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Carbon Nanotube NanoNeedle Nanomeniscus

Jean-Pierre Aimé
jp.aime@cpmoh.u-bordeaux1.fr

Frontier in Scanning Probe Microscopy


PURDUE October 2006
I- Carbon Nanotubes as AFM probes:
competition between adhesion and elasticity
C. Bernard et al

Carbon Nanotube: C.V. Nguyen (NASA), A. M. Bonnot (LEPES)

II- Oscillating NanoNeedle at Air liquid Interface:


Dynamical behavior of NanoMeniscus
C. Jai et al

Nano-Needle / FIB: D. Mariolle, F. Bertin, A. Chabli LETI-Minatec


CNT Possible Tip-Sample Interactions

Interaction
• Attractive interaction: van der Waals
• Repulsive interaction: (compression) / bending
• Boundary conditions : sticked (clamped) / non sticked (sliding)

Geometry effects:
• kbending k~r4L-3
• kcompression~ 103kbending

D. Dietzel, et al Physical Review B 72, 035445 (2005), Nanotechnology


(2005) 16, p.S73-S78, JSPM (2006)
Nanotube mechanical cycle

Approach:
Compressive part
tube bending F Start to touch

Elastic bending

k NT ≈ Eπ r L
4 3 D
Extension phase

CNT Pull off


force Extension stiffness
kadh
1
Cycle area: E diss T
≈ k adh Δ2 = cste
2
U. Dürig, New J. of Physics 2 , 5.1 (2000).
SWNT’s FM AFM
frequency and damping curves
Δf (Hz)
35
A = 50nm
30
Δz
25
(ΔZ < 2A)
20
1. Non contact
15

10

0,16
2. Intermittent
0,12 contact Contact
permanent

0,08
non contact
contact
0,04 intermittent
3. Permanent
0 Contact
0 50 100 150 200
Damping (V) Piezo displacement (nm)
Nanotube mechanical cycle
F
Adhesion force gives constant area
1
∆ 〈 E diss
int
〉T ≈ k adh Δ2 = cste
D 2

〈 E diss
int
〉 T = πγ int ωA 2

2
γ /γ *A
in t 0 2
6 γ /γ *A
in t 0
6 A=87nm
A=25nm
5 A=50nm
A=75nm 5
MWNT A=116nm

A=100nm A=145nm
4 A=174nm
4

3 SWNT
3

2
2

1
1

0
0

-1
-1
-1,5 -1 -0,5 0 0,5 1 1,5 2
Z/A -1.5 -1 -0.5 0 0.5 1 1.5
Z/A
SWNT vs MWNT

Δf (Hz)
300
SWNT(A=50nm)
250 MWNT (A=58nm)

200

150
Δf
100
MWNT : typ. 200 Hz
50
SWNT : typ. 20 Hz
0

-50
-2 -1.5 -1 -0.5 0 0.5 1 1.5 2

Z/A
Elastic contribution

(ω 2
− ω 02 )= k (NT
d 1 − d 2 − cos −1 (d ) ) d=Z/A
ω 2
0 πk c
600

450 k N T = 0 .0 5 6 N m
-1

300

Δf (Hz)
150
-1
k N T = 0 .0 4 N m

kNT = -1 .0 -0 .5 0 .0
d
0 .5 1 .0 1 .5

0.048 Nm-1

F Adhesion Contribution

∆ Δω ⎡τ res +τ Δ ⎛z ⎞ ⎤
⎢ ∫ k adh ⎜ − cos(ωt )⎟ cos(ωt )dt ⎥
D 1
=−
ω0 k cT ⎢⎣ τ res ⎝A ⎠ ⎥⎦

. D. Dietzel, et al Physical Review B 72, 035445 (2005), C. Bernard et al (submitted)


Single Wall NT Mechanical properties

kSWNT = 1*10-3 N.m-1

E
dis = 1.5 10-17 J

Adhesion mostly governs SWNT behavior


Multi Wall NT mechanical properties
Δf (Hz)
Δf (Hz)
300 250

A=58nm A = 116 nm ; Δ = 75 nm
-2
250 A=87nm 200 k = 3.9*10 N.m-1
A=116nm
A=145nm
∆ MWN T
-2 -1
200 k = 9.3*10 N.m
A=174nm 150 adh

