Atomic Force Microscopy

Measurement Techniques

Alex Robinson
a.p.g.robinson@bham.ac.uk
Synopsis
•  Scanning Probe Microscopy (SPM)

•  Atomic Force Microscopy (AFM)

•  Cantilevers

•  Surface Topography

•  Force Measurement and its Applications

•  Summary

•  Learning outcomes

2
Scanning Probe Microscopy
Scanning Probe Microscopy
•  The Atomic Force Microscope (AFM) was developed as a measurement
technique in the mid-1980s.

•  AFM was an iterative advancement on the Scanning Tunnelling

Microscope (STM), the original form of Scanning Probe Microscope
(SPM).

•  STM allowed imaging of super/conductive sample surfaces with atomic

resolution, through the use of a sharp metal tip.

•  The current between the tip and the sample surface is used as the
feedback system.
–  Maintaining a constant current allows surface topography to be imaged in 3D.

4
Scanning Probe Microscopes

STM

AFM

SNOM

5
Scanning Tunnelling Microscopy

6
Operation
•  Image quality related inextricably to tip shape.
–  Wider tips = feature broadening
–  Tips made from W or Pt/Ir
–  Sharp tips produced using mechanical cutting, chemical etching, or ion milling

•  Constant tunnelling current maintained by moving tip vertically.

7
Surface topography
•  Pt(111) heated to 600 oC in O2 •  Atomic resolution of Au(111).
for 10 mins. •  Imaged structure depends on
•  Dissociation of O2 on the Pt surface current and voltage applied.
causes etching. •  Which electron orbital is being
•  Atomically flat terraces; monoatomic probed?
steps.

8
Molecular Dissection

P.A. Sloan, Nature, 434, 367, (2005) 9

Research tool
•  The surface structure of Si(111) was a puzzle for many years, before
STM analysis provided a clear picture.

•  Termination of the Si(111)

crystal at the surface causes a
change in the equilibrium
positions of the final layer(s)
of atoms.
•  Analogous to the surface tension
of a liquid.

•  At the surface, each Si atom is

left with two ‘dangling bonds’,
resulting in a surface
reconstruction.

10
Research tool
•  The surface structure of Si(111) was a puzzle for many years, before
STM analysis provided a clear picture.

11
Nobel Prize for Physics
•  Gerd Binnig and Heinrich Rohrer won the Nobel Prize for Physics in
1986, for their invention of the Scanning Tunnelling Microscope.

Binnig

Rohrer
Phys. Rev. Lett. 1982, 49, 57-61

12
SNOM (Scanning Near-Field Optical Microscopy)
•  The SNOM or NSOM permits non-contact imaging of surface features:
–  Light of a fixed wavelength is shone through a small aperture.
–  The aperture-surface distance is closer to the surface than the wavelength of light.
–  The size of the aperture becomes limiting and not the wavelength of the light.
–  Aperture diameter and distance to surface typically < 200 nm.
–  Accurate fabrication and positioning required.

Plasmonics 2011, 6, 171-176 13

SPM family
•  Force
•  Normal
•  Lateral
•  Magnetic
•  Electrostatic
•  Kelvin force
•  Eddy current
•  Acoustic

•  Optical

•  Thermal

•  Electrical
Whitehouse, Handbook of Surface and Nanometrology, 2003, IoP (London)
14
Atomic Force Microscopy
Atomic Force Microscopy
•  STM suffers from the limitation that samples have to be conductive.

•  AFM was an iterative advancement on the Scanning Tunnelling

Microscope (STM), and can be used to measure insulating and
conductive samples.

•  AFM and STM are both types of Scanning Probe Microscope (SPM),
employing piezoelectric translation stages for precise nanoscale motion.

•  Piezoelectric materials expand and contract upon the application of a

potential difference.
–  Example of a piezoelectric material is lead-zirconium-titanate (PZT).
–  PZT instead of Pb[ZrxTi1-x]O3.
–  Typically PbZr0.52Ti0.48O3.
–  PZT is classed as a ceramic material.

16
Atomic Force Microscopy
•  AFM employs reflective microfabricated cantilevers, and a laser beam
(typically a red or infra-red laser) is used to monitor deflection.

