WORKSHOP Nanoscience on the Tip

Non-Covalent Short Range Interactions

Table of Contents:
1. Motivation ............................................................................................................ 1
2. Short Range Interactions and Surface Forces ...................................................... 1
3. Van der Waals Interactions for Point Interactions ............................................... 3
4. Surface Forces ...................................................................................................... 4
5. Hamaker Constant ................................................................................................ 5
6. Van der Waals Retardation Effects ...................................................................... 6
7. Adhesion and Surface Energies............................................................................ 6
8. Cutoff Distance for Van der Waals Calculations ................................................. 7
9. Capillary Forces due to Vapor Condensation ...................................................... 8
10. Critical Humidity for Capillary Neck Formation................................................. 9
11. Estimation of the Tip Radius Utilizing the Capillary Effects ............................ 10
12. Modification of Hydrophobicity (Wettability)................................................... 12
13. Force Displacement Curves ............................................................................... 13
References ................................................................................................................. 14
Recommended Reading ............................................................................................. 14

1. Motivation
As technology moves more towards miniaturization in novel product
developments, it is imperative to integrate interfacial interactions into design strategies.
Consequently, interfacial forces have to be explored. Interfacial forces are on the order of
10-6 to 10-10 N, strong enough, for instance, to freeze gears in micro-electrical mechanical
systems (MEMS), to affect the stability of colloidal system, or to wipe out magnetically
stored data information in hard drives. There are multiple ways of exploring the strength
of interfacial interactions, one of which is by force spectroscopy, also known as force-
displacement (FD) analysis. The FD analysis involves a nanometer sharp scanning force
microscopy (SFM) tip that is moved relative to the sample surface in nanometer to
micrometer per second, as illustrated at end of this document in Figure 10. Before we
discuss FD analysis, we first discuss interaction forces, particularly weak interactions
between molecules and solids.

2. Short Range Interactions and Surface Forces

There are three aspects that are of particular importance for any interaction: Its
strength, the distance over which it acts, and the environment through which it acts. Short
range interactions, as summarized in Table 1, can be of following nature: ionic, covalent,
metallic, or dipolar origin. Ionic, covalent, metallic and hydrogen bonds are so-called
atomic forces that are important for forming strongly bonded condensed matter. These
short range forces arise from the overlap of electron wave functions. Interactions of
dipolar nature are classified further into strong hydrogen bonds and weak Van der Waals

1
(VdW) interactions. They arise from dipole-dipole interactions. Both hydrogen and VdW
interactions can be responsible for cooperation and structuring in fluidic systems, but are
also strong enough to build up condensed phases. Following is a description of these
short range forces:

A. Ionic Bonds: These are simple Coulombic forces, which are a result of electron
transfer. For example in lithium fluoride, lithium transfers its 2s electron to the
fluorine 2p state. Consequently the shells of the atoms are filled up, but the
lithium has a net positive charge and the Flourine has a net negative charge.
These ions attract each other by Coulombic interaction which stabilizes the ionic
crystal in the rock-salt structure.
B. Covalent Bond: The standard example for a covalent bond is the hydrogen
molecule. When the wave-function overlap is considerable, the electrons of the
hydrogen atoms will be indistinguishable. The total energy will be decreased by
the “exchange energy”, which causes the attractive force. The characteristic
property of covalent bonds is a concentration of the electron charge density
between two nuclei. The force is strongly directed and falls off within a few
Ǻngstroms.
C. Metallic Bonds and Interaction: The strong metallic bonds are only observed
when the atoms are condensed in a crystal. They originate from the free valence
electron sea which holds together the ionic core. A similar effect is observed
when two metallic surfaces approach each other. The electron clouds have the
tendency to spread out in order to minimize the surface energy. Thus a strong
exponentially decreasing, attractive interaction is observed.
D. Dipole Interactions:
D.1. Hydrogen Bond Interaction: Strong type of directional dipole-dipole
interaction
D.2. Van der Waals Interaction: The relevance of VdW interactions goes beyond
of building up matter (e.g., Van der Waals organic crystals (Naphthalene)).
Because of their “medium” range interaction length of a few Ǻngstroms to
hundreds of Ǻngstroms, VdW forces are significant in fluidic systems (e.g,
colloidal fluids), and for adhesion between microscopic bodies. VdW forces
can be divided into three groups:
o Dipole-dipole force: Molecules having permanent dipoles will interact by
dipole-dipole interaction.
o Dipole-induced dipole forces: The field of a permanent dipole induces a
dipole in a non-polar atom or molecule.
o Dispersion force: Due to charge fluctuations of the atoms there is an
instantaneous displacement of the center of positive charge against the
center of the negative charge. Thus, at a certain moment, a dipole exists
and induces a dipole in another atom. Therefore non-polar atoms (e.g.
neon) or molecules attract each other.

