Interplay between theory and experiment

in AFM nanomechanical studies of polymers

Sergey Belikov and Sergei Magonov
 Agenda

Introduction

Simulation of Dynamic AFM Modes

Euler-Bernoulli & Krylov-Bogoljubov-Mitropolsky approach
Tapping Mode and Frequency Modulation

High-Resolution Imaging of Molecular Lattices: Experiment & Modeling

Compositional Mapping of Model Polymer Blends

Local Mechanical Probing: DvZ (indentation) & AvZ curves

Tapping Mode Curves: Modeling & Experiment

Summary

©2006 Veeco Instruments Inc.

 Introduction
Main AFM Functions:
High-Resolution Imaging
Compositional Mapping
Quantitative Probing of Materials Properties
Outstanding Technical Issues:
Sensitivity of Optical Detection, Fast Imaging & Mapping, Minimization of Thermal Drift,
Efficient Drive of Probe, Imaging under Liquids, Probes …

Key Hurdle:

Tip-Sample Forces: Understanding, Measurements & Control

Dynamic AFM & Quantitative Mechanical Data:

Dream or Reality

©2006 Veeco Instruments Inc.

 Simulation of Dynamic AFM

1. Point mass - spring model with “effective parameters” (Giessibl et al,

Garcia et al, Anczykowski et al, Aime et al, Tsukada et al …)
2. Euler-Bernoulli with some parameters and zero boundary conditions;
then first-mode approximation (Butt et al, Sadler et al, Stark et al, ….
3. Using Krylov-Mitropolsky-Bogoliubov method to mass-spring model
(Wang, Tsukada et al)
4. Nonlinear dynamics (Raman et al, Stark et al)

B. Cappella, G. Dietler “Force-distance curves by atomic force microscopy” Surface Science Reports 1999, 34, 1-104
R. Garcia, R. Perez “Dynamic atomic force microscopy methods” Surface Science Reports 2002, 197-301

©2006 Veeco Instruments Inc.

 Simulation of Dynamic AFM
Main features of our approach
1. Euler-Bernoulli with boundary conditions including piezodrive of the cantilever base
(rare considered by others)
2. Solution as a composite
3. Van der Pole coordinates (amplitude, phase) transformation & separation of fast and
slow variables
4. Application of KBM averaging method
5. Analysis of KBM-derived differential equations
6. Classification of dynamic AFM modes (tapping mode, frequency modulation)
⎧ ⎧1 π x⎫ x = Asp Fa – force in approach
⎪sin θ =
1
⎨ ∫ a [F − Fr ](Z C + x cos y ) sin ydy + ⎬
⎛ 2g ⎞ ⎩ 0 N d ⎭
2
⎪ d = A0 Fa – force in retract
⎪ 1 + ⎜
⎜ω ⎟ ⎟
⎪ ⎝ 1⎠ θ − phase
⎨
⎪ ⎧1 π 2g x ⎫
⎪cos θ = −
1
⎨ ∫ a [F + F ](Z + x cos y ) cos ydy + ⎬ g=
ω − ω1
= Q1 (ω − ω1 )
⎛ 2g ⎞
2
⎩ N
r C
ω d ⎭
⎪ 1 + ⎜⎜ ⎟⎟
0 1
ε
⎪ ⎝ ω1 ⎠
⎩
©2006 Veeco Instruments Inc.
 Probe Motion in Dynamic AFM
Z L

A0 sin ωt Δ
Z0

p
x

∂ 2 Z ( x, t ) ∂Z ( x, t ) 2 ∂ 4 Z ( x, t )
+ 2 β (ω ) +a = [H (Z ( x, t )) − p ]δ ( x − (L − Δ ))
∂t 2
∂t ∂x 4

Boundary conditions: Z (0, t ) = Z 0 + A0 sin ωt ∂Z

(0, t ) = 0 ∂2Z
(L, t ) = 0 ∂ 3Z
(L, t ) = 0
∂x ∂x 2 ∂x 3
EI ⎡ m4 ⎤ ωn ωn
a = β= H (Z ) × ρ × 1m × S [N ] P = p × ρ × 1m × S [N ]
2
⎢ sec 2 ⎥ ≈
ρS ⎣ ⎦ 4Qn2 − 1 2Qn
The tip weight
Solution as a composite Z ( x, t ) = U ( x, t ) + z ( x, t ) + z p ( x, t ) + ξ ( x, t )

