The Nanomechanics of Compositional Mapping by Amplitude Modulation AFM

Laboratorio de Fuerzas y Túnel
Frontiers of SPM, 5 Oct. 2006
The nanomechanics of
Compositional Mapping by
Amplitude Modulation AFM
Outline
i). Forces and molecular resolution
ii). The physics of phase Imaging:

elastic vs. Inelastic processes
iii). Identification of energy dissipation

Quantitative information
iv). Enhancing Force Sensitivity: Beyond

1st mode Imaging
v). Summary
Ricardo García
Instituto de Microelectrónica de Madrid
a
10 nm
8 nm GroEL in liquid, T. Ando et al. PNAS 98, 12468 (2001)
PM in liquid, D.J. Muller et al.

Biophys. J. 77, 1150 (1999)
50 nm
IgG, SanPaulo, Garcia, Biophys.

J. 78, 1599 (2000)

Forces and Resolution in AM-AFM (biomolecules)

verified values
Medium Force (pN) Force Resolution*

sensitivity (nm)
Air IgG 300 0.1 3
Liquid 1 PM 100 0.05 1.1

crystal
Liquid 2 No available No available 2
GroEL patches
Some forces in molecular biology

Process Force (pN) length scale
DNA entropic 0.01-10 0.8 L
elasticity
DNA intrinsic 10-70 0.8-1 L
elasticity
Protein 15-50 3-5 nm
unfolding
Amplitude modulation AFM (AM-AFM)

amplitude, phase-shift and resonance frequency
Free amplitude
tip’s oscillation
External excitation
φ
A= constant
Phase Image 20º
Topography
500 nm
500 nm
Surf. Sci. Rep. 47, 197 (2002)

Resonance Curves
Free oscillating tip (10 nm ) Interacting tip (10 nm size )
Mechanics of vibrating
nanosystems:
Coexistence of oscillation SIMULATION
states: Bi-stability R= 10 nm, A0=10 nm, zc=8 nm,
ω/ω0
E=1 GPa, k=40 N/m, f0=325
kHz
AS Paulo, R García, PRB 66, 041406(R) (2002)
18
Exps.
Amplitude (nm)
simulations 15 L
12 H
10 (a)
Amplitude (nm)
9
8
H and L states have 6 6
different properties 4 6 9 12 15 18 21 24
z piezo displacement (nm)
2 High amplitude solution
0 Low amplitude solution 40 nm
1.0 (b)
<Fint> (nN) 0.5
0.0
-0.5
-1.0
(c)
1.0
Contact time
0.5
Simulation data: R=20 nm 180
f0=350 kHz, Q=400, H
Phase (deg)
135
H=6.4x10-20, E*=1.52 GPa 0.0
0 2 4 6 8 10 12 90
Tip-surface separation (nm)
45
Garcia, San Paulo, PRB 61, R13381 (2000);
Garcia, Pérez, Surf. Sci. Rep. 47, 197 (2002) 0
Phase Imaging
The dynamic response of the cantilever is modified by the
tip-surface interactions
Driving signal:F(t) = F0cos(wt)

Topography Phase Image
1 μm
Wood pulp fiber, D.A. Chernoff (1995)
b
c
2 μm 2 μm
S. Typhimurium cells, R. Acvi, Biophys. J. (2006)

a
10 nm
GroEL in liquid, T. Ando et al. PNAS 98, 12468 (2001)

Polymers: Morphology and Structure
Topography Phase Image
Polymer morphology and structure as a

function of temperature. Hydrogenated diblock
copolymer (PEO-PB). Crystallisation of PEO
blocks occurs individually for each sphere
(light are crystalline, dark amorphous). Reiter
et al., Phys. Rev. Lett. 87, 2261 (2001)
Phase Image,
size 1μm2
Sources of Phase Imaging Contrast
TOPOGRAPHIC EFFECTS
ELASTIC TAPPING ↔ NON CONTACT

CONTRIBUTIONS TRANSITIONS
YOUNG MODULUS
(In presence of dissipative channels)
PHASE
CONTRAST
VISCOELASTICITY
ADHESION HYSTERESIS
INELASTIC
CONTRIBUTIONS CAPILLARY FORCES
HIDROPHILIC/HIDROPHOBIC
INTERACTIONS
Phase shift and tip-surface interactions

