical ber
window etch (KOH), (e) mechanism of self aligned pyramid formation. Figures (a-d) are shown
front side up; (e) front side down.
35
anisotropic dry etching steps are required; one to dene the leg geometry and one to
create the tip hole, with etching depths of about 15m and 100m respectively. This
implies that the patterning step for the legs has to be done after the etching of the hole
structure or vice versa, giving rise to severe step coverage problems in the resist spin
coating.
A second problem is introduced by the convex structure of the pyramid at the rear
side of the cantilever. Its facets are not easily obtained from a KOH etch along 111
planes because of underetching at the corners [85]. Sacricial corner compensation
structures to retard the underetching may help [86]. However, with the pyramid height
comparable to the lateral dimension (see above), this approach has serious limitations
for the resulting facet area and the shape of the central detection body.
A third problem is that the pyramid is deeply embedded in the wafer as seen from
the rear side. This can be understood as follows. The tip must extend out from the
cantilever structure in order to interact with a sample. Hence, the front side of the can-
tilever has to be ush with one face of the 525m thick silicon wafer. With the central
detection body approximately 100m high, the top of the pyramid is recessed about
400m with respect to the rear side of the wafer. Therefore, a wide, recessed window
is needed on the rear side to allow room for the detection bers to access the pyramid
faces. As a consequence, fabrication of the pyramidal structure at the rear side would
have to be done at a depth of about 400m, which would further complicate the pro-
cessing involved.
In the following, we will show how a procedure of anisotropic dry etching of spe-
cic geometries at the front side, followed by a protective thermal oxidation and a
subsequent wet crystallographic etch at the rear side solves all of the problems listed
above.
3.3 Fabrication process
In this section we qualitatively describe the fabrication process. For a more complete
overview of the entire process, we refer to appendix A.
Starting with a Si (100) substrate, the rst step is to create alignment marker patterns
at the front and the rear side by anisotropic dry etching, 2m deep , with a 200nm ther-
mal oxide serving as the mask. The mutual alignment of front and backside marker
patterns is performed by IR detection through the wafer. All lithographic steps are
36
3.3 F A B R I C A T I O N P R O C E S S
done with photoresist (HPR) in a mask aligner (K. S uss MA 56). Oxide patterning is
done by anisotropic reactive ion etching (RIE) in a CHF
3
/O
2
plasma (25:1) in a paral-
lel plate reactor (Leybold Z401). Typical plasma conditions are 10bar gas pressure,
50sccm
1
gas ow and 0.16W/cm
2
rf power with rf bias voltage of 330V, giving an
oxide etch rate of 20 25nm/min. All anisotropic dry etching in Si is achieved in a
high density plasma setup (Alcatel DECR200) with a SF
6
/O
2
gas mixture (7.5:1), at
a substrate temperature of 95
C. Plasma process conditions are 2.3bar pressure,

25.5sccm gas ow, 750W microwave power (at 2.45GHz) and 10V substrate bias.
Si etch rates are in the order of 1m/min, with a typical slope angle of 90 3
. All
dry etch processes are monitored with in situ laser interferometry.
After stripping the oxide used for the marker step, the actual processing for the Tri-
bolever follows as depicted in gure 3.2. The wafer is thermally oxidized (1.3m
oxide thickness) and after lithography of the leg pattern and central cross patterns,
these patterns are etched anisotropically in the oxide with a CHF
3
plasma. The two
patterns are etched with different depths, the cross pattern down to the silicon and the
leg pattern somewhere halfway through the oxide thickness (gure 3.2b). The idea
is to transfer one pattern after the other into the Si substrate. In this way, the resist
step coverage problem at the front side (legs, central cross) is reduced to spin coating
of about one micron topography in the oxide mask layer. The cross pattern is etched
rst, about 85m deep into the Si. Next the leg pattern is opened down to the silicon
(with CHF
3
plasma) and the silicon etching (of leg and cross patterns) is continued for
15m. Resulting depths of cross and leg patterns are approximately 100m and 15m
respectively. The pattern quality is superior due to the extreme oxide mask selectivity
of about 1000 : 1 in the silicon etching process. This is because the ion energy can
be tuned independently from the reactive species in the high density plasma [87]. The
most decisive element in the overall fabrication process is the cross-shaped pattern in
the middle at the front side, rotated 45
with respect to the central square block. The

center of the cross forms the hole for the scanning tip. In addition, the cross is used
to realize the 111 faceted pyramid, which is central to the detection system (gure
3.2c-e). After thermal oxidation of the freshly etched surfaces of both the leg and cross
patterns (gure 3.2c), the wide recessed window at the rear side of the cantilever is
made using a crystallographic wet KOH-etch through the wafer (gure 3.2d). As the
etching front from the rear side reaches the oxidized cross (gure 3.3a), the 111
facets are exposed while the corners are protected by the oxidized sidewalls (gure
1. 1sccm = 1.69 10
3
Pa m
3
/s
37
Figure 3.3: Optical (a-c) and scanning electron micrographs (d) of the KOH etching process:
(a) At t = 3h22 the etching front passes halfway through the oxidized cross and part of the
pyramid becomes visible; (b) at t = 4h the etching front reaches the leg pattern; (c) at t = 4h08
the KOH etching is completed. A thin oxide layer still connects the pyramid, the legs and the
wafer; (d) SEM image of the pyramid after KOH etching, with the oxide sidewalls still present.
3.3b-d).
The pyramid with a central hole for a tip is made in a self-aligned way and in
one wet etch step. In this way, complicated fabrication on the bottom of the optical
ber window to realize a pyramid structure by convex KOH etching is avoided. The
area of the 111 facets can be precisely tuned by the etch depth difference between the
cross and leg pattern. Finally, after a nal all-sided oxide strip, the Tribolever structure
38
3.4 M I C R O F A B R I C A T I O N R E S U L T S
Figure 3.4: First prototype of the Tribolever integrated in a silicon wafer: (a) central part of
the device showing the pyramid side; (b) Tribolever with a tungsten tip glued in the central hole;
(c) zoom-in on the tungsten tip, which was mounted without damage to the tip; (d) cross-section
of the device showing (1) the optical ber window, (2) two of the three elements of the kinematic
mount.
is released and the sidewall passivation layer removed.
3.4 Microfabrication results
The rst generation of the Tribolever integrated in a Si(100) wafer is shown in gure
3.4. The Tribolever (g. 3.4a) includes the four 111 facets, the high aspect ratio legs
with a width of 1.4m, a height of 10.6m, a length of 351m and a cross-shaped
hole for the scanning tip.
39
Figure 3.4b shows a Tribolever from the front side with a metal tip tted in the
central cross. The tip shown is an electrochemically etched tungsten wire, of 50m di-
ameter, which extends approximatly 5060m out of the front side. It was positioned
into the Tribolever using micromanipulators and attached with wax (wax was used in
this rst test, in the FFM experiments the tip was attached using silver epoxy). Figure
3.4d shows a part of the Tribolever environment embedded in the Si wafer. The big
window around the Tribolever (indicated by arrow 1) is for proper access of the optic
bers as discussed earlier. The other KOH-etched windows (2) serve as a kinematic
mount for a highly reproducible t of the Tribolever chip in the FFM setup. These ad-
ditional recesses complicate the overall process scheme and require all oxide patterns
to be buried in an all-sided CVD nitride layer (300nm) before opening one pattern
after the other. The nitride serves as a mask for intermediate local thermal oxidation
of Si structures existing already, to protect them against deterioration in subsequent
etching steps.
Reduced lateral spring constants of the four legs are crucial for proper operation and
essential to these spring constants are the widths of the legs. We explored several tech-
niques to tune a given Tribolever to the right operation regime. One successful method
is to thermally oxidize the total device and stripping the oxide selectively in a buffered
HF solution in an iterative approach until the required leg thinning has been obtained
(g. 3.5a). In this way, we can reduce the leg width from 10m to 13m, but some
width variation due to rounding of corners has been observed. Another option is to
dene precise hole joints in the crucial corners of the leg construction, either with a
focused ion beam (FIB) or by lithographic means (Table 2.6). Results of both methods
are depicted in gure 3.5c-d.
The lateral accuracy of the FIB treatment (FEI 200) is around 100nm. Prelimi-
nary FIB experiments show that a single ion milling step is highly reproducible within
one cantilever structure, but is not homogeneous over the full leg height and requires
additional trimming.
Calibration (see chapter 4) of the Tribolevers shows that the spring constants k
x
and
k
y
of the prototype are 1.67N/m, close to the calculated value of 1.48N/m. The slight
difference might be due to roundings and increased thickness at the bends of the legs.
The measured k
z
= 10.32N/m is signicantly different from the calculated value of
25.8N/m. This is due to the fact that the Tribolever is positioned in the center of the
large ber window, which is only 10.6m thick (like the leg height) and acts as an
additional spring.
40
3.4 M I C R O F A B R I C A T I O N R E S U L T S
Figure 3.5: Tuning of the Tribolever to proper operation regime of the spring constants: (a)
leg thinned by thermal oxidation and stripping of the oxide in HF; (b and c) hole joints created
by focused ion beam milling; (d) hole joint by integral patterning, the inset shows the top view.
41
Figure 3.6: SEM image of the miniaturized Tribolever showing: (a) the chip, including the
Tribolever structure, the cross-shaped ber window and the kinematic mounts; (b) a close-up
view of the Tribolever through the ber window.
3.5 Miniaturized Tribolever
As mentioned before, we need a smaller device than the prototype device, for com-
bining our FFM with scanning electron microscopy (SEM) as well as transmission
electron microscopy (TEM). For the case of TEM, the dimensions of the Tribolever
are simply too large to place the FFM inside the TEM column. For the case of SEM,
the quality of the SEM images depends on the dimensions of the Tribolever. The
resolution of SEM critically depends on the working distance, which is the distance
between the objective lens of the SEM and the object that is to be imaged (the tip of
the Tribolever). Hence, by reducing one side of the Tribolever we will be able to also
reduce the working distance and obtain high-resolution images with the SEM.
The new layout contains only one Tribolever per device, which allows a bisection of
the long side of the device. A major problem in further reducing the dimensions, is
the size of the large window for the glass bers, which would form a predetermined
breaking point of the device. Since a reduction of the size of the ber window is not
possible, we rotated the ber window by 45
and with it the Tribolever. In addition,

we changed the window geometry to a cross. It is not possible to rotate the pyramid
and the kinematic mounts on the wafer, so we rotated the pattern of the device except
the Tribolever pattern on the wafer. The result of the second processing run, using the
new layout, is shown in gure 3.6. The dimensions of the miniaturized version could
be reduced to 52mm, thus making the device t in the typical gap between the pole
shoes of a high-resolution TEM column, and reducing the minimum working distance
42
3.6 S U M M A R Y
for SEM to 1mm.
3.6 Summary
We presented the fabrication process of a novel all-silicon force sensor, the Tribolever.
Difculties in the microfabrication could be solved using deep reactive ion etching
from one side of a silicon wafer and wet etching from the opposite side of the wafer.
The rst prototype device was shown to meet the requirements formulated in chapter 2
and to have properties close to the predictions that were obtained from nite element
analysis prior to the fabrication. In addition, we presented the microfabrication of
a miniaturized second generation Tribolever that can be used in combination with
transmission electron microscopy and scanning electron microscopy.
43
44
IV
Design and performance of a high-resolution frictional
force microscope

In this chapter, the construction and initial tests of a prototype
version of the friction force microscope is described. Our main objec-
tive was to develop an instrument which achieves high-resolution force
detection in three directions with the Tribolever (chapter 3). In order to
allow for quick modications, the prototype operates in ambient condi-
tions. Some of the requirements for the ideal nanotribology experi-
ment (chapter 2) are therefore not yet included. However, consideration
of these requirements and future additions played an important role in
some of the design decisions for this prototype.
45
4. D E S I G N A N D P E R F O R M A N C E O F A H I G H - R E S F F M
4.1 Detection principle
As mentioned already in chapter 2, the detection system of the Tribolever motion is
formed by four ber optic interferometers. In an optical glass ber, light is partially
reected at the endface of the ber, while most of the light is leaving the ber. By
means of an external mirror, a fraction of that light can be made to reenter the ber.
This leads to a phase difference between the two backward travelling coherent waves,
which depends on the distance between the endface and the external mirror. With
a ber coupler (the analog to a beam splitter) the backwards travelling light can be
coupled out and detected with a photodiode. The interferometers output is given by
I = I
0
_
1+Acos
_
2
2D
__
, (4.1)
where I is the output current, A is the relative interference amplitude, D is the
ber-sample distance, and is the wavelength of the laser (780nm in our case). The
offset I
0
and the amplitude A are both determined by the reectivities of the two in-
terfaces responsible for the interference signal. Taking a refractive index of n
1
= 1.5
for a well-cleaved quartz glass ber and n
2
= 1 for air, the maximum reectance of
the endface is (
n
1
n
2
n
1
+n
2
)
2
= 4%. For the pyramid surface a maximum reectance in the
order of 60% is expected. The 111 facets of the pyramid are at a well-dened angle,
= 54.74
, with respect to the (100) surface plane of the wafer.

If each of the four glassbers is adjusted such, that the light intensity increases
when the ber-pyramid distance decreases (equation 4.1), the three-dimensional dis-
placement with respect to the xed bers can be extracted from the normalized sum
and differences of the signals coming from the four interferometers [44].
These linear combinations need to be weighted by the appropriate geometrical
projection (gure 4.1):
X =
X
2
X
1
2sin
(4.2)
Y =
Y
2
Y
1
2sin
(4.3)
Z =
X
1
+X
2
+Y
1
+Y
2
4cos
(4.4)
The design of our interferometers follows closely those discussed in the litera-
ture [88, 89], with attention given to the stability of the laser diodes output intensity
46
4.1 D E T E C T I O N P R I N C I P L E
Figure 4.1: Schematic drawing depicting two of the four glass bers. If the pyramid moves
laterally (panel a), the distance X1 between the left glass ber and the pyramid increases and
the distance X2 between the right glass ber and the pyramid decreases or vice versa. If the
pyramid moves normal to the sample surface, both distances either decrease or increase. This
allows one to extract the displacements of the pyramid in the X- and Z-directions. Similarly, from
the other ber pair one obtains the displacements in the Y- and Z-directions. The displacements
are extracted from the distance changes, according to equation 4.1.
and wavelength [90]. One unique aspect of our design is that each opposing pair of
interferometers is driven by a single laser diode so that the inuence of uctuations in
laser intensity and wavelength is greatly reduced, while the remaining variations can
be divided out by use of a reference signal. A schematic of one such pair (e.g. the X
pair) is seen in Figure 4.2.
Light coming from the laser diode is rst divided over two branches using a
bidirectional 22 ber coupler. The two branches are denoted with X1 and X2, re-
spectively. A second 22 coupler in each arm completes the interferometer, by cou-
pling out the backwards travelling reected light into the photodiode detector. The
same coupler couples out 50% of the primary light into the reference signal detector.
We see no evidence for optical cross-talk between the two ber pairs. Such coupling
was not expected, as little diffuse reection occurs at the pyramid faces. As a result,
we see no change in one pair, even when the other pair is optically disconnected. In
order for the 125m diameter bers to be positioned close to the pyramid faces, they
must be tapered to a maximum endface diameter of 80m. Methods developed for
making sharp near-eld scanning microscopy tips cannot be used in our application
because they stretch the core and decrease its diameter as it is melted. This would in-
troduce spurious backreections into our interferometer. We have used both sharpened
bers with cleaved endfaces [91] and bers chemically etched using the liquid layer
47
Figure 4.2: Components of one interferometer pair. The interferometer can be divided in three
distinct sections: the laser system, the ber system and the detection system. The laser system
consists of the laser diode with integrated Faraday isolator and the controlling power supplies.
The ber system consists of couplers, connectors, adapters and the ber itself. The detection
system consists of photodiodes and supporting electronics.
48
4.2 T H E F I B E R H E A D
protection procedure [92]. In this method a sharp glass tip is etched at the interface of
the etching liquid (40% hydrouoric acid) and a protective immiscible organic uid.
The process is self-terminated when the tip is formed. The cone angle of the tips can
be varied from 8
to 41
depending on the protection uid [93]. To create a at end-

face and to remove the part of the ber core that was reduced in diameter by the HF
etch, the ber tips were rst embedded in wax and then mechanically polished using
12, 3, 1, and 0.3m aluminium oxide polishing paper for the nal polishing step [94].
The former method results in slightly stronger interference signals (presumably due
to the better endface quality by a cleave with respect to a polished endface). The latter
method routinely produces endface diameters on the order of 30m, which allows for
more exibility when positioning all four bers.
4.2 The berhead
Two versions of the the berhead were constructed. In the rst version, the bers
were xed with respect to each other. Once glued into place, the four bers could be
positioned together with respect to the pyramid using an x-y table formed by a sys-
tem of exure hinges and micrometer screws. This design had the disadvantage that
the positioning of the bers relied on a precise glueing step of the glass bers, since
misalignments of a single ber could not be corrected afterwards. In addition, the me-
chanical path between the bers and the Tribolever in this design was approximately
35cm, which caused high thermal drift between the bers and the Tribolever. The
variation in the distance between each endface and the pyramid was in the order of
1530nm/hour even though the temperature was kept constant within 0.2
C.
Because of these disadvantages, we constructed a second, much smaller ber-
head that allowed to individually mount and position each ber. The improved second
version of the berhead is shown in gure 4.3. The berhead was machined by spark-
erosion from a single block of low-thermal-expansion metal (Invar). The distance of
the endface of each ber with respect to the pyramid face is adjusted by miniature in-
ertial piezomotors ( Nanomotors R [95]), which can be driven either in discrete steps
over a maximum distance of approximately 4 mm or be adjusted continuously with
sub-
A resolution over a range of 400 nm. The rst mode allows one to retract the glass
49
Figure 4.3: Schematic drawing of the ber positioning head cut open for illustration (a) and
solid model (b). (1) Tribolever, (2) Tribolever support plate, (3) Nanomotor R , (4) exure hinge
and, (5) adjustment screws.
bers to a safe distance during an exchange of sensors, the latter is used to calibrate the
interferometer signals and to position the bers at the distance of maximumsensitivity.
Additionally, the continuous mode can be used to compensate possible drift between
the bers and the pyramid due to residual thermal expansion of the microscope (see
electronics section). The Nanomotors are mounted in miniature exure hinge springs,
which are part of the ber head. These springs allow the adjustment of each ber axis
in a plane parallel to the pyramid plane.
Different types of the Tribolever device (see chapter 3) can be clamped onto exchange-
able support plates by means of two stiff leaf springs. Three ruby spheres, glued on
the Tribolever support plate, make each Tribolever click in with its kinematic mount,
with a reproducibility of better than 10m, which is a fraction of the ber endface.
4.3 Electronics
The system electronics can be split into two main components: data acquisition and
sample motion (see g. 4.4). As discussed in section 4.1, the signal coming from each
interferometer consists of a sinusoidal interference component plus an offset, which
50
4.3 E L E C T R O N I C S
Figure 4.4: Block diagram of the microscopes electronics (again shown only for the X pair).
From the X1 and X2 signals coming from the interferometer, an adjustable fraction of the ref-
erence signal is subtracted before the rst amplication. The result is divided by the reference
signal. This procedure allows the maximum amplication of the signal while introducing the
lowest noise level. In the addition and subtraction electronics, the outputs from the X1 and X2
dividers are combined according to equations 4.1-4 in order to obtain voltages that correspond
to the true displacement of the Tribolever (X and Z). These voltages are then fed into a commer-
cial scan electronics system, which acquires the measured data and controls the sample motion
(scanning and feedback).
51
is due to the difference in reection amplitudes. In our detection electronics, we rst
subtract a fraction of the reference signal and amplify only the interference compo-
nent. The amplied signal is then divided by the reference signal to reduce the effect
of uctuations in laser diode intensity. The four resulting signals are then added and
subtracted according to equations 4.1-4 to produce the three-dimensional Tribolever
displacement information. All signals are then used as input for an RHK STM200 [96]
system with added input capabilities so that the full, three-dimensional motion of the
tip can be monitored in real time.
Although we have used materials with low thermal expansion coefcients for
the ber head components, the ber-pyramid distance drifts slowly due to temperature
variations in our non-climatized laboratory, which is typically 5
C during a day. Us-

