Lecture 7

Interaction forces III –

Tip-sample interaction forces
Ron Reifenberger
Birck Nanotechnology Center
Purdue University

1
 Summary of last lecture
Type of interaction
Q1 Q2 Ion-ion electrostatic Q1Q2
r U (r ) =
4πεε 0 r
p θQ Dipole-charge electrostatic Qp cos(θ )
r U (r ) = −
4πεε 0 r 2
Dipole-dipole electrostatic
p1 p2
θ1 φ θ2 p1p2 [ 2cos(θ1 )cos(θ 2 ) − sin(θ1 )sin(θ 2 )cos(φ )]
r U (r ) = −
r 4πεε 0 r 3
Angle-averaged electrostatic (Keesom force)
p1
p2 p12 p22 1
UKeesom (r ) = −
3 ( 4πεε 0 ) kBT r
2 6
r
p1 p2 Angle-averaged induced polarization force (Debye force)
p12α 02 +p22α 01 1
r UDebye (r)= -
(4πε 0ε )2 r 6
Dispersion forces act between any two molecules or atoms
(London force) 3 α 01α 02 ( I1 )( I 2 ) 1
U London (r ) = −
2 (4πε 0ε ) 2 I1 + I 2 r 6
2 Adapted from J. Israelachvilli, “Intermolecular and surface forces”.
From interatomic to tip-sample interactions-simple theory
First consider the net interaction between an isolated atom/molecule and a flat
surface.
Relevant separation distance will now be called “d”.
Assume that the pair potential between the atom/molecule and an atom on the
surface is given by U(r)=-C/rn.
Assume additivity, that is the net interaction force will be the sum of its inter-
actions with all molecules in the body – are surfaces atoms different than bulk
atoms?
No. of atoms/molecules in the infinitesimal ring is ρdV= ρ(2πx dx dζ) where ρ is
the number density of molecules/atoms in the surface.

dζ  x =∞ ζ =∞

dx  dx 
U (d ) = −2π C ρ ∫ dζ  ∫ 
x
( )
n

ζ
= ζ d=  x 0 ζ 2
+ x 2

 
ζ=0 ζ=d
ζ −2π C ρ
= n −3
, for n > 3
( n − 2)( n − 3)d
−π C ρ
= UVdW = 3
, for n 6 3
6d
Number Densities of the Elements

Introduction to Solid State Physics, 5th Ed. C. Kittel, pg. 32

4
From interatomic to tip-sample interactions-simple theory
Next integrate atom-plane interaction over the volume of all atoms in the AFM
tip. Number of atoms/molecules contained within the slice shown below is
πx2 dζ = ρ π[R2-(R-ζ)2] dζ = ρ π(2Rtip-ζ)ζ dζ.
Since all these are at the same equal distance d+ζ from the plane, the net inter
action energy can be derived by using the result on the previous slide.

ζ = 2 Rtip
ζ=0 −2π C ρ
2 2
(2Rtip − ζ )ζ dζ
U (d ) =
( n − 2)( n − 3) ∫ (d + ζ )n −3
ζ ζ =0

If d << Rtip ,
ζ+d
Rtip −2π 2C ρ 2
ζ =∞
Rtipζ dζ
(n − 2)(n − 3) ζ ∫=0 (d + ζ )n −3
U (d ) ~
d x
4π 2C ρ 2Rtip
= −
2Rtip-ζ (n − 2)(n − 3)(n − 4)(n − 5)d n −5
For d << Rtip , n = 6
dζ
π 2C ρ 2Rtip HRtip
UVdW (d ) ~ − =−
6d 6d
H : Hama ker' s constant (also A or AH )
5
From interatomic to tip-sample interactions-some caveats

 If tip and sample are made of different materials replace

ρ2 by ρ1ρ2 etc.
 Tip is assumed to be homogeneous sample also! Both
made of “simple” atoms/molecules
 Assumes atom-atom interactions are independent of
presence of other surrounding atoms
 Perfectly smooth interacting surfaces
 Tip-surface interactions obey very different power laws
compared to atom-atom laws

6
 Measuring Macroscopic Surface Forces
An interface is the boundary region between two adjacent bulk phases

L G S

L S S

V L L = Liquid
G = Gas
S = Solid
L S
V = Vapor
We call (S/G), (S/L), and (L/V) surfaces
We call (S/S) and (L/L) interfaces

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 Surface Energetics
Atoms (or molecules) in the bulk of a material have a low relative energy
due to nearest neighbor interactions (e.g. bonding).
Performing work on the system to create an interface can disrupt this
situation...

8
 (Excess) Surface Free Energy
Atoms (or molecules) at an interface are in a state of higher free energy
than those in the bulk due to the lack of nearest neighbor interactions.

interface

9
 Surface Energy

The work (dW) to create a new surface of area dA is proportional to

the number of atoms/molecules at the surface and must therefore
be proportional to the surface area (dA):

dW = γ ⋅ dA
γ is the proportionality constant defined as the specific surface free
energy. It is a scalar quantity and has units of energy/unit area, mJ/
m2.
γ acts as a restoring force to resist any increase in area. For liquids γ
is numerically equal to the surface tension which is a vector and has
units of force/unit length, mN/m.
Surface tension acts to decrease the free energy of the system and
leads to some well-known effects like liquid droplets forming spheres
and meniscus effects in small capillaries.

