Lecture: P1_Wk3_L1

Tip-Sample Interactions:
the Water Meniscus
Ron Reifenberger
Birck Nanotechnology Center
Purdue University
2012

Week 3 Overview
Deflection
vs. z

Piezos

Force
Spectroscopy

Static
Cantilever
Contact

Cantilever

Instrumentation

AFM

Topographic
Imaging

Controller
Calibration

Force Sensing
and Control

Theory

Controller

Tip-Sample
Interaction

Local Material
Property Map

Air
Adhesion

P1_Wk3_L1

Elasticity

The asymmetry in number density at a liquidvapor surface gives rise to a pressure

differential and a surface curvature
Vapor (~2x1019 molecules/cm3)

(~1015

Surface
molecules/cm2)

Vapor

Local radius of
curvature R

Liquid

Liquid water
(~3x1022 molecules/cm3)

Solid substrate (~6x1022 atoms/cm3)

P1_Wk3_L1

The Curvature of a Liquids Surface

has far reaching consequences
See Appendix for a general discussion on how to quantify the curvature
of a surface using the radius of curvature. Two important consequences:
1. If the surface of a liquid is curved, there must be a pressure

difference: Young-Laplace Equation

b) Liquid/vapor interface in equilibrium

a) Fill tube with liquid:
Liquid

Curvature implies Pin > Pout

Liquid

Curvature implies Pin < Pout

Liquid

1
1
(Pin Pout ) = R + R
2
1
for a spherical surface , R=
R=
R and
1
2
1
P ( Pin Pout ) =
2
R

P1_Wk3_L1

see Appendix 2 for derivation

Implications of the YoungLaplace Equation

If the shape of a liquid surface is known, its curvature is known and the
pressure difference can be calculated.
In equilibrium, the pressure is the same everywhere in a liquid (otherwise
there would be a flow of liquid to regions of lower pressure). Thus, Pin is
constant and the YoungLaplace equation tells us that the surface of the
liquid must have the same curvature everywhere.
Example: Calculate the pressure difference that develops for a spherical drop of
water at STP with a radius of 1 m?

1
P = ( Pin Pout ) = 2 = 2 75 10 3J / m 2

6
R
1 10 m
1atm .
1.5 10 5 N / m 2 =
1.5 10 5 Pa
=
1 10 5 Pa
P 1.5 atmospheres pressure drop across interface

Using the YoungLaplace equation, the equilibrium shape of a liquid

surface can be calculated if we know the pressure difference and
boundary conditions (volume of liquid and its contact line).
P1_Wk3_L1

2. It may not be so obvious, . . . but if the surface of a liquid is

curved, the equilibrium vapor pressure of the liquid must also
change: Kelvin Equation
Flat interface:
Liquid film

Curved interfaces:
drop

f
o

condensation
into pores

bubbles

The equilibrium vapor pressure measures a liquid's evaporation

rate: smaller drops evaporate faster

RgasT
Vmol

J
0.072
=
T temperature in K
2

H O

Vmol

c
Pvap

1
1
n f =
+
Po
R1 R2

H2O

18cm 3
=
R1 , R2 radii of curvature of liquid surface

Rgas = 8.314 J
P1_Wk3_L1

mole

K mole

see Appendix 3 for derivation

6

Application to AFM
In humid air, both tip and substrate will be coated with thin layer of
adsorbed water. When the tip contacts the surface, the adsorbed
water will form a meniscus neck around the AFM tip.

Rtip

Temperature T

water
meniscus
neck

Pressure P

Rtip
R2

R1

System in equilibrium

Sign convention for radius: R1 is negative, R2 is positive

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How thick is h?

(measured thickness of water layer on a silicon oxide substrate)

Asay and Kim, J. Phys. Chem B 109, 16760 (2005)

~0.8 nm at
RH=30%

How long does it take for this layer of water to form? The answer
depends on relative humidity, but for a typical ambient humidity of say
30%, the time is very fast, much less than one second see Appendix 3.
P1_Wk3_L1

At contact - what determines R1, R2?

