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Atomic Force Microscopy (AFM)Atomic Force Microscopy (AFM)

Arvind Raman, Associate ProfessorMechanical Engineering

Birck Nanotechnology CenterNASA Institute of Nanoelectronics and Computation (I

NAC)

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Further readingFurther reading

§ J. Gomez-Herrero, and R. Reifenberger, “Scanning Probe Microscopy”, to appear in Encyclopaedia of Condensed Matter Physics, edited by F. Bassani, J. Leidl, and P. Wyder, Elsevier Science Ltd., 2004.

§ D. Sarid, Scanning Force Microscopy with Applications to Electric, Magneticand Atomic Forces, Revised Edition, Oxford University Press, 1994.

§ U. Dürig, “Interaction sensing in dynamic force microscopy”, New Journal of Physics, Vol. 2, pp. 5.1-5.12, 2000.

§ F. Giessibl, “Advances in atomic force microscopy”, Reviews of Modern Physics, Vol. 75, pp. 949-983, 2003.

§ R. García, R. Pérez, “Dynamic atomic force microscopy methods”, Surface Science Reports, Vol. 47, pp. 197-301, 2002.

§ B. Cappella, G. Dietler, “Force-distance curves by atomic force microscopy”Surface Science Reports, Vol. 34, pp. 1-104, 1999.

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OutlineOutline

§ History of Atomic Force Microscopy (AFM)§ Instrumentation§ Static force-distance curves and force

spectroscopy§ Dynamic AFM and force gradient spectroscopy§ Imaging§ Applications and emerging areas

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§ Binnig, Gerber, Rohrer, Wiebel (1982)§ Binnig and Rohrer awarded Nobel Prize in Physics in 1986 for STM§ If |Vt| is small compared to workfunction , and tunneling current is given

by where z is the gap I0 is a function of the applied voltage and the density of states in the tip and the sample, and

§ For most metals, Φ˜ 4eV, so that κt=1Å-1

§ Most current carried by “front atom”blunt tips , so atomic resolution possible even with relatively blunt tips

§ Only electrically conductive samples, restricting its principal use to metals and semi-conductors

The starting point- STMThe starting point- STM

Φ2

0( ) t ztI z I e κ−=

2 /t mκ = Φ h

F. Giessibl’sRev. Mod. Phys.

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The AFMThe AFMG. Binnig, C. F. Quate and Ch. Gerber, PRL 56, 930 (1986)

§ Binnig invented the AFM in 1986, and while Binnig and Gerber were on a Sabbatical in IBM Almaden they collaborated with Cal Quate (Stanford) to produce the first working prototype in 1986

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G. Binnig, C. F. Quate and Ch. Gerber, PRL 56, 930 (1986)

Early AFM ImagesEarly AFM Images

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OutlineOutline

§ History of Atomic Force Microscopy (AFM)§ Instrumentation§ Static force-distance curves and force

spectroscopy§ Dynamic AFM and force gradient spectroscopy§ Imaging§ Applications and emerging areas

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The microcantilever – the force sensorThe microcantilever – the force sensor

www.olympus.co.jp

www.nanosensors.com

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Detecting deflectionDetecting deflection

§STM tip

§Capacitance/laser interferometry

§Beam deflection

Courtesy- J. Gomez, UAM, Spain

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Photodiode

Laser

The beam deflection methodThe beam deflection method

a) Normal force

Up

Down

b)Lateral Force

Right

leftA+B= UP

C+D=DOWN

A+C= LEFT

B+D=Right

Courtesy- J. Gomez-Herrero, UAM, Spain

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AFM Block DiagramAFM Block Diagram

Personal Computer

SPM Signals

HV Amplifiers and signal conditioning

SPM tip

Signaldetector

Piezoelectricscanner

SFM 3 dimensional image of a tumor cell HeLa (37x37µm2 )

Digital SignalProcessor

Courtesy- J. Gomez-Herrero, UAM, Spain

z dither piezo

xy

z

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OutlineOutline

§ History of Atomic Force Microscopy (AFM)§ Instrumentation§ Static force-distance curves and force

spectroscopy§ Dynamic AFM and force gradient spectroscopy§ Imaging§ Applications and emerging areas

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§ Long-range electrostatic and magnetic forces (upto 100 nm)

§ Capillary forces (few nm)§ Van der Waals forces (few nm) that are

fundamentally quantum mechanical (electrodynamic) in nature

§ Casimir forces§ Short-range chemical forces (fraction of

nm) § Contact forces § Electrostastic double-layer forces§ Solvation forces§ Nonconservative forces (Dürig (2003))