Attractive regime (L
180 Repulsive regime (H
branch) branch)
Phase (deg)
135
90
45
0
separation
The virial theorem applied to the tip allows to deduce
ω=ω0 and A>>z0
2Q ⎡ < Fts > 2 1 2⎛ ω 2 ⎞⎤ 2 Q < F ts · z >

cosφ = ⎢ − < Fts ·z > + kc A ⎜⎜1 − 2 ⎟⎟⎥ cos φ ≈ −
k c AA0 ⎣ kc 2 ⎝ ω 0 ⎠⎦ k c AA 0
Conservative interactions and
small contact times F ts
cos φ ≈ 2
F0
The phase shift depends on the sign
of the interaction
A Sanpaulo, R García, PRB 64, 193411 (2001)

Phase shift and energy dissipation

How to measure dissipation in amplitude modulation AFM

steady state solution
z = z0 + A cos(ωt − φ )
Dynamic equilibrium in AM-AFM
Eext = Emed + Edis

dz
E EXT = ∫ F0 cos(ωt) dt = (1 / Q)πkA 0 A(ω)· sinϕ topography composition
dt
ωAsp=cte
⎛ mω 0 dz ⎞ dz πkωA 2 (ω )
E med = ∫ ⎜⎜ ⎟⎟ dt = A sp QE dis
sin φ =
Qω 0
⎝ Q dt ⎠ dt
+
E dis = ∫ (FTS )
dz
dt
dt ω 0 A0 π kA 0 A sp
Asp=cte.; phase shifts are linked to tip-surface inelastic interactions
A A πkA 02
Tamayo, García, APL 71, 2394 (1997)
E dis = (sinφ − )
Tamayo, García APL73, 2926 (1998) A0 A0 Q
A A πkA 2
E dis = (sin φ − ) 0
A0 A0 Q
Numerical simulations
analytical expression
1.0
0.8
Edis (eV)
0.6
0.4
0.2
0.0
0.2 0.4 0.6 0.8 1.0
A/Ao
2z mω dz
m d = −kz + 0 + F + F cosωt Fixed by the observer A0,Q,k,ω0, ω
dt 2 Q dt ts 0
From Phase shifts to energy dissipation
A A πkA 02
E dis = (sinφ − )
A0 A0 Q
180
Ao=32.5 nm
10
160 Ao = 23.4 nm attractive
140 regime (low 8 Ao=26.6 nm
Edis per cycle (eV)

Ao = 26.6 nm amplitude)
Phase shift (deg)
120 Ao = 6.6 nm
6
100
Ao=23.4 nm
80
4
60
40 Ao = 32.5 nm 2
Ao=6.6 nm
20
repulsive 0
0 regime (high
10 15 20 25 30 35ampl.)40 45
0,0 0,2 0,4 0,6 0,8 1,0
Z piezo displacement (nm)
A/A
o
Martinez, Garcia, Nanotechnology 17, S167 (2006)

12 (b) A ttractive
11
Repulsive
10
9
E dis per cycle (eV)
A 0=23.4 nm
8
7
6
5
4
3
2
1
0
0.0 0.2 0.4 0.6 0.8 1.0
A /A 0
The dissipated energy is higher on the repulsive regime

Dissipation avoids artefacts due to regime changes of contrast

Applications of Phase Imaging
Identification of Nanoscale dissipation Processes

Dissipation at the Nanoscale:
Surface Adhesion Hysteresis
Short range Long range
Edis = ∫ Fdz=4πRδ (γ r −γ a ) α 1 1
2
Edis = ∫ 2
dz =Δα ( − )
z d1 d2
5
F (nN)
0
F (nN)
-2 F
0
-4
-6
-5
-8
-0.05 0.00 0.05 0.10 0 1
d (nm) d (nm)
A0 = 6.6 nm, E=150GPa, Zc =3 nm. ΔH=2.5 Ei=20mJ/m2. Ev=40 mJ/m2
A0 = 40 nm, E=150GPa, Zc =20 nm; ΔH=1
α
Ei=33mJ/m2; Ev=66 mJ/m2; k=2N/m, Q=150
FDMT = Y R δ − 4πRγ
* 1/ 2 3/ 2
F LR = − 2
z
Dissipation at the Nanoscale:
viscoelasticity
2
0
F (nN)
-1
dissipa
-2
tion
-3
-4
-5
-6
-1 0 1 2
d (nm)
A0 = 15 nm, η= 500 Pa.s; E=500MPa; Zc =6.5 nm
dδ
F =η Rδ
v dt
Tamayo, Garcia, Langmuir 12, 4430 (1996)
Red: viscosity
Blue: long range adhesion hysteresis
6
Black: short range ad. hystersis (b)
4
1.0 (a)
δ E*dis / δ (A/A0)
Normalized Dissipation
0.8 2
0.6 0
0.4
-2
0.2
-4
0.0
0.0 0.2 0.4 0.6 0.8 1.0
Amplitude Ratio (A/A0) -6
0.0 0.2 0.4 0.6 0.8 1.0
Amplitude Ratio (A/A0)
The derivative of the dissipative energy singles out the dissipative process
Analogy: Tersoff-Hamann theory of STM
dI
G≡ ∝ ρ Sample (EF + eV)× ρTip (EF ) × T(eV,z,φp )
dV
Identification of dissipation mechanisms

