Nano1 SFM Courses2 3 2024
Nano1 SFM Courses2 3 2024
Nano1 SFM Courses2 3 2024
Morphological characterization of
surface and objects from micronic down
to atomic scale
Dr. Florence Marchi
florence.marchi@neel.cnrs.fr
http://neel.cnrs.fr/
• UE Evaluation : After each PW a report has to be written and send to the teacher(s)
for evaluation. An final exam will take place at the end of the semester.
The global mark of this UE is a balance between the mark related to the PW reports
evaluation and the final exam. 2
How to come and access to CIME Nanotech ?
University area in MINATEC campus
https://cime.grenoble-inp.fr/
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Minatec
Campus
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After the first course (09/01/2024) You should be able to:
• Definitions about Nanosciences & Nanotechnology
You should be able to give the a definition and an example about : nano)object,
nanomaterial, nanosciences, nanotechnology.
• Review of the forces acting at nanoscale and comparison with the weight
You should be able to give their name and the main physical parameters playing a
role for each of them.
http://www.microscopyu.com
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Atomic Force Microscopy
Idea: To measure the tip-sample forces and interactions acting on
the tip when the tip-surface gap reaches the nanoscale.
Table of contents
1. Review of the nanoscopic forces
2. AFM probe description
3. Optical detection system and map process
4. Principles of the three main working modes:
• Spectroscopy mode
• Contact and friction mode
• Dynamic mode
• Peak Force mode
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1.Forces acting at nanoscale in air environment
! ! ! ! !
Ft/s = FE/M + Fcap + FVdW + Frep
Sample sphere distance
Magnetic force
Fmi= Vi μ0 Mi (H)ÑH (z) Long-range
Electrostatic Capacitive
Force (1<n<2) interactions
1 ∂C 2 1 ε0εr S 2
Felect = U n
U z ≈ 20nm
2 ∂z 2 z
z≈ 5nm
HaR
FVdW ( z ) = Van der Waals Force
A 6z 2
Frepulsive ( z ) = z< 0.5nm
zm Repulsive force(m>3)
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At Short Range : Van der Waals and repulsive interactions
Reversible effect : Elastic regime
A HaR
FSR (z) = m − 2
z 6z
F Graphical representation of tip-sample interaction in
function of the tip-sample gap (sphere-plane geometry)
Repulsive term A
Frepulsive ( z ) =
Pauli exclusion: zm
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Impact of these forces on a sphere closed to a surface
The impact of the weight P : F : surface forces
!
! = !" = !!" = ! !
!!! !!
! P : Weight force; V: sphere volume, R sphere radius;
ρ: volume density of the sphere material P
g : nominal gravitational acceleration
Water
meniscus
12
Capillary force Fcap versus weight P
How a perfect gold (micro)sphere (roughness-free) can stick
on a flat roof in air?
! + !!!" = 0
Substrate : perfect gold
plane Capillary vs weight
F(mN)
!! Θ = 0°
R γ : surface tension : 73mJ
! Θ: contact angle
Θ = 60°
Capillary force:
!!"# = !"#$%&'(
0 R(mm)
! !
! = !" = !!" = ! !! !!
!
In air the capillary force can be stronger than the weight for
sphere with a radius of several hundred of microns
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1.Forces acting at nanoscale in air environment
! ! ! ! !
Ft/s = FE/M + Fcap + FVdW + Frep
Sample sphere distance
Magnetic force
Fmi= Vi μ0 Mi (H)ÑH (z) Long-range
Electrostatic Capacitive
Force (1<n<2) interactions
1 ∂C 2 1 ε0εr S 2
Felect = U n
U z ≈ 20nm
2 ∂z 2 z
z≈ 5nm
HaR
FVdW ( z ) = Van der Waals Force
A 6z 2
Frepulsive ( z ) = z< 0.5nm
zm Repulsive force(m>3)
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Electrostatic Force: the case of the capacitive force between two conductive electrodes
z U: Tip-sample voltage
U= VTip-VSample (potential difference)
U = Vtip-VS 1 ∂C 2 1 ε0εr S 2
Where Vtip and Vs are respectively the tip
Felect = U n
U
potential and the surface potential
2 ∂z 2 z
Where:
S is the surface of the capacitance
(geometry dependence)
ε0: electrical Vacuum permeability
εr: electrical material permeability
z: probe-sample distance
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For a sphere-plane geometry and a constant sphere-plane voltage, it has been
demonstrated that the capacitive force is expressed as:
( " 1 %+
C ≈ 4πε 0εr R *1+ 12 log $1+ '-
) # ξ &,
2
! 1 $ 2
! R $
U z
Felect = πε0εrU # 2&
= πε0εrU # 2&
z
"ξ + ξ % "z + R %
With ξ= z/R where z is the sphere-plane distance and
R the sphere radius
Z<<R
Z#R • If R>>z then F α R/z
‘Simple expressions for force and capacitance for a conductive sphere near a conductive wall’,
J. M. Crowley, Proc. ESA. Annual Meeting on Electrostatics Paper D1 (2008) 16
Magnetic Force
Two main configurations for the tip-sample
magnetic interactions 1:
Magnetic
object (V, M) 1. Negligible mutual interaction of the
Fm(attractive or magnetic field of the sample and the
repulsive force) magnetization orientation of the object.