Tip-sample gap

Tip-sample interaction force

Attractive

Repulsive

Nanosensors Gmbh

Tip-sample interaction forces in AFMTip-sample interaction forces in AFM

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The microcantilever – the force sensorThe microcantilever – the force sensor

§ From elementary beam theory, if E=Young’s modulus, I=bh3/12 then

§ δ=w(L)=F L3/(3EI), and θ=dw(L)/dx=FL2/(2EI)

§ Deflection and slope linearly proportional to force sensed at the tip§ k=3EI/L3 is called the bending stiffness of the

cantilever

www.olympus.co.jp

F

L

b h δθ

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d

Force-displacement curvesForce-displacement curves

Z

δkδ

F(d)

F(d)=kδ

d

F(d)

Z

k

Z

δ

WAdhesion=blue shaded area above

1

WCantilever=shaded area above

13 3

Inaccessible region

Snap-in

2

2’2

2’

4’

4

Pull-off

4

4’

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Force spectroscopy Force spectroscopy

§ Three distinct regions§ If k is known then from the static-force distance curve, F(d)

can be calculated for all d except for inaccesible range near snap-in§ It can be shown that WCantilever is related to the WAdhesion

§ Slope in III is good measure of repulsive forces (local elasticity)

Z

IIIIII

Animation courtesy J. Gomez-Herrero, UAM, Spain

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OutlineOutline

§ History of Atomic Force Microscopy (AFM)§ Instrumentation§ Static force-distance curves and force

spectroscopy§ Dynamic AFM and force gradient spectroscopy§ Imaging§ Applications and emerging areas

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Dynamic AFMDynamic AFM§ Cantilever driven near resonance§ Non-contact AFM, Tapping mode AFM, Amplitude

Modulated AFM, Frequency Modulated AFM are all dynamic AFM§ The cantilever's resonant frequency, phase and

amplitude are affected by short-scale force gradients

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Dynamic AFM & force gradient spectroscopyDynamic AFM & force gradient spectroscopy§ Variation of amplitude,

resonance frequency, and phase measured as Z is decreased § From this it is possible to

reproduce the Force gradients between the tip and the sample§ Even non-conservative

interactions can be resolved§ Offers many advantages over

static-force distance curve based force spectroscopy§ Quantitative information is hard

to come by because the forces are nonlinear

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OutlineOutline

§ History of Atomic Force Microscopy (AFM)§ Instrumentation§ Static force-distance curves and force

spectroscopy§ Dynamic AFM and force gradient spectroscopy§ Imaging§ Applications and emerging areas

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ss

x

xy

First tip contacts surface with some setpoint normal force which is kept constant during the scan

Contact Mode ImagingContact Mode Imaging

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In Tapping mode the tip is oscillated at the resonance frequency and the amplitude of oscillation is kept constant while the tip intermittently enters the repulsive regime

Surface interaction

Tapping ModeTapping Mode

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Phase ImagingPhase Imaging

AFM height (left) and phase (right) images of poly(methylmethacrylate)

(Digital Instruments, Inc.)

n Regular tapping mode implemented but signal phase monitoredn Phase contrasts are related to differences in local dissipation

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OutlineOutline

§ History of Atomic Force Microscopy (AFM)§ Instrumentation§ Static force-distance curves and force

spectroscopy§ Dynamic AFM and force gradient spectroscopy§ Imaging§ Applications and emerging areas

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Carbon nanotube tips (CNT)Carbon nanotube tips (CNT)

§ Provide high resolution§ Show little evidence of wear§ Promising technology for critical dimension metrology of

semiconductors, and nanobiological investigations§ Buckling, friction and stiction of CNT become important

Dynamic AFM images of a 100 nm trench on Si using conventional silicon probe (left) and a MWCNT probe (right)

Raman et al, Ultramicroscopy (2003), Nanotechnology (2003, 2005)

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71.5 7 2 72.5 7 3 73.50

2 0

4 0

6 0

8 0

1 0 0

1 2 0

Exci ta t ion f requency (kHz)

Tip

am

plitu

de (

a.u.

