Carbon Nanotube NanoNeedle Nanomeniscus

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Carbon Nanotube NanoNeedle Nanomeniscus

Jean-Pierre Aimé

[email protected]

Frontier in Scanning Probe Microscopy

PURDUE October 2006



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

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

I- Carbon Nanotubes as AFM probes:

competition between adhesion and elasticity

C. Bernard et al

II- Oscillating NanoNeedle at Air liquid Interface:

Dynamical behavior of NanoMeniscus

C. Jai et al



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~r 4L-3

• kcompression~ 103kbending

D. Dietzel, et al Physical Review B 72, 035445 (2005), Nanotechnology (2005) 16, p.S73-S78, JSPM (2006)



Nanotube mechanical cycle

F

D

Compressive part

tube bending

Extension phase

∆ Elastic bending

34 Lr E k NT π ≈

Extension stiffness

k adh

cstek E adhT diss =Δ≈ 2

2

1Cycle area:

Approach:

Start to touch

CNT Pull off force

U. Dürig, New J. of Physics 2 , 5.1 (2000).



SWNT’s FM AFM

frequency and damping curves

0

0,04

0,08

0,12

0,16

0 50 100 150 200Damping (V) Piezo displacement (nm)

Δz

contact

permanent

contact

intermittent

non contact

0

5

10

15

20

25

30

35

Δf (Hz)

A = 50nm

1. Non contact

2. Intermittent

Contact

3. Permanent

Contact

(ΔZ < 2A)





SWNT vs MWNT

-50

0

50

100

150

200

250

300

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

SWNT(A=50nm)

MWNT (A=58nm)

Δf (Hz)

Z/A

Δf MWNT : typ. 200 Hz

SWNT : typ. 20 Hz



( ) ( ))(cos1 122

0

2

0

2

d d d k

k c

NT −−−=− π ω ω ω d=Z/A

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

-1.0 -0 .5 0.0 0.5 1.0 1.5

0

15 0

30 0

45 0

60 0

kNT

=0.056 Nm-1

Δ f ( H z )

d

kNT

=0.04 Nm-1

kNT =0.048 Nm-1

Elastic contribution

F

D∆ ( ) ( )⎥⎥⎦⎤

⎢⎢⎣⎡ ⎟

⎠ ⎞⎜

⎝ ⎛ −−=Δ ∫

Δ+dt t t

A

zk T k

res

res

adh

c

ω ω ω

ω τ τ

τ

coscos1

0

Adhesion Contribution



Single Wall NT Mechanical properties

Adhesion mostly governs SWNT behavior

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

E

dis= 1.5 10 -17 J



Multi Wall NT mechanical properties

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

-50

0

50

100

150

200

250

300

-1.5 -1 -0.5 0 0.5 1 1.5 2

A=58nm

A=87nm

A=116nm

A=145nmA=174nm

Z/A

Δf (Hz)

-50

0

50

100

150

200

250

-1.5 -1 -0.5 0 0.5 1 1.5 2

Z/A

Δf (Hz)

A = 116 nm ; Δ = 75 nm

kMWNT

= 3.9*10-2

N.m-1

kadh

= 9.3*10 -2 N.m-1

∆



SWNT vs MWNT

1

10

100

20 40 60 80 100 120 140 160 180

MWNT Si lice

MWNT GraphiteMWNT Mica

SWNT Silice

Energie dissipée par période (10-17

J)

A (nm)

kMWNT

= 3.9*10-2

N.m-1

kSWNT

= 1.2*10-3

N.m-1

0 50 100 150 200

0.0001

0.001

0.01

0.1

MWNT helicoidal

MWNT

SWNT

kélastique

A (nm)

Energy loss

MWNT : 1.5*10-16J

SWNT : 1.5*10-17JkMWNT≈

30 kSWNT

Edissip (10-17 J)kNT (Nm-1)



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



( ) nN f cap 51cos −== θ γφ

pN

e

v f dis 100102 −=≈ φ η

nma

r h 100ln ≈≈δ

Dynamical behavior of NanoMeniscus



( ) ( )

2 2sin cos

log log

mk

R R

γ γ π θ θ π θ

δ δ

≈ ≈

km

( )2

0 0 *

1

sin cos2 ln 2

added m

k R m

π γ

ν ν θ θ ν δ Δ ≈ −

= 10-2 Nm-1

Frontier Elasticity : Triple line Air-Liquid-Solid



Water

η=1.10−3 Pa.s

γ=72.8mN/m²

ρ=1000g/L

Glycerol

η=1.485 Pa.s

γ=63.4mN/m²

ρ=1260g/Lm

d dis

v

f θ η ≈2

0

d k

vθ

γ

ν ≈Δ

FrequencyshiftMeniscusShape ViscousDamping

Thinningeffect



Oscillating at the air-liquid interface

Nano-Meniscus

C. Jai et al

•High Viscosity: 103 water viscosity

•Stable Interface

Glycerol



( ) ( )2 2cos cos2

d el e d e f γφ

γφ θ θ θ θ = − ≈ −

Meniscus Dynamical Shape

dis

d

f v

≈θ

η =

Θd

v

Θe

Θd

Δν

f dissipation

V

2

1d d

c

v

v

θ θ − −⎛ ⎞

= −⎜ ⎟⎝ ⎠



f dissipation

ΔνΘ

d

v

Θe

Meniscus Dynamical Shape

Critical velocity vc : v > vc complete wetting of the nanoneedle

2

1d d

c

vv

θ θ − −

⎛ ⎞= −⎜ ⎟⎝ ⎠



IMAGING air-LIQUID interface



WATER

Evaporation and ultra thin meniscus



Θ(nΔτ)

Θe (t=0)

Viscosity very low, dynamical effect small

Pinned triple line Ultra thin meniscus

Water

Θ(Δτ)

Ultra thin meniscus until it

breaks

to zero

« Infinite »

2

θ ν ≈Δ

θ

1≈dis f



f dissipation

Δν

« Infinite »

to zero

until it breaks



Relationship between nanomeniscus shape and dissipation

2θ ≈

( ) 2

2int2

1ln2e

A A Rk θ

ω γφ ν φ

ω δ γ +Δ−≈



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Carbon Nanotube NanoNeedle Nanomeniscus