2
 Force Spectroscopy Analysis

Table 1: Short Range Interaction Forces

Nature of Bond Type of Force Energy (kcal/mol) Distance

180 (NaCl) 2.8 Å

Ionic bond Coulombic force
240 (LiF) 2.0 Å

Electrostatic force 170 (Diamond)

Covalent bond (wave function overlap)
N/A
283 (SiC)

free valency electron sea 26 (Na) 4.3 Å

interaction
Metallic bond (sometimes also partially
96 (Fe) 2.9 Å
covalent (e.g., Fe and W) 210 (W) 3.1 Å

a strong type of directional

Hydrogen Bond dipole-dipole interaction
7 (HF)

(i) dipole-dipole force

significant in the
(ii) dipole-induced dipole force
Van der Waals (iii) dispersion forces
2.4 (CH4) range of a few Å to
hundreds of Å
(charge fluctuation)

3. Van der Waals Interactions for Point Interactions

The attractive VdW pair potential between point particles (i.e., atoms or small
nonpolar spherical molecule) is proportional to 1/r6, where r is the distance between the
point particles. The widely used semi-empirical potential to describe VdW interactions is
the Lennard-Jones (LJ) potential, referred to as the 6-12 potential because of its (1/r)6
and (1/r)12 distance r dependence of the attractive interaction and repulsive component,
respectively. While the 6-potential is derived from point particle dipole-dipole
interaction, the 12-potential is based on pure empiricism. The LJ potential is provided in
the following two equivalent forms as function of the particle-particle distance r:
Cvdw Crep ⎡⎛ σ ⎞12 ⎛ σ ⎞ 6 ⎤
φ( r ) = − + = 4ε ⎢⎜ ⎟ − ⎜ ⎟ ⎥ (1a) φ(ε)
r6 r12 ⎢⎣⎝ r ⎠ ⎝ r ⎠ ⎥⎦
where r(ε)
1
⎛ Cvdw 2
Crep ⎞ 6 0
⎜
σ=⎜ ⎟ ; ε= (1b) r
⎟
⎝ Cvdw ⎠ 4Crep
σ
Cvdw and Crep are characteristic constants.
C = Cvdw is called the VdW interaction -ε
parameter. The empirical constant ε represents
the characteristic energy of interaction between
the molecules (the maximum energy of Figure 4: Lennard Jones (6-12)
attraction between a pair of molecules). σ, a potential (empirical Van der Waals
characteristic diameter of the molecule (also Potential between two atoms or
called the collision diameter), is the distance nonpolar molecules).

3
between two atoms (or molecules) for φ(r) = 0. The LJ potential is depicted in Figure 4..