Oscillation of the base

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U ( x, t ) ≡ Z C + A0 sin ωt
 Probe Motion in Dynamic AFM

Solution near the

Z ( x, t ) = U (l , t ) + z1 (l , t ) + z p (l ) + ξ1 (l , t )
1st resonance

U (l , t ) = Z C + A0 sin ωt
(
z1 (l , t ) = A1 cos(ωt + ϕ ωβ − ϕ1 ) + a10 e − βt cos ω12 − β 2 t + α 0n )
⎧ p 3
⎪
⎪ 6a 2
(x − 3lx 2
), x<l
z p (x ) = ⎨ 2
⎪− pl
⎪⎩ 6a 2
(3x − l ), x ≥ l

ξ1 + 2 βξ1 + ω1 ξ1 = H (U (l , t ) + z (l , t ) + z (l ) + ξ1 (t ))
  2 p 1
2
Z1l

HρS = FQ1 tip-sample force

©2006 Veeco Instruments Inc.
 Probe Motion in Dynamic AFM

ξ1 + 2 β1ξ1 + ω ξ = 2 (
F Z c + η1 + ξ1 ; sgn η1 + ξ1 ( ))
1 1
l 2
ρS Z 1
F (z; sgn z )
( )
where η1 = A0 sin ωt + A1 cos ωt + ϕωβ − ϕ1 = d cos(ωt + ϕ d ) H (z; sgn z ) =
m
,

ω1 ω1 ω − ω1 Fa (z ) F (z )
β1 = ≈ ε = Q1−1 << 1 g= = Q1 (ω − ω1 ) H a (z ) = , H r (z ) = r
4Q12 − 1 2Q1 ε m m

ξ + ω1 ξ = εΦ ξ , ξ + εf (t )
 2
( ) more complicated
than U (l , t ) = ZC + A0 sin ωt
( ) ( )
Φ ξ , ξ = H Z 0 + ξ ; sgn ξ − ω1ξ εf (t ) = −d [(ω 2 − ω12 )cos(ωt + ϕ d ) + 2 β1ω sin(ωt + ϕ d )]
εf (t ) = −εdω1 [ω1 sin (ωt + ϕ d ) + 2 g cos(ωt + ϕ d )] ω1 π
f (t ) = dω1 ω12 + 4 g 2 cos ζ ζ = ωt + ϕ d + arccos +
ω12 + 4 g 2 2
⎧ ε
⎪ x = − ω [Φ ( x cos y ,−ω1 x sin y ) + f (t )]sin y Van der Pole coordinates
⎪ 1 ξ = x cos y ξ = −ω1 x sin y
⎨
⎪ y = ω1 − ε [Φ ( x cos y ,−ω1 x sin y ) + f (t )]cos y
⎪⎩ ω1 x
©2006 Veeco Instruments Inc.
 Probe Motion in Dynamic AFM

⎧ ⎡1 ⎤
⎪ x = −ε ⎢ω Φ ( x cos y , −ω1 x sin y ) + d ω1
2
+ 4 g 2
cos ζ ⎥ sin y
⎪ ⎣ 1 ⎦
⎪ ⎡ 1 ⎤
⎪ d ω12 + 4 g 2
⎨ y = ω1 − ε ⎢ Φ ( x cos y ,−ω1 x sin y )cos y + cos ζ ⎥ cos y
⎪ ⎢⎣ ω1 x x ⎥⎦
⎪
⎪ζ = ω
Two fast variables
⎪
⎩ Introducing phase difference
θ =ζ − y
(slow variable)
⎧ ⎡1 ⎤
⎪ 
x = −ε ⎢ω Φ ( x cos (ζ − θ ), −ω 1 x sin (ζ − θ )) + d ω1
2
+ 4 g 2
cos ζ ⎥ sin(ζ − θ )
⎪ ⎣ 1 ⎦
⎪ ⎧⎪ ⎡ 1 ⎤ ⎫⎪
⎪ d ω12 + 4 g 2
⎨θ = ε ⎨ ⎢ Φ ( x cos(ζ − θ ),−ω1 x sin (ζ − θ ))cos(ζ − θ ) + cos ζ ⎥ cos(ζ − θ ) + g ⎬
⎪ ⎪⎩ ⎢⎣ ω1 x x ⎥⎦ ⎪⎭
⎪
⎪ζ = ω
⎪
⎩ Averaging over fast variable ( ζ ) gives:
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 KBM Approach