Vapor pressure in handbooks are measured for liquids having a flat surface
Vapor pressure depends on the curvature of the liquids surface
Use Kelvin equation - derived from the Young-Laplace Equation:
Pvapc
RgasT =
n f Vmol
Po

1
1
+

R
R
1
2

Pvacp = vapor pressure of liquid having curved surface with radii R1 , R2

Pof = vapor pressure of liquid having flat surface
Pvapc
Po

Relative Humidity

for water:
V
RgasT

mol
=
water

c
Pvap
= Pof e

P1_Wk3_L1

(0.072J m )
2

0.52 1 + 1
R
1

18cm 3
1nm

mole 10 7 cm
1m
0.52nm

=
9
10 nm
J
8.314
300K

K mole

R 1, R 2 in nm
9

~0.5 nm at
RH=30%

Equilibrium |R1| (in nm)

Results for water meniscus

Rtip

10.0
R2

8.0

R1

Assumin g

1
1
>>
R1
R2

6.0
System in equilibrium

4.0
2.0
0.0
0.0

0.2

0.4
0.6
0.8
Relative Humidity

1.0

Will the liquid evaporate from the meniscus neck? No, the
liquid will not evaporate due to the curvature of the
air/vapor interface.
P1_Wk3_L1

10

Conclusion: A capillary meniscus force

binds a sphere to a flat plane

Flift off
Rtip

Water meniscus forms:

R1 is small (and negative)
R2 is large (and positive)
Curvature implies Pin < Pout

Rcap
Pvapc
1
1 RgasT
PLaplace Laplace pressure =
=
+
n f
Po
R1 R2 Vmol

Pvapc
RgasT
2

F
P
A
n
R
=
=

capillary
Laplace
Pof cap
Vmol

Relative humidity

Rcapwill depend on h , Rtip , R 1 and R

P1_Wk3_L1

2
11

Estimate magnitude of capillary force

(see Appendix 4 for geometric details)

Fcapillary PLaplace A =

RgasT
Vmol

Pvapc
n f
Po

2
Rcap

RgasT

Relative Humidity

2
Pvacp

=
n f 2 R tip h + R 1
Po
Vmol

c
R T

P
gas
vap
h + R 1 ) n f 4 R tip
4 R tip
=
(
Po
Vmol

(1.3/0.5) x 1.2 3

c
(h + R )

P
vap
1

n f
Po
0.52nm

Compare to:
FvdW (Derjaguin ) = 4 Rtip independent

FJKR = 3 R tip
of RH

DATA:
Asay and Kim, J. Phys. Chem B 109, 16760 (2005)
He et al., J. Chem. Phys. 114, 1355 (2001).

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12

Effect of capillary condensation important

modifications to the DMT model

Fcapillary

capillary neck
breaks

Capillary force models range from simple to complex

Strong dependence on humidity
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Next Lecture: An overview of VEDA

the online AFM simulation software

P1_Wk3_L1

14

Appendix 1: Defining the Curvature of a

Surface in 3D?
Surprisingly, the curvature of any surface
can be specified by two numbers, the two
radii of curvature at a point P.

P1_Wk3_L1

15

plane defining L

Surface

qrst

Define a point P on surface qrst by the vector S.

n
u2

u1

y S = f(x , y , z )

r = S (u1 , u2 , n )

Define the orientation of the surface by the

normal vector n.

Define two tangent unit vectors u1 and u2 that

are normal to each other and to n.
This local coordinate system (u1,u2,n) can be
used to specify any point on the surface.
How much a surface bends and twists along a
line L can be defined by the largest circle tangent
to the line (positive radius when located on the
concave side of the surface).

The reciprocal of the tangent circle radius R=PP is called the curvature (=1/R units:
radians/m) of the surface along the line at the point P. For gently curving surfaces, the
curvature is basically the second derivative of the line L at the point P.
The curvature of the surface will be a continuous function as the plane defining L is
o
rotated through 180 .
As the plane is rotated, there will be a maximum and a minimum radius of curvature.
These two extrema are called the principal curvatures at the point P.
P1_Wk3_L1

16

Defining the curvature of qrst requires finding the radii of

two circles tangent to the surface.
B

F
E

A
P

A
t

L
C

G
r

D
F

C
E

H
N

Circle 2

O
Curvature: 2=1/R2

R2

Mean radius of curvature:

1
1 1
1
= +
Rmean 2 R1 R2
Gaussian curvature: = 1 2

Curvature: 1=1/R1

R1

O
q

Circle 1
M

17

Further Considerations
1. An important theorem in differential geometry proves that so
long as plane ABCD is perpendicular to plane FEHG (see previous
slide), the mean radius of curvature is invariant, independent
of the alignment of the two planes wrt the surface qrst.
2. Once the curvature is known at a point, it can be used to
derive a differential equation that describes the equation of the
surface at that point.
3. A few surfaces with their of radii of curvature:
R1