17
Cantilevers
Si3N4 AFM cantilever

19
Si AFM cantilever
with SiO2 colloid
probe at apex

20
Cantilever tip

21
Cantilever tip

22
Microcantilever fabrication

23
Beam mechanics

24
Beam mechanics
•  Cantilever spring constant, k, is a measure of
the beam stiffness.

Ewt 3
k =
4L3
•  E = elastic modulus
•  w = width
•  t = thickness
•  L = length

•  The above relation applies for rectangular

beams.

•  Other geometries exist, and are

correspondingly more complicated to model.

•  There exist a range of spring constant

calibration methods.
Width
and
length
are
rela-vely
easy
to
fabricate
accurately.
However,
it
is
very
difficult
to

fabricate
 the
 thickness
 with
 precision.
 However,
 note
 the
 cubic
 rela-on
 between

thickness
and
the
spring
constant.
This
is
why
there
is
a
need
to
calibrate
each
can-lever.

 25
Beam mechanics
•  Cantilever spring constant, k, is a measure of
the beam stiffness.

Ewt 3
k =
4L3
•  E = elastic modulus
•  w = width
•  t = thickness
•  L = length

The cantilever’s natural frequency of oscillation is

related to the spring constant and the mass:

1 k
f=
2! m
Ideally the resonant frequency should be high,
which requires the spring constant to be low.
26
Cantilever calibration

Meas. Sci. Technol. 2010, 21, 115106 27

Surface topography
AFM imaging modes
Contact mode AFM
•  Constant compressive force
applied to sample
•  Tip moves across sample
•  Fixed end of cantilever moved
up and down to maintain
constant compressive force
•  Surface topography is the
output
Non-contact mode AFM
•  Also called Intermittent Contact
mode and Tapping mode
•  Cantilever is oscillated at its first
resonant frequency
•  Tip moves across sample
•  Fixed end of cantilever moved up
and down to maintain constant
oscillation amplitude
•  Surface topography is the output
29
AFM imaging modes
Repulsive Attractive Far away
(Contact Mode) (Non-contact Mode)
Tip – Surface Force (no feedback)

Tip – Surface Separation 30

AFM imaging issues

https://en.wikipedia.org/wiki/Atomic-force_microscopy 31
Non-contact mode AFM

32
Atomic structure
•  Non-contact mode AFM image of Si(111) unit cell.
•  Image has dimensions approx. 5 nm x 6 nm.

33
Polymer nanoparticles (120 nm)

34
Synthetic lipid bilayer

35
Synthetic lipid bilayer

36
Human chromosomes

37
Bacterium

38
DNA

39
Viruses

40
NIH 3T3 fibroblasts

41
Cracks in Si membrane

42
Surface roughness
•  There are a range of analyses which can be performed on acquired
data.

http://www.imagemet.com/WebHelp6/Default.htm#RoughnessParameters/Roughness_Parameters.htm
43
Force measurement
and its applications
Force measurement

45
Adhesion force measurement

AR
F (H ) = −
6H 2
Approach

•  F(H) = van der Waals attraction

Retract
•  A = Hamaker constant
•  R = probe radius
•  H = separation distance

•  This applies only for sphere-on-flat

geometries.

46
Influence of surface forces
Hertz model

JKR model
Deformation due to surface energy

47
Chemical modification of surfaces

48
Influence of environment

Vacuum conditions

Under solvent

In presence of meniscus force, often

due to water vapour condensation
on a surface

49
Effect of surface chemistry

50
Statistical distribution of forces

51
Chemical force titration

•  Performing measurements as a
function of local chemical
environment

•  Titration refers specifically to

change in pH

52
Friction force microscopy
•  Adhesion between tip and
sample varies

•  This can be mapped using

normal interactions or lateral
interactions

53
Functionalization choices

54
Single polymer interactions
•  Where polymer tethers exist between surfaces, due to discrete chemical bonds,
the stretching and unravelling of the polymer can be assessed

55
Protein unfolding

56
Worm-Like Chain (WLC) model

fWLC = force x = separation

kB = Boltzmann’s constant b = contour length
T = temperature L = persistence length

The WLC model describes the force versus extension behaviour of an flexible rod
and represents that measured for unfolded proteins and polymer tethers.