)

CNT tips – tapping mode CNT tips – tapping mode

(SEM images: NASA & Purdue, 2002)

Straight MWCNT

§ CNT attached strongly to Force modulation etched Si probe (Ni evaporation)§ Straight MWCNT, diameter 10 nm, length 7.5µm, Frequency 72.5 kHz§ Repulsive and attractive states do not appear to co-exist for long CNT tips

Raman et al, Ultramicroscopy (2003), Nanotechnology (2003)

Z gap decrease

Buckling signature

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Displacement towards sample (nm)

AB

CD

EF

GH

J

I

A B C D E

J I H G F

§ CNT buckles, slips, and slides§ High adhesion on the CNT sidewalls

Raman et al, Nanotechnology (2003)

Static force-distance curvesStatic force-distance curves

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Shorter CNT tips- noncontact modeShorter CNT tips- noncontact mode

§ Divot artifacts associated with switching between attractive (noncontact) and repulsive (tapping states)

§ Ringing artifacts associated with CNT adhesion and stiction to sidewalls

100 nm Si grating

300 nm Tungsten nanorods

0.4 µ CNT

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Exploiting anharmonic oscillationsExploiting anharmonic oscillations

§ NC vibration spectrum depends on local adhesion properties§ Experiments performed using 47 kHz microcantilever on wild and mutant bacteriorhodopsinmembrane §2nd bending mode freq ~7*1st

0 100 200 300 400 500

-60

-40

-20

0

20

40

a)

B2/H7

H1

PS

D (d

B)

Frequency (kHz)0 2 4 6 8 10

-60

-40

-20

0

20

40

b)

H3H2B2/H7

H1

PS

D (

dB)

Frequency (kHz)0 2 4 6 8 10 12

-60

-40

-20

0

20

40

c)

H3H2B2/H7

H1

PS

D (

dB)

Frequency (kHz)

Thermal vibration Driven in air On mica (50 % setpoint)

“Probing Van der Waals forces at the nanoscale using higher harmonic dynamic force microscopy”, Crittenden, Raman, Reifenberger (in press PRB)

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Application to local adhesion estimationApplication to local adhesion estimation3500 nm x 3500 nm scans

proteins Lipid deposits

Topography Second harmonic image

Seventh harmonic image

§ Clear distinction between lipids and proteins§ Presence of internal resonance critical in the method§ The method shows promise for the measurement of

local attractive forces of soft biomolecules§ Can be extended to electrostatic force microscopy or

capacitance microscopy for dopant profiling“Probing Van der Waals forces at the nanoscale using higher harmonic dynamic force microscopy”Crittenden, Raman, Reifenberger (in press PRB)

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Virus capsid mechanics studied using AFMVirus capsid mechanics studied using AFM

BacteriophageP22 (in buffer)

A computer model of the proheadstructure of the P22 and HK97 virus capsids. (T. Ferrin, UCSF Computer Graphics Lab)

Loca

l

Glo

bal

buck

ling

Experimental force-indentation

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Friction Force MicroscopyFriction Force Microscopy

3.0µm

Friction force image of a self assembled monolayer(Riefenberger Group)

www.chem.nwu.edu/~mkngrp/Dip-pen lithography

Contact mode oxidationlithography

Conley, Raman, Krousgrill, submitted JAP

§ Torsional vibrations due to atomic and molecular friction§ Lateral forces are specific§ Applications to nanotribology, probe

based lithography

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AcknowledgementsAcknowledgements§ Students§ Sebastian Rützel (Darmstadt)§ Mark Strus§ Shuiqing Hu§ Mau Deridder§ Xin Xu§ Bill Conley

§ Postdocs§ Soo-Il Lee (Univ. of Seoul)

§ Collaborators§ Steve Howell (Sandia) § Scott Crittenden (ARL)§ Cattien Nguyen (NASA Ames)§ Ron Reifenberger (Physics, Purdue)§ Amy McGough (Biology, Purdue)

§ Funding Agencies§ NSF Korean Center for Nanomechatronics and Manufacturing§ NASA§ DoE§ Purdue Research Foundation

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Questions & AnswersQuestions & Answers

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Application to local adhesion estimationApplication to local adhesion estimation3500 nm x 3500 nm scans

proteins Lipid deposits

Topography Second harmonic image

Seventh harmonic image

§ Clear distinction between lipids and proteins§ Presence of internal resonance critical in the method§ The method shows promise for the measurement of

local attractive forces of soft biomolecules§ Can be extended to electrostatic force microscopy or

capacitance microscopy for dopant profiling“Probing Van der Waals forces at the nanoscale using higher harmonic dynamic force microscopy”Crittenden, Raman, Reifenberger (in press PRB)

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Phase ImagingPhase Imaging

AFM height (left) and phase (right) images of poly(methylmethacrylate)

(Digital Instruments, Inc.)

n Regular tapping mode implemented but signal phase monitoredn Phase contrasts are related to differences in local dissipation