ing home-built electronics we apply slow voltage ramps to the Nanomotors, to keep
the ber-pyramid distance constant for several hours without additional temperature
stabilization of the microscopes chamber.
4.4 Sample movement
The sample, with maximum lateral dimensions of 10 10mm
2
, sits on a piezo scan
tube [97], which rests inside a set of nested inertial piezo motors that allow for four-
dimensional motion of the sample with respect to the tip: X, Y, Z and rotation ().
The scan piezo tube is directly coupled to the Z coarse approach motor. The Z
motor is located in the center of a X-Y- motor. The Z and XY motors are similar
to those discussed in the literature [98]. The nested design is new, therefore it will be
described in more detail. The X-Y- motor consists of a sapphire disk of 100mm di-
ameter, which is clamped between three pairs of piezo stacks using CuBe leaf springs
(Figure 4.5) .
Each of the stacks contains 3 shear piezoplates. (see gure 4.6). Two plates are
used for the X and Y motion [99], the third one (77 mm) is oriented tangetially for
the motion .
The sapphire disk slides on a thin polished Al
2
O
3
plate, which is glued on the
piezo stack (gure 4.6). For the electrical connections of the piezo plates copper beryl-
lium foil [100] is used, which is glued on the shear plates using two-component silver
epoxy glue [101]. Special care is taken regarding the amount of glue used and the
52
4.4 S A M P L E M O V E M E N T
Figure 4.5: The sample stage. (a) perspective drawing of the X-Y- motor showing: (1) CuBe
leaf springs; (2) motor house; (3) v-grooves of the kinematic mount for the berhead; (4) sap-
phire disk; (5) z coarse approach motor; (6) upper piezo support plate. (b) cut open view of
the z-motor showing (7) sapphire hexagon; (8) z-motor house; (9) shear piezos; (10) CuBe leaf
spring; (11) ruby ball.
53
Figure 4.6: Exploded view of one piezo stack. Figure (a) shows a side view of the stack.
Figure (b) shows a top view of the piezo stack parts:(1) polished Al
2
O
3
-plate (2) Y-electrode
(CuBe-foil) (3) Y-shear piezo plate (4) Ground electrode (5) X-shear piezo (6) X-electrode (7)
Al
2
O
3
-plate (insulation) (8) -electrode (9) -shear piezo.
mixing of the two components of the glue. Non-ideal mixing of the epoxy can lead
to elasticity in the stack, which degrades the motors performance or can even cause
failure of the motor. Therefore, the amount of the two components of the epoxy is
weighed with highest care using a micro balance with a resolution of 0.01 mg. A thin
layer of glue is then applied on both piezo electrodes as well as on the electrodes us-
ing an optical microscope at 63 magnication. A hole in the center of the electrodes
provides room for excess glue (g. 4.6). The two piezos are afterwards clamped in a
special holder and the glue is annealed at 150
C for one hour.

We use commercial electronics from Omicron to drive the piezos with a sawtooth-
shape waveform at a frequency of 1kHz [102]. We reach a maximum speed of 600
m/s in X- and Y-direction, and 0.5
/s for rotation. The smallest step size in the Z-

direction is approximately 30nm, in the X- and Y-directions it is 45nm.
4.5 Experimental setup and procedures
4.5.1 Calibration
One of the extreme advantages of the Tribolever is that it allows easy, yet very precise
calibration. We routinely calibrate each Tribolever prior to its rst use. By exciting
the Tribolever acoustically with a loudspeaker, which is placed close to the berhead,
frequencies of the resonances in the X-, Y- and Z-directions can be measured. Small
Sodalime glass beads [103] are placed on the central cross of the pyramid before a tip
is mounted inside the central cross. The diameters of the beads are determined using
54
4.5 E X P E R I M E N T A L S E T U P A N D P R O C E D U R E S
Figure 4.7: Calibration data for one Tribolever using the added mass method. Plots of the
added mass versus frequency of the resonance peak (a) for the X-direction, (b) for the Y-
direction, and (c) for the Z-direction. (d) Typical resonance spectrum of the microscope and
the Tribolever without added mass in the X-direction (solid line) and in the Y-direction (dashed
line).
a scanning electron microscope (SEM) prior to the calibration. The masses are then
calculated from the diameter, and are ranging from 1.57g to 9.01g. By measuring
the resonance frequencies as a function of the added mass, extremely accurate values
of the Tribolevers lateral and vertical spring constants are determined [104].
Figure 4.7 is an example of one such calibration run. This calibration procedure
has no effect on the Tribolever because the sphere is held in place by gravity on the
central cross of the Tribolever (i.e. no glue is needed). Calibration of the lateral (tor-
sional) spring constant on traditional AFM cantilevers is more time consuming, more
complex, and signicantly less accurate [105].
Measured lateral spring constants in this example (gure 4.7) are k
X
= (1.670.03)N/m
and k
Y
= (1.67 0.04) N/m. These two spring constants are virtually identical and
they are close to the value of 1.48N/m calculated from the dimensions of the legs
55
of the Tribolever using nite element analysis. The measured vertical spring constant
for the Tribolever is k
Z
= (10.3 0.1) N/m as compared to the calculated value of
25.8N/m. The large deviation is due to the additional exibility of a thin diaphragm
(2mm2mm10.6m), which supports the Tribolever on the silicon chip. This dia-
phragm is the result of a wet etch step that forms a wide, recessed window to allow
room for the detection bers access to the pyramid. In the new design of the Tri-
bolever device the geometry of the window was changed to overcome this problem
(Chapter 3) .
We also used the resonance spectra of the Tribolever to estimate the noise levels
of the optical detection and the electronics. With a spectrum analyzer, we measured
the thermally excited X- and Y- resonances of a Tribolever with lateral spring con-
stants of 5.75N/m. The amplitude of the resonant motion can be calculated by the
equipartition theorem
1
2
k
x
x
2
rms
=
1
2
k
B
T, where x
rms
is the root mean-square thermal
motion amplitude, k
B
is the Boltzmann constant and T is the temperature. If the elec-
tronic instrument noise is much smaller than the thermal motion of the sensor, the root
mean square voltage noise V
rms
at the resonance frequency is given by the relation
V
rms
= x
rms
=
_
k
B
T/k
x
[106]. is a known calibration factor that relates the output
voltage to the displacement of the Tribolever. We compared the measured V
rms
with
the calculated value of V
rms
at the thermal limit. We found that the detected noise in
the frequency range of the lateral resonances (9.38 kHz) is a factor of 1.9 (X1) to 4.8
(Y2) higher than the thermal noise. In a FFM measurement, the noise levels are cer-
tainly different. Typical signal frequencies are lower (below 23kHz) and the tip is in
contact with a surface. However, the measured noise levels provide a good indication
that the detection is operating close to the thermal limit, which is conrmed by test
measurements on a graphite sample (see next section).
The differences in the noise levels between X and Y might be due to specic details
of the interferometer branches (especially the quality of connectors and of the endface
of each ber). We assume that the signal to noise ratio can be further improved by
coating the ber endfaces with a metal layer to increase the reectance of the ber/air
interface (see section 4.1).
4.5.2 Tip mounting
After the calibration is performed, a specimen has to be mounted in the center of the
Tribolever that provides the counter surface that will slide over the sample surface.
In most cases this specimen will be a sharp tip as it is used in scanning probe ex-
56
4.5 E X P E R I M E N T A L S E T U P A N D P R O C E D U R E S
periments, but we also used small coated balls to create a ball-on-at geometry. It
would be also possible to create other interesting geometries, like e.g attaching a small
at or bent crystal to the Tribolever and perform experiments similar to surface forces
apparatus (SFA) experiments.
In our rst tests of the microscope, we use a sharp tungsten tip. The tip is electrochem-
ically etched with NaOH from a 50m thick tungsten wire. After the tip is formed,
the wire has to be shortened to a length of about 200m using a scalpel. Then the
tip is carefully picked up and transferred to the arm of a homebuilt micromanipulator,
which is constructed from a three-axis stage [107]. The arm consists of a 1mm thick
wire, which is etched to a sharp point at the end. The scanning tip is held at the arm of
the micromanipulator by adhesion. Therefore, the material of the arm has to be chosen
such that it provides sufcient adhesion force to allow the tip to be manipulated but a
sufciently low adhesion force such that the tip cannot be released inside the center
cross of the Tribolever. For the case of tungsten tips, tungsten was found to work well
as arm material.
When the tip is hanging downwards with the sharp end, the tip is lowererd from the
pyramid side through the center of the cross of the Tribolever and then released from
the micromanipulator. Then, the Tribolever is carefully turned around, such that the
tip is pointing up. The tip is held in place at that point again by adhesion forces, so
that it can be carefully adjusted before it is nally glued to the pyramid. The micro-
manipulator arm is used again to bring a small amount of silver epoxy to the sides of
the tip. After this procedure the epoxy is annealed.
4.5.3 Setup
After the sample holder is mounted on the scan piezo tube, the berhead is placed
on the sample stage. Three stainless steel balls, which are connected to the matching
plate of the berhead rest in the V-grooves of the sample stage (gure 4.5, item 3).
The complete microscope assembly is shown in gure 4.8. The microscope is built
up inside a small chamber [108], which damps acoustical noise. In addition, the at-
mosphere inside the chamber can be controlled by owing e.g. dry nitrogen through
it. The relative humidity is monitored using a humidity/temperature meter [109] with
an accuracy of 2%. If we ow dry nitrogen through the chamber, we can achieve a
relative humidity below 1%. The microscope chamber is mounted on an optical table,
which is resting on a vibration isolation frame [110].
57
Figure 4.8: (a) Perspective drawing of the microscope assembly. (b) Side view with (1) Fiber
positioning head, (2) X-Y- motor, (3) z-coarse approach motor, (4) kinematic mount between
the motor/sample stage and the ber positioning head.
58
4.6 P E R F O R M A N C E
4.6 Performance
For a rst testing of the instrument and the complex data acquisition we used a ca-
libration sample with a regular structure of known dimensions [111]. The employed
sample is a glass substrate that has parallel aluminium ridges with a period of 2781
nm and a height exceeding 30nm.
Figures 4.9(a)-4.9(c) show topography and friction images that were recorded
simultaneously at a constant normal load of 0.85nN. The topography image shows
parallel ridges although some piezo creep and hysteresis is observed. The height of
the ridges is 33nm. The lateral force images show high frictional forces on top of the
aluminium stripes both in X- and Y-direction plus an additional lateral force, where
the tip ran against the stripes. A plot of a scan line in the forward and one in the
backward direction of image 4.10b shows a typical friction loop (g. 4.10d).
To estimate the force resolution of our microscope we used a highly oriented
pyrolytic graphite (HOPG) sample. Figures 4.10(a-e) show forward and backward
friction maps in X- and Y-direction of a 3nm3nm wide area measured at a normal
load of 35.8nN. Here, the X-axis of the piezo was aligned with the X-axis of the Tri-
bolever. However, the measurement was performed in a scan direction, which was not
aligned along either the X- or the Y-direction of the Tribolever, and atomic scale varia-
tions in the friction force could be observed in two directions. The friction loops show
a sawtooth-like signal, measured in the X-direction of the Tribolever (g. 4.10c) and
a square-wave-like signal for the Y-direction (g. 4.10f). From these signals it can
be deduced that the tip follows a zig-zag trajectory on the graphite lattice [112]. It is
important to note that the lateral forces measured with our new microscope are much
lower than in previous studies (e.g. [4]). From the noise in the X- and Y-channels dur-
ing the friction measurements, we estimate that the lateral force resolution (rms) in the
measurement is 15pN in the X-direction and 41pN in the Y-direction. The topography
image (not shown) does not show any structure (the corrugation amplitude of 0.21

A
rms is due to noise), although the feedback system had been set for constant normal
force. This implies that the topography and friction signals are completely decoupled.
59
Figure 4.9: Simultaneously measured topography and lateral force images of a TDG01 cali-
bration sample. (a) Topography (feedback) image. The grey scale corresponds to a height range
of 39.8nm; (b) lateral force image in the X-direction. The grey scale corresponds to 115nN; (c)
lateral force image in the Y-direction. The grey scale corresponds to 258nN; (d) Friction loop
formed by a forward (solid) and backward (dashed) scan line measured in the X-direction. The
image size is 1.5m1.5m and the constant normal force is F
N
= 0.85nN.
60
4.6 P E R F O R M A N C E
Figure 4.10: Lateral force maps for a W-tip on HOPG moving in the X-direction. Lateral
forces in the X-direction: (a) Forward scan. The grey scale corresponds to 1.4nN; (b) Backward
scan; grey scale: 1.5nN; (c) friction loop.
61
Figure 4.10: continued (e) Lateral forces in the perpendicular Y-direction: (d) Forward scan;
grey scale: 222pN; Backward scan; grey scale: 243pN; (f) friction loop. All images were mea-
sured simultaneously with F
N
=35.8nN; Image size 3nm3nm
62
V
Superlubricity of graphite

Graphite is known to be a good solid lubricant. The low-friction
behavior is traditionally ascribed to the low resistance to shear. In this
chapter we show that the ultra-low friction found in friction force mi-
croscopy experiments on graphite is caused by superlubricity and we
speculate about the signicance of this for the lubricating properties of
graphite.
63
5. S U P E R L U B R I C I T Y O F G R A P H I T E
5.1 Introduction
Graphite is one of the four allotropic forms of carbon found in nature; the other three
forms are amorphous carbon, diamond, and most recently discovered, fullerenes. The
word graphite is derived from the greek word (graphein: to write).
Graphite is found in natural form in lenses or layers as lump or crystalline ake, de-
pending on the geological origin. Synthetic or pyrolytic graphite is produced by ther-
mal decomposition of a hydrocarbon gas over a hot substrate. The world production
of graphite in 2001 was estimated to be 873000t with China accounting for 52% of
the overall production [113].
5.1.1 Structure and mechanical properties of graphite
A ball and stick model of the crystal structure of graphite is depicted in gure 5.1. It
can be viewed as a layered structure with three-fold symmetry. The elastic properties
are highly anisotropic, being very different in the direction of the basal planes and
perpendicular to the planes, which makes graphite exible but not elastic. The in-
plane Youngs modulus of pyrolytic graphite is 1.02TPa [114]. This is more than two
times higher than the Youngs modulus of typical metals (e.g. tungsten has a Youngs
modulus of 411GPa). Perpendicular to the basal planes, the elastic modulus is only
36.5GPa.
5.1.2 Tribological Properties
Graphite is undoubtedly the most common solid lubricant. Mainly used as aky pow-
der, it is applied for this purpose where liquid lubricants cannot be used, especially
in high-temperature applications. It is further used as friction-reducing additive in oils
and solid materials ranging from cast-irons to plastics. Graphite is also used as bush-
ings, brushes in electrical motors, and for face seals.
It is not surprising that the research on the tribological properties of graphite has a
long history and it is well established that the friction coefcient for many materials
against graphite in ambient conditions is in the range of 0.08 0.18 (see e.g. [115]).
In 1928 Bragg argued, based on crystal x-ray structure determinations, why graphite
possesses a low friction coefcient [116]:
64
5.1 I N T R O D U C T I O N
Figure 5.1: Ball and stick model of the graphite structure. Graphite possesses a layered struc-
ture with AB stacking. The cell parameters are a = 0.2464nm, c = 0.6711nm. The nearest
neighbor distance between carbon atoms is 0.1423nm.
Graphite is a aky substance; when beaten in a mortar it breaks up con-
tinually into thinner and thinner akes, but it does not become a powder.
[...] Two neighbours in any one layer are drawn together more closely
than two carbon atoms in diamond. But the great distance between layer
and layer is naturally associated with weakness in their mutual attrac-
tion. It is just this peculiarity that makes graphite so perfect a lubricant.
20 years later, the intuitive idea of easy shear was shown to be incomplete and
unsatisfactory. Finch [117] pointed out, that the cleavage by simultaneous rupture of
bonds in a plane requires very high energy, which is supported by the fact that graphite
does not shear readily, unless a high compression is superimposed [115]. Savage and
others [118120] found that the friction coefcient for graphite in vacuum was much
higher (0.8) and that the wear was very heavy. The high friction was still observed
after admission of hydrogen or nitrogen. After admission of a few ppm of oxygen
65
or certain organic vapors, low friction and wear was restored. It has been shown that
when metal is sliding on graphite in air, graphite is transferred to the metal surface,
while in vacuum metal is transferred to the graphite surface [121]. Moreover it has
been shown, that a metal oxide layer tends to x the transferred graphite to the metal,
leading to a smooth transfer lm [122]. These observations strongly suggest that the
low friction is only obtained when graphite slides over graphite.
5.1.3 Nanotribological properties
The rst atomic-scale friction experiment was performed by Mate et al. [4] using a
tungsten tip sliding over a highly ordered pyrolytic graphite (HOPG) surface. They
found friction coefcients between 0.005 and 0.015. Unlike FFM experiments on
other materials, where usually a power law behavior is found, the dependence of the
friction force as a function of the load was found to be almost linear. Similar friction
coefcients and friction versus load behavior were observed also in subsequent FFM
experiments with a variety of tip materials. Table 5.1 gives an (incomplete) overview.
Tip material Normal force range [nN] Friction coefcient Ref.
Tungsten 02000 0.0050.015 [4]
Amorphous carbon 040 0.0080.005 [123]
Si
3
N
4
N/A 0.006 [124]
Si
3
N
4
30350 0.0010.01 [125]
Si
3
N
4
3020 0.0040.001 [126]
Table 5.1: Comparison of the friction coefcient of HOPG found in previous FFM experi-
ments.
FFM experiments also revealed that the scanning tip in FFM experiments on
graphite performs a so-called stick-slip movement, where the tip jumps discontin-
uously over single lattice spacings. Fujisawa et al. [61] have shown, using a two-
dimensional FFM, that lateral force images can be explained by two-dimensional, i.e.
zig-zag atomic-scale stick-slip movement. A simple classical mechanics model [49]
(see also chapters 1 and 6), the so-called Tomlinson model, where a single-atom tip is
moved along in a sinusoidal potential, reproduced the experimental lateral force maps
of the graphite surface quite well [58, 60]. However, the normal forces that were used
in the simulations had to be chosen one to two orders of magnitude lower than in the
experiments [127].
66
5.2 E X P E R I M E N T A L
5.2 Experimental
We performed measurements on HOPG samples with two different grades. Initial
measurements have been performed on grade ZYH, which has a nominal grain size in
the range of 3040nm and a mosaic spread of 3.5
1.5
according to the supplier.