⎧ ε ⎧ 2π ⎫
⎪ 
x = − ⎨∫ Φ ( x cos y , − x ω sin y ) sin ydy − π d ω ω 2
+ 4 g 2
sin θ ⎬
πω
1 1 1
⎪ 2 1 ⎩0 ⎭
⎨
⎪ ε ⎧ 2π ⎫
⎪θ = 2πω x ⎨ ∫ Φ ( x cos y ,− xω1 sin y ) cos ydy + πdω1 ω1 + 4 g cos θ ⎬ + εg
2 2

⎩ 1 ⎩0 ⎭

( )
Φ ξ , ξ =
( )
F Z c + ξ , sgn ξ
− ω1ξ Fa (z ) = F (z,−1); Fr (z ) = F (z,+1) Viscoelasticity will
m be added!

⎧ ε ⎧1 π ⎫
⎪ x = − ⎨ ∫ [Fa − Fr ](Z c + x cos y ) sin ydy + πω1 x − πdω1 ω1 + 4 g sin θ ⎬
2 2 2

⎪ 2πω1 ⎩ m 0 ⎭
⎨
⎪ ε ⎧1 π ⎫
⎪θ = 2πω x ⎨ m ∫ [Fa + Fr ](Z c + x cos y ) cos ydy + πdω1 ω1 + 4 g cos θ ⎬ + εg
2 2

⎩ 1 ⎩ 0 ⎭

The transition to stationary solutions gives:

©2006 Veeco Instruments Inc.
 KBM Approach
Stationary solutions:
⎧ ⎧1 π x = Asp
x⎫
⎪sin θ =
1
⎨ ∫ a [F − Fr ](Z C + x cos y ) sin ydy + ⎬
⎪ ⎛ 2g ⎞
2
⎩ N 0
d ⎭ d = A0
⎪ ⎜
1+ ⎜ ⎟ ⎟
⎪ ⎝ ω1 ⎠ θ− phase
⎨
⎪ ⎧1 π 2g x ⎫
⎪cos θ = −
1
⎨ ∫ a [F + F ]( Z + x cos y ) cos ydy + ⎬
Zc – height
⎛ 2g ⎞ ⎩ 0
2 N
r C
ω d ⎭
⎪ 1
ω − ω1
⎪
1 + ⎜⎜ ⎟⎟ g= = Q1 (ω − ω1 )
⎩ ⎝ ω1 ⎠ N = πdω12 m ε
Tapping mode (Amplitude modulation) Frequency modulation Two FM modes
g – constant (usually 0) θ – constant (usually π/2) constant excitation
Curves: AvZ, θvZ Curves: ωrvZ, AvZ, constant amplitude

(A and θ are obtained by solving the (ωr and A are obtained by solving
equations for each Zc) the equations for each Zc)
Images: Fa and Fr depend on surface location (XY)
Height ZvXY, Phase θvXY (A =Asp) ZvXY, ΑvXY (ωr=ωsp)
(Z and θ are obtained by solving the (Z and Α are obtained by solving the
equations for fixed Asp) equations for each ωr)
©2006 Veeco Instruments Inc.
 KBM Approach

Tapping mode ( ω = ω1 ) Conservative case Fa = Fr = F

π ⎧ x
⎧ θ =
[ ]
sin
1
( ) x ⎪
N ∫0
⎪sin θ = F a − F r Z c + x cos y sin ydy + ⎪ d
⎪ d ⎨ π
⎨ ⎪cosθ = − 2
F (Z 0 + x cos y )cos ydy
N ∫0
π
⎪ cos θ = − 1 [F + F ](Z + x cos y )cos ydy ⎪⎩
⎪ N ∫0
a r c
⎩

Frequency modulation (θ = π 2)
J. Cleveland et al APL 1998, 72, 2613
⎧ π 2
⎛ 2g ⎞
⎪1
∫0 [Fa − Fr ](Z c + x cos y )sin ydy = 1 + ⎜⎜⎝ ω1 ⎟⎟⎠ − d
x
⎪N Δω
⎨ =−
1 1
∫ F ( z + a (1 + u )) u
du
⎪1 π u = cos y ω πak −1
1− u 2