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high surface energy ↔ strong cohesion ↔ high melting temperatures

Material Surface energy ( mJ/m2 )

mica 4500
gold 1000 Values depend on
mercury 487  oxide contamination
 adsorbed contaminants
water 73  surface roughness
benzene 29  etc….
methanol 23

Materials with high surface energies

tend to rapidly adsorb contaminants

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 Work of Cohesion and Adhesion

For a single solid (work of cohesion):

1
γ 1 ⋅ 2 dA =
dW11 = 2γ 1dA 1
γ1

For two different solids

(work of adhesion): 1 γ1
1
dW12 = (γ 1 + γ 2 − γ 12 )dA
γ2
γ1 2 2 2
interfacial
energy
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 Surface-surface interactions
Following the steps in previous slides it is possible calculate the inter-
action energy of two planar surfaces a distance of ‘d ’ apart, specifically
ρdV = ρ dA dζ for the unit area of one surface (dA=1) interacting with
an infinite area of the other.
ζ =∞
unit area −2π C ρ 2 dζ
( n − 2)( n − 3) ζ ∫=d (ζ )n −3
U (d ) =
dζ

ζ 2π C ρ 2 1
= −
( n − 2)( n − 3)( n − 4) d n − 4
For n = 6
ζ U (d ) = U (d )plane − plane
πCρ 2
= − 2
( per unit area )
12d
=AH Hama ker constant ≡ π 2C ρ 2
ζ=d
AH 1
U (d )plane − plane = − per unit area
ζ=0 12π d 2

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 Typical Values for Hamaker Constant

Typically, for solids interacting across a vacuum,

-77 6 28 -3
C ≈ 10 Jm and ρ ≈ 3x10 m

AH ≈ π ⋅10 2 −77
J m ⋅ ( 3 ×10 m
6 28
)
−3 2

 10−19 J

Typically, most solids have

AH  (0.4 − 4.0) × 10−19 J

See Butt, Cappella, Kappl, Surf. Sci. Reps., 59, 50 (2005) for more complete list

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 Implications
 σ 12  σ 6  atom-atom
=
Equilibrium U (r ) 4Uo *   −   
 r   r   interaction
separation
r=σ
1
r*= 12  6
σ = 1.12σ
 6  Positive energy
1
U or F rF=max=  12 ⋅13  6
σ = 1.24σ Repulsive force
 6 ⋅ 7 

dU (r )
U (r) F (r ) = −
dr Negative energy
Attractive force

Umin
Flocal max

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 Estimating the interfacial energy

unit area
When d≈r*, then per unit
dζ
ζ area, we should have:
AH
UvdW (=
d r=
*
)
12π ( r * )2
= dW
= 11 2γ 1
ζ
AH
γ1 =
24π (r * )2
ζ=d=r* This approach neglects the
atomicity of both surfaces.
ζ=0
Require an “effective” r*.

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 In general, vdW interactions between
macroscopic objects depends on geometry

17
Source J. Israelachvilli, “Intermolecular and surface forces”.
 The Derjaguin approximation
Plane-plane interaction energies are fundamental quantities and
it is important to correlate tip-sample force to known values of
surface interaction energies. For a sphere-plane interaction we
saw that
4π 2C ρ 2Rtip 1
U (d ) = −
(n − 2)(n − 3)(n − 4)(n − 5) d n −5
dU 4π 2C ρ 2Rtip 1
F (d ) =
− =
−
d (d ) (n − 2)(n − 3)(n − 4) d n −4
Comparing with previous slides we find that
F (d )sphere − plane = 2π RtipU (d )plane − plane

It can be shown that for two interacting sphere of different radii

 RR 
F (d )sphere −sphere = 2π  1 2  U (d )plane − plane
 R1 + R2 

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 Implications of Derjaguin’s approximation

 We showed this when U(r)=-C/rn - however it is valid for

any force law - attractive or repulsive or oscillatory - for
two rigid spheres.
 As mentioned before, if two spheres are in contact
(assuming no contamination), then d=r*.
 The value of U(d=r*)plane-plane is basically dW11 the
conventional surface energy per unit area to create a
solid surface. Thus:
−1
 1 1 
Fadhesion ≡ Fsphere −sphere (d =r *) =2π U plane − plane (d =r *) ⋅  + 
 1
R R2 

dW11
 This approximation is useful because it converts measured
Fadhesion in AFM experiments to surface energy dW11
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 How to Model the Repulsive Interaction
at Contact?
Atom-Atom? Sphere-Plane?

tip
apex

substrate
Source: Capella & Dietler

Maybe if the contact area involves tens or hundreds

of atoms the description of net repulsive force
is best captured by continuum elasticity models
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