Long range dissipation adhesion hysteresis viscoelasticity
1.0 (a) 10 (b) 30 (c)
0.8 8
Dissipation (eV)
blue: exps. 20
0.6 6
black: theory 0.4 4
10
0.2 50n 2 50n 500 nm
m m
0.0
1.0 1
Experiment
(d) Simulation (e) (f)
0.5
δ E*Dis / δ (A/A0)
0
0.0
-0.5
-1
-1.0
0.0 0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0
A /A0
Garcia, Gomez, Martinez, Patil, Dietz, Magerle, Phys. Rev. Lett. 97, 016103 (2006).

20
H.A. (continous) Point-mass model
amplitude (nm)
L.A. (continous)
15 H.A. (point-mass)
L.A. (pont-mass) 1
(a)
low amplitude
10
normalized amplitude
10-4
5 0
0 2 4 6 8 10 12
0
1x10
0 high amplitude
(b)
0 5 10 15 20
-4
tip-sample distance (nm) 8x10
-4
4x10
0
0 2 4 6 8 10 12
frequency (normalized to 350.6 kHz)
Continuous model
1
normalized amplitude
low amplitude (a)
10-4
0
0 2 4 6 8 10 12
50 μm 1 high amplitude (b)
10-4
LA
15 0
0 2 4 6 8 10 12
0
frequency (normalized to 350.6 kHz)
) (nm)
-15
The components of higher order modes and harmonics are several
HA
15
orders of magnitude smaller than the fundamental
w ( x=1,t
-15 Rodríguez and García, Appl. Phys. Lett. 80, 1646 (2002)
0 time ( μ s) 15
Forces and Molecular Resolution in AM-AFM
2
F (nN)
0
F (nN)
-2
0
-4
-6
-5
-8
-0.05 0.00 0.05 0.10 0 1
d (nm) d (nm)
Some forces in molecular biology
Process Force (pN) length scale
DNA entropic 0.01-10 0.8 L
elasticity
DNA intrinsic 10-70 0.8-1 L
elasticity
Protein unfolding 15-50 3-5 nm

Improving force sensitivity
Beyond 1st mode Imaging

EI ∂ 4 ⎡ ∂w 2 ( x , t ) ⎤ ∂w 2 ( x , t )
⎢w ( x, t ) + a ⎥ + μbh = Forces
L4 ∂x 4 ⎢⎣ 1 ∂t 2 ⎥
⎦ ∂ t 2

ForceTool
Multipurpose Force Tool for Quantitative Nanoscale Analysis and

Manipulation of Biomolecular, Polymeric and Heterogeneous Materials
ForceTool
CSIC, CNR (F. Biscarini) , Utwente (J. Vancso) , Ludwig-Maximilians-

Universität (R. Stark), Chemnitz University of Technology (R. Magerle) ,
Universidad Autónoma de Madrid (R. Pérez), Nanoworld (C. Ritchter ) ,
Johannes-Kepler University (P. Hinterdorfer) , Electrónica y Diseño
Aguado (I. Rodriguez)
ForceTool : NMP4-CT-2004-013684
ForceTool AFM
Non-linear dynamics Nanomechanics, material design
ForceTool AFM
display
AFM controller
A1 A2 φ1 φ2
Fi cos ωit + Fj cos ωjt
Z scanner Feedback
Patents: PCT/ES 2006/070016; PCT/ES 2006/070096

ForceTool: Proposal submitted: 12 May 2004; final: 28 October 2004;
Project started: 1 February 2005

Tapping mode versus ForceTool phase shift
Sexithiophene on Si(100)
Phase Shift (º)