∫0 [Fa + Fr ](Z c + x cos y )cos ydy = − ω1 d

2g x
⎪
⎩N F a = F r = F ts J.E. Sader & S.P.Jarvis APL 2004,84, 1801
x =A0=const; k = ω1ρS Z1l
2
2π
Δf (d , k , A0 , f 0 ) = − Fts [d + A0 + A0 cos ϕ ]cos ϕdϕ
1 f0
2π kA0 ∫
0

Experimental data (x(A), θ , Zc, g ) and use of two equations might Garcia&Perez Surf Sci Rep 2002, 47, 197
help to restore Fa and Fr in dynamic AFM modes
©2006 Veeco Instruments Inc.
Tapping Mode Imaging of Polydiacetylene Crystal
Carbon spike (~3nm) Diamond probe (~5nm) How true is “true” molecular resolution?
0.8 nm 0.4 nm 0.8 nm

TXTY
TX 0.5TX
20 nm 15 nm 15 nm 15 nm
Si probes (5-10 nm)
2TX TY 2TX

Ty
b Tx
c
0.49 nm c 1.41 nm
20 nm 20 nm
How to explain the presence of 2Tx and 0.5Tx spacings in AFM images?
©2006 Veeco Instruments Inc.
 LabVIEW AFM Simulator

D
Tapping mode: Hertz model F = ∑ α i Pi 3 / 2 cos θ i
O P
Z P
2
1 R

O O
Z 1 2
1
R R
2
1

θ θ
2
1

X X X
1 2

0.5T

2T

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 Lattice Pattern: Dependence on Tip Radius
Imaging in Light Tapping (Asp=20 nm)
R = 0.15 nm R = 5 nm R = 100 nm

Y Y Y

X X X

X X X

Y Y Y

Height corrugations ~ Height corrugations ~ Height corrugations ~

0.2 nm 0.03 nm 0.01 nm

©2006 Veeco Instruments Inc.

 Lattice Pattern: Imaging at Different Forces
Asp =20 nm Tip with R = 5 nm Asp =19 nm Asp =17 nm
Y Y Y

X X X

X X X

Y Y
Y
12 peaks 11 peaks 9 peaks 8 peaks
Y-bifurcation X-bifurcation
Y-bifurcation

Experimental patterns

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Lattice w/Defects: Effect of Tip Radius & Force

R = 150 pm, Asp = 19 nm R = 1 nm, Asp = 18 nm R = 5 nm, Asp = 18 nm

Y Y Y

X X X

X X X

Y Y Y
Atomic-scale images change their pattern as tip size and/or tip force increases
that makes their assignment to real surface structures very difficult.
A presence of single atomic or molecular defects in AFM images does not mean that
true atomic-scale resolution in imaging of the surrounding lattice was achieved.
©2006 Veeco Instruments Inc.
Imaging with Sharp & Spherical Probes

Sharp Spherical

76
10 nm nm
Olympus Team-Nanotec

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 Phase Imaging of Multilayer Polyethylene

PE-0.86 PE-0.92
Asp/A0
height phase, θ sin θ
76 nm
0.93
light tapping

0.50
hard tapping

0.07
quasi-contact

7 μm

Hard tapping leads to a most pronounced phase contrast

whereas the dissipation map shows inferior contrast!? J. Cleveland et al APL 72 (1998) 2613
©2006 Veeco Instruments Inc.
Indentation & Phase Imaging of iPP/EPDM Blend

EPDM PP

PP EPDM PP Asp/A0
height phase,θ sin θ 0.93

0.73

0.50

0.33
0.20
10 μm 10 μm 10 μm
14.9 MPa (8.2%) 2.2 GPa (6.0%)

EPDM PP

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 Indentation of Multilayer Polyethylene

Sneddon & Oliver-Pharr Models

PE-0.86 PE-0.92 (adhesion and viscoelasticity will be added!)