The configurational space available to a polymer is reduced when its ends are held,
and reduces further as the ends are held at increasing separations, which reduces
the entropy of the polymer, thus requiring work.

The work done in separating the ends is equal to the loss of entropy of the system;
the polymer behaves as an entropic spring.
57
Adhesion of E. Coli biofilms

Colloid. Surface. B 2012, 89, 152-160

58
Disruption of hydrogen bonding

Langmuir 2012, 28, 4648-4653 59

Thin film polymer melts

Langmuir 2011, 27, 11489-11500 60

Young’s modulus of thin films

Microelectronic Eng. 2012, 97, 34-37 61

Softening of baked organic films

62
 Dip-pen nanolithography (DPN)
•  Tip is dipped in chemical “ink” and transfers nanoparticles, biomolecules, etc.
to substrate through contact “writing”.
•  In a high-humidity atmosphere, a nanoscale water droplet condenses
between the AFM tip and the substrate.
•  The drop of water acts as a bridge over which the ink molecules migrate
from the tip to the substrate surface where they are deposited.
•  Demonstrated resolution: 15nm.

63
 Dip pen nanolithography patterns

A)  Ultra-high resolution pattern of mercaptohexadecanoic acid on

atomically-flat gold surface.
B)  DPN generated multicomponent nanostructure with two aligned
alkanethiol patterns.
C)  Richard Feynman's historic speech written using the DPN
nanoplotter.

64
 AFM manipulation of carbon nanotube

IBM nanotube
manipulation for position
nanotube on transistors.

65
 AFM oxidation (STM also works)
Voltage bias between a sharp
p ro b e t i p a n d a s a m p l e
generates an intense electric
field at the tip, which leads to
oxidation of silicon or
anodization (oxidation) of
metals.

•  Resulting oxide affected by experimental

parameters
o  Voltage (typically from 5-10V)
o  Tip Scan Speed (stationary to tens of µm/s)
o  Humidity (20% to 80%)
•  Detected current can be used for process control
66
Etching into Si by KOH using SiO2 as mask
Produced by chemical etching of AFM written lines

67
 De-passivation of Si:H by STM
H- terminated Si resulted from HF etch of Si whose top
surface (∼2nm) is usually oxidized in air.

STM image of a Si(100)–2×1–H surface. M

corresponds to a STM induced hydrogen Hydrogen desorption yield as a
desorption obtained with a constant current function of the sample bias
of 2nA, an electron dose of 4×10-4 C/cm, voltage.
and a sample bias voltage of 6V.

Syrykh, JAP, 85, 3887 (1999). 68

Molecular Dissection

P.A. Sloan, Nature, 434, 367, (2005) 69

Pushing/pulling atoms using STM
STM Lithography:
•  Atomic scale patterning technique
•  Manipulation of both single atoms or molecules

Hla et al., Phys. Rev. B 67, 201402 (2003) 70

Atomic Manipulation

71
 Atomic Manipulation

Circular corral (radius

71.3Å), 48 Fe atoms on
copper (111).
Quantum-mechanical
interference patterns

M.F. Crommie, Science 262, 218-220 (1993)

72
Atomic Manipulation

Images: Don Eigler

73
 Atomic Manipulation

The presence of a quantum mirage might be used to represent one bit of data
in a region far smaller than any current electronic device can manage.

M.F. Crommie, Science 262, 218-220 (1993).

M.F. Crommie, Nature 363, 524-527 (1993).
74
Atomic Manipulation

Image: Don Eiglar

75
Sub-Atomic Manipulation (?)

http://www.youtube.com/watch?v=j3QQJEHuefQ

Nature Nanotechnol, 4, 168 (2009) 76

Summary
Summary
•  The Atomic Force Microscope is one of a family of Scanning Probe
Microscopes

•  Can be used to obtain topographical information.

•  Can be used to measure adhesion forces and nanomechanical

properties.

•  Understanding the mechanical behaviour of systems is crucial to

successfully interpreting acquired data.

78
Learning outcomes
Learning outcomes
•  SPM / STM / AFM

•  Cantilevers

•  Topography

•  Force measurement

•  Many possible applications

80