Si T6 Si
P h a s e S h ift (º)
23
Si T6 Si
2
Tapping mode PHASE SHIFT 1
1
00
-1- 1 Δφ1 = 0.1 º Δφ1
-2 Δφ2 = 0.9 º Δφ1
-2- 3 Δφ2
0 200 Δφ6 020=9Δφ
400 800 1000 1200
1 1400
SXe c(nm)
tio n (n m )
-3
0 200 400 600 800 1000 1200 1400
Section
X (nm) (nm)
ForceTool Phase shift
Tapping mode vs. ForceTool mode
DB-TTF
topography
Tapping mode
phase shift
ForceTool Δφ1 = 0.1 º

Phase shift Δφ2 = -1.3 º Δφ2 =13 Δφ1
Two routes to compositional contrast: Conservative and non-

conservative processes.
Phase Imaging
Application 1: Identification of nanoscale energy dissipation
processes
Application 2: Measurement of material properties
The 3D character of the microcantilever allows to develop

methods based on elastic processes. ForceTool Sensitivy is
100 times higher than in AM-AFM.

Agradecimientos
Prof. Ricardo Dr. Shiva Patil

Nicolás F. Carlos
García Martínez Gómez
Thank you for your attention!

+José L. Lozano
+Elena Tomás
Financiación
Programa Nacional de Materiales, MEC; CAM
European Commission: ForceTool

The Nanomechanics of Compositional Mapping by Amplitude Modulation AFM

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Laboratorio de Fuerzas y Túnel

Frontiers of SPM, 5 Oct. 2006

i). Forces and molecular resolution

ii). The physics of phase Imaging:

iii). Identification of energy dissipation

iv). Enhancing Force Sensitivity: Beyond

8 nm GroEL in liquid, T. Ando et al. PNAS 98, 12468 (2001)

PM in liquid, D.J. Muller et al.

IgG, SanPaulo, Garcia, Biophys.

Instituto de Microelectrónica de Madrid

Forces and Resolution in AM-AFM (biomolecules)

Medium Force (pN) Force Resolution*

Liquid 1 PM 100 0.05 1.1

Some forces in molecular biology

Amplitude modulation AFM (AM-AFM)

Surf. Sci. Rep. 47, 197 (2002)

Instituto de Microelectrónica de Madrid

<Fint> (nN) 0.5

Driving signal:F(t) = F0cos(wt)

Instituto de Microelectrónica de Madrid

Wood pulp fiber, D.A. Chernoff (1995)

S. Typhimurium cells, R. Acvi, Biophys. J. (2006)

GroEL in liquid, T. Ando et al. PNAS 98, 12468 (2001)

Polymer morphology and structure as a

ELASTIC TAPPING ↔ NON CONTACT

Phase shift and tip-surface interactions

2Q ⎡ < Fts > 2 1 2⎛ ω 2 ⎞⎤ 2 Q < F ts · z >

A Sanpaulo, R García, PRB 64, 193411 (2001)

Phase shift and energy dissipation

Instituto de Microelectrónica de Madrid

How to measure dissipation in amplitude modulation AFM

Eext = Emed + Edis

Asp=cte.; phase shifts are linked to tip-surface inelastic interactions

From Phase shifts to energy dissipation

Edis per cycle (eV)

Martinez, Garcia, Nanotechnology 17, S167 (2006)

Instituto de Microelectrónica de Madrid

The dissipated energy is higher on the repulsive regime

Instituto de Microelectrónica de Madrid

Applications of Phase Imaging

Identification of Nanoscale dissipation Processes

Instituto de Microelectrónica de Madrid

Identification of dissipation mechanisms

1.0 (a) 10 (b) 30 (c)

Instituto de Microelectrónica de Madrid

frequency (normalized to 350.6 kHz)

low amplitude (a)

50 μm 1 high amplitude (b)

Instituto de Microelectrónica de Madrid

Improving force sensitivity

Beyond 1st mode Imaging

Instituto de Microelectrónica de Madrid

Instituto de Microelectrónica de Madrid

Multipurpose Force Tool for Quantitative Nanoscale Analysis and

CSIC, CNR (F. Biscarini) , Utwente (J. Vancso) , Ludwig-Maximilians-

Fi cos ωit + Fj cos ωjt

Patents: PCT/ES 2006/070016; PCT/ES 2006/070096

Instituto de Microelectrónica de Madrid

Tapping mode versus ForceTool phase shift

Phase Shift (º)

ForceTool Δφ1 = 0.1 º

Two routes to compositional contrast: Conservative and non-

The 3D character of the microcantilever allows to develop