Scanning Tunneling Microscopy (STM)

Scanning Probe --- G. Binnig, H. Rohrer et al, (1982)

Microscopy (SPM) Near-Field Scanning Optical Microscopy (NSOM)
--- D. W. Pohl (1982)
Atomic Force Microscopy (AFM)
--- G. Binnig, C. F. Quate, C. Gerber (1986)
Scanning Thermal Microscopy (SThM)
--- C. C. Williams, H. Wickramasinghe (1986))
Magnetic Force Microscopy (MFM)
--- Y. Martin, H. K. Wickramasinghe (1987)
Friction Force Microscopy (FFM or LFM)
--- C. M. Mate et al (1987)
Electrostatic Force Microscopy (EFM)
--- Y. Martin, D. W. Abraham et al (1988)
Scanning Capacitance Microscopy (SCM)
--- C. C. Williams, J. Slinkman et al (1989)
Force Modulation Microscopy (FMM)
--- P. Maivald et al (1991)
 Atomic Force Microscopy (AFM)

F = kΔz
F = 10-9 – 10-6 N
k = 0.1 – 1 N/m

References:
•  G. Binnig, C. F. Quate, and C. Gerber, Phys. Rev. Lett. 56, 930 (1986).
•  C. Bustamante and D. Keller, Physics Today, 32, December (1995).
•  R. Wiesendanger and H.J. Güntherodt, Scanning Tunneling Microscopy II ,
Springer-Verlag, (1992).
 Structure of AFM

Detection
mechanism Display

Cantilever
Local probe Feedback
Sample mechanism

X-Y-Z Piezo
transducer
(Fine positioning)
Coarse approach
and positioning

Vibration isolation
Core components of AFM

Laser
Detector
Tip and
cantilever

Sample

Piezoelectric
Tube Scanner
 Interaction between the probe and sample

Short-range: Long-range:
1)  Bonding 1)  Van der Waal
2)  Repulsion ～50nm 2)  Capillary
3)  Magnetic
4)  Electrostatic

Lennard-Jones potential φ(r) = - A/r6 + B/r12

Reaction of the probe to the force
Deflection of Cantilever vs Piezo displacement
 Position-sensitive Photo Diode (PSPD)

d
D

D ~ 10mm d ~ 1mm s ~ 0.01mm

Piezo Scanner
Three scanning modes of AFM

(Tapping mode)
 Two imaging methods in contact mode

•  Constant force method：By using a feedback loop the

tip is vertically adjusted in such a way that the force
always stays constant. The tip then follows a contour
of a constant contact force during scanning. A kind of
a topographic image of the surface is generated by
recording the vertical position of the tip.

•  Constant height method： In this mode the vertical

position of the tip is not changed, equivalent to a slow
or disabled feedback. The displacement of the tip is
measured directly by the laser beam deflection. One
of its advantages is that it can be used at high
scanning frequencies.
 Constant-force scan vs.
constant-height scan

Constant-force mode Constant-height mode

www.ntmdt.com
 Constant-force scan vs.
constant-height scan
Constant-force Constant-height
•  Advantages: •  Advantages:
–  Large vertical range –  Simple structure (no
–  Constant force (can be feedback control)
optimized to the –  Fast response
minimum) •  Disadvantages:
•  Disadvantages: –  Limited vertical range
–  Requires feedback (cantilever bending
control and detector dynamic
–  Slow response range)
–  Varied force
Problems with the contact mode

100 nN
 AC imaging mode

ω1 = ω0 (1 + F’/2c)
Amplitude A

No interaction
With attractive F’

ω1 ω0 ωD Frequency ω
 Comparison of three scanning modes
接觸式

Contact
非接觸式 暫接觸式

Non-contact Intermittent-contact
 Tapping mode

System
Controller

Laser
Oscillation Piezo (10K – 1MHz)
Photo-
detector

“Free” amplitude
Silicon Cantilever (> 20 nm)
with Tip
Sample
Fluid layer
“Tapping”

Amplitude reduced
Images by tapping mode

Topography Phase

AFM image of a fresh

Alfalfa root section
Fabrication of AFM probes

Typical Tip Dimension: Typical Tip Dimension:

150µm x 30µm x 0.5µm 150µm x 30µm x 3µm
k ~ 0.1 N/m fr ~ 100 kHz
Materials: Si3N4 Materials: Si
 V-shaped
Materials: Si, SiO2, Si3N4
Ideal Tips: hard, small radius of curvature, high
aspect ratio

Pyramid Tip
Ultrasharp Tip

Rectangular-shaped

Diamond-coated Tip
 Criteria for AFM probe

1)  Small spring constant (k) F = k Δz

To detect force of ~ nN
2) High resonant frequency (fr) fr ∝ (k /m)1/2
To enable scanning and other operations

3) Highly anisotropic stiffness

Easy to bent and difficult to twist

4) Sharp protrusion at the apex

To better define the tip-sample interaction
 Tip of small shear force
(for Contact mode)

Typical Tip Dimension:

150µm x 30µm x 0.5µm
k ~ 0.1 N/m
Materials: Si3N4
 Tip of high resonant frequency
(for Tapping mode)

Typical Tip Dimension:

150µm x 30µm x 3µm
fr ~ 100 kHz
Materials: Si
 AFM versus STM

1.  Generally, STM has “better” resolution than AFM.

2.  The force-distance dependence in AFM is much
more complex when characteristics such as tip
shape and contact force are considered.
3.  STM is generally applicable only to conducting
samples while AFM is applied to both conductors
and insulators.
4.  AFM offers the advantage that the writing voltage
and tip-to-substrate spacing can be controlled
independently, whereas with STM the two
parameters are integrally linked.
 AFM versus EM

1.  AFM only reveal the surface and EM can probe

the interior structure of the sample with higher
resolution.
2.  AFM provides direct topographic measurements
and EM provides only 2D projection of the
sample structure.
3.  No charging effect occurs in AFM. So, for
insulating samples, no metallic coating is
necessary.
 AFM versus Optical Microscope

1.  AFM has much better resolution than Optical

Microscope (OM).
2.  AFM provides unambiguous measurement of
step heights, independent of reflectivity
differences between materials.
3.  OM can be applied to much faster dynamic
studies with the pump-probe method.
Effects of the Tip Shape
Ultra-sharp tip
 AFM Tip + Carbon Nanotube

Carbon
AFM Nanotube
tip φ ≅ 20nm
L ≅ 80nm

10µm 1µm
Image of high aspect ratio
 AFM images
CD pits Integrated circuit Chromosomes

Bacteria DNA
DVD pits
 Interaction between the probe and sample

Short-range: Long-range:
1)  Bonding 1)  Van der Waal
2)  Repulsion 2)  Capillary
3)  Magnetic
4)  Electrostatic

Lennard-Jones potential φ(r) = - A/r6 + B/r12

Force spectroscopy by AFM
Atomic Image of Si(111)-(7×7) Taken with AFM

F.J. Giessibl et al., Science 289, 422 (2000)

 Measurement of Mechanical Properties

1.  The load-displacement curves provide a “mechanical fingerprint” of

material’s response to deformation, from which parameters such as
hardness and young’s modulus of elasticity can be determined.
2.  In measuring the mechanical properties of thin coated system, the size of
contact impression should be kept small relative to the film thickness.
Nanolithography of Tapping-Mode AFM

(1.2μm× 1.2μm) (2.5μm× 2.5μm)

Image of polycarbonate film on silicon surface

 Lateral Force Microscopy

Topography LFM
Nature rubber/EDPM blend

(A+C) – (B+D)

•  LFM is sensitive to friction and chemical forces.

•  Image contrast depends on the scanning direction.
•  Surface roughness will contribute to the contrast.
 Chemical Force Microscopy

CFM scan of well-defined regions that terminate in either methyl or

carboxylic acid groups. When a carboxylic acid-terminated tip is used for
imaging (left), the carboxylic acidterminated regions exhibit greater frictional
force (lighter color) than the methyl-terminated regions. When a
methylterminated tip is used (right), the friction contrast is reversed. No
differences are revealed by the topographic AFM scan (not shown) since the
functional groups are structurally quite similar. Image courtesy of Dr. C.
Lieber, Harvard University.
 Magnetic Force Microscopy (MFM)

F = ∇(m • H)