However, on our particular sample we found only larger grains. Later measurements
were done on grade ZYA, which possesses a lateral grain size of up to 10mm and a
mosaic spread of 0.4
0.1
. The samples were cut to a size of 2mm2mm. There-

fore, the grade ZYA sample consisted probably of a single graphite crystal, while
the grade ZYH sample was polycrystalline. The HOPG was freshly cleaved using
Scotch tape and then mounted in the FFM inside a small chamber, which was con-
tinuously ushed with dry nitrogen. The measurements were typically performed at
humidities of 1101% RH. We used a calibrated Tribolever with lateral spring con-
stants of k
Tribolever
x,y
= 5.750.15N/m and a normal spring constant of 261N/m. A
tungsten tip was glued into the Tribolever using silver epoxy [101], such that it ex-
tended about 50 to 60m out of the device. The scanning speed in the experiments
was v = 30nm/s. All force maps were recorded in the form of two-dimensional im-
ages with 512512pixels.
We performed two different types of measurements. In the case of lateral force
imaging, the external normal load F
N
was set to a constant value using the feedback
loop of the scan electronics. Zero normal load was dened as the load at which the
Tribolever was not bent in the normal direction. When the tip was scanned over the
surface, we recorded the lateral forces in the two perpendicular directions dened by
the X- and the Y-axes of the Tribolever, both during the forward and during the re-
verse scan lines. Other than with a conventional AFM cantilever, with the Tribolever
it is possible to choose any sliding direction in the measurement. The lateral force was
dened as the lateral spring constant times the lateral displacement of the Tribolever
pyramid with respect to the FFM base: F
lat
X,Y
= k
X,Y
x
Tribolever
X,Y
. In general, the X di-
rection of the Tribolever and the fast scanning direction (which is the X direction
in a lateral force image) will be rotated with respect to each other. Therefore in the
following we denote X and Y as the directions of the Tribolever axes and x and y as
the scan axes of the lateral force image. By changing the sliding direction, also the
angle between the x direction and the lattice orientation changes.
One forward scan line and the subsequent reverse scan line together form a
67
Figure 5.2: Lateral force image of a tungsten tip on HOPG at F
N
=3.2nN. The tip is sliding
in the x direction, which is aligned with one symmetry direction of the surface. Lateral forces
in the X direction (a) Forward scan. Grey scale: 1.7nN, (b) Backward scan. Grey scale: 1.9nN.
Lateral forces in the Y direction (c) Forward scan. Grey scale: 93pN, (d) Backward scan. Grey
scale: 102pN. Image size 3nm 3nm.
68
5.3 R E S U L T S
closed hysteresis loop, that is often referred to as the friction loop. An example
of such a friction loop is shown in gure 5.3a. The area that is enclosed inside the
friction loop corresponds to the dissipated energy during the back and forth sliding. We
calculated the average friction force in the X and in the Y direction of the Tribolever
by taking the difference of the mean value of the lateral force in the forward direction
and in the reverse direction:
F
F
X,Y

_
F
lat
f wd
F
lat
rev
2
_
. (5.1)
Here, we also dene the friction force against the sliding direction as a positive
quantity. The mean value of the lateral force F
lat
was only obtained from those parts
of the friction loop where the lateral force had fully developed, e.g for x> 0.7nm in
the forward scan line and for x< 2.3nm in the reverse line.
To obtain the friction force in the sliding direction, we computed the appropriate
vector addition of the friction forces in the X- and the Y-direction:
F
F
= F
F
X
cos+F
F
Y
sin, (5.2)
where denotes the angle between the X direction of the Tribolever and the sliding
direction of the tip (x).
The second type of measurement that we performed is referred to in the litera-
ture to as friction force spectroscopy [128]. Here, we initially set the normal force
F
N
to a positive value and lowered it during scanning until the tip lost contact with
the surface. From a single line, one (F
N
, F
F
X
, F
F
Y
) data point was obtained using equa-
tion 5.1, for each value of F
N
. Together, the scan lines resulted in a friction spectrum
F
F
(F
N
).
5.3 Results
5.3.1 Lateral force images
Figure 5.2 shows typical lateral force images measured simultaneously in the X-
direction of the Tribolever (a,b) and in the direction perpendicular to that (c,d) on
the polycrystalline HOPG surface. The x- and X-directions were aligned. Not shown
is the topography image (Z), which does not reveal any surface features. The rms
roughness of 0.27

A, measured from the topography image is caused only by the noise
69
Figure 5.3: Comparison between an experimental friction loops and a force loop calculated
using a Tomlinson model for a single-atom tip (for details see chapter 6). The calculation was
performed using a potential energy amplitude of V
0
= 0.08eV and lateral spring constants
k
x
= k
y
= 2.65N/m.
in the measurement. As has been shown in several experiments [4, 61, 62, 123], the
lateral force in the sliding direction exhibits typical sawtooth waveform, which can be
explained by atomic-scale stick-slip motion. Depending on the sliding direction, the
lateral force image in the perpendicular direction shows different patterns. If the slid-
ing direction is parallel to one of the six symmetry directions of the HOPG surface,
the lateral force measured perpendicular to the sliding direction shows a horizontal
stripe pattern (Fig. 5.2 c,d). If the tip is scanned under a different angle, the patterns
in the X- and the Y-images change. A second example is shown in Figure 4.10, where
the Y-image exhibits a checkerboard-like pattern. There, the tip performs a zig-zag
stick-slip movement over the graphite lattice, and the forces in the sliding direction
cannot be regarded independently from those in the perpendicular direction.
Figure 5.3 shows a comparison between a friction force loop, that was obtained
from one forward and one reverse scan line of gure 5.2 and a friction loop, obtained
from a Tomlinson model calculation (chapter 6). The comparison shows good qualita-
tive agreement between the experimental and the calculated friction loops, suggesting
that our measurements can be understood using a two-dimensional Tomlinson model.
However, to obtain quantitative agreement between the force magnitudes in the
calculated and experimental force loops, we had to use a lateral spring constant in the
70
5.3 R E S U L T S
calculation which differed from the known k
Tribolever
.
This suggests that also the elastic compliance of the contact contributes to the
total spring constant. The effective spring constant can be obtained directly from the
slope those parts of the measured force loops where the contact sticks [31, 129]. To
understand this, one can view the measurement system as a set of springs in series.
The effective spring constant is constituted of
dF
lat
X
dx
=
_
_
k
Tribolever
x
_
1
+
_
k
contact
x
_
1
_
1
, (5.3)
where k
Tribolever
x
is the known spring constant of the Tribolever and k
contact
x
is called
contact stiffness [31]. This contact stiffness can be separated further in
k
contact
x
=
_
_
k
add
x
_
1
+
_
k
inter f ace
x
_
1
_
1
, (5.4)
where k
inter f ace
x
=
2
V/x
2
=
_
2
a
_
2
V
0
is the spring formed by the local curvature in
the wells of the potential energy landscape of the substrate as experienced by the tip,
and k
add
x
is the spring formed by additional elastic compliances such as the elastic
compliance of the tip and that of the sample. Since we cannot distinguish between the
compliances introduced by the tip and those introduced by the surface, we will take
these together.
From equation 5.3 we nd a contact stiffness in gure 5.3a of 2.30.3N/m. Be-
cause the curvature of a corrugated potential energy landscape acts also in the Tomlin-
son model as a spring that contributes to the contact stiffness, also the calculated fric-
tion loop possesses an effective stiffness that differs from k
Tribolever
, but since k
add
x
=
in the model, we simply have k
contact
x
= k
inter f ace
x
=
_
2
a
_
2
V
0
in the model calculation.
From the force at which the slip events take place, we obtain the amplitude of the
potential to be 0.08eV. For the potential corrugation of V
0
= 0.08eV, the potential
spring constant is k
inter f ace
x
= 15.9N/m. This k
inter f ace
x
also contributes to the experi-
mentally found contact stiffness, so that we can now estimate the additional stiffness
to be k
add
x
= 2.7 N/m. We nd indeed good agreement between the experimental force
loops and the calculated one, if we use 2.7N/m in the calculation. The precise origin
of the additional elastic compliance cannot be determined from these measurements.
Aclear difference between the simulated friction loop and the experimental one,
is that the positions where the slip occurs in the experimental data display variations
71
in the order of 25 % of the lattice spacing. In the parts of the friction loop where the tip
is sticking, the lateral force uctuations are much too small to account for these vari-
ations. This is clearly seen also in all lateral force force images, which look noisy,
despite good lateral force resolution. We believe that these uctuations, which can be
seen also in other FFM experiments with comparable effective spring constants and
normal loads (e.g. [55]), are thermally induced. Using a modied Tomlinson model
that included a term representing the effect of random thermal uctuations, Sang et
al. [130] recently studied thermal effects on atomic friction. With an effective spring
constant of k
e f f
= 0.86N/m to t the data from Gnecco et al. [55], they found that
the distribution function of the maximum lateral force in the friction trace, which is
equivalent to the slip position, had a full width at half maximum (FWHM) of approx-
imately 17 %.
In order to evaluate thermal uctuations in our experiment, we simulated them in the
Tomlinson model calculations using a simple Monte-Carlo approach. At every time
step t, where t is x
t
/v, we calculated the transition rate , which is an inverse
measure of the time needed before a thermally induced jump over the energy barrier
takes place,
= f
0
exp
_
V(x
t
)
k
B
T
_
, (5.5)
where f
0
is the eigen frequency of the Tribolever, V(x
t
) is the remaining energy
barrier with respect to the momentary tip position, k
B
is the Boltzmann constant and
T is the temperature. The probability t for a thermally induced jump over the
barrier was then compared with a number R [0, 1] obtained from a random number
generator and, if R was lower than t, a jump at position x
t
was induced.
Figure 5.4 shows the normalized distribution for 15000 simulated slip events
using k
x,y
= 2.68N/m, V
0
= 0.08eV, v = 30nm/s and an effective mass of the Tri-
bolever of 10g. The distribution possesses a FWHM of 33pm, which is 13.5% of the
graphite unit cell. In addition, the jumps occurred on average 38pm before the static
case, recover in the Tomlinson model at T = 0.
5.3.2 Friction versus load
Figures 5.5a-f show three lateral force maps and friction loops measured in the for-
ward X-direction at different normal loads. Again, the x-direction was aligned with
the X-direction of the Tribolever. Figures 5.5g-i display the average waveform of the
lateral force variations over one lattice period. Already at a negative load of 3.4nN,
72
5.3 R E S U L T S
Figure 5.4: Normalized distribution of the slip position at temperature T = 293K. The origin
of the x-axis lies at the slip position of x
t
without thermal uctuations. The calculation was
performed using V
0
= 0.08eV and k
x,y
= 2.65N/m.
variations in the lateral force with lattice periodicity are faintly visible. However, these
variations do not have a sawtooth shape, typical for stick-slip motion but a cycloid
shape (g. 5.5g). At this normal force, the area enclosed inside one friction loop (g.
5.5d) is very small. In other words, the energy dissipated during one sliding cycle is
nearly negligible. Correspondingly, the average friction force obtained from the com-
plete lateral force map, according to the procedure described in section 5.2 (eq. 5.1)
is as low as 1.8
+16
1.8
pN. At a higher normal load of 11.6nN, the variations in the lat-
eral force increased, and the lattice can be seen more clearly in the force map, but
the average friction force did not increase signicantly, as can be seen from the force
loop in gure 5.5e. This is surprising, because increasing the normal load by about
15nN is usually expected to lead to an increased contact area and thus, to an increase
in the friction force. Note, that the waveform of the lateral force variations changed
and appears sawtooth shaped (g. 5.5h). At a still higher normal load of 41nN we
73
Figure 5.5: Lateral force images in the forward X direction (a-c) and force loops (d-f) for
different normal loads; (a) F
N
= 3.4nN, (b) F
N
= 11.6nN, (c) F
N
= 42.6nN; Image size
3nm3nm. Graphs (g-i) showthe typical waveformobtained fromthe forward scan lines shown
in (d-f) by averaging over three lattice spacings.
observed clearly sawtooth shaped lateral force variations (g. 5.5i) and an increase
in the average friction force to 6219pN, (g 5.5f).
Complete friction versus load curves were obtained from friction force spec-
troscopy measurements (see sect. 5.2 for precise procedure). Figure 5.6a shows an
example for a contact that behaved similarly to the one shown in gure 5.5. The nor-
mal force was reduced from 45nN until the tip lost contact with the surface at 24nN,
74
5.3 R E S U L T S
Figure 5.6: Friction force versus normal load curves for two different contacts. Notice that in
both curves the friction force varies little, but the average friction force in (b) is about a factor
of 16 higher than in (a).
at which point the tip was fully retracted by the feedback electronics. The data in g-
ure 5.6a are representative for a large number of measurements. In the normal force
range from 24 to approximately +30nN the friction force stays almost constant at
a very low value of 28 16pN. The frictional behavior as a function of normal load
obtained from the friction force spectroscopy experiment shown in gure 5.6a is in
agreement with the friction forces obtained from individual lateral force images at
different, constant normal loads. As in gure 5.5, we see very low energy dissipation
up to about F
N
= 40nN. For normal loads above 40nN we observe a slight increase.
To our surprise, a smaller number of measurements produced entirely different fric-
tion versus load curves. An example is shown in gure 5.6b. The curve was measured
under similar conditions as the one in gure 5.5a. Now, the friction force between 11
and +24nN normal load is on average 453 16pN, which is a factor 16 higher than
in the measurement shown in 5.6a. The friction force remained at a high and almost
constant level until the tip lost contact at F
N
= 16nN. In these high-friction mea-
surements, the typical increase in friction between loads of 0 and 25 nN was as low
as 0.050.4%. Each friction versus load measurement on the polycrystalline HOPG
surface resulted in a curve of one of the two types shown in gure 5.5, but with dif-
ferent precise values of the average friction force. The measured friction force curves
switched back and forth between the two types (gs. 5.5a and b) randomly in intervals
75
ranging from days to several weeks. Subsequent measurements that were performed
within a short period of several hours were highly reproducible. The switching in the
average friction force could not be attributed to changes in the ambient conditions
such as the humidity inside the FFM chamber, since we did not observe systematic
changes in friction when we varied the humidity from 9 to 42%RH during one experi-
ment. Also, no systematic differences were found between the friction force on freshly
cleaved HOPG and HOPG surfaces that had been exposed to ambient conditions for
several days.
These results raise several important questions. First, why does the friction force
remain almost unchanged over a wide range of normal forces? For other substrates,
FFM measurements usually show a substantial dependence, which, for modest loads,
can be attributed to the elastic variation in the contact area with the load (e.g. [74]).
Secondly, what is the nature of the difference between the two completely different
friction versus load curves? Thirdly, what is responsible for the switching between the
two different states of the contact? Trivial tip changes can be ruled out directly, since
all experiments were performed using the same tip. Finally, what is the mechanism,
that allows the tip to slide with near-zero friction, even at a normal load as high as
30nN? It has been pointed out by Tom anek et al. [50] that it is possible to obtain fric-
tionless sliding in the framework of the Tomlinson model when a single-atom tip is
moving over the surface without instabilities, i.e. without the familiar stick-slip mo-
tion. This can occur when the tip is moving through a potential energy landscape with
a corrugation amplitude that is small with respect to the stiffness of the measurement
system (see chapter 1). However, in our case, this would require a spectacularly low
potential corrugation and an unrealistically high yield strength of the tip to remain a
single-atom contact at a normal load of 30nN.
One single mechanism that could provide a natural answer to all four questions
is that of superlubricity, which was introduced already in chapter 1. Superlubricity
has been proposed to cause two parallel surfaces to slide over each other without
energy dissipation when they are in incommensurate contact [63, 64]. Although this
phenomenon has been proposed already in 1990, it has found little attention, in spite
of the promise that it can dramatically reduce friction in dry, unlubricated contacts,
which would make it highly relevant for a wide variety of applications, such as e.g.
nanoelectromechanical systems (NEMS).
76
5.3 R E S U L T S
In the light of superlubricity, the difference between the high- and low-friction force
loops can be the result of a difference in commensurability, the high friction corre-
sponding to a fully commensurate contact and the low friction to an incommensurate
contact. The large variation in commensurability strongly suggests that the sliding has
been taking place between two graphite surfaces, one being the HOPG substrate, and
the other being a small piece of graphite, i.e. a graphite ake, that is attached to the
tungsten tip. A ake introduces a at surface parallel to the graphite substrate from
which it originates, a geometry needed for superlubricity to occur. Depending on the
degree of commensurability between the lattice of the substrate and that of the ake,
the friction would be high, as in gure 5.6b, when the ake and the substrate are in reg-
istry, or close to zero, as in gure 5.6a, when they are out of registry. The presence of a
ake would also explain the almost complete absence of a dependence of the friction
on the normal load. Load-independent friction has also been observed in FFM ex-
periments on thermally oxidized MoS
2
, and it was proposed that MoO
3
nanocrystals,
that grew during the oxidation process on the MoS
2
surface [131], acted as a spacer
between the tip and the sample, such that the contact area remained unchanged upon
loading. In the present case, the contact area would be completely determined by the
ake size, which would be independent of the loading force. Hence, the friction would
only increase slightly with normal load as the result of the increase in contact pres-
sure. Finally, the seemingly random selection of either low or high friction states can
be explained easily by the slow drift of the FFM or the irreproducibility of the mount-
ing procedure of the HOPG sample holder after cleaving. This results in a change of
the measurement location from one grain of the ZYH-quality polycrystalline HOPG
substrate to the next, differently oriented grain. We will return to this point in section
5.3.5.
5.3.3 Friction vs. sample rotation
In order to obtain further evidence for our interpretation, we rotated the graphite sam-
ple in small steps with respect to the tip, using the -motor of our FFM. Because the
-motor does not rotate perfectly concentrically around the tip, the tip did not stay on
the same area of the sample during rotation. Therefore, we used a single crystalline
HOPG sample (ZYA-grade) to make sure that the lattice orientation of the sample
would not change because the tip would land on a different grain after a few rotational
steps. For each orientation, we performed a complete friction force spectroscopy mea-
surement for loading forces between +25nN and pull-off (22nN). We recorded the
77
Figure 5.7: Lateral force images (forward direction) and friction loops measured in the X-
direction at 60
(a), 72
(b) and 38
(c) rotation angle . Normal force (a) and (c) F