4. Surface Forces
The integral form of interaction forces between surfaces of macroscopic bodies through
a third medium (e.g., vacuum and vapor) are called surfaces forces. To apply the VdW
formalism to macroscopic bodies, one has to integrate the point interaction form
presented above. Consequently, the dipole-dipole interaction strength C but also the
exponent of the distance dependence become geometry dependent. For instance, while
for point-point particles the exponent is -6, it is -1 and -3 for macroscopic sphere-sphere
and sphere-plane interactions, respectively. Thus, while, VdW point particle interactions
are very short ranged (~1/r6), macroscopic VdW interactions are long ranged (e.g.,
sphere-sphere: ~1/D, where D represents the shortest distance between the two
macroscopic objects). Table 3 provides a list of geometry dependent non-retarded VdW
interaction strengths and exponents.
In vacuum, the main contributors to long-range surface interactions are the Van
der Waals and electromagnetic interactions. At separation distance < 2 nm one might also
have to consider short range retardation due to covalent or metallic bonding forces. Van
der Waals and electromagnetic interactions can be both attractive or repulsive. In the case
of a vapor environment as the third medium (e.g., atmospheric air containing water and
organic molecules), one also has to consider modifications by the vapor due to surface
adsorption or interaction shielding. This can lead to force modification or additional
forces such as the strong attractive capillary forces.
The SFM tip-sample interaction potential W are typically modeled as a sphere-
plane interaction, i.e.,
− AR
W( D ) = (2a)
6D
with the force
/W − AR
− = F( D ) = (2b)
/D 6D 2
where R is the radius of curvature of the tip, and D is the distance between the tip and
the plane. The interaction constant A, is called the Hamaker constant, defined as
A = π2Cρ1ρ2, with the interaction parameter of the point-point interaction C, and the
number density of the molecules in both solids ρi (i = 1,2). The Hamaker constant is
based on the mean-field Lifshitz theory. If known, A provides the means to deduce the
material specific (i.e., geometry independent) interaction parameter C. Typical values
for A, C and ρ are provided in Table 2. Table 3 summarizes the Van der Waals
interaction potential for various geometries.

Table 2: Hamaker constants of Hydrocarbon, CCl4, and water.

Medium C (10-79 Jm6) ρ [1028m-3] A [10-19 J]
Hydrocarbon 50 3.3 0.5
CCl4 1500 0.6 0.5
Water 140 3.3 1.5

4
 Force Spectroscopy Analysis

Table 3: Van der Waals interaction Potential

Geometry of Interaction Interaction Potential (W)

Point Interaction Two Atoms −C

r6

− πCρ
Atom-Surface
6D 3

− A R1 R2
Sphere-Sphere
6 D ( R1 + R2 )

Plane-Sphere
− AR
6D
Body Interaction

12
AL ⎛ R1 R2 ⎞
Two Cylinders ⎜⎜ ⎟⎟
12 2 D 3 2 ⎝ ( R1 + R2 ) ⎠

− A R1 R2
Two Crossed Cylinders
6D

−A
Plane-Plane
12πD 2

Two Parallel Chain − 3πCL

Molecules
8σ 2 r 5

5. Hamaker Constant
Originally the Hamaker constant was determined based on a purely additive
method in which polarization was ignored. The Lifshitz theory has overcome the problem
of additivity. It is a continuum theory which neglects the atomic structure. The input
parameters are the dielectric constants, ε, and refractive indices, n. The Hamaker constant
for two macroscopic phases 1 and 2 interacting across a medium 3 is approximated as:
3 ⎛ ε 1 − ε 3 ⎞⎛ ε 2 − ε 3 ⎞ 3hυ e
2 2 2
(
n1 − n3 n2 − n3 )(
2
)
){ ( )}
A ≈ kT ⎜⎜ ⎟⎜ ⎟+ (3)
1 (3 2 )(
4 ⎝ ε 1 + ε 3 ⎟⎠⎜⎝ ε 2 + ε 3 ⎟⎠ 8 2 n 2 + n 2 n 2 + n 2
3 n1
2
+ n 3
2
+ n 2
2
+ n 3) (
2

15
where νe is the absorption frequency (e.g., for H2O: νe = 3 x 10 Hz). Table 4 provides
non-retarded Hamaker constants determined with the Lifshitz theory (eq. 3).
In general, there is an attractive VDW interaction for A > 0, and the two
macroscopic phases are attracted to each other. In cases where it is desired to have
repulsive forces, the medium must have dielectric properties which are intermediate to
the macroscopic phases.