Tips: silicon probes are magnetically sensitized by sputter

coating with a ferromagnetic material.
Resolution: 10 ~ 25 nm.
Applications: hard disks, magnetic thin film materials,
micromagnetism.
 AC imaging mode

ω1 = ω0 (1 + F’/2k)
Amplitude A

No interaction
With attractive F’

ω1 ω0 ωD Frequency ω
 Lift mode of AFM

2nd pass
1st pass
Lift Height
Magnetic or Electric
Field Source
Topography

Non-contact force
 MFM Images

mT = mZ

Tip as a point dipole

Fz = ∂(mxHx + myHy + mzHz )/∂z

Tip as a long rod

Fz = mzHz
mT = mx + mz
AFM MFM

Bits (50 nm) on a magneto-optical disk

Scan area (5µm× 5µm)
 Probes of various functions

thermocouple tip

sample
Scanning Thermal Microscopy (SThM)
Scanning Capacitance Microscopy (SCM)
SCM CV Curve
 Scanning Capacitance Microscopy

SCM AFM

InP/InGaAsP
Diode Laser
1.  All SPMs are based on the ability to position various types of probes
in very close proximity with extremely high precision to the sample
under investigation.
2.  These probes can detect electrical current, atomic and molecular
forces, electrostatic forces, or other types of interactions with the
sample.
3.  By scanning the probe laterally over the sample surface and
performing measurements at different locations, detailed maps of
surface topography, electronic properties, magnetic or electrostatic
forces, optical characteristics, thermal properties, or other
properties can be obtained.
4.  The spatial resolution is limited by the sharpness of the probe tip,
the accuracy with which the probe can be positioned, the condition
of the surface under study, and the nature of the force being
detected.
Near-field Scanning Optical Microscopy (NSOM)

Shear force detection is used to regulate

the tip/sample separation
Probes for NSOM
Imaging modes for NSOM
Topography NSOM Image

Polystyrenes of 100 nm on glass

 Recent development: AFM-IR system

Scheme of the AFM–IR setup. The AFM cantilever ring-down amplitude

plotted as a function of laser excitation wavelength produces the IR spectrum.

Alexandre Dazzi et al., APPLIED SPECTROSCOPY OA 66, 1365 (2012)

(a) AFM topography picture of the bacterium; the position of the tip is indicated in blue. (b)
FT–IR spectrum; the bacterium absorption spectrum is drawn in green, and the wavenumber
of the CLIO laser is indicated by the red arrow. (c) Oscillations recorded by the four-
quadrant detector (in red) as function of time superposed on the CLIO pulse laser (blue).

Alexandre Dazzi et al., APPLIED SPECTROSCOPY OA 66, 1365 (2012)

Recent development: High resolution AFM

STM and AFM imaging of pentacene on Cu(111). (A) Ball-and-stick model of the
pentacene molecule. (B) Constant-current STM and (C and D) constant-height AFM
images of pentacene acquired with a CO-modified tip

L. Gross et al., Science 325, 1110 (2009)

 Discriminating Chemical Bonds

Forceful discrimination. Gross et al. used AFM with a CO-functionalized tip (A) to map the
subtle differences in charge density (B) and bond length (C) associated with nonequivalent C-C
bonds in a fullerene (C60) molecule and to correlate them with their bond order.

L. Gross et al., Science 337, 1326 (2012)

 Recent development: High speed AFM

Why High Speed AFM?

•  Most dynamic biological processes occur
within milliseconds time scale or less.
Example:
1. Photocycle of Bacteriorhodopsin (Nature
Nanotechnology 5, 208-212 (2010))
WT: ~10 ms D96N bR mutant: ~10 s
2. F1-ATPase’s rotary rate: 0.5 r.p.s (Nature 386,
299-302(1997))
 Ando’s High-Speed AFM
•  Small cantilever of
small spring constant
(150-280 pN/nm) to
reduce tip forces
•  Small cantilever of
high resonance
frequency (450-650
kHz) to decrease
response time
•  Effective dynamic
PID control
•  Low-noise sensor Obtain consecutive images of a 240 x
amplifier 240 nm2 area in as little as 80 ms
 Hand-Over-Hand Movement

Noriyuki Kodera, Daisuke Yamamoto, Ryoki Ishikawa & Toshio Ando, Nature 468, 72 (2010)