N
= 18nN;
(e) F
N
= 30.1nN; grey scale (a) 590pN (c) 270pN (e) 265pN; Image size 3nm 3nm.
78
5.3 R E S U L T S
lateral forces in the X- and the Y-direction and calculated the average friction force in
the sliding direction of the tip according to equations 5.1 and 5.2.
Figure 5.7 shows lateral force maps and force loops measured in the X-direction
for different rotational orientations. Note that the X- and x-direction are not aligned
here, because the scan piezo rotates together with the sample. A typical force loop is
shown in gure 5.7b, which was measured at a normal force of 18nN. The lateral force
in Fig. 5.7b displays clearly resolved atomic-scale stick-slip sliding and the average
friction force parallel to the sliding direction is 203.320pN. Figures 5.7c,d and e,f
show FFM measurements measured with the graphite substrate rotated +12 and 22
degrees around an axis normal to the surface, and parallel to the tip. The rotation by
12
has caused the average friction force to reduce by more than one order of mag-
nitude, to 15 15pN. Rotating 22
away from the rst measurement in the opposite

direction also has caused a reduction to 8
+16
8
pN, which is equal to zero friction within
the detection limit of our instrument. This variation of the friction force with angle
was completely reversible. Notice that the ultra-low lateral forces in gures 5.7c-f still
exhibit regular variations with the periodicity of the graphite substrate.
Figure 5.8 displays the average friction forces measured over a 100
range of
substrate rotation angles. We recognize two narrow angular regions with high friction,
separated by a wide angular interval with nearly zero friction. The distance between
the two friction peaks is 612
, which corresponds well with the 60
symmetry of in-
dividual atomic layers in the graphite lattice. This result corresponds precisely with the
expectation within the scenario of superlubricity. After every 60
rotation, the lattices

of the substrate and the graphite ake align and the friction is high. For intermediate
angles, the lattices are incommensurate and the friction force is close to zero.
The maximum friction forces of the two peaks were found to differ by 103pN. This
possibly reects the fact that due the AB stacking, graphite does not really possess
a 60
symmetry but rather a 120
symmetry, which should have an inuence in case

the ake is more than one layer thick. Unfortunately, we could not measure a third
peak in the present experiment, so that we have not been able to test this hypothesis
experimentally.
We can use the peak width in gure 5.8 to estimate the ake diameter. As an illus-
tration, a single-atom tip should show high friction for all orientations, while an in-
nitely large contact would be completely superlubric, except for innitely narrow
79
Figure 5.8: Average friction force versus rotation angle of the graphite sample around an
axis normal to the sample surface. Two narrow peaks of high friction were observed at 0 and 61
degrees, respectively. Between these peaks a wide angular range with ultra-low friction close
the detection limit of the instrument was found. The rst peak has a maximum friction force of
30640 pN, and the second peak has a maximum of 20320 pN. The curve through the data
points shows results from a Tomlinson model for a symmetric 96-atom ake (see chapter 6).
angular ranges around perfect registry, if we assume that no energy can be dissipated
via elastic deformations within the contact. For nite-size contacts, the cancellation of
lateral forces, which causes superlubricity, can be considered complete when the mis-
match between the two lattices adds up to one lattice spacing over the diameter of the
contact. The mismatch condition provides us with the estimate that tan() = 1/D,
where is the full width at half maximum of the friction peak, and D is the ake
diameter, expressed in lattice spacings. From the widths of the two peaks in gure
5.8, of 5.41.0
for the rst peak and 6.50.8
for the second, we estimate that the

ake diameter is between 7 and 12 lattice spacings. How good this estimate is, will
be demonstrated in chapter 6, where we compare the experimental data with a series
of results obtained from a modied Tomlinson model calculation in which we moved
various rigid graphite akes, connected to the Tribolever springs, in a rigid hexagonal
potential, reecting the periodicity of the graphite surface. The solid curve in gure
80
5.3 R E S U L T S
5.8 is the calculation for a symmetric 96-atom ake (diameter of 11 atomic spacings).
It provides an excellent t to the experimental friction data.
We have to mention here that reproducible measurements, such as those in g-
ure 5.8, in which the same relative orientations always led to the same friction loops,
were rare, the xed-ake situation occurring as the exception, rather than the rule.
More often, results were obtained of the type described in the next section.
5.3.4 A loose ake
Figure 5.9 shows two lateral force maps, measured in the X-direction, before (a) and
after (b) a deliberate, modest misalignment by less than 2
of an initially aligned
contact. While the friction force in gure 5.9a is as high as 550 21pN (see also
g. 5.9c), the friction force in the upper part of gure 5.9b is reduced to 27 16pN
(see also g. 5.9d). In the course of a few scan lines, the friction force gradually
restores back to about 431 17 pN (g. 5.9e) and at the last scanline of gure 5.9b
the friction is as high as in gure 5.9a. We interpret these events as the effect of the
torque exerted by the surface on a nearly aligned ake, which was attached to the
tungsten tip sufciently loosely to rotate back into registry. During the restoration of
the high friction force the lateral force exhibited irregular sharp peaks, which might
have been caused by the dynamic process of reorientation of the ake.
5.3.5 Large-scale images on polycrystalline graphite
The effect of a change in commensurability between a ake and the surface was also
observed on the polycrystalline graphite sample. In section 5.3.2 we already ascribed
the switching from low friction to high friction and vice versa to the different orien-
tations of neighboring grains on the polycrystalline substrate. Figure 5.10a is a large-
scale topographic image of the polycrystalline grade ZYH sample. The image shows
a grain boundary that runs across the surface. The height and lateral dimensions of the
boundary are similar to those for grain boundaries on HOPG that have been observed
in STM experiments [132]. Figure 5.10c shows the lateral force image in the forward
direction of the same area. The grain in the upper right corner of the image exhibits a
signicantly lower friction force, than the grain in the lower left corner. This can be
also seen from the friction loop shown in 5.10d, measured in the x-direction, where
the friction force on the left grain was found to be 31930pN and on the right grain
222 29pN. However, the friction force in the Y-direction changed by only 10%.
81
Figure 5.9: Lateral force images (a,b) and friction force loops (ce) before and after a modest
rotation of less than 2
of an initially aligned contact. The three pairs of markers at the

sides of the images indicate the positions where the three force loops were taken. The lateral
force in (ce) in the forward scan direction is shown in black and in the backward direction in
grey; Normal force (a) F
N
= 23nN; (b) F
N
= 0.9nN; Image size 3nm 3nm.
82
5.3 R E S U L T S
Figure 5.10: Topography image (a) and lateral force map in the forward x-direction (c), show-
ing a grain boundary running across the polycrystalline HOPG surface. Graph (b) shows a
cross section along the line indicated by the markers in (a). Graph (d) shows a force loop along
the line indicated by the markers in (c); normal Force F
N
=5.1nN; Image size 500nm 500nm.
Also from atomic-scale measurements (3nm3nm) we found a change in the friction
force in the sliding direction from 32633pN on the left grain to 22118pN on the
right grain. The height line (5.10b) taken from the topographic image shows also a
change in the slope by 0.7
between the two grains. Ruan et al. [133] have proposed

a ratchet mechanism, in which the local friction coefcient in microscale measure-
ments should scale with the slope of the sample as =
0
_
1+tan
2
_
. Therefore
83
it might be possible that the change in friction between the two grains was slope in-
duced. However, using this equation to compute the change in the friction coefcient
due to the change in slope we nd =0.05%. Thus, the small change in slope cannot
explain the observed large change in the friction. Again we conclude that the change
in the friction from one grain to another is the effect of a change in commensurability
between a ake and the substrate.
5.3.6 TEM analysis of the tip
We have used high-resolution transmission electron microscopy (TEM) to image the
tungsten tip after our friction experiments. For this purpose, we glued the pyramid of
the force sensor onto a holder that tted inside the TEM holder (the pyramid had to
be broken out of the Tribolever chip). The TEM analysis showed that the tungsten tip
had a radius of about 80 nm and was covered with a smooth amorphous layer of 7 nm
thick tungsten oxide (g. 5.11a). Unfortunately, thorough TEM inspection of the tip
was not possible due to rapid removal of the amorphous layer by the electron beam.
Before the tip was modied by the electron beam, which occurred within minutes,
it was not possible to properly correct for astigmatism. This is seen in gure 5.11b,
which displays the tip after approximately 5 minutes. The amorphous layer has been
almost completely removed by the electron irradiation. In the same image we nd
several locations that look like layered structures similar to graphite sheets. At a rst
glance, one might be tempted to identify these as graphite akes. However, at that
point of the TEM experiment the tip was already strongly modied by the electron
beam and, in addition, it is possible that these features merely appeared like layered
structures due to astigmatism. Therefore, the present TEM analysis cannot provide
clear evidence for the presence or the absence of either a multilayer ake or a single
layer of graphite.
5.3.7 Friction anisotropy
The measurements of the friction force versus sample rotation, presented in section
5.3.3, were taken for a single sliding direction with respect to the substrate. Miura et.
al found for the sliding of a 1mm1mm large MoS
2
ake on a MoS
2
surface [134],
as well as for a 1mm 1mm large graphite ake on HOPG [135], a variation in the
friction force between 0 and 2nN as a function of sliding direction. Before we discuss
friction anisotropy in our experiment, we rst clarify the terminology. Often friction
anisotropy refers to the variation in friction as a function of the sliding direction [136],
84
5.3 R E S U L T S
Figure 5.11: High-Resolution TEM micrographs of the tungsten tip initially (a) and about 5
minutes after the tip was rst exposed to the electron beam (b). The circles in (b) show areas
in which layered structures were observed. A zoom-in into one of these regions is shown in the
inset.
85
Figure 5.12: Friction as function of the sliding angle for a commensurate contact ( = 0).
The open circles denote the friction F
F
X
measured in the X-direction of the Tribolever, the open
squares the friction F
F
Y
in the Y-direction. The closed circles show the friction F
F
in the sliding
direction calculated from these components, according to equation 5.2. The dashed lines are a
cosine and a sine t to the friction components in the X- and the Y-direction. The dotted line
shows calculated friction forces, obtained using a Tomlinson model (see chapter 6).
whereas other authors use this term also for changes in friction as a function of com-
mensurability [34] (superlubricity) or for both phenomena [134]. To avoid misunder-
standings, we will use the term friction anisotropy strictly for the variation of friction
with respect to the sliding direction. In the measurements of gures 5.7, 5.8 and 5.9,
where we recorded the friction force as a function of the rotation angle of the sam-
ple, the sliding direction did not change with respect to the substrate lattice because
the scan piezo rotated together with the sample. This is why we can directly rule out
anisotropy as a cause for the observed peaks. However, if a graphite/graphite contact
does exhibit high friction anisotropy, the dependence of the friction force on the de-
gree of incommensurability might change dramatically with sliding direction. In order
to investigate this, we measured the friction force for a number of sample rotation an-
gles as a function of the sliding direction . We invariably observed that the friction
86
5.4 D I S C U S S I O N
force F
F
varied between high and low simultaneously, for all sliding directions .
The friction anisotropy was very modest (at most 25%) and did not interfere with the
commensurability effect. As an example, gure 5.12 shows the friction force in the
X-direction and in the Y-direction as a function of sliding angle for a commensurate
contact, with high friction. Whereas the friction forces in the X- and Y-directions of
the sensor strongly varied as a function of the sliding angle, the total friction force
in the sliding direction remained nearly constant. The difference between our results
and those in Refs. [134, 135] might be explained by the fact that in Refs. [134, 135]
the friction versus sliding direction was measured using a traditional AFM cantilever
with different sensitivities in the X- and Y-directions. It might be possible that only
the friction component along one direction was measured rather than the full friction
force in the sliding direction. We will show in chapter 6 that in the framework of the
Tomlinson model, for a graphite ake on a graphite substrate, a modest anisotropy is
to be expected for all sample rotation angles .
5.4 Discussion
All measurements presented in this chapter were consistent with friction between a
graphite ake and the graphite substrate. In fact, the notion that graphite akes adhere
frequently to the tip of scanning probe microscopes has originated already many years
ago in order to explain unusual contrast in scanning tunnelling microscopy images
(e.g [137, 138]). Although we have not been able to directly observe the presence of a
graphite ake with TEM, our friction measurements provide rm evidence that a ake
caused the observed superlubricity.
A few earlier experiments provided indications of superlubricity. Hirano et al. [34]
found a modest reduction in friction between two mica sheets from 8 10
4
N to
2 10
4
N, caused by rotating the two sheets with respect to each other. In a modi-
ed scanning tunnelling microscope (STM) experiment [66] the same authors claimed
the observation of superlubricity between a tungsten tip and a Si(001) sample. How-
ever, the evidence provided in the paper is rather incomplete. No normal force was
measured or controlled, and the tip was actually only in tunnelling range from the
substrate. The friction force was measured only for two relative orientations. No typ-
ical friction loops were shown. Ko et al. [67] showed that variations in the friction
coefcient caused by the rotation of two (100) metal surfaces with respect to each
87
other do not necessarily have to be the result of a change in lattice mismatch (see also
chapter 1).
Beyond showing the existence of superlubricity between graphite surfaces on the
nanometer scale, which might explain the ultra-low friction coefcients as well as
the large variations found in previous FFM experiments on graphite (table 5.1), our
observation might also have important implications for understanding the macroscopic
lubrication properties of solid lamellar lubricants.
Indications that also in a macroscopic sliding contact of lamellar solids rotated
akes are created, come from Transmission Electron Microscopy (TEM) observations
by Martin et al. [139] on MoS
2
. In contrast to our single-contact FFM experiment,
macroscopic-scale friction involves multiple micro-contacts with different sizes and
orientations. Based on our observations, one may speculate that in the case of macro-
scopic lubrication by graphite a large fraction of the graphite-graphite contacts will be
in the superlubric state, while only a small fraction will be in registry. This should lead
to a tremendous reduction in the average friction force, experienced in the ensemble
of micro-contacts, and thus might explain the excellent lubrication by graphite and
similar, layered materials, such as MoS
2
and Ti
3
SiC
2
. It was shown by Liu et al. [140]
that under sliding conditions, a graphitized tribolayer is formed on top of of diamond-
like coatings (DLC), which leads to a decrease of the friction coefcient after run-in.
Therefore, probably also the excellent lubrication properties of DLC lms might be
caused by superlubric graphitic contacts.
We suppose that for sufciently large contacts superlubricity might break down, as the
two lattices are not perfectly rigid, and a network of mist dislocations should form
between the two [141]. Therefore, to give an estimate to what percentage superlubric-
ity contributes to the good lubrication properties of solid lubricants, more experiments
are needed to nd out at which contact size and normal load superlubricity breaks
down and to nd out, how many of the loose akes, which might form the majority
species in a real tribological contact, twist back into registry. Indications that superlu-
bricity breaks down at higher contact pressures might be found in gure 5.6a, where
we observed a slight increase in the friction above 40nN normal load.
Other graphitic systems have been found that show remarkable tribological proper-
ties, which might also be attributed to the phenomenon of superlubricity. TEM obser-
vations [142] imply that nested carbon nanotubes (CNT) possess very low inter-wall
friction. In most cases, the inner and outer tubes in a multiwall CNT form an in-
88
5.5 C O N C L U S I O N S
commensurate graphitic system, similar to a rotated ake that slides over a graphite
surface. Falvo et al. found that carbon nanotubes slide over HOPG when they are out
of registry but rotate when they are in registry with the underlying surface [68, 69].
5.5 Conclusions
By measuring atomic-scale friction as a function of the rotational angle between a
tungsten tip and a graphite surface we have shown that the origin of the ultra-low fric-
tion of graphite in friction force experiments lies in the incommensurability between
between a ake that is attached to the tip and the graphite surface. The observation of
two narrow peaks in the friction force that are separated by 60
provided clear exper-

imental evidence of superlubricity. The width of the two peaks allowed us to estimate
the contact diameter to be 7 to 12 lattice spacings. The occurrence of superlubricity in
layered materials might explain on why these materials are good solid lubricants.
89
90
VI
Superlubricity in the Tomlinson model