The generic expression of the magnetic force Fmi acting on the unit volume of the object2,3:
Fmi= Viμ0Mi(H)ÑH(r)
Where Mi is the magnetisation and Vi the magnetic unit volume of the object and H is the
magnetic field induced by the sample at the r distance.
1 Scanning Probe Microscopy, E. Meyer et al, Chapter 4, p102_113-50 (2004), Springer
2 Thermomagnetically patterned micromagnets, F. Dumas-Bouchiat et al, Appl. Phys. Lett. 96, 102511 (2010)
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3 CADES software develop by G-INP group : www.cades-solutions.com
Summary of the forces between the tip and the
sample above a Domain wall centre
Ft/s In case of repulsive magnetic force z M
Van der Waals
Magnetic Fm(repulsive force)
Repulsive
Sum
Z (tip-surface gap)
Fmi= Viμ0Mi(H)ÑH(r) M
Ft/s
In case of attractive magnetic force Fm(attractive force)
Z (tip-surface gap)
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Two main AFM cantilever shapes: beam or V-shape
Rectangulaire chip,
Chip size about few
mm
Lever (few hundred
of µm)
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3. Optical Detection system
In this situation, the force acting on
the tip is repulsive, the lever is
photodiode
mirror bending up
laser
d
d
Zt
Feedback Zt DZ
loop ZpZ
p
Piezo tube
surface
X,Y,Z
d~Dz and Fi = K • Dz = K (zi-z0)
Measurement of d [adjustment of Z K Є [0.01; 1] N/m, soft lever
(tip-sample distance) to keep d=0
Dz Є [0.1-103]nm
[cantilever deflection constant, 22
[pressure force constant [Fi Є [10-3- 104]nN
A little bit of History
• In 1880, Pierre and Jacques Curie discovered the piezoelectricity effect
Image Resolution/Definition :
N pixel/line N measurements/line
N/scan size = Image definition
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4. Principles of the main working modes
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Spectroscopy mode in static mode in air.
A spectroscopy curve recorded in static mode is called a force curve
In air, the capillary force dominates when the tip-sample gap is
small enough to have the formation of a water meniscus
Tip 𝜃1 : contact angle between the
end R
Tip sphere and the liquid
apex 𝜃2 : contact angle between the
Liquid 𝜃2
Fcap𝜃1
bridge liquid and the sample surface
28
Spectroscopy curve in static mode (force curve)
in vacuum or dry atmosphere on hard sample.
z
k𝜟ZC = F ZP In each point (Zi) of the force
Zt 𝜟ZC
curve (in first approximation):
! ! !
0 Ft/s + Fc/t = 0
With in Z direction :
Repulsive term A
Frepulsive ( z ) = m
F9
Pauli exclusion:
z 𝐹!/# = 𝑘∆𝑍$%
Z9
Z8 Z7 Z6 Z5 Z4 Z3
Z2 Z1 𝐹"/# = 𝐹./&01#23/ − 𝐹345
F1,2,3 0
F5
sum 𝜟 Zc = Zt-ZP
F7
Van der Waals/Casimir term :
F6 HaR
FVdW ( z ) =
6z 2
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Force curve measurement by AFM Measurement of
adhesive properties
Jump to Zero line
contact
200 nm
13 nN
Adhesion
Core level
repulsion
2D Display 3D Display
10nm
surface
ZP#Zt/s d~DZC and Fi = K • DZC = K (zt-zP)
K Є [0.01; 1] N/m, soft lever
Dz Є [0.1-103]nm
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[Fi Є [10-3- 104]nN
4. Contact Mode at constant force
On a homogenous sample
In this situation, the force acting on
Definition of the working point the tip is repulsive, the lever is
bending up
Approach curve d
Zt
Zt DZ
ZpZ
p
2D Display 3D Display
The contact mode is easy to use and the image interpretation is straightforward BUT be
aware to the possible artefacts….