5
 Table 4: Non-retarded Hamaker constants for two interacting media across a vacuum
(air) (Source: intermolecular & Surface Forces, J. Israelachvili, Academic Press) 3
a
Dielectric constant Refractive Index Absorption frequency Hamaker Constant

ε n ν Amedium/air/medium
15 -1 -20
Medium (10 s ) (10 )

Acetone 21 1.359 2.9 4.1

Benzene 2.28 1.501 2.1 5.0
Calcium Flouride 7.4 1.427 3.8 7.0
Carbon tetrachloride 2.24 1.460 2.7 5.5
Cyclohexane 2.03 1.426 2.9 5.2
Ethanol 26 1.361 3.0 4.2
Fused quartz 3.8 1.448 3.2 6.3
Hydrocarbon (crystal) 2.25 1.50 3.0 7.1
Iron oxide (Fe3O4) 1.97 3.0 est 21
Liquid He 1.057 1.028 5.9 0.057
Metals (Au. Ag, Cu) 3-5 25--40
Mica 7.0 1.60 3.0 10
n-Pentane 1.84 1.349 3.0 3.8
n-Octane 1.95 1.387 3.0 4.5
n-Dodecane 2.01 1.411 3.0 5.0
n-Tetradecane 2.03 1.418 2.9 5.0
n-Hexadecane 2.05 1.423 2.9 5.1
Polystyrene 2.55 1.557 2.3 6.5
Polyvinyl chloride 3.2 1.527 2.9 7.5
PTFE 2.1 1.359 2.9 3.8
Water 80 1.333 3.0 3.7
a
UV absorption frequencies obtained from Cauchy plots mainly from Hough and White (1980)
and H. Christenson (1983, thesis).

6. Van der Waals Retardation Effects

The van der Waals forces are effective from a distance of a few Ǻngstroms to several
hundreds of Ǻngstroms. When two atoms are a large distance apart, the time for the
electric field to return can be critical, i.e., comparable to the fluctuating period of the
dipole itself. The dispersion can be considered to be retarded for distances more than
100 Å, i.e., the dispersion energy begins to decay faster than 1/r6 (~1/r7). It is important
to note that for macroscopic bodies retardation effects are more important than for atom-
atom interactions. This is of particular importance for the SFM force displacement
method.

7. Adhesion and Surface Energies

The energy of adhesion (or just adhesion), W", i.e., the energy per unit area necessary
to separate two bodies (1 and 2) in contact, defines the interfacial energy γ12 as:
W ' ' = 2γ 12 ; γ 12 = γ 1 + γ 2 − 2 γ 1γ 2 (4)
where γi (i= 1,2) represent the two surface energies. Assuming two planar surfaces in
contact, the Van der Waals interaction energy per unit area is
−A
W1 (D ) = (see above) (5)
12πD 2

6
 Force Spectroscopy Analysis

which was obtained by pairwise summation of energies between all the atoms of medium
1 with medium 2. The summation of atom interactions within the same medium have
been neglected, which yields additional energy terms, i.e.,
A
W2 = − const . + 2
(6)
12πDo
consisting of a bulk cohesive energy term (assumed to be constant), and an energy term
related to unsaturated "bonds" at the two surfaces in contact (i.e., D = Do). Notice that
contact cannot be defined as D = 0 due to molecular repulsive forces. Do is called the
"cutoff distance". Hence the total energy of two planar surfaces at a distance D ≥ Do apart
is (neglecting the bulk cohesive energy)
A ⎛ 1 1 ⎞ A ⎛ Do ⎞
2
W = W1 + W2 = − ⎜⎜ 2 − 2 ⎟⎟ = ⎜ 1 − ⎟. (7)
12π ⎝ Do D ⎠ 12πDo 2 ⎜⎝ D 2 ⎟⎠
In contact (i.e., D=Do) W = 0. In the case of isolated surfaces, i.e., D = ∞,
A
W= . (8)
12πDo 2
Thus, in order to separate the two surfaces one has to overcome the energy difference
A
ΔW=W(Do)- W(D=∞)=- 2
, (9)
12πDo
which corresponds to the adhesive energy per unit area of W''=2γ12. Hence, the interfacial
energy can expressed as function of the Hamaker constant and the cutoff distance:
A
γ 12 = , (10)
24πDo2