In this chapter, the friction between a nite nanometer-sized
graphite ake and a graphite surface is analyzed in the framework of
a modied Tomlinson model with nite contact size. The calculation
shows that the orientation dependence of the friction provides informa-
tion on the contact size and demonstrates the effect of the shape of the
ake.
91
6. S U P E R L U B R I C I T Y I N T H E T O M L I N S O N M O D E L
6.1 Introduction
In the previous chapter we reported atomic-scale measurements, which demonstrated
that the friction between two graphite surfaces depends strongly on the commensura-
bility between the two lattices.
Atomic-scale friction in the absence of wear, plastic deformation, and impurities
has been studied theoretically using simple ball-and-spring models (see chapter 1)
such as the Tomlinson model [49, 143], the Frenkel-Kontorova [53, 144] model, or
a combination of these models, known as the FKT (Frenkel-Kontorova-Tomlinson)-
model [145]. A recent, extensive overview of the eld of computer simulations and
modelling of friction, lubrication and wear by Robbins and M user has been published
in Ref. [146].
Lateral force maps, obtained from FFM experiments, have been explained qual-
itatively using a two-dimensional Tomlinson model. Most of these models have in-
volved either point-like tips or innite surfaces [58, 60, 127, 147, 148]. However, it is
likely that in the experiments the contact consisted of a large, but nite number of
atoms, performing a collective, atomic-scale slip-stick motion. This is conrmed by
the fact that the normal force in the model, needed to obtain quantitative agreement
with experimental friction force maps, is usually substantially lower than observed
experimentally [58].
Lateral forces in nite, nanometer-sized contacts recently have received atten-
tion in a few theoretical studies. Molecular dynamics and total-energy minimization
calculations (T = 0) of a at Cu(111) tip consisting of 25 to 361 atoms sliding over
a Cu(111) surface have been performed by Srensen et al. [65]. For matching surfaces
a collective atomic-scale slip-stick motion was found. For misaligned surfaces, the av-
erage friction force vanished. When the friction force did not vanish, this was found
to be due to local pinning at the corners of the contact, a nite-size effect that disap-
peared when the contact area was increased sufciently. Similar results were found
by Tamura et al. [149] who studied talc(001) surfaces in an MD simulation and He
et al. [150]. Recently, Buldum et al. [151] performed total-energy minimization and
molecular dynamics calculations to study the motion of carbon nanotubes (CNT) on
a graphite surface. They found sharp, unique energy minima for different types of
CNTs as a function of the orientation of the tube axis with respect to the surface lat-
tice. These energy minima were separated by 60
. They marked the transition from

sliding to rolling, when the CNTs were subjected to a lateral force.
92
6.2 M O D E L
Here, we explore whether a simple modied Tomlinson model, adapted for a -
nite, multi-atomtip, can reproduce the observed superlubricity of graphite. In addition,
we use the model to estimate the size of the graphite/graphite contact in the measure-
ments of chapter 5 and to study the effect of the shape of the ake. In graphite, the
van der Waals forces between sheets are weak when compared to the covalent bond-
ing between atoms within the sheet. This makes graphite (and other lamellar materials
such as mica and MoS
2
) very well suited to be modelled with the Tomlinson model,
because the strong bonds within the sheets will make them slide with respect to each
other, almost without internal deformation. However, by completely neglecting elas-
ticity of the ake, we should not expect the model to fail for large contact sizes, as
will be discussed in section 6.4.
6.2 Model
The graphite ake is modelled as a rigid, nite lattice, composed of hexagonal carbon
rings as shown in gure 5.1. The ake is coupled to a support by springs in the X- and
Y-directions. Via these springs, the support pulls the ake through a periodic potential.
The interaction between a single carbon atom and the graphite surface is ap-
proximated by the interaction potential used in [35]:
V
int
(x, y, z) = V
0
(z)[2cos(a
1
x)cos(a
2
y) +cos(2a
2
y)] (6.1)
with a
1
= 2/(0.246nm) and a
2
= 2/(0.426nm), determined by the periodicity of
the unit cell. Equation 6.1 represents the rst order fourier expansion of the interaction
between a single atom or a point-like tip and the rst layer of a graphite surface,
assuming pairwise Lennard-Jones potentials [152]. The corrugation of the potential
energy surface V
0
(z) depends on the separation z between the ake and the surface.
Because the relative positions of the atoms in the ake are xed, the ake-
surface interaction potential is simply obtained by the summation over N atomic con-
tributions. The ake can now be treated as a point-like object moving through an
effective interaction potential:
V
f lake
int
(x
t
, y
t
, z
t
) =
N
i=1
V
int
(x
t
+x
i
, y
t
+y
i
, z
t
). (6.2)
The FFMis operated in contact mode at a range of normal loads of up to +40nN
(chapter 5). Therefore, the system, including the normal force F
N
can be described by a
93
Figure 6.1: Illustration of the modied Tomlinson model used in our calculations. A rigid ake
consisting of N atoms (here N=24) is connected by an X-spring and a Y-spring to the support
of the microscope. The support is moved with constant velocity v
m
in the X-direction.
total potential V(x
t
, y
t
, z
t
) =V
f lake
int
(x
t
, y
t
, z
t
)F
N
z
t
. The equilibrium height z
min
t
(x
t
, y
t
)
is given by the minimum of V(x
t
, y
t
, z
t
) with respect to z
t
. Combining these potential
energy values for all positions (x
t
, y
t
), we obtain an effective ake-surface potential
V
f lake
int
(x
t
, y
t
) [50]. The total potential energy including the elastic energy stored in the
springs is given by
V (r
t
,r
m
) =V
f lake
int
(r
t
) +
1
2
k(r
t
r
m
)
2
, (6.3)
where r
t
is the (x
t
, y
t
) position of the center of mass (CM) of the tip, r
m
the (x
m
, y
m
)
position of the microscope support and k = k
x
= k
y
is the spring constant in the X-
and in the Y-direction. The support is displaced in the pulling direction with steps of
0.001nm (the basic length unit in the calculation). After each step, the position of
the ake is allowed to relax towards the nearest local energy minimum. The system
is assumed to be in equilibrium at each step of the simulation, since typical FFM
94
6.2 M O D E L
scanning velocities are much smaller than the sound velocities of the materials. In the
simple Tomlinson approximation, phonons generated during the slip are assumed to
carry the excess energy away. Since phonon frequencies are much higher than typical
scanning frequencies, this relaxation is therefore assumed to occur very quickly (in
reality, one should expect a variety of sizeable deviations from the Tomlinson model
since the relaxation time is not innitely short [153]).
The energy is minimized by an iterative procedure that moves the contact one
length unit in the direction of steepest decrease in potential energy per iteration. In-
stabilities in the total energy surface as a function of support (x
m
, y
m
) coordinates can
cause atomic scale stick-slip motion, where the contact non-adiabatically (discontin-
uously) jumps to a new position. The potential energy built up in the springs is
removed during the energy minimization step, resulting in a non-zero average force
along the pulling direction. After the contact is relaxed the force at the support is given
by
F = k (r
t
r
m
). (6.4)
Scanning motion of the support in the pulling direction (dened here as X-direction)
occurs in steps of 0.001nm. The CM position of the ake initially coincides with
the origin of the support. Then the support is scanned 3nm in the pulling direction.
The system is now considered initialized. The support is then scanned backwards and
forwards, again over 3nm. Static friction is dened as the force required in the X-
direction to cause the rst slip event. Kinetic friction is dened as the average force
in the X-direction after that rst event. The area in a closed friction loop equals the
energy dissipated (removed during the energy minimization steps during the entire
loop). Note that the slope of the force loop of 4.64N/m is lower than the stiffness
of the spring of 5.75N/m (g. 6.3a): within the framework of the model a lateral
interface stiffness k
inter f ace
exists, that is caused by the curvature
2
V
f lake
int
/x
2
of
the periodic potential energy surface at the sticking positions of the tip. This interface
stiffness and the cantilever springs act in series to produce the effective stiffness that
is observed in the simulated friction loops (see chapter 5).
After every forward plus backward line in the X-direction, the support steps
0.006nm in the Y-direction perpendicular to the scan direction. In this way the support
covers a distance of 3nm, and a two-dimensional lateral force image is generated. The
orientation angle of the ake with respect to the substrate is set prior to calculating
the effective interaction potential for the contact. The angle under which the ake is
pulled through the interaction potential is set independently. The friction force for a
95
Figure 6.2: Symmetric akes used in the calculations consisting of (a) 6, (b) 24, (c) 54, (d) 96,
and (e) 150 atoms.
certain mist angle of the contact and/or sliding direction of the support is dened
here as the average of all kinetic friction values for all different Y-coordinates within
one lateral force map, and also averaging over forward and backward lines.
6.3 Results
6.3.1 Symmetric contacts
Figure 6.2 displays symmetric akes of various sizes that were considered in the cal-
culation. The friction force (as dened in section 6.2) is maximal if the mist angle
is zero, i.e. the lattices form a commensurate structure, as is illustrated for the 96-
atom ake in gure 6.3. The friction force then increases linearly with the number
of atoms N in the contact. In order to compare different ake sizes for a xed total
interaction between the contact and the surface, the potential amplitude per atom V
0
was lowered with increasing contact size such that V
0
N =0.52eV. In this way the total
96
6.3 R E S U L T S
Figure 6.3: Calculated friction loops for a 96-atom ake in registry (a) and 30
out of registry
(b).
interaction energy was chosen such that the calculated friction force with the ake and
substrate in registry (260pN for 0.52 eV) was the same for all akes, and comparable
to the value measured experimentally. Figure 6.3 shows that when the 96-atom ake
is misoriented by 30
the lateral force displays a continuous, sine-like variation, with

an average value close to zero. Figure 6.4a displays the computed friction force as a
function of for the ve akes shown in gure 6.2. Like in the experiment, we nd
angular regions with high friction around 0 and 60
. At intermediate angles, we cal-

culated near-zero friction, except for the 6-atom ake, for which the friction drops to
51.7pN. Clearly, the calculations predict superlubricity.
As already discussed in chapter 5, the angular width of the friction maxima should
depend on the contact size and we estimated that
tan() = 1/D, (6.5)
where is the full width at half maximum (FWHM) of the friction peak, and
D is the ake diameter, expressed in lattice spacings. This relation is shown in gure
6.4b, where the FWHM is plotted as a function of contact diameter, using the in-plane
graphite nearest neighbor distance of 0.142nm as lattice spacing. The agreement be-
tween the estimate of equation 6.5 and the peak widths calculated for the ve akes is
excellent. For a symmetric ake of 96 atoms we nd a FWHM of 5.5
, very similar to
the experimental observations.
97
Different peak heights at 0
and 60
mist angle, as found in the experiment, can-

not be expected in our calculation, since the simple potential that we used to model
the graphite surface and the ake, has 60
symmetry. This potential only models the

interaction between adjacent graphite layers and ignores the more subtle, long-range
interactions responsible for the AB-stacks in graphite.
In order to investigate the dependence on the pulling direction, calculations have
been performed for a 6-atom, a 96-atom and a 150-atom ake, both in and out registry
with the surface. The variation in the friction force was found to be 24% for both com-
mensurate akes, and incommensurate akes. One example of the calculated friction
force as a function of sliding angle is plotted in gure 6.5, together with the measured
friction between 10
and 90
. The calculation shows that the force depends modestly

on the sliding direction. A very similar dependence on the pulling direction was found
by Gyalog et al. [147, 148] within a FKT model for two identical innitely extended
crystal surfaces with a square symmetry. However, in our model the friction force is
lowest 2
left and right of the symmetry directions of the graphite surface and slightly
higher precisely in the symmetry directions. Probably this is caused by the complete
rigidity of the two surfaces and the discretization of the model.
6.3.2 Asymmetric contacts
In spite of the success in tting the measured friction with the interaction between
a symmetric ake and a graphite substrate, it is unlikely that the real ake in the
experiment has had perfect hexagonal symmetry. Even when the contact has been
dened by a large ake, curved around the metal tip, we would be forced to assume our
tip to have been symmetric, which is again unlikely. In this section, we investigate the
effect of asymmetric ake shapes. Taking the symmetric 96-atom ake that produced
a good t to the measured data as a starting geometry, we removed rows of carbon
rings at the top and at the bottom (gure 6.6a-b) until a single row of carbon rings was
left (gure 6.6c). This yielded three model akes with length over width ratios of 1.5,
2.4 and 6.1, respectively.
Figure 6.7 shows the dependence of the friction on the mist angle. As for the
symmetric akes, we nd regions with high friction that appear every 60
, separated
by angular regions that are superlubric. The high friction peaks now possess shoul-
ders, which become more prominent the more asymmetric the shape of the ake is.
Due to the stretched shape, the total potential energy surface (PES) becomes elon-
gated along the long axis of the rotated ake (gures 6.8b,d,f). For a misaligned ake,
98
6.3 R E S U L T S
Figure 6.4: (a) Friction as function of the mist angle for different symmetric akes ranging
from 6 to 150 atoms; (b) Width of the friction peaks (FWHM) versus ake diameter (circles).
The solid line is the peak width according to equation 6.5.
99
Figure 6.5: Comparison between calculated (solid line) and measured (circles) dependence
of friction on the sliding direction, for a 150-atom ake, in registry with the substrate.
this causes the CM of the tip to follow different types of pathways in the forward scan
than in the backward scan. In addition, the changes in the PES cause the force buildup
in the X- and Y-springs of the Tribolever to differ left and right of the friction peaks in
gure 6.7, which results in asymmetric shoulders. This introduces a 90
mirror sym-
metry instead of the 60
symmetry of the corrugation expected from V

int
. Note, that
in gure 6.7 the mirror angles were xed to 30
and 120
by choosing the pulling

direction to be 60
.
Calculated lateral force images in the forward X-direction and potential energy
surfaces for an asymmetric ake consisting of 78 atoms are shown in gure 6.8. The
images were calculated for a sliding angle of 70
and for mist angles of 120
(a,b),
132
(c,d) and 94
(e,f), in order to resemble measured images shown in gure 5.7.

It is obvious that the lateral force patterns are also affected by the asymmetry in the
potential energy surfaces. The grey areas in gures 6.8b,d and f show positions that
have been visited by the CM of the tip during sliding. In gure 6.8b the CM is pinned
at the potential energy minima of the PES and performs zig-zag stick-slip motion.
In gure 6.8d the PES is elongated such, that the sticking areas are connected and
100
6.3 R E S U L T S
Figure 6.6: Three asymmetric akes consisting of (a) 78,(b) 56, and (c) 30 atoms.
form channels that run across the image. These low energy channels in which the
tip slides continuously are still separated by energy barriers over which the tip has to
jump. Finally, when the ake is rotated 26
away from commensurability, the PES is

shallow enough that the tip continuously slides over the entire surface. Depending on
the ake orientation, the sticking zones are elongated in different directions, which
creates the impression that the lateral force pattern is rotating although the pulling
direction is the same for all three images. This is also observed in the measurements,
(g. 5.7) although the measurement cannot reproduce all of the ne structure that is
seen in the calculated images, which is probably due to the fact that the lateral forces
are close to the thermal noise of the Tribolever and the noise limit of the instrument.
Comparing our calculations with our experimental results, we conclude that the ake,
that was responsible for the data in gure 5.8, was mildly asymmetric. The calculations
for the 30- and 56-atomakes do not showsimilarity with the measured data. The peak
shapes and widths for the 78-atom ake and the measured ones are similar (see g.
6.9), but at this stage we have not attempted to improve the t further by optimizing
the shape and size with respect to the present 78-atom model.
101
Figure 6.7: Friction as function of the mist angle for three different asymmetric akes with
(a) 78 atoms, V
0
= 0.0068eV; (b) 56 atoms, V
0
= 0.0093eV; (c) 30 atoms, V
0
= 0.017eV; All
calculations were performed for a pulling angle of 60
. The dashed lines indicate the angles

with respect to which the pattern should be symmetric.
6.4 Discussion
We have shown that a very simple Tomlinson model for a graphite ake against a
graphite substrate reproduces the measured orientational dependence of the friction
rather well. However, the model lacks several important elements of reality. For ex-
ample, when we increase the number of atoms to innity in the contact the model
predicts that the peaks of high friction become innitely narrow. In registry, the cor-
rugation amplitude of the interaction potential is predicted to increase linearly with
the number of atoms in the contact. To move a large, aligned ake consisting of a few
thousand atoms would require a very high force, but in our model, only a tiny bit of
rotation out of registry would cause superlubricity. When we model a disordered tip by
placing atoms randomly, the high friction peaks vanish. This means, that in our model
every misaligned crystalline or amorphous tip that is large enough, is fully superlu-
102
6.4 D I S C U S S I O N
Figure 6.8: Lateral force images (3nm3nm) and total potential energy surfaces
(1nm1nm), calculated in the forward X-direction for an asymmetric, 78-atom ake, for mist
angles of 120
(a,b), 132
(c,d) and 94
(e,f). The grey areas in the contour plots denote po-

sitions that were visited by the center of mass of the ake. The grey scale in the lateral force
images corresponds to (a) 2.2nN, (c,e) 92pN;
103
Figure 6.8: continued Solid and dashed contour lines in the PES denote positive (V >0), and
negative (V < 0) energy values, respectively. The contour lines are separated by (b) 0.1eV (d)
0.02eV and (f) 2 10
3
eV.
Figure 6.9: The data points show the average friction force versus the rotation angle of the
graphite sample (chapter 5). The curve through the data points shows results from the Tomlin-
son simulation for the asymmetric 78-atom ake; The calculation was performed for a sliding
direction of 60
; in other words, at = 0 the long axis of the ake is oriented at +60
with
respect to the sliding direction.
104
6.5 C O N C L U S I O N S
bric. Therefore, friction between macroscopic surfaces should almost always be zero
in wearless sliding situations. Yet, macroscopic surfaces that exhibit superlubricity
have not been discovered so far. He et al. [150] have shown in an MD simulation that
third bodies, such as hydrocarbon molecules can cause locking of the two surfaces and
hence destroy superlubricity. Another mechanism that might prevent superlubricity at
larger scales is internal elasticity in the contact [141], which will allow the ake to
lock locally into registry. Our model does not include any elasticity, and is not suited
to estimate the transition to the behavior for larger contacts. It is surprising that the
Tomlinson model works so well to t the experimental data. This is probably due to the
high in-plane Youngs modulus of graphite in combination with the relatively small
ake size. We speculate that precisely these two ingredients namely the presence of
small, rigid akes might be the key elements making graphite a good solid lubricant.
6.5 Conclusions
In summary, we have set up a Tomlinson model, describing a rigid N-atom cluster with
the symmetry of a graphite ake that was moved through a two-dimensional sinusoidal
potential representing the graphite surface. The calculated friction force shows high
friction and near-zero friction, depending on the (in)commensurability between the
two lattices. By changing N, we vary the width of the peak in the friction vs. orien-
tation plot, so that we can t the measured peak width. The calculations revealed that
the shapes of the high-friction peaks depend on the precise shape of the ake.
105
106
VII
Towards the ideal friction experiment