150
100

100
50
50

0
0

-50 -50
-1.5 -1 -0.5 0 0.5 1 1.5 2
-1.5 -1 -0.5 0 0.5 1 1.5 2
Z/A
Z/A

MWNT with diameters 15-30 nm mixing of elastic and adhesion contribution


SWNT vs MWNT
kk NT (Nm-1)
él astiq ue
E dissip
Energie
(10-17 J)
dissipée par période (10
-17
J)
0.1 100
MWNT Silice
-2
MWNT Graphite k = 3.9*10 N.m-1
MWNT
MWNT Mica
SWNT Silice

0.01 MWNT helicoidal


MWNT
SWNT
10

0.001

-3 -1
k = 1.2*10 N.m
SWNT

1
0.0001 20 40 60 80 100 120 140 160 180
0 50 100 150 200
A (nm)
A (nm)

Energy loss
MWNT : 1.5*10-16J
kMWNT ≈ 30 kSWNT
SWNT : 1.5*10-17J
Summary
CNT Adhesion / elasticity

SWNT:
- adhesion governs CNT-Surface interaction,
- strong modification may occur due to change of contact area between
SWNT and surface

MWNT:
-Mixing of the rwo (adhesion and elasticity) strongly dependant on tube diameter.

FM-AFM: tool to make accurate analysis for nanomaterials contact mechanics.


Oscillating NanoNeedle at Air liquid
Interface Dynamical behavior of NanoMeniscus

C. Jai, J.P. Aimé, R. Boisgard (University Bordeaux I)


D. Mariolle, F. Bertin (LETI-MINATEC)
(Nanoletter Vol 6 issue 11, 2006)

• Q>>Qwater
• Φ interface
• Nanometer scale Wetting deWetting
processes
• Dynamical stability attoliter
• No- substrat
• Weak perturbation for Membranes
and proteins
Dynamical behavior of NanoMeniscus

f cap = γφ cos(θ ) = 1 − 5nN


δ
h ≈ r ln ≈ 100nm v 2
a f dis ≈ η φ = 10 − 100 pN
e
Frontier Elasticity : Triple line Air-Liquid-Solid

km

γ γ
km ≈ π sin θ cos θ ≈ π
2
θ2 = 10-2 Nm-1
log ( δ R ) log ( δ R )

π γ 1 madded
Δν ≈ ν 0 sin θ cos θ − ν 0
2

2 k ln (δ R ) 2 m*
Δv γ f dis ≈ η
v
≈ θ d2
ν0 k θd

Meniscus Frequency Thinning Viscous


Shape shift effect Damping

Glycerol
Water
ƒη=1.485 Pa.s
ƒη=1.10−3 Pa.s
ƒγ=63.4mN/m²
ƒγ=72.8mN/m²
ƒρ=1260g/Lm
ƒρ=1000g/L
Oscillating at the air-liquid interface
Nano-Meniscus
Glycerol
C. Jai et al

•High Viscosity: 103 water viscosity


•Stable Interface
Meniscus Dynamical Shape

γφ
f el = γφ ( cos θ e − cos θ d ) ≈ ( ) =
v
θ 2
−θ 2
η ≈ f dis
2
d e
θd

Θe
Δν
V
Θd
Θd fdissipation

v −⎛ − 2

= θ d ⎜1 − θ d ⎟
vc ⎝ ⎠
Meniscus Dynamical Shape

v fdissipation
Θe

Θ
d Δν

v − ⎛ −2 ⎞
= θ d ⎜1 − θ d ⎟
Critical velocity vc : v > vc complete wetting of the nanoneedle
vc ⎝ ⎠
IMAGING air-LIQUID interface
Evaporation and ultra thin meniscus

WATER
Water
Viscosity very low, dynamical effect small

Pinned triple line Ultra thin meniscus

Δν ≈ θ 2

to zero

Θ(nΔτ) « Infinite »
1
f dis ≈
θ

Ultra thin meniscus until it


breaks
Θ(Δτ)
Θe (t=0)
« Infinite »

fdissipation

until it breaks

Δν

to zero
Relationship between nanomeniscus shape and dissipation

≈θ2

γ int ≈ −
( R ) φ Δν +
2k ln δ 1 γφ 2
θe
ω2 A 2 Aω
air glycerol interface

Viscous fluid: Dynamical non linear thinning effect.


ΘD behaves as the order parameter of a first order phase transition.
Critical tip velocity, above which complete wetting occurs : ΘD=0

air water interface

-Hot problems related to evaporation at nm scales.


-Diverging behavior of the Dissipation: viscous contribution dominant for very
thin meniscus (!?).

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