8. Cutoff Distance for Van der Waals Calculations

The challenge is to determine the repulsive cutoff distance Do, which
unfortunately cannot be set equal to the collision diameter, σ (i.e., the distance between
atomic centers). Let us assume a planar solid consisting of atoms that are close-packed.
Each surface atom (of diameter σ) will have nine nearest neighbors (instead of 12 as in
the bulk). When surface atoms come into contact with a second surface each atom will
gain (12-9)w=3w=3C/σ6 in binding energy. Thus, the energy per unit area,
S=σ2sin(60 deg) = σ2√3/2, is
1 3w 3C 3Cρ 2 2
γ 12 = ⎛⎜ ⎞⎟ = 8 = ; ρ= 3, (11)
2⎝ S ⎠ σ 2σ 2
σ
where ρ reflects the bulk atom density for a close packed system. Introducing the
definition of the Hamaker constant, it follows
3Cρ 2 3A A
γ 12 = = ≈ , (12)
2σ 2
2π σ
2 2
⎛σ ⎞
2

24π ⎜ ⎟
⎝ 2.5 ⎠
For σ = 0.4 nm and γ12 = A/(24πDo2) it follows that Do = 0.16 nm. Do = 0.16 nm is a
remarkable "universal constant" yielding values for surface energies γ that are in good
agreement with experiments as shown in the Table 5.

7
 Table 5: Surface energies based on Lifshitz theory and experimental values.(Source:
intermolecular & Surface Forces, J. Israelachvili, Academic Press) 3

Surface Energy, γ (mJ/m 2)

Lifshiz Theory
Material A Experimental*
A/24 π Do2
-20
(10 ) {Do=0.165nm} (20oC)

Liquid helium 0.057 0.28 0.12 - 0.35(at 4-1.6K)

Water 3.7 18 73
Acetone 4.1 20.0 23.7
Benzene 5.0 24.4 28.8
CCl4 5.5 26.8 29.7
H2o2 5.4 26 76
Formamide 6.1 30 58
Methanol 3.6 18 23
Ethanol 4.2 20.5 22.8
Glycerol 6.7 33 63
Glycol 5.6 28 48
n- Pentane 3.75 18.3 16.1
n -Hexadecane 5.2 25.3 27.5
n -Octane 4.5 21.9 21.6
n -Dodecane 5.0 24.4 25.4
Cyclohexane 5.2 25.3 25.5
PTFE 3.8 18.5 18.3
Polystyrene 6.6 32.1 33
Polyvinyl chloride 7.8 38.0 39

9. Capillary Forces due to Vapor Condensation

In the discussion above we have considered a continuous medium in-between the
two surfaces to deduce the surface forces. Thereby, we have assumed that this third
medium fills up the vacuum space entirely, i.e., does not introduce interfaces. We have to
drop this assumption, however, should the third medium form a finite condensed phase
within the interaction zone of the two bodies. Any condensed phase within the interaction
zone will exhibit interfaces towards the vapor, and thus, if deformed (e.g., stretched)
contribute to the acting forces. These new forces, called capillary forces, are on the order
of 10-7 N for single asperity contacts with radii of curvatures below 100 nm.
Capillary forces are meniscus forces due to condensation. It is well known that
micro-contacts act as nuclei of condensation. In air, water vapor plays the dominant role.
If the radius of curvature of the micro-contact is below a certain critical radius, a
meniscus will be formed. This critical radius is defined approximately by the size of the
Kelvin radius rK = l/(l/rl + 1/r2) where rl and r2 are the radii of curvature of the meniscus.
The Kelvin radius is connected with the partial pressure ps (saturation vapor pressure) by

8
 Force Spectroscopy Analysis

γ LV
rK = , (13)
⎛ p⎞
RT log ⎜⎜ ⎟⎟
⎝ ps ⎠
where γL is the surface tension, R the gas constant, T the temperature, V the mol volume
and p/ps the relative vapor pressure (relative humidity for water). The surface tension γL
of water is 0.074N/m (T=20°C) leading to a critical Van der Waals distance of water of
γLV/RT = 5.4 Å. Consequentially, we obtain for p/ps=0.9 a Kelvin radius of 100 Å. At
small vapor pressures, the Kelvin radius gets comparable to the dimensions of the
molecules, and thus, the Kelvin equation breaks down.
The meniscus forces between two objects of spherical and planar geometry can be
approximated, for D « R, as:
4πRγ L cos Θ
F R >> D = , (14)
(1 + D / d )
where R is the radius of the sphere, d the length of PQ , see Figure 5, D the distance
between the sphere and the plate, and θ the meniscus contact angle.