We present a miniaturized version of the dedicated friction force
microscope introduced in chapter 4 that operates in ultra-high vacuum
(UHV). Because of its small size, the FFM can be combined with other
techniques, to image or otherwise characterize the sliding contact dur-
ing force measurements. In the rst part, we discuss how the miniature
FFM has been combined with a high resolution transmission electron
microscope. In the second part, we will introduce the design of a new
UHV setup, in which the miniature FFM is combined with a eld ion
microscope to characterize and modify the tip before and after contact
with the surface, and with a scanning electron microscope to observe
the contact during sliding.
107
7. T O W A R D S T H E I D E A L F R I C T I O N E X P E R I M E N T
7.1 Introduction
7.1.1 The need for ultra-high vacuum
In chapter 2 we envisioned the ideal friction experiment necessary to bridge the gap
between nanotribology and micro-/macrotribology. We formulated a set of require-
ments, that our instrument needs to full in order to enable this ultimate experiment.
Several of these requirements, such as quantitative three-dimensional force detection
with high sensitivity, rotation of the sample lattice with respect of the tip lattice, and
free choice of the tip and sample materials, have already been met by the FFM that
is described in the chapter 4. Using that FFM, tribological systems can be studied
in a controlled ambient environment (e.g. air or nitrogen with controlled humidity).
However, the ambient FFM cannot be used to study any desired material combination,
since most materials are immediately oxidized or otherwise altered under ambient
conditions. Only in ultrahigh vacuum (UHV) one can produce and maintain atomi-
cally clean, well-characterized crystal surfaces of various materials, such as metals
and semiconductors, and deposit well-dened monolayers of adsorbates that can e.g.
act as model lubricants. A second important requirement that is not met by the ambi-
ent FFM, is to provide full information on the tip size and orientation. Only in special
cases can this information be deduced indirectly from the measurements, as is demon-
strated in chapter 5. Techniques that allow one to image the tip with high, e.g. atomic
resolution use electron or ion beams, and therefore require high vacuum. It is evident
that both requirements involve the new FFM setup to be placed in UHV.
7.1.2 Imaging the contact
We can think of two methods to obtain information on the contact with atomic res-
olution. The rst method is to look at the contact from the side using a high-
resolution transmission electron microscope (HRTEM). The combination of scan-
ning tunnelling microscopy and transmission electron microscopy was recently shown
to be possible and to provide a deep understanding of the relationship between the
structure and electronic properties of nanocontacts [154]. In a similar way, with the
combination of a friction force microscope with a HRTEM, it should be possible to
perform quantitative friction force measurements and at the same time know exactly
how many atoms are contributing to the measured lateral and normal forces. A great
advantage of such a combination will be that it will make it possible to observe atomic
recongurations inside the contact in real time while the tip is sliding over the surface
108
7.1 I N T R O D U C T I O N
or while the normal force is changed. One of the difculties introduced by combining
a FFM with a HRTEM is that the lens geometry of the HRTEM puts severe restrictions
on the dimensions of both the FFM (see section 7.2) and the sample.
We have constructed a miniaturized UHV version of our friction force micro-
scope that can be mounted into a dedicated UHV HRTEM [155] at the Tokyo Institute
of Technology. We will briey discuss the design of the FFM/HRTEM combination in
section 7.2, since it forms the basis for the new UHV setup. Due to time limitations,
our rst attempts to perform a FFM measurement inside the HRTEM had only limited
success. A brief account of the results can be found in appendix B.
The UHV setup, which is under construction in Leiden, uses a second method
to obtain atomic-scale information of the scanning tip, which is to combine the FFM
with eld-ion microscopy (FIM), to view and to shape the tip [156159]. With a com-
bined STM/FIM apparatus, Cross et al. [160] studied the adhesion interaction between
an atomically dened W(111) and a Au(111) surface and demonstrated the power of
combination of these two methods. In a FIM, a sharp tip, usually of a high-melting-
point metal, is imaged by placing it in a high electric eld in the presence of a low
density of a noble gas, e.g. He. The eld strength is highest where the curvature of the
tip is at its maximum, which is at or near the apex. The highest elds are sufcient to
ionize the noble gas atoms. The ions are accelerated from the ionization position to a
phosphor screen, where they build up a strongly enlarged image of the high-curvature
regions at the tip apex. In this way, high-quality FIM images show the tip apex with
atomic resolution, which allows one to directly identify the crystallographic orienta-
tion of the tip and to count the number of atoms at the perimeter of the outermost
atomic facet, from which one immediately obtains the total number of atoms in that
facet. When the tip is brought into contact with the sample surface with a low load-
ing force, these outermost atoms dene the contact area. There are several additional
advantages that the FIM provides. The FIM image shows not only which crystallo-
graphic plane terminates the tip apex, but also in which precise direction the surface
normal is pointing. In our setup, we will be able to tilt the sensor and tip assembly
in two independent directions, so that we can align the surface normal of the tip with
that of the extended counter-surface, in order to make these surfaces really parallel.
The FIM can further be used to shape the tip and thereby modify the area of the
outermost atomic facet. This is achieved by increasing the electrical eld to the point
109
where the tip atoms are eld-desorbed. In this way, the tip apex is stripped away atom
by atom. A beautiful illustration of these methods can be found in [159], where tips
are produced with perfect hexagonal facets of Ir(111) that have sizes of 7, 19, 37, 61,
and 91 Ir atoms. However, unlike in a HRTEM, with the FIM we can only image the
tip prior to the formation of a contact and after the contact is broken again.
In order to also view the contact during sliding, the UHV setup in Leiden will be com-
bined with a third type of microscope. We will use a scanning electron microscope
(SEM) to look at the tip and the sample from the side. Although the SEM will not
reach atomic resolution, it will provide the possibility to study e.g. the deformations
in and around the contact, the ageing (growing) of a contact when it is resting on the
surface, or the wear debris formation when the tip is moving under high normal loads.
The SEM column and the FFM have to be mechanically strongly coupled, so that vi-
brations between the SEM and the FFM will not compromise high-resolution SEM
imaging. Using a traditional SEM column, this would imply abandoning a vibration
isolation stage for the FFM. This, in turn, would strongly deteriorate the quality of
FFM measurements. However, if the SEM column is sufciently small and compat-
ible with UHV, it is possible to mount the complete SEM on the vibration isolation
stage of the FFM. Therefore, we use two dedicated miniature SEM columns, which
operate in UHV. The Mini-SEMs are of a prototype version that was developed at the
Philips Research laboratories in Eindhoven [161].
7.2 Design of a miniaturized FFM for use in combination with HRTEM or
SEM
A number of technical specications have to be met to make our specialized
FFM suitable for operation inside a UHV system with either HRTEM or SEM: (1)
Most importantly, the FFMs dimensions have to be reduced. To image the scanning
tip, the Tribolever together with part of the berhead has to be placed in between
the pole shoes of the objective lens (OL) of the HRTEM. In the 200keV JEOL mi-
croscope, the pole shoes are separated by a gap of 2.5mm. (2) The FFM has to be
transferrable from a loading chamber to the sample stage that is connected to a go-
niometer inside the HRTEM. This goniometer is needed to position the tip apex in the
110
7.2 D E S I G N O F A M I N I A T U R I Z E D F F M . . .
Figure 7.1: Drawing of the miniaturized FFM for combination with HRTEM. Panel (a) shows
an overviewwith: (1) sample holder; (2) sample/FFMstage; (3) nonmagnetic UHV Nanomotor;
(4) scan piezo tube; (5) Inchworm motor; (6) FFM transfer holder; (7) connection rod and tube.
Panel (b) depicts a zoom-in of the berhead with: (8) glass ber with aluminium cladding; (9)
tip bumper and sample (in form of a wire); (10) Tribolever.
111
Figure 7.2: Solid model of the berhead of the miniaturized FFM in between the two pole
shoes of the TEM, cut open for illustration: (3) non-magnetic UHV Nanomotor; (10) Tribolever;
(11) berhead; (12) pole shoe.
eld of view of the electron beam and to optimize the position in the direction parallel
to the beam in order to place the tip apex precisely in the focal plane. In addition,
the goniometer is used to tilt the sample stage and to optimize the viewing angle. (3)
Because of the construction of this goniometer, the mass of the sample stage, includ-
ing the entire FFM, should not exceed 30 gram. (4) Finally, the FFM has to be UHV
compatible and completely non-magnetic, because the FFM has to operate in the high
magnetic eld of the OL.
Figure 7.1 shows the design of the sample stage plus FFM. The FFM assembly
consists of a miniature berhead, which is directly glued onto a scan piezo tube (4).
Unlike the ambient version of the FFM, the berhead does not remain at a xed posi-
tion but is scanned together with the tip of the Tribolever. The piezo tube is mounted
on the shaft of a commercial inchworm motor (5) [162], which is used to approach
the tip towards the sample (8). Two rods, that are connected to the inchworm motor
house, guide the FFM into the sample stage (2) and form a stable connection.
112
7.2.1 FFM/HRTEM berhead
Figure 7.3: Video microscope image during the alignment procedure of the Nanomotors prior
to glueing.
The berhead was made by spark erosion from titanium. The contours of the
berhead are dened by the shape of the pole shoes of the OL. At the end, the berhead
is reduced to a thickness of 2.5mm in order to to t between the pole shoes (see
g. 7.2). Because the Tribolever can easily be damaged while the FFM is mounted
inside the HRTEM, it is covered by a titanium strip, that serves as a bumper, in
case the berhead were to hit one of the pole shoes. A groove, cut in the bumper
allows the scanning tip to be brought into contact with the sample. Several holes have
been drilled into the berhead to reduce its mass to 2.1 gram. As in the berhead in
113
chapter 4, we used UHV-compatible Nanomotors to approach and position the four
glass bers close to the four faces of the pyramid of the Tribolever. Because of the
OL, it was not possible to mount the four Nanomotors completely symmetrically,
at 90
angles. The X1 axis is therefore placed under an angle of 68.5
with respect
to the Y1 axis. This results in slightly lower interferometer signals. Less light can
reenter into the glass bers if they are not perfectly orthogonal to the faces of the
detection pyramid. Also because of the geometry of the pole shoes, we had to leave
out the exure hinges, which were used in the ambient version of the microscope
to adjust the Nanomotor positions. Because the positions of the Nanomotors in this
design are xed, the glass bers needed to be aligned with respect to the pyramid
before the motors were glued into the berhead. To this end, the glass bers [163] were
rst mounted into the Nanomotors and then the motors were positioned with respect
to the berhead using a x-y-z positioning stage. The process was monitored using a
video microscope (gure 7.3). Without changing the alignment, the Nanomotors were
then glued into the berhead. In the original version of the Nanomotor, the carrier
tube, which holds the ber, is free to rotate. Such rotation can cause a change in
the alignment of the ber, because the carrier tube is not exactly in the center of the
Nanomotor. In order to avoid rotation, we constructed, in collaboration with Klocke
Nanotechnik GmbH [164], a special non-magnetic version of the Nanomotor, in which
the rotation of the carrier tube is inhibited. This was achieved by replacing the glass
tube inside the Nanomotor by a glass tube with an oval bore that allows the carrier
tube to run easily in only one rotational orientation.
7.2.2 HRTEM-FFM assembly
After mounting the Nanomotors, the berhead was glued [165] onto the scan piezo
tube [166]. Scan piezo and berhead were then glued on the shaft of an inchworm
motor via a ceramic plate that matches the inner diameter of the piezo tube and the
outer diameter of the shaft. Like the axis of the original Nanomotors, the shaft of the
inchworm is normally free to rotate. In our case, this rotation is not tolerable, since it
would cause also the rotation of the complete FFM. We attached a precision ceramic
pin to the body of the inchworm, which slides inside a groove of the matching ceramic
plate to completely inhibit rotation of the shaft.
114
7.2.3 HRTEM-FFM sample stage
Like the berhead, the sample stage was made from titanium to save weight (7.1g)
and to ensure that the stage is non-magnetic. The stage is attached by three screws to
the goniometer of the HRTEM. The sample holder (g. 7.1, item 1) ts precisely into
a dovetail-shaped groove on the left side of the stage. The sample holder is designed
such that it can be transferred to the stage via magnetic transfer rods that are part of the
HRTEMs sample preparation chamber. From the opposite side, the FFM is brought
into the stage using a second transfer rod.
When the FFM approaches the sample stage, two rods, that are connected to the
inchworm house, move into two tubes that are connected to the sample stage (g. 7.1,
item 7). The tubes are used to guide the FFM into the correct position. When the FFM
is pushed into the end, its position is exactly dened with respect to the stage by a tight
t of the rods inside the tubes. The FFM is then released from the magnetic transfer
rod by turning the transfer rod. Once the FFM is free from the magnetic transfer rod,
the sample stage can be positioned with respect to the OL, using the goniometer of the
HRTEM.
The FFM makes use of the same interferometer system and electronics that were de-
scribed in chapter 4. Also, calibration of the Tribolever and mounting of a scanning
tip is done by the procedures that were described earlier.
After mounting the FFM inside the HRTEM, we could use electron microscopy
to observe the scanning tip approach and make contact to the sample. We were also
able to measure normal and lateral forces between a gold tip and a gold sample.
However, we have not been able to perform a truly simultaneous FFM and HRTEM
measurement, because the uncladded and tapered parts of the four glass bers were
charged up by the electron beam (see also appendix B). The charging and discharging
caused a strong periodic disturbance in the interferometer signals. It also caused sud-
den motion of the scanning tip every time when a discharge between the bers and the
Tribolever occurred. This problem will be solved by coating the tapered parts of the
glass bers with a conducting material and grounding the bers, to prevent charging.
Initial results from combined FFM and HRTEM measurements can be found in
appendix B. The version of the FFM, developed for use in combination with HRTEM,
is almost identical to the one described in the next section for use in combination with
115
a SEM.
7.3 Design of the UHV setup for FFM
In the following, we will give a brief overview over the general design of the UHV
system for FFM. This instrument will be a combination of the FFM introduced in the
previous section with a FIM and SEM. The setup is at present being assembled at the
Kamerlingh Onnes Laboratory.
7.3.1 UHV chamber
The newFFMwill be placed in a UHVchamber with a base pressure below1 10
8
Pa.
The chamber is pumped by a magnetically levitated turbomolecular pump (5) [167]
and an ionization pump (7) with combined titanium sublimation pump (8) [168]. The
chamber has two dedicated compartments, a sample preparation compartment and the
FFM compartment. In the rst compartment, a carrousel will be placed that will house
6 sample holders (g. 7.4, item 10 and g. 7.5, item 5). Concentrically around the
carrousel, instruments are placed to prepare and characterize an atomically at and
clean sample. The structure of the sample will be inspected with low energy electron
diffraction optics (LEED, item 4). The LEED system is combined with Auger electron
spectrometry (AES) [169] to analyze the material composition and cleanliness of the
sample surface. A sputter ion gun (12) [170] allows cleaning the sample. A quadrupole
mass spectrometer (11) [171] is used to monitor the vacuum quality and will be used
to perform thermal desorption spectroscopy (TDS) of lubricant molecules that are
adsorbed at the sample surface. Extra anges allow expanding the system in the future,
e.g. by a Knudsen evaporation cell. The carrousel will be rotatable by means of a
rotary drive, such that each sample in the carrousel can be positioned in front of every
of these instruments. The samples will be transferred from the carrousel to the FFM
compartment using a wobble stick [172].
The FFM compartment will contain a platform (g. 7.5, item 4) that is con-
nected to a CF419 ange. On that platform we will mount a spring-suspended stage
(3) with eddy-current vibration damping that will house the FFM as well as the two
Mini-SEM columns (see below). Also the FIM will be in the FFM compartment of the
UHV chamber (1).
116
7.3 D E S I G N O F T H E U H V S E T U P F O R F F M
Figure 7.4: The chamber for the UHV-FFM in a perspective view (a) and a side view (b)
showing: (1) FFM ange (2) FIM ange; (3) window for quartz rod; (4) LEED-AES; (5) turbo
pump;
117
Figure 7.4: continued (6) vibration isolation feet; (7) ion pump; (8) titanium sublimation
pump; (9) gate valves; (10) sample carrousel ange; (11) quadrupole mass spectrometer; (12)
sputter ion gun.
Figure 7.5: Schematic drawing of the interior of the UHV chamber showing: (1) retractable
FIM screen assembly; (2) Mini FFM; (3) spring-suspended FFM stage; (4) FFM platform; (5)
sample carrousel.
118
7.3.2 UHV-FFM stage
The FFM will be a slightly adapted version of the HRTEM version, discussed in sec-
tion 7.2. The FFM will be mounted with the tip pointing up (gure 7.6, position 2)
on a goniometer (4,5,10,11) that allows tilting of the FFM to a maximum angle of 13
degrees in order to orient the endface of the scanning tip parallel to the sample sur-
face. The center of the tilt motion has to coincide with the tip apex position. Therefore
the FFM position will be adjustable in two directions by means of exure hinges. The
goniometer consists of two connected parallel spherical shells (4,11) that are sprin
loaded against sapphire spheres (10). The goniometer will be tiltable in two directions
by two separate inchworm piezomotors (6) [173].
7.3.3 Mini-SEM
The Philips miniature SEM [161] consists of a small electron optics column and a
thermal eld emission (Schottky) electron gun. The overall length of the SEM column
including the gun is about 90mm. The electron optics consist of electrostatic lenses
and scan units. Secondary electrons are detected by a scintillator that is located inside
the column. The light from the scintillator plate is guided by a quartz rod to a CF63
viewport and there the signal is amplied by a photomultiplier outside of the UHV
chamber. When the tip of the FFM is making contact to the sample, the separation be-
tween the berhead and the sample will be about 50m. This means that the electrons
have to travel through a narrow gap of 50m over a distance of 1mm. If the FFM is
tilted with respect to the surface of the sample, this gap will become smaller, there-
fore obstructing the view from the SEM towards the tip apex. By using two electron
columns that aim at the tip from the left and from the right side, we will always be
able to obtain an image of the tip from at least one of the two sides, regardless of the
FFM tilt.
The narrow gap between the sample and the Tribolever has also a negative ef-
fect on the collection efciency of secondary electrons. This effect can be very severe
(see gure 7.7) when using the internal scintillation detector in the Mini-SEM col-
umn. Because the collection efciency can be improved when the secondary electron
source is close to the detector we will place a channeltron electron detector [174] in-
side the berhead. With this miniature detector (item 14 g. 7.6d) it will be possible
to collect secondary electrons through the central hole of the Tribolever. Figure 7.7
shows a comparison between SEM images of a test structure that were recorded with
119
Figure 7.6: The FFMstage in front (a) and rear view(b). Cross-section of the rear view(c) and
solid model of the modied berhead (d). Not shown are the sample and the second (identical)
SEM. (1) Philips Mini-SEM; (2) berhead; (3) coarse approach inchworm motor; (4) upper
goniometer shell; (5) goniometer housing; (6) goniometer inchworm motor; (7) SEM linear
translation stage; (8) SEM inchworm motor; (9) exure hinge SEM x-y table; (10) sapphire
spheres; (11) lower goniometer shell; (12) goniometer axis; (13) Tribolever; (14) channeltron
detector.
120
Figure 7.7: SEM images of a 50m long tip sticking out of the Tribolever. The tip makes
contact to a silicon sample. Image (a) was recorded using the internal scintillation detector of
the Mini-SEM. Panel (b) shows the same image, recorded with an external channeltron detector.
Printed with kind permission of M. Krans, Philips Research [161].
the internal detector of the Mini-SEM and with an external channeltron detector. The
test structure constisted of a tungesten tip between two silicon plates with the size
of the Tribolever, forming a 50m-wide gap. The image taken with the channeltron
detector clearly shows higher contrast inside the gap and it resolves the tungsten tip
much better.
To obtain high resolution images of the tip, the SEM columns have to be aligned
such that the tip is in the focus of the electron optics to within 10m. This means that
both columns need to be adjustable in two directions with respect to the berhead.
This adjustment will be performed by moving exure hinges ex-situ using microme-
ter screws. Once the columns are optically adjusted, the position of the SEM is xed
and the micrometer screws removed. After the stage is transferred to UHV, residual
misalignment of the columns can be directly measured using the SEMs themselves. In
this way the columns can be ne adjusted iteratively.
In addition to the ex-situ alignment of the column axis, also the distance be-
tween tip and OL of the columns needs to be adjustable in-situ. This has two reasons.
First, the columns need to be brought to a safe position when the FFM is moved using
the goniometer. Secondly, the working distance should be changeable, depending on
the magnication. Therefore the two columns will be mounted on two linear stages,
which can be moved using inchworm motors [175].
121
7.3.4 Field ion microscope
One side of the eld ion microscope is formed by the metal tip that is glued inside
the Tribolever. To ionize the imaging gas atoms, a high voltage in the order of several
kilovolts has to be applied to the tip. In our FFM, we will apply this high voltage to the
entire berhead, which therefore has to be electrically insulated from the scan piezo.
In order to obtain atomic resolution FIM images, the metal tip needs to be cooled
below about 90K . We have constructed a liquid nitrogen dewar that cools a copper rod
inside the UHVchamber to 77K. The copper rod will be connected to the berhead via
a exible copper braid (not shown in gure 7.6). The copper braid has to be electrically
insulated from the berhead but thermally well connected.
The FIM is completed by a combined dual chevron channel plate and phosphor
screen assembly (g. 7.5, item 1) [176]. Together, the channel plates provide a gain of
8 10
6
at 2000V applied voltage between the front- and the backside of the channel
plate stack and thus intensify the FIM image. Electrons leaving the channel plates
will be accelerated towards the phosphor screen over a voltage of 2keV. The screen
assembly will be located directly above the sample stage. When no sample holder is
placed in the sample stage, the ions can travel through the empty sample stage and
form an image on the screen. After a FIM experiment, the sample will be placed into
the sample stage. The FIM screen assembly will be mounted on a linear translation
stage, which is supported from a CF150 ange (g. 7.4, item 2). The linear translation
stage makes it possible to retract the FIMscreen while a sample is loaded in the sample
stage.
7.4 Summary
We presented the conceptual design of a new UHV setup, with which the ideal
experiment can be performed that that was introduced in chapter 2. The heart of this
setup is formed by a miniaturized version of our friction force microscope. This FFM
is based on a special prototype that was used to perform friction measurements inside
a HRTEM. Together with eld ion microscopy and scanning electron microscopy this
instrument will enable friction experiments with completely in-situ characterized and
modied sliding contacts.
122
A
Processing steps of the Tribolever fabrication