Ea x2 f ′(x)dx
1
kD(a, E) =
(1−ν 2 ) ∫0 1− x2

Force, nN
Smax

hi penetration, nm hmax

PDMS

40.4 MPa (4.0%) 380.5 MPa (4.8%)

1.4 MPa (7.7%)

76 nm

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AFM Nanoindentation : nm-Scale Depth

Elastic and Plastic Deformation of Single Crystals of Alkane C390H782

~ 11 nm
1st
elastic plastic
2nd

2nd 1st 3rd

2nd 1st

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 AFM Nanoindentation : Lateral Resolution
Deflection curves (nanoindentation) Amplitude curves (tapping mode)
90 nN 250 nN 1.3 uN Asp/A0=0.5V/1.0V Asp/A0=1.0V/2.0V

A Force Volume (AvZ curves) of SBS triblock copolymer

A

z z
A

z
©2006 Veeco Instruments Inc. 500 nm 100 nm
Simulation of AvZ & θvZ Curves in Tapping Mode

Tapping mode
π
⎧ 1
[ ]( ) x
N ∫0
⎪sin θ = F a − F r Z c + x cos y sin ydy +
⎪ d
⎨ π
⎪ cos θ = − 1 [F + F ](Z + x cos y )cos ydy
⎪
⎩ N ∫0
a r c

8γ ⎡ 1 ⎛ z0 ⎞ 8 ⎛ z0 ⎞ 2 ⎤
Derjaguin Frp (z ) = 2πRU pp (z ) U pp (z ) = ⎢ ⎜ ⎟ −⎜ ⎟ ⎥ Lennard-Jones
3 ⎣⎢ 4 ⎝ z ⎠ ⎝ z ⎠ ⎦⎥

Maugis
Material-related avalanche Instrument- or environment-
related avalanche

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 Simulation of TM Amplitude & Phase curves
Modeling Experiment (Si substrate)
Asp/A0 Asp/A0 Asp/A0

Phase, θ Phase, θ Phase, θ

Saddle-node bifurcation in amplitude/phase coordinates is a

birth or annihilation of stable and unstable stationary points that
happened as Z is changing.
©2006 Veeco Instruments Inc.
S. L. Lee, S. W. Howell, A. Raman, R. Reifenberger Ultramicroscopy 2003, 97, 185
 Simulation of TM Amplitude & Phase Curves

Conservative case: Tip size effect (R1<R2<R3<R4)

A Phase, θ A Phase, θ
R3
R1

R4
R2

z z
Energy dissipation (avalanche)
Adhesion avalanche
Asp/A0 Phase, θ

©2006 Veeco Instruments Inc.

TM Amplitude & Phase Curves of Polymer Blends

PE0.92/PE0.86 blend PP/EPDM blend

A Phase, θ A Phase, θ
PE0.92 PP

PE0.86 EPDM

PE0.92 PP

PE0.86 EPDM

©2006 Veeco Instruments Inc.

z z
 Description of Tip-Sample Interactions

Combining Lennard-Jones solid and elastic solid

{ 1.5πRγ ± }
1/ 3
⎛ 3R ⎞ 2/3
a ( P) = ⎜⎜ ⎟⎟ P + 1.5πRγ
⎝ 4 Er ⎠

a2 2πγa
h( P ) = −
R Er

JKR

1/ 3
⎛ 3R ⎞
a ( P ) = ⎜⎜ ⎟⎟ {P + 2πRγ }1/ 3
⎝ 4 Er ⎠
Lennard-Jones solid (R, γ, z0) elastic solid (R, γ, E*, λ)
a2
h( P ) =
R

DMT

S. L. Lee, S. W. Howell, A. Raman, R. Reifenberger Ultramicroscopy 2003, 97, 185

©2006 Veeco Instruments Inc.
 Summary

1. We presented a model of dynamic AFM based on a rigorous consideration of

the probe motion using KBM method. The case near first resonance is
considered.
2. The model was applied to simulation of molecular-lattice images and this
simulation revealed several important issues regarding imaging resolution.
3. Simulation of amplitude and phase curves for conservative/dissipative cases
and for probes with different radius is compared with experimental curves
obtained on different materials
4. A set of experimental data related to nanomechanical studies of polymer
materials in different modes was analyzed. It was shown that high lateral
resolution can be achieved in probing of mechanical properties using
amplitude curves.
5. Quantitative analysis of mechanical data obtained in amplitude curves is of
high importance.
Acknowledgment
This work was supported by NIST/ATP Award #70NANB4H3055
©2006 Veeco Instruments Inc.