Figure 5: Capillary meniscus between two objects of spherical and planar geometry

R >> d
The maximum force, found at at D = 0 (contact), is Fmax = 4πRγ cos θ . While this
expression estimates the capillary forces of relatively large spheres fairly accurately, the
capillary forces of highly wetted nanoscale spheres requires a geometrical factor K.
(1 + cos φ ) 2
K= (15)
4 ⋅ cos φ
where φ is the filling angle.

10. Critical Humidity for Capillary Neck Formation

SFM force displacement analysis studies involving hydrophilic counter-surfaces
and water vapor have identified three humidity regimes with significantly different
involvement of the third medium, as shown in Figure 6. At very low humidity (regime I),
below a critical relative humidity (RH) of ~40 %, no capillary neck is developed, and the
forces measured truly reflects VdW interactions. A capillary neck is formed at about
40 % RH, which leads to a force discontinuity observed between regimes I and II. We
can understand this transition-like behavior of the pull-off force by considering the

9
minimum thickness requirement of a liquid precursor film for spreading. The height of
the precursor film can not drop below a certain minimum, e, which is
1/ 2 1/ 2
⎛γ ⎞ ⎛ A ⎞
e = a0 ⎜ ⎟ ; a0 = ⎜⎜ ⎟⎟ ; S = γ SO − γ SL − γ , (15)
⎝S⎠ ⎝ 6πγ ⎠
where ao is a molecular length, S the spreading coefficient, A the Hamaker constant, γSO
the solid-vacuum interfacial energy, and γSL the solid-liquid interfacial energy. As the
water vapor film thickness depends on the RH (i.e., p/ps), a relative humidity smaller than
40 % does not provide a minimum thickness for the formation of a capillary neck. Once a
capillary neck forms between the SFM tip and the substrate surfaces, the pull-off force
increases suddenly, and provides over regime II a pull-off force that contains both, VdW
and capillary forces. VdW forces from SFM FD analysis as determined, for instance,
from regime I, see Figure 6(b), are on the order of 1-10 nN. The capillary force, on the
other hand, is on the order of up to 100 nN, and thus, dominates VdW interactions in
regime II.
Pull-off Force

I II III
Relative Humidity
Figure 6(a): Generic sketch of the functional Figure 6(b): Pull-off force vs. RH measured
relationship between the pull-off force and the between a hydrophilic silicon oxide SFM tip
relative humidity (RH). Regimes I, II and III and a ultra-smooth silicon oxide wafer. ●
represent the van der Waals regime, mixed van measured for increasing RH, ▼ measured for
der Waals – capillary regime, and capillary decreasing RH. .1
regime decreased by repulsive forces,
respectively.

In the high RH regime (III) the pull-off force decreases with increasing RH for
hydrophilic counter-surfaces. At such high humidity, the water vapor film thickness
dimensions exceeds the contact size ( asperity flooding), and the effect of the capillary
interface decreases.

11. Estimation of the Tip Radius Utilizing the Capillary Effects

The capillary effect, commonly not desired, can be useful in estimating the SFM
tip radius. Assuming the absence of the flooding effect and the ionic salvation effect
within regime III, as discussed in the previous section, the humidity dependent adhesion
forces can be described as a mathematical model of sigmoidal form4,

Fstv − ( Fstw + Fcap )

Fmea = ( Fstw + Fcap ) + (16)
1 + exp[(ϕ 0 − ϕ ) / m]

10
 Force Spectroscopy Analysis

where Fmea is the experimentally determined pull-off forces,

Fstv is the van der Waals interaction force between the sample and the tip
in water vapor,
Fstw is the van der Waals interaction force between the sample and the tip
in liquid water,
Fcap is the capillary force, φ is the relative humidity (in fraction),
ϕ0 is the mid-point of the transition regime, and
m is the transition width.