A.1 Overview
This appendix gives a very detailed guideline for the microfabrication of the tri-
bolever. The processing recipe was used during fabrication of the small version
of the tribolever at the Delft Institute of Microelectronics and Submicron Technol-
ogy (DIMES), therefore it is written specicly for the cleanroom facilities available at
DIMES. The processing consists of
- seven lithography steps:
mask alignment markers at the front side of the wafer.
markers at the back side.
space for attaching the chip with clips to the microscope (clip space) at the
front side.
protective crosses for the pyramid at the front side.
legs at the front side.
laserwindows (back side).
kinematic mounts.
- seven plasma etch steps (uorine etching):
markers front side.
markers back side.
clip space (front side).
crosses (front side).
legs (front side).
laser window (back side).
kinematic mounts.
123
A. P R O C E S S I N G S T E P S . . .
- six deep reactive ion etching steps for pattern transfer (MET system uo-
rine):
mask front side.
markers back side.
clip space (front side).
crosses (front side).
legs (front side).
- two KOH wet etch steps:
kinematic mounts.
- two deposition steps (LPCVD Si
3
N
4
):
mask for the wet etch of the kinematic mounts.
- three thermal oxidation steps:
thin oxide mask for etching markers (front side and back side).
thick oxide mask for deep etching.
thick oxide mask for wet etching
and
sawing of the devices.
A.2 Processing
pattern denition and transfer of markers at the front- and back side;
1. thermal oxidation:
recipe: dry oxide; 8 hours; thickness of the oxide 225nm.
2. lithography of markers at the front side:
spin coating of the mask using HMDS; 5s @ 500rpm ; 55s @ 2500.
spin coating of the wafer using HPR; recipe H: 5s @ 500rpm ; 55s @
3500; thickness 1.2m.
prebake: 30min @ 90
C.
exposure: 8s.
development (Microposit developer): 3 parts H
2
O : 1 part developer; 55s.
postbake: 30min @ 120
C.
124
A.2 P R O C E S S I N G
3. etching of the oxide at the front side in CHF
3
plasma (Leybold Z401-S or Z401)
(dry development of the marker at the fronside):
CHF
3
: 50sccm.
O
2
: 1.3sccm.
pressure: as low as possible.
rf power: 50W (reverse power must be zero to ensure a plasma impedance
of 50).
bias voltage: 33030V.
4. Stripping of resist:
removal of resist in concentrated HNO
3
.
cleaning: DI H
2
O rinse ; dry with N
2
.
cleaning and drying
removal of teon contaminants in O
2
plasma (125W, 5min)
5. HF dip and DI H
2
O rinse: 1min in 3% solution.
6. etching of the markers at the front side in the MET system (Alcatel RLE200):
SF
6
: 22.5sccm.
O
2
: 2.8sccm.
ICP power: 1000W.
Potential: 13V.
chuck temperature: 95
C.
work pressure: 1.95Pa.
etch depth: 3m; 7min.
7. lithography of markers at the back side:
HMDS; 5s @ 500rpm ; 55s @ 2500.
HPR; recipe H: 5s @ 500rpm ; 55s @ 3500; thickness 1.2m.
prebake: 30min @ 90
C.
exposure: using the back side aligner of ICAT; 10s exposure time.
development (Microposit developer): 3 parts H
2
O : 1 part developer; 55s.
postbake: 30min @ 120
C.
8. etching of the oxide at the front side in CHF
3
plasma (procedure analogous to
the front side markers)
9. stripping of resist (procedure analogous to the front side markers).
10. HF dip and DI H
2
O rinse: 1min in 3% solution.
11. etching of the markers at the back side in the MET system (analogous to front
side markers).
125
12. stripping of the oxide in buffered HF and DI H
2
O rinse.
pattern denition of the clip space:
13. RCA cleaning; standard recipe:
removal of native oxide (HF).
solution 1 (removal of organic contaminants): 5 parts H
2
O, 1 part H
2
O
2
,
1 part NH
4
, T=80
C.
solution 2 (removal of metallic contaminants): 5 parts H
2
O, 1 part HCl, 1
part H
2
O
2
, T=80
C.
cleaning and drying.
14. thermal oxidation (recipe wet oxide); 5h; oxide thickness 1m.
15. lithography of the clip space (following the steps analogous to the lithography
of the front side markers).
16. etching of the oxide in uorine plasma (same parameters).
17. stripping of the resist (analogous to markers front side).
pattern denition of the crosses:
18. lithography for patterning the crosses at the front side.
19. etching of the oxide in uorine plasma; etch depth: 650 nm.
20. stripping of the resist.
pattern denition of the legs:
21. lithography for patterning the legs at the front side.
22. etching of the oxide in uorine plasma; etch depth: 250 nm.
pattern denition of the laser window:
24. lithography for patterning the legs at the back side.
25. etching of the oxide in uorine plasma; etch depth: 1.3m.
27. optical inspection of the line width of the legs.
28. measurement of the oxide depth using -step prolometer.
pattern denition of the kinematic mounts:
29. deposition of low stress LPCVD Si
3
N
4
; thickness 400nm.
30. lithography for patterning the kinematic mounts at the back side.
31. etching of the silicon nitride and the oxide in uorine plasma; etch depth 1.3m
(300nm Si
3
N
4
and 1m SiO
2
).
pattern transfer of the kinematic mounts:
126
A.2 P R O C E S S I N G
33. HF dip and DI water rinse.
34. wet etch in KOH; 35 wt. %; 60
C; depth: 100m.
pattern transfer of the clip space:
35. etching of Si
3
N
4
in uorine plasma (front side).
36. stripping of teon contaminants in O
2
plasma.
37. HF dip and DI water rinse.
38. deep etch of the clip space in MET system (front side):
etch depth: 90m.
pattern transfer of the crosses:
39. back etching of the oxide in uorine plasma (front side) to open up the cross
pattern.
etch depth: depends on the selectivity SiO
2
/Si in step 38.
40. deep etch of the crosses in MET system (front side).
etch depth: 90m.
pattern transfer of the legs:
etch depth: depends on the selectivity SiO
2
/Si in step 38/40.
41. back etching of the oxide in uorine plasma (front side) to open up the leg
pattern.
42. deep etch of the crosses in MET system (front side):
etch depth: 20m.
pattern transfer of the laser window:
43. deep etch of the laser windows in MET system; etch depth: 350m.
44. deposition of low stress LPCVD Si
3
N
4
in the ber window.
backline processing:
45. sawing of the devices.
46. removal of sawing foil in acetone and propanol.
pattern transfer of the pyramid:
47. RCA clean; standard recipe.
48. passivation of the clamp spaces, crosses, legs, kinematic mounts and the sides
of the devices with thermal oxide:
8 hours oxidation; 200nm oxide.
49. etching of the Si
3
N
4
using boiling H
3
PO
4
to open up the ber window.
50. stripping of teon contaminants in O
2
plasma.
51. wet etch in KOH; 35 wt. %; 60
C; depth: until legs are free.

127
backline processing:
52. stripping of oxide in HF (40%) and DI water rinse.
53. cleaning and drying in hot propanol.
128
B
FFM-TEM observations

This appendix provides a brief account of a combined FFM and
TEM experiment. The goal was to observe metallic nanocontacts with
atomic resolution, using high-resolution (HR) TEM, and simultaneously
measure the normal and lateral forces acting on the contact with our
miniaturized FFM (chapter 7). Experiments of this type will be neces-
sary to explore the full mechanical behavior of atomic-scale wires and
contacts. This project was carried out in a collaboration with the group
of Prof. K. Takayanagi at the Tokyo Institute of Technology, where a
combined UHV-STM-TEM setup had been constructed already [177].
The measurements reported here, have been carried out with our FFM
mounted inside this TEM setup, during three short research stays in
Japan.
129
B. F F M - T E M O B S E R V A T I O N S
B.1 Introduction
Nanometer-sized asperities behave qualitatively differently from contacts of larger
dimensions. The relative inuence of local atomic rearrangements under either nor-
mal or shear forces on the total energy of the contact can be dramatic, leading to a
wealth of new phenomena, such as atomic-scale stepwise changes in contact length,
the existence of stable, atomic wires [154,178,179], the preference for shell structures,
the occurrence of helical structures [180], etc. Although the initial motivation for in-
vestigations of atomic-scale contacts was dominated by the special, e.g. quantized
electrical conductance [181] properties of these contacts, nowadays the atomic-scale
and mechanical aspects receive a lot of attention. Knowledge of the forces acting on
nanocontacts are of great importance for the fundamental understanding of dry fric-
tion of metals. Mechanical properties in the direction normal to the surface of atomic-
sized metallic contacts have been studied experimentally using scanning tunnelling
microscopy (STM) and related techniques [182184] and recently in an AFM-TEM
combination experiment [185] and a mechanically controllable break-junction [186]
experiment using a quartz-crystal tuning fork as the force sensor. For a single-atom
gold wire, the breaking force was found to be in the order of 1.5nN [184]. For the
understanding of friction, the forces that are generated when a nanocontact is sheared
in the lateral direction are of special interest. For this purpose, the combination of
our FFM and HRTEM should be ideal, because measured forces can directly be re-
lated to structural changes inside a nanocontact. At present, several research groups
in Japan, Sweden and Finland are attempting to study nanotribological phenomena
using AFM-TEM combination setups. The observations reported here were made for
contacts between a gold tip and a gold foil.
B.2 Experimental
The experiments described here were carried out with the miniature, TEM-compatible
FFM, presented in chapter 7. The FFM, together with its electronics and control
system were transported to the Tokyo Institute of Technology, where the FFM was
mounted in one of the UHV-TEM setups [155]. The sample stage of the FFM (see
g. 7.1, item 2) was attached the goniometer of the TEM. The berhead (g. 7.1b)
130
B.3 N A N O S C A L E W E A R O F A G O L D S U R F A C E
was positioned on one of the magnetic transfer arms. The glass bers were threaded
through a CF63 blind ange, in which they were glued with torr seal epoxy [187] to
obtain a UHV-tight seal. The sample (see next section) was introduced via a separate
load-lock system.
Unfortunately, we have not been able to obtain truly simultaneous high-resolution
measurements with the TEM and the FFM because of a technical problem that could
not be solved in the short remainder of the research visit. When running the FFM and
TEM simultaneously, we found that the glass bers of the FFM electrically charged
inside the electron beam. Each ber was covered with an aluminium cladding, but in
order to t inside the ber window of the Tribolever each ber had been tapered over
the last 10mm. Precisely over this length, the cladding was absent and the bers could
charge up. The problem occurred each time when the ber discharged, which caused
the Tribolever and the bers to move abruptly with respect to each other. The move-
ment also caused a strong periodic disturbance in the force signals. Therefore, it was
not possible to measure forces with the electron beam switched on. The frequency and
intensity of this disturbance increased with higher electron beam current and with the
size of the electron beam. By withdrawing the glass bers slightly from the pyramid
and using low beam currents, we managed to reduce the motion of the tip and could
observe the tip to interact with the gold sample while it was scanned. In principle, it
is possible to still measure the two components of the force in the plane of the TEM
image from the displacements of the tip in the image, but the charges on the FFM also
affected the TEM image and caused the image to shift when the FFM was moved.
Therefore, the actual tip position was difcult to determine. In the remainder of the
appendix we show one example of the observation of plastic deformation of asperities
on a gold surface on the atomic-scale.
B.3 Nanoscale wear of a gold surface
The scanning tip was electrochemically etched from a 60m thick gold wire using
CaCl
2
and then glued into the Tribolever. The sample was prepared from a 30m
thick gold foil. To obtain lattice resolution, the foil was thinned below 50nm using
double-beam argon ion milling. The foil was then spot welded to a CuBe leaf spring.
By moving a small rod at the goniometer against the leaf spring, the sample
could be adjusted in height in order to make contact to the tip. Figure B.1 shows a
131
Figure B.1: Low resolution TEM image showing the thinned gold foil in the upper part and
the apex of the scanning tip in the lower part.
low-resolution image of the tip approaching the sample. The pressure inside the TEM
column was 1.9 10
6
Pa. During imaging of the tip, an amorphous hydrocarbon layer
was growing on the tip due to deposition of cracked hydrocarbon molecules from
the residual gas. The tip radius grew hereby from initially approximately 250nm to
950nm during a few hours observation.
Figure B.2 displays the gold sample on the top part of the image at a magni-
cation of 400,000. The lighter gray (thinner) areas of the surface exhibited lattice
resolution. At the bottom part, the surface of the tip is visible. Figures B.2b,c shows
the tip in contact and directly after the contact was broken again. Upon approach, the
tip jumped into contact at a distance of about 3.5nm. After the tip snapped out of
contact the asperity was left behind plastically deformed by about 2.4nm in the z-
132
B.4 S U M M A R Y
direction. Before the tip had jumped into contact, we observed already that a few atom
rows were pushed upwards along the side of the gold asperity, probably due to a much
smaller hydrocarbon asperity on the tip, not visible in the video.
A second example of rearrangements before full physical contact is established,
is shown in gure B.3. The tip was scanned at a close distance from the sample with
a speed of 8nm/s. Due to the scanning motion the tip was only faintly visible in the
images. When scanning the tip, we observed also that the entire eld of view moved
slightly, even when tip and surface were completely out of contact, probably due to the
charging of the FFM, which caused a deection of the electron beam. In gures B.3a-f
we observed several pyramidal shaped asperities on the gold sample to be swept over
the surface from the right to the left by the scanning motion of the tip. We observed
that the transport of material occurred mostly by gliding along the {111}-planes. The
close-packed {111}-planes are the preferred slip planes in fcc metals and the slip di-
rections are the 110 direction, which leads to four slip planes and 12 slip directions.
The critical shear stress is lowest between these planes. This has also been observed
in an MD simulation, where a Cu(100) tip was sheared over a Cu(100) surface [65]. In
a right to left scan, material was transported to the left, in a left to right scan, material
was transported back to the right. In the observation of gure B.3, more atoms were
moved to the left than to the right causing a net ux to the left. In between Figures
B.3e and f the tip was moved closer to the gold surface, causing the tip to cut deeply
into the surface. Thereby a new, larger asperity was created, that was pushed back to
the right.
B.4 Summary
The observations described in the appendix demonstrate that a combination of a three-
dimensionally sensitive force probe is possible without compromising the capabilities
of either technique. The combined instrument will be ideal for a range of investigations
of mechanical and structural properties of nanoscale structures, such as nanocontacts
and breaking wires. Due to a charging problem in the current version of the FFM we
have not been able yet to explore the full potential of simultaneous FFM and TEM
measurements.
133
Figure B.2: A tip covered by a hydrocarbon layer touching a gold asperity of 4nm radius.
Panel (a) shows the tip shortly before snap-into-contact; (b) depicts the contours (solid line)
of the scanning tip and the asperity (c) during contact; (d) contour as hollow line; (e) directly
after breaking the contact; (f) contour as dashed line; Magnication 400, 000.
134
B.4 S U M M A R Y
Figure B.3: Grabbed frames from a video showing a gold surface (upper part of images),
while a gold tip (faintly visible) is scanned against it from below. The dashed line indicates the
approximate position of the tip surface. The arrow indicates the position of the asperity that was
modied by the scanning tip. The numbers indicate the time scale of the observation in minutes.
Magnication 400, 000.
135
136
Summary

