Académique Documents
Professionnel Documents
Culture Documents
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
(~1015
Surface
molecules/cm2)
Vapor
Local radius of
curvature R
Liquid
Liquid water
(~3x1022 molecules/cm3)
P1_Wk3_L1
Liquid
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
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
Curved interfaces:
drop
f
o
condensation
into pores
bubbles
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
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
P1_Wk3_L1
How thick is h?
~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
1
1
+
R
R
1
2
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%
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
Flift off
Rtip
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
2
11
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).
P1_Wk3_L1
12
Fcapillary
capillary neck
breaks
13
P1_Wk3_L1
14
P1_Wk3_L1
15
plane defining L
Surface
qrst
n
u2
u1
y S = f(x , y , z )
r = S (u1 , u2 , n )
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
F
E
A
P
A
t
L
C
G
r
D
F
C
E
H
N
Circle 2
O
Curvature: 2=1/R2
R2
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
P1_Wk3_L1
19
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
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
liq
P1_Wk3_L1
P hvap
liquid
h
P liq
vap
h
x
r1 r2
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
22
m
vi
ri
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
N2 molecule
dv
v
Shaded area represents probability that
molecule will have a speed v dv/2
P1_Wk3_L1
24
P(v1 v v2 )
v2
f (v) dv
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
z
y
x
=
vz
v=
cos
1
cos
=
2
v=
cos
1
2
v avg
cos =
sin d
=
sin
2
1
1
=
n vz
nv
2
4 avg
26
6 3 = 2.7 1019 cm 3
3
V
22.4liters
mole
0.001m 10 cm
=
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
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
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
( 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
Hydrophilic surfaces
31
Water Facts
[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) .
P1_Wk3_L1
32