R2=

Cylinder

R1

Rm
P1_Wk3_L1

Sphere, radius R

R2=R1
1 1
1 1 1
+
=
2 R1 R2 2 R1

Rm

1 1
1 1 2 1
+ = =
2 R1 R2 2 R R

18

Appendix 2: Derivation of Young-Laplace and

Kelvin Equations

1. If the surface of a liquid is curved, there must be a pressure

difference: Young-Laplace Equation

2. If the surface of a liquid is curved, the equilibrium vapor

pressure of the liquid must also change: Kelvin Equation

P1_Wk3_L1

19

Young Laplace Equation:

Pressure difference across a curved interface

a liquid
surface

A =(u1 + du1 )(u2 + du2 ) (u1u2 )

dn

u1 + du1 u1
dn
= du1 =u1

R1 + dn R1
R1

u2 + du2 u2
dn
= du2 =u2
R2 + dn R2
R2

u1
u2

R2

u1du2 + u2du1

R1

By convention, the radii of

curvatures R1. R2 are assigned
positive values if they fall
inside the concave surface
under consideration .

Work =
(Pin Pout )(A )dn =
(Pin Pout )(u1u2 )dn
A (u1du2 + u2du1 )

see P1_Wk2_L2

dn
dn
= u1 u2
+ u2 u1

R
R
2
1

1
1

=
+
P
P
( in out ) R R (Laplace Pressure)
2
1
for a spherical surface , R=
R=
R and
1
2
P =

P1_Wk3_L1

similar triangles

(Pin Pout )= 2

20

The vapor pressure above a curved surface:

the Kelvin equation
The situation: Insert open tube into liquid. Assume the liquid
does not wet the tube. Liquid will fill tube to a depth h as shown.
In general, the vapor-liquid interface will be curved, and will be
characterized by the radii of curvature r1 and r2. In equilibrium at
temperature T, the pressure difference between the vapor at
h
) must be described by
depth h (P hvap) and the liquid at depth h (P liq
the Young Laplace Equation. Let the vapor/liquid density be
designated by vap , liq respectively.
Let pressure of vapor
above flat surface= Po

liq

P1_Wk3_L1

P hvap

liquid

h
P liq

vap
h

x
r1 r2

Note: The end result is completely general and is identical

to that obtained using more general arguments that are not
so physically transparent.

21

h
What is P vap ?

Pressure of vapor
above flat surface= Po
A

z
mg
Pliqh= Po +
A
( h A) g
= Po +
A
= Po + gh

h
vap

vap

Po
h

for ideal g as :
vap=

P hvap

1 1
h
=
+ (Young Laplace)
Pliqh Pvap
r1 r2
1 1
h
+

P
gh
P
( o ) vap r + r
1
2
1 1
h
gh =
+ + Pvap
Po
r
r
1
2
h
1 1 Pvap Po
=
h
+ +
g r1 r2
g

(
(

)
)

MPvap
RgasT

molar mass
M
=
molar volume Vm

M
= nRgasT
PvapVm = Pvap
vap

; now,

n =1

Pvap ( z=
) Po + vapgz

dPvap ( z )
MPvap
= =
g
g
vap
dz
RgasT

r1 r2

In equilibrium:

P1_Wk3_L1

=
= vap
vapor density

small - neglect

Po

dPvap
=
Pvap

M
0 R T gdz
gas

h
Pvap

=
n
gh
Po RgasT

Pvhap
M 1 1

n
+
Po RgasT r1 r2

Vmol 1 1
=
+
RgasT r1 r2
h
Pvap

1 1
=
RgasT n
Vmol +
Po
r1 r2

see K.P. Galvin, Chem. Engin. Sci. 60, 4659 (2005)

22

Appendix 3: Kinetic Theory of Gases

T

m
vi
ri

How to describe velocity of

N gas molecules of mass m at
a temperature T: Maxwell
Speed Probability
Distribution function (1852)
3

4 m 2
f (v ) =

v e
2k B T
2

mv

( 2 k BT )

v vx2 + v y2 + vz2 =
speed of gas molecule

P1_Wk3_L1

23

Maxwell Speed Distribution Function

Note asymmetry there are more ways to get a large speed than a small one.

N2 molecule

dv

v
Shaded area represents probability that
molecule will have a speed v dv/2
P1_Wk3_L1

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Why Are Distribution Functions Useful?