This thesis deals with the development and application of new experimental tech-
niques for nanotribology, the science of friction and wear on the atomic scale. Chapter
1 provided a brief overview over this relatively new subject within the eld of inter-
face physics.
In chapter 2, we introduced a list of fundamental questions, which we considered to
be of importance in order to create a link between atomic-scale friction experiments
and experiments on the micro- and macroscale and to compare experiments with the-
oretical calculations and computer simulations. The ideal nanofriction experiment
should be able to address these questions. The corresponding requirements on the
ideal nanofriction could be only met by introducing a new friction force sensor.
This device was rst modelled and optimized using nite element analysis. In chapter
3, we described the fabrication process of this novel all-silicon force sensor, the Tri-
bolever. Difculties in the microfabrication could be solved using deep reactive ion
etching from one side of a silicon wafer and wet etching from the opposite side of the
wafer. The rst prototype device was shown to meet the design specications obtained
from the nite element analysis prior to the fabrication. In addition, we showed the re-
sults from the microfabrication of a miniaturized second generation Tribolever, which
can be used in combination with transmission electron microscopy and scanning elec-
tron microscopy. The design and performance of a frictional force microscope, which
makes use of the Tribolever, is presented in chapter 4. Using four glass-ber interfer-
ometers, which are positioned close to the central detection body of the Tribolever, its
motion can be simultaneously tracked in 3 directions. The positioning and manipula-
tion of the glass bers with respect to the Tribolever is performed by a special ber
positioning head, which we constructed by spark erosion from a single block of invar.
For the manipulation of the glass bers we made use of miniature piezo Nanomotors.
As a rst test application of the ambient frictional force microscope, we chose to study
atomic-scale friction on graphite surfaces. To our great surprise, although this system
has been studied intensively, the experiment revealed new phenomena. By measur-
137
S U M M A R Y
ing the friction as a function of the rotational angle between a tungsten tip and a
graphite surface we have shown in chapter 5 that the origin of the ultra-low friction of
graphite in friction force experiments lies in the incommensurability between between
a graphite ake that is attached to the tip and the graphite surface. The observation of
two narrow peaks in the friction force that are separated by 60
of ultra-low friction
provided clear experimental evidence of superlubricity: the nearly complete disap-
pearance of the friction force. The width of the two peaks allowed us to estimate the
contact diameter to be 7 to 12 lattice spacings. To verify this assumption, we have
set up a Tomlinson model, describing a rigid N-atom cluster with the symmetry of
a graphite ake that was moved through a two-dimensional sinusoidal potential rep-
resenting the graphite surface (chapter 6. The calculated friction force shows high
friction and near-zero friction, depending on the (in)commensurability between the
two lattices. By changing N, we indeed varied the width of the peak in the friction
vs. orientation plot, so that we could t the measured peak width. The calculations
revealed that the shape of the high-friction peaks depend on the precise shape of the
ake.
In chapter 7, we then presented the conceptual design of a new UHV setup, with which
the ideal experiment can be performed, which was introduced in chapter 2. The heart
of this setup is formed by a miniaturized version of our ambient version of the fric-
tional force microscope. This FFM is based on a special prototype that was used to
perform friction measurements inside a HRTEM. Together with eld ion microscopy
and scanning electron microscopy, this instrument will enable friction experiments
with completely in-situ characterized and modied sliding contacts.
In the two appendices, we listed the detailed etching recipe for the Tribolever and gave
a brief account of the rst attempts of simultaneous FFM-HRTEM experiments at the
Tokyo Institute of Technology.
138
Samenvatting

Wrijving is de welbekende kracht, die altijd optreedt als voorwerpen in contact komen
en over elkaar bewegen. Deze kracht probeert men sinds millennia te beheersen. Vaak
willen we wrijving reduceren, omdat wrijvingskrachten energie verlies en slijtage
veroorzaken, maar soms is ook een zo groot mogelijke wrijvingskracht gewenst. Dit
wordt bijvoordeeld gellustreed door een skilanglaufer, die in de klassieke stijl loopt.
De langlaufer verwacht van een goede ski, dat deze zo lang mogelijk vooruit glij-
dt, maar om de langlaufer zich goed te kunnen laten afzetten, mag dezelfde ski niet
achteruit glijden. Zon combinatie van hoge en lage wrijvingseigenschappen bestaat
in veel technische systemen en ingenieurs hebben door empirische studies veel ken-
nis opgedaan over hoe de wrijvingseigenschappen benvloed kunnen worden. Het is
eigenlijk verbazingwekkend dat ondanks de technische ontwikkeling en de uitgebreide
toepassingen er nog maar weinig bekend is over de fundamentele processen die aan
wrijving ten grondslag liggen.
In de jaren 80 van de laatste eeuw wordt de rasterkrachtmicroscoop ofwel AFM door
drie fysici uitgevonden. In dit apparaat wordt een extreem scherpe naald in contact ge-
bracht met het oppervlak van een preparaat. Het naaldje is verbonden met een veertje
waarvan uitwijking nauwkeurig gemeten kan worden met behulp van een laserbundel.
Omdat de uitwijking van de veer een maat is voor de kracht tussen de naald en het
oppervlak, kunnen kleine krachten in de orde van een nanoNewton
1
en kleiner geme-
ten worden. Met een variant van de AFM, de wrijvingskrachtmicroscoop ofwel FFM,
kan ook de wrijving gemeten worden als de naald over de atomaire landschap van
het oppervlak glijdt. Door de komst van met name de FFM heeft het onderzoek naar
de oorzaken van wrijving een tweede lente ervaren. Deze nieuwe onderzoeksrichting
staat nu bekend onder de naam Nanotribologie.
In dit proefschrift staat de ontwikkeling beschreven van een bijzondere rasterkracht-
microscoop, die gebruik maakt van een nieuwe, speciaal voor dit doel geontwikkelde
krachtsensor, waarmee (wrijvings)krachten vanaf 2/100 nanoNewton niet alleen in
1. Een nanoNewton is ongeveer 1/10.000.000.000 van de kracht die nodig is om een kilogram te tillen.
139
S A M E N V A T T I N G
e en richting, zoals met conventionele krachtsensoren, maar in drie ruimtelijke richtin-
gen tegelijk gemeten kunnen worden. Met deze nieuwe microscoop hebben we de
wrijvingseigenschappen van graet onderzocht. Graet is een bekend droog smeer-
middel en bezit een gelaagde structuur. De koolstof-atomen in een graetlaag vormen
een soort heuvellandschap, dat op een eierdoos lijkt. Twee over elkaar glijdende lagen
ondervinden uiteraard weerstand als de heuvels van de ene laag precies in de dalen
van de andere laag passen. Als de twee lagen echter tegen elkaar verdraaid worden,
dan valt de wrijving weg. Dit effect wordt superlubriciteit, ofwel supersmering ge-
noemd. Met een simpel model konden wij het gemeten superlubriciteits effect ook
met behulp van de computer berekenen en de resultaten daarvan stemden heel goed
overeen met wat er in de meting waargenomen was. In een spuitbus met graet smeer-
middel zijn de graetlaagjes zeker ook tegen elkaar verdraaid. Daarom zou het goed
kunnen, dat de goede smeringseigenschappen van graet tot stand komen door de door
ons gevonden superlubriciteit. De resultaten aan graet konden worden verkregen met
de microscoop en het preparaat blootgesteld aan de lucht. De meeste materiaalcom-
binaties kunnen helaas niet onder dergelijke omstandigheden worden bestudeerd. Da-
room wordt in dit proefschrift ook de ontwikkeling van de wrijvingskrachtmicroscoop
gepresenteerd, die in ultrahoog vacuum gaat werken. Door combinatie met andere mi-
croscopie soorten zoals veldionenmicroscopie en rasterelektronenmicroscopie zal hi-
ermee in de toekomst een volledige karaterisering van wrijvingssystemen op atomaire
schaal mogelijk worden.
140
Zusammenfassung

Reibung ist eine physikalische Kraft, die allgegenw artig ist, wenn sich Gegenst ande
bewegen. Diese Kraft versucht der Mensch seit Jahrtausenden zu beherrschen. Oft
versuchen wir dabei Reibung zu minimieren, da Reibungskr afte Energieverlust und
Verschlei verursachen, aber h aug ist auch eine hohe Reibungskraft erw unscht. Dies
l asst sich zum Beispiel an einem klassischen Skilangl aufer gut illustrieren. Der Lang-
l aufer erwartet von einem guten Ski, dass er m oglichst lange gleitet, zum anderen
will er mit dem gleichen Ski gut beschleunigen, wobei der Ski nicht r uckw arts gleiten
sollte. Eine solche Kombination von hohen und niedrigen Reibungseigenschaften n-
det sich in vielen technischen Systemen und Ingenieure haben durch empirische Stu-
dien umfangreiche Kenntnisse erlangt, wie dies technisch erreicht werden kann. Er-
staunlicherweise sind jedoch die fundamentellen Prozesse, die f ur hohe oder niedrige
Reibung verantwortlich sind, noch weitgehend unbekannt. In den 80er Jahren des
letzten Jahrhunderts wurde das Rasterkraftmikroskop (atomic force microscope oder
AFM) von drei Physikern erfunden. Ein AFM besitzt eine kleine, sehr spitze Nadel,
die mit einem Federbalken verbunden ist. Kommt diese Nadel nun in Kontakt mit der
Ober ache einer Probe, dann verbiegt sich der Federbalken. Dessen Verbiegung kann
mit Hilfe eines Lasers sehr genau gemessen werden. Da die Verbiegung ein Ma f ur
die Kraft zwischen Nadel und Probe ist, lassen sich kleinste Kr afte im Nanonewton-
bereich
2
nachweisen. Mit einer Variante des Rasterkraftmikroskops, dem Reibungs-
kraftmikroskop (frictional force microscope, FFM), k onnen zus atzlich Reibungskr afte
gemessen werden, welche die Nadel erf ahrt, wenn sie uber die atomare H ugelland-
schaft einer Probe gleitet. Vor allemdurch die Entwicklung des FFMhat die Forschung
nach den Ursachen von Reibung einen zweiten Fr uhling erfahren und ein neues For-
schungsgebiet aus der Taufe gehoben, Nanotribologie genannt.
Im Rahmen dieser Dissertation wurde ein spezielles Rasterkraftmikroskop ent-
wickelt, welches einen neuen, speziell f ur Reibungsmessungen entwickelten Kraftsen-
sor verwendet, mit dem sich (Reibungs-)Kr afte gr oer als 2/100 Nanonewton nicht
2. Ein Nanonewton ist etwa 1/10.000.000.000 der Kraft, die ben otigt wird, um ein Kilogramm zu heben.
141
Z U S A M M E N F A S S U N G
nur in einer Richtung, wie bei einem konventionellen Rasterkraftmikroskop, son-
dern in drei Raumrichtungen gleichzeitig messen lassen k onnen. Mit diesem neuen
Mikroskop wurden die Reibungseigenschaften von Graphit untersucht. Graphit ist ein
bekanntes Schmiermittel, welches eine Schichtstruktur besitzt. Unsere Messungen er-
gaben uberraschend, dass wenn man einzelne Graphitschichten gegeneinander ver-
dreht, die Reibung zwischen diesen Lagen nahezu verschwindet. Dieser Effekt, der
Superlubricity, w ortlich ubersetzt etwa Superschmierung, genannt wird, konnte
damit erstmals auf atomarer Ebene deutlich nachgewiesen worden. Anschaulich kann
man sich Graphitschichten wie ubereinander gestapelte Eierkartons vorstellen, wobei
die Struktur des Eierkartons die atomare Struktur repr asentiert. Legt man die Eier-
kartons passend aufeinander, lassen sie sich nur schwer gegeneinander verschieben,
verdreht man sie aber gegeneinander, lassen sie sich wesentlich leichter gegeneinan-
der verschieben. Der gemessene Superlubricity-Effekt konnte zudem mit Hilfe eines
einfachen Modells im Computer berechnet werden. In einer Dose Gratspray sind
die Graphitschichten sicherlich auch gegeneinander verdreht, daher ist zu vermuten,
dass die die von uns gefundene Superlubrizit at f ur die guten Schmiereigenschaften
mit verantwortlich ist. Graphit geh ort zu den wenigen Materialien, die an Luft oder
in einer Stickstoffatmosph are untersucht werden k onnen. Daher wurde zudem eine
miniaturisierte Weiterentwicklung unseres Mikroskops pr asentiert, welches im Ultra-
hochvakuum operieren wird. Durch die Kombination von Rasterkraftmikroskopie mit
anderen Mikroskopietechniken (Rasterelektronenmikroskopie und Feldionenmikros-
kopie) wird in Zukunft eine vollst andige Charakterisierung eines Reibungssystem auf
atomarer Ebene m oglich.
142
Nawoord

Hoewel het nu al vijf jaar geleden is dat ik naar Nederland ben gekomen, lijkt de
tijd voorbij gevlogen. Gedurende deze tijd hebben een groot aantal personen op vier
verschillende locaties bijgedragen aan het tot stand komen van dit proefschrift. Toen
ik op AMOLF begon, was Jenny Heimberg al onderweg richting het ideale wrijv-
ingsexperiment en ik heb in het begin veel van haar geleerd. Voor de opbouw van
de microscoop was de technische ondersteuning op AMOLF onmisbaar: Dirk Jan
Spaanderman met wie ik prettig samengewerkt heb tijdens het ontwikkelen van de
triboscoop (in de werkplaats ook troublescope genoemd) en verder Dick Glastra van
Loon, Wim Basingerhorn, Martijn Witlox, Wim Brouwer, Hans Zeijlemaker, Jan Ver-
hoeven en Ren e Koper. Onmisbaar waren ook Emile van der Drift en Tony Zijstra van
DIMES in Delft, die voor het etsen van sensoren verantwoordelijk waren en met wie
ik twee leuke maanden in de cleanroom heb mogen samenwerken.
I would like to mention also the great support from Dr. Yukihito Kondo and Dr. Nouari
Kebaili at the ERATO project in Akishima, as well as Takehiko Shinzawa, Dr. Yoshi-
fumi Ohshima and Prof. Hiroyuki Hirayama at the Tokyo Institute of Technology, and
the great hospitality of my host, Prof. Kunio Takayanagi.
Terug in Nederland konden de experimenten weer op gang komen door de hulp van in-
strumentmakers en elektronici in Leiden: Arjen Geluk, Bert Crama, Raymond Koehler
en Ewie de Kuyper. Zeer van belang waren de discussies met en de waardevolle kri-
tiek van mijn kamer- en lotgenoot Bas Hendriksen en de goede sfeer gecre eerd door
alle collegas in de groep Grensvlakfysica. Ook de korte samenwerking aan quartz
stemvorken met Tjerk Oosterkamp, Matthijs Suijlen, Henriette Jensenius, Masami
Kageshima en Suzi Jarvis had veel stemming. Vlak voor het einde leverde de samen-
werking met de terugkerende Gertjan Verhoeven nog vele interessante resultaten op.
Ik wil mijn ouders bedanken voor hun continue steun en belangstelling tijdens mijn
studie en de promotie bedanken. Vooral mijn vriendin Hiroko wil ik bedanken voor
haar steun en liefde in de laatste twee jaren.
143
N A W O O R D
144
Curriculum Vitae

M A R T I N D I E N W I E B E L
Op 9 december 1971 ben ik geboren in Lich in Duits-
land. Na het behalen van het eindexamen (Abitur) aan
het Helene-Lange Gymasium in Dortmund en het verrichten
van militaire dienst aan de Heeresiegerwaffenschule in
B uckeburg, ben ik in oktober 1992 met de studie natuurkunde
begonnen aan de Universit at Dortmund. Na het behalen van
het Vordiplom zette ik mijn natuurkundestudie voort aan de
Rheinische-Friedrich-Wilhelms Universit at Bonn. In 1996 be-
gon ik mijn afstudeeronderzoek onder supervisie van Prof. dr.
Peter Zeppenfeld in de group van Prof. dr. George Comsa aan het Institut f ur Grenz-
achenforschung und Vakuumphysik van het Forschungzentrum J ulich GmbH. Mijn
onderzoek betrof de groei en de structuur van edelgas lagen op koper eenkristallen,
die ik met behulp van lage-temperatuur rastertunnelmicroscopie bestudeerde. Daarna
begon ik een promotieonderzoek in de groep van Prof. dr. Joost W.M. Frenken, toen
nog aan het FOM-Instituut voor Atoom en Molecuulfysica (AMOLF) in Amsterdam.
In 1999 en 2000 bezocht ik voor drie korte onderzoeksverblijven het Tokyo Institute
of Technology in Japan met het doel om wrijvingskrachtmicrosopie te combineren
met transmissie elektronenmicroscopie. Aansluitend zette ik mijn promotieonderzoek
voort aan het Kamerlingh Onnes Laboratorium van de Universiteit Leiden, waar de
groep intussen naartoe verhuisd was. Het onderzoek dat ik tijdens mijn promotietijd
verrichte, staat grotendeels beschreven in dit proefschrift.
145
C U R R I C U L U M V I T A E
146
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A T O M I C - S C A L E F R I C T I O N

out of registry, the friction force vanished. However, for small

Hz). The lateral

) for AFM cantilevers

simple beam cantilever 4.03 101.1 0.2 71.6

C. Plasma process conditions are 2.3bar pressure,

with respect to the central square block. The

and with it the Tribolever. In addition,

, with respect to the (100) surface plane of the wafer.

depending on the protection uid [93]. To create a at end-

C during a day. Us-

C for one hour.

/s for rotation. The smallest step size in the Z-

according to the supplier.

. The samples were cut to a size of 2mm2mm. There-

(c) rotation angle . Normal force (a) and (c) F

away from the rst measurement in the opposite

, which corresponds well with the 60

rotation, the lattices

symmetry but rather a 120

symmetry, which should have an inuence in case

for the rst peak and 6.50.8

for the second, we estimate that the

of an initially aligned contact. The three pairs of markers at the

between the two grains. Ruan et al. [133] have proposed

provided clear exper-

. They marked the transition from

the lateral force displays a continuous, sine-like variation, with

. At intermediate angles, we cal-

mist angle, as found in the experiment, can-

symmetry. This potential only models the

. The calculation shows that the force depends modestly

symmetry of the corrugation expected from V

by choosing the pulling

and for mist angles of 120

(e,f), in order to resemble measured images shown in gure 5.7.

away from commensurability, the PES is

. The dashed lines indicate the angles

(e,f). The grey areas in the contour plots denote po-

; in other words, at = 0 the long axis of the ake is oriented at +60

angles. The X1 axis is therefore placed under an angle of 68.5

C; depth: until legs are free.

rotatable wobblestick, Thermo Vacuum Generators, Hast-

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