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5. Image Artefacts
• « Convolution »effect between the tip and the surface
A. Barski CEA/ESRF
The Tip-sample
convolution effect:
the wires appear as
triangles
𝚹2 𝚹1
We consider: 𝚹1 = 𝚹2
A. Barski CEA/ESRF
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6. Friction mode
38
Local measurement of friction/adhesion:
contact AFM
Friction:
Constant tip velocity
Typical 10nm/sec-1micrometer/sec
a d
Laser beam di a q
as Ffriction= Kfriction • q
di
b c [di is a indirect measure of Ffriction
Kfriction = f (e, L, l, Young module)
e, L, l : geometry tip parameters
q
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Friction measurement on isolated nanotube
Si surface
d~10 nm
• High dimension aspect ratio : L/d
1<L<10 µm
• Hydrophobic L
• Chemically inert 10 < < 1000 • Tunicin whisker is a full cellulose
rod with a good crystalline structure
d
• Crystalline structure • Polarized molecules on surface
whisker
M. N. Angles and al, Macromolecules, 33, 8344, (2000) 41
Friction on tunicin whiskers
deposited on silicon oxide surface
carbon nanotubes
• Lower friction force measured
on CNT is NOT due to a geometry
or shape effect
• AFM technique allows to
measure individual friction
property of nano-object
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7-B. Adhesive properties of individual CNT
Scan process
In classical process:
• triangular signal applied on the piezo-scanner in Z direction
• Frequency of the triangular signal : 1Hz ie 1s/pixel (point of measurement)
1s/pixel means 256s (#4mins) for each line
An image contains 256 lines, therefore : 256*256(s) = 65 536s = 1092min= 18hours
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Optical and Atomic Force microscopies
Morphological characterization of
surface and objects from micronic down
to atomic scale
Dr. Florence Marchi
florence.marchi@neel.cnrs.fr
http://neel.cnrs.fr/
actuator
At (w)
Graphical representation of tip-sample
F interaction in function of the tip-sample gap
Z0
Feedback
loop
(X, Y, Z)
Scanner piezo tube
Z0 Z0+At
sum
Tip-sample gap
What is the evolution of the cantilever oscillating
movement (A, Phase, ω0) for a constant drive
frequency and intensity when the tip interacts
with a sample through surface forces ?
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AFM in Dynamic mode
actuator
KL 𝐹!/# (𝑍$ ) a
A(w) m
Piezo actuator m*
p
ZT l
ZP = AP cos(ωt) e
A1(w) where AP= (F0/m*)
Z0 Equation System :
Z0’ Z!!T + γ Z!T + ω 02 ZT = mFo* cos(ω t)
𝐹!/# (𝑍$ )
Solution of the equation:
(X, Y, Z)
Scanner piezo tube With:
F0
A(ω ) = m*
1
(ω 02 −ω 2 )+γω 2
How A(ω), ω0 and Φ(ω) are modified
due to the tip-surface interactions
when the Z0 tip-sample average
distance is reduced ?
48
Graphical representation
A(w) : Free amplitude of the position 1 𝛟(w) : Free phase of the cantilever
cantilever
actuator
F0 A(w)
A(ω ) = m* 1
(ω 02 −ω 2 )+γω 2
A(w) j(w)
A0 w is the drive
frequency of the
actuator signal, it
90° can be tuned by
the user
w0 w
KL : Spring constant
of the cantilever
No direct solution because F(ZT/S) is unknown A1(w)
Hypothesis: small oscillations around Z0 :
Limited development at 1st order
Z0
𝐹!/# (𝑍$ )
sample
therefore:
w 12
w1 » w0 (1 - 2 K1 L
¶F
¶Z ( Z 0 ))
50
Effect of the Variation of Tip-surface interaction on the oscillator
response : graphical representation
A(w)
Dw = w’0 - w0 A(w) j(w)
A0 Dw
A0
At
A1 -90°
Dj
wt
w0 w1 w0 w
wO : AFM probe resonnance frequency Attractive Force => Phase decrease: Δj <0
Repulsive force => shift of the amplitude curve A=g(w) on the right (from red to blue)
Attractive Force => opposite shift 51
AFM in Dynamic mode : Imaging process
Simplistic description
Position 2 position 1
actuator
ZP = AP cos(ωt)
At (w) where AP= (F0/m*)
A1(w)
A
AP
Z0
DZ = (Z0-h) Feedback -AP t
loop
h ó F1 > F0, A1 < A0
(X, Y, Z)
DZscanner
piezo tube Scanner
thickness : 160nm
width : 200nm-2um 560nm
step : 130 nm
( nm Z[nm]
300
Z (nm)
560nm 15
ZZ(nm)
(2)
)
200 10
100 5
0
0 1.0µm 0 0.5
0 0.5 1 1.5 2 2.5 1
XX [(µm)
µm ] X[µm] 53
• The dynamic mode is well adapted to fragile and/or deformable samples
because friction effect is avoid.
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Summary of the third course
• Dynamic Mode
You should be able to explain it and to underline its
advantage/limitation compared to the contact and Force mapping
modes.
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