Once you know f(v), you can answer many questions:

P(v1 v v2 )

v2

f (v) dv

probability of finding molecule with velocity v1 v v2

v1

< x (v ) > x (v ) f (v ) d v
0

where <x> is the expected (average) value for some quantity x that you define.
For example, the average velocity will be

4 m
v =
vavg v f (v)dv =

2
k
T
B
0

x
0

2 n +1 ax 2

3
v
e

mv

2 k BT

dv

n!
m
=
;=
dx
n 1;=
a
n +1
2kT
2a
=
v v=
avg

P1_Wk3_L1

8k B T
m
25

Standard Results
n = molecules/volume

What is the mean value of velocity in the

z-direction?

z
y
x

=
vz

v=
cos

1
cos
=
2

v=
cos

1
2

v avg

cos =
sin d

=
sin
2

What is the molecular flux (number of molecules/sec) that will hit a

unit area of the plate?
For n molecules in the volume, will be moving up, the other half
will be moving down
=
J Collision rate / unit=
area

1
1
=
n vz
nv
2
4 avg

Assuming an ideal gas, how does n depend on T and P?

PV = NkBT
N
P
n
=
V
kBT
P1_Wk3_L1

26

Assuming an ideal gas, what is the number of molecules that

fill a 1cm3 volume at STP (0oC (273.15 K), 1 atm (100 kPa))?
N
1mole
6 1023 molecules
1liter
1m 3
n
=

6 3 = 2.7 1019 cm 3
3
V
22.4liters
mole
0.001m 10 cm

Assuming an ideal gas, what is the incident molecular flux in the z

direction?
8kBT
1 P
P

=
4 kBT
m
2 mkBT

1
4

J = nv avg =

units : s 1 m 2

Assuming an ideal gas, how many molecules will strike a unit area of the
surface in a time t?
=

=
Jdt
0

P1_Wk3_L1

P
2 mkBT

units : m 2

27

How many gas atoms strike a unit area of

a surface in a given time t?
J= molecular flux (number/unit area) in unit time
n = molecules/volume
Temperature T
Pressure P

mass m
y

surface

The answer is found by integrating the molecular flux over the time t

=
Jdt
0

P
2 mkBT

units : number / m 2

If the gas has some fraction of water molecules, then it is not surprising
that a thin layer of water will form on a surface.
P1_Wk3_L1

28

Estimate the length of time for a monolayer of gaseous atoms to

accumulate on a surface?
The answer depends on the flux of gas atoms on the surface, the sticking
probability of each gas atom, and the number of active adsorption sites on the
surface. If the sticking probability is assumed to be 1, then a minimum estimate
for the monolayer deposition time can be made. Furthermore, it is customary to
assume there are ~1019 adsorption sites per square meter on a surface, roughly
equal to the number of atoms per square meter that characterize most surfaces.

J tmonolayer 1019
tmonolayer

P1_Wk3_L1

where

1019 2 mkBT

P
J =
2 mkBT
assume 18 gm / mole m =mH O =3 10 26 kg ; T =300K
2

Vacuum

P (Torr)

P (Pa)

n (m-3)

tmonolayer (s)

atmospheric

760

1x105

2.4x1025

2.8x10-9

low

~1

130

3.1x1022

2.2x10-6

medium

~1x10-3

0.13

3.1x1019

2.2x10-3

high

~1x10-6

1.3x10-4

3.1x1016

2.2

ultra-high

~1x10-10

1.3x10-8

3.1x1012

2.2x104
29

Appendix 4: Geometric details

required to calculate Rcap
Here, treat R1, R2 as positive numbers
an ideal tip!
Rtip

( R + (h + R ) ) = ( R (h + R ) ) + ( R + R )
0
R + 2R R + (R 4R (h + R ) ) =
2R 4R 4 (R 4R (h + R ) )
R =
2

tip

2
2

tip

1 2
1

2
1

tip

2
1

2
2

2
1

Rtip h-R1
Rcap=R2+R1

2
1

tip

R2

2R1
h~R1

=
+2 Rtip (h + R1 ) R1

Rcap R1 =
+ R2 2 Rtip (h + R1 )
P1_Wk3_L1

30

Appendix 5: Further Considerations

Hydrophobic surfaces

Hydrophilic surfaces

B. Bhushan, Springer handbook of nanotechnology, 2nd Edition, Vol. 2; p. 960 (2007).

P1_Wk3_L1

31

Water Facts

A water molecule has a diameter do of approximately 0.3 nm.[1,2]

The areal density of water is x/(do)2, where x is the adsorbed water
layer thickness.
A water monolayer (i.e., x=1) consists of about 11 molecules/nm2.

[1]. Karis, T. E. Water Adsorption on Thin Film Media, Jour. Colloid Interface
Sci., 225, 196-203, (2000).
[2]. Adamson, A. W., Hu, P. and Tadros, M. E. Adsorption and Contact
Angle Studies, Jour. Colloid Interface Sci., 49, 184-195 (1974) .

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