As shown in Figure 7, the forces, Fstv, Fstw, and Fcap, are components of the measured
pull-off force Fmea. When the relative humidity is below the transition regime, i.e., ϕ <
ϕ0, the Fmea consists Fstv only, represents the lower limit of the sigmoidal fit. Above the
transition regime, Fmea is the sum of Fstw and Fcap, represents the upper limit of the
sigmoidal fit.

Figure 7: The components of full-off forces in humid environment.

The Fstw and Fstv can be expressed by assuming that the contact is between an
incompressible sphere and a hard flat surface, i.e. Bradley’s model (see page 24),
Fstv = 2π ⋅ R ⋅ Wstv or Fstw = 2π ⋅ R ⋅ Wstw (17a or 17b)
where R is the sphere radius (i.e. SFM tip radius), W is the work of adhesion which is
expressed as,
Wijm = γ im + γ jm + γ ij (18)
where γ is the interfacial energies of the two materials, and i, j, m represents solid i, solid
j, and the medium m in which the contact take place, respectively. If the contact is
between two solids with the same material, i.e., i = j, Eq. (18) reduces to Wijm = 2γ im .
In order to determine the tip radius R, Eq. (17a) is solved for R using experimentally
determined Fstv. The R value is then used to determine Fstw through Eq. (17b), and Fcap is
deduced. Employing the geometric coefficient K for the capillary force equation,
(1 + cos φ ) 2
Fcap = 4π ⋅ R ⋅ γ water cosθ ⋅ (19)
4 ⋅ cos φ

11
the filling angle φ can be deduced. For example, the result obtained by He et. al.1 on the
silicon wafer surface, was analyzed using this model. Using the value of γ SiO/air 100
mJ/m25, γSiO/water 24.5 mJ/m25, γ water 72.8 mJ/m2, and the contact angle Θ of 0 °, the tip
radius R and the filling angle φ was determined to be 8.7 nm and 85.6 ° respectively.

12. Modification of Hydrophobicity (Wettability)

Capillary effect is absent when the surface is hydrophobic, i.e., non-wetting, and
hydrophobic silicon surfaces can be created with appropriate treatment. In general, the
degree of hydrophobicity (wettability) depends on the surface chemistry and micro
roughness. One most common technique to measure hydrophobicity is the contact angle
measurement. As shown in Figure 8, a droplet of water is placed on a surface of interest
and the angle Θ which the water forms with the surface is evaluated. When the angle is
smaller than 90 °, the surface is said to be more hydrophilic or wetting. When the angle is
larger than 90 °, the surface is rather hydrophobic (non-wetting). The contact angle
results from the energy balance between the solid surface, vapor, and the liquid, hence
the contact angle, although it is not straightforward, can be used to deduce the surface
energy γ. It should be noted that the surface energy (interchangeably called interfacial
energy, surface tension), is an important parameter in evaluating the surface forces, as it
can be seen in multiple equations presented in previous sections.

Figure 8: The contact angle measurement. The contact angle Θ is the measure of
hydrophobicity (wettability). Left: hydrophilic surface. Right: hydrophobic surface.

The hydrophobicity is a major concern in semiconductor industries, such as IC

(integrated circuit) board manufactures and microelectronic technology. Because such
devices are used in ambient environment, i.e. humid air, the surfaces are prepared
carefully to have both the desired functionalities and the surface characteristics. A silicon
wafer is made out of pure silicon, Si, but the surface without any special treatment, is in
an oxidized form silicon, SiOx, a hydrophilic surface. This oxide layer can be etched out
by HF (hydrofluoric acid), leaving the surface with hydrogen-terminated silicon, more
hydrophobic. Figure 9 is actual photographs of the contact angle measurement on a series
of silicon surfaces. Figure 9(b) is as-is silicon surface which is cleaned with organic
solvent. This surface is SiOx covered with residual organic impurities, generating
partially wetting (hydrophilic) surface. When the solvent cleaned surface was further
treated with UV/Ozone cleaner, which removes the residual organics on the surface, the
surface showed complete wetting with the contact angle of 0 °, Figure 9(a). On the other
hand, if the surface was treated with HF, the contact angle is rather large ~ 72 °, thus it is
rather hydrophobic surface, Figure 9(c). Although this HF treated surface posses
desirable hydrophobicity, the surface is not stable due to its high surface energy. Studies
found that the hydrogen-terminated surface in ambient air is oxidized within several
hours, resulting in creating naturally grown SiOx layer on the surface.

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 Force Spectroscopy Analysis

(a) (b) (c)

Figure 9: The contact angle measurement of silicon surfaces (a) clean SiOx surface, (b) SiOx
covered with organic impurities, (c) HF treated Si surface.

13. Force Displacement Curves

In SFM force displacement (FD) analysis, the normal forces acting on the cantilever are
measured as a function of the tip-sample displacement. In other words, the tip-sample
distance could not be precisely controlled due to the flexibility of the cantilever. As a
result, the FD curve jumps the path of the force curve as illustrated in Figure 10. Figure
10(a) shows the cantilever approach from point Do. When the distance reaches point A0
an instability occurs resulting in a jump into contact to point B0. On the retraction out of
contact an instability occurs at point C0 causing the cantilever tip to snap out of contact
back to point D0. As a result the typical force distance curve is shown in Figure 10(b).
Each segment of the curve is described as follows.

F(r)

A0 D D0

A
C
B0

C0
B

(a) (b)
Figure 10: (a) The actual path taken by a SFM cantilever. The inset illustrates the snap-in
instability at A0 where the second derivative of the interaction potential exceeds the spring constant
of the cantilever. (b) Typical force distance curve. D = displacement, F(D) = force.

1. Line 1-A0: The probe and sample are not in contact but the tip is moving toward
the sample.
2. Line A0-B0: Jump into contact caused by the attractive van der Waals forces
outweighing the force of the cantilever spring between the tip and the sample
causing the cantilever to bend.
3. Line B0-2: Shows upward deflection of the cantilever in response to the sample
motion after they are in contact. The shape of the segment indicates whether the
sample is deforming in response to the force from the cantilever. (may not always
be straight) If the sample is assumed to be a hard surface, the slope of this line is
the sensitivity (springiness) of the cantilever.

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 4. Line 2-C0: As the tip moves away, the slope follows the slope of line B0-2 closely.
If line 2-C0 is parallel to line B0-2, no additional information can be determined.
However, if there is a difference in the in and out-going curves (hysteresis) gives
information on the plastic deformation of the sample. Once it passes point 2’, the
cantilever begins to deflect downward due to adhesive forces..
5. Line C0-D0: A jump out of contact occurs when the cantilever force exceeds the
adhesive forces.

The jump out of contact distance will always be greater than the jump into contact
distance because of few possible causes are:
a. During contact, some adhesive bonds are created.
b. During contact, the sample buckles and “wraps” around the tip, increasing the
contact area.
c. Hysteresis contributions
d. Capillary forces exerted by contaminants such as water.

FD analysis is widely used for adhesion and force interaction studies. Recently
biological materials have been studied by force spectroscopy, such as adsorption strength
of proteins on a substrate and folding/unfolding energy of DNAs.

References
1
M. He, A. Blum, D. E. Aston, C. Buenviaje, and R. M. Overney, Journal of chemical
physics 114 (3), 1355 (2001).
2
H. Hertz, J. Reine und Angewandte Mathematik 92, 156 (1882).
3
J. N. Israelachvili, Intermolecular and surface forces. (Academic Press, London,
1992).
4
D. L. Sedin and K. L. Rowlen, Analytical Chemistry 72, 2183 (2000).
5
C. Ziebert and K. H. Zum Gahr, Tribology Letters 17 (4), 901 (2004).
6
J. A. Greenwood, Proc. R. Soc. Lond. A 453, 1277 (1997).

Recommended Reading
Contact Mechanics by K. L. Johnson, Cambridge University Press, Cambridge, 1985.
Gases, liquids and solids and other states of matter by D. Tabor, Cambridge Univ.
Press, Cambridge, 3rd ed. 2000.
Intermolecular and surface forces by J. N. Israelachvili, Academic Press, London, 1992.
Nanoscience: Friction and Rheology on the Nanometer Scale by E. Meyer, R. M.
Overney, K. Dransfeld, and T. Gyalog, World Scientific Publ., Singapore, 1998.

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