Week 8 Lecture

Nanocharacterisation

A/Prof Matthew Hill

Room 361, Building 82 (New Horizons)

matthew.hill@monash.edu
How?
 What we can see…

➢➢Light microscope (LM)

➢➢Transmission Electron
Microscope (TEM)
➢➢Atomic Force Microscope
(AFM)
➢➢Scanning Tunneling
Microscope (STM)
 Learning Objectives

(1)To know some basic physics of light

(2)To know how light microscopes work in general
(3)To be familiar with various light microscopes
(4)To understand diffraction limits in light
microscope imaging
(5)To know some basics of electrons
(6)To understand how electron microscope works
(7)To know the similarity and difference between
light microscope and electron microscope
 Physics of Light

➢➢light is refracted (bent) when passing from one

medium to another
➢➢refractive index
a measure of how greatly a substance slows the
velocity of light
➢➢direction and magnitude of bending is determined by
the refractive indexes of the two media forming the
interface
 Lenses
➢➢focus light rays at a specific place called the focal
point
➢➢distance between center of lens and focal point is the
focal length
➢➢strength of lens related to focal length
short focal length more magnification
 The Light Microscope

LM types
– bright-field microscope
– dark-field microscope
– phase-contrast microscope
– fluorescence microscopes
 The Bright-Field Microscope

• produces a dark image against a brighter

background
• has several objective lenses
– parfocal microscopes remain in focus
when objectives are changed
• total magnification
– product of the magnifications of the
ocular lens and the objective lens
 The Dark-Field Microscope
• produces a bright image of the object against a
dark background
• used to observe living, unstained preparations

http://www.olympusmicro.com/primer/techniques/rheinberg.html
 Examples

(Left) Schematic of surface plasmonc resonance where the free conduction

electrons in the metal nanoparticle are driven into oscillation due to strong
coupling with incident light. (Middle) Dark field microscopy image of 50
nm gold nanoparticles. (Right) Dark field microscopy image of 60 nm
silver nanoparticles.
http://nanocomposix.com
 The Fluorescence Microscope

• exposes specimen to ultraviolet, violet, or blue light

• specimens usually stained with fluorochromes
• shows a bright image of the object resulting from the
fluorescent light emitted by the specimen
 An Example

Yeast cell membrane visualized by some membrane proteins

fused with RFP and GFP fluorescent markers. Imposition of light
from both of markers results in yellow color.

http://en.wikipedia.org/wiki/
Fluorescence_microscope
 The Confocal Microscope
Confocal microscopy is an optical imaging technique used to increase optical
resolution and contrast of a micrograph by using point illumination and a
spatial pinhole to eliminate out-of-focus light in specimens that are thicker
than the focal plane. It enables the reconstruction of three-dimensional
structures from the obtained images. This technique has gained popularity in
the scientific and industrial communities and typical applications are in life
sciences, semiconductor inspection and material science.

http://en.wikipedia.org/wiki/
File:Confocalprinciple_in_English.svg
 Microscope Resolution

• Definition. It is the ability of a lens to separate or

distinguish small objects that are close together.
Quantitative definition is in the next slide.
• wavelength of light used is major factor in
resolution
shorter wavelength  greater resolution.
Quantitative definition is in the next slide.

• working distance
— distance between the front surface of lens and
surface of cover glass or specimen
Definition of resolution
Electron Microscopes
Why not use electrons?
 Electron Microscopy
• beams of electrons are used to produce images
 Ruska and Knoll's Electron Microscope.

The first electron microscope was a transmitted electron instrument shown here in a
wonderful mad-scientist photograph (Knoll is at left). Image source: http://
www.microscopy.ethz.ch/history.htm
Basic Electron Optics
Theoretical Resolution
Electron wavelength vs accelerating voltage
Electron wavelength vs accelerating voltage
 The electron gun

Filament (20-100 KV)

Bias (Wehnelt)
Cylinder

Anode

stream of electrons originating

from outer shell of filament atoms
LM vs TEM vs SEM

From Google online resources

Magnetic Lens and Glass Lens
 Why high vacuum ?
• m e a n free path of electrons v short in air

- at least 10 -5 mbar usually aimed for

• also

- tungsten filaments burn out in air

- columns must be kept dust free

• achieved by 2-fold pumping:

rotary (mechanical) p u m p + diffusion p u m p

or + turbo p u m p
 Transmission Electron Microscope

• electrons scatter when they pass through thin sections

of a specimen
• transmitted electrons (those that do not scatter) are
used to produce image
• denser regions in specimen, scatter more electrons and
appear darker
• analogous to procedures used for light microscopy
• for transmission electron microscopy, specimens
must be cut very thin
• specimens are chemically fixed and stained with
electron dense material
 Transmission Electron Microscope

From Google online resources

Nb – you can also do electron diffraction with TEM – we will cover diffraction in week 10
3D TEM imaging

Wenlong Cheng et al, Nature Material, 2009, 8, 519

Graphene
 TEM image galleries

Bacteriophage
(negatively-stained)

http://www.lifesci.sussex.ac.uk/home/Julian_Thorpe/TEMimages.htm
An example – lithium ion batteries

What we wanted to know

- Have we made LiFePO4 or something else?
- Is it porous like we hoped?
- Are the pores regular?
Here’s what we saw first
- Have we made LiFePO4 or something else? ???? Don’t know yet
- Is it porous like we hoped? YES
- Are the pores regular? SORT OF
Here’s what we did next
- Have we made LiFePO4 or something else? Well, all the
right elements are there, and carbon is not next to oxygen
- Is it porous like we hoped? YES
- Are the pores regular? SORT OF
How did we finally confirm it? X-Ray diffraction! You’ll have to come back later for that!
 How did we do that?
• beams of electrons are used to produce images
Energy Dispersive Spectroscopy (EDS)
A battery you can charge 23 times an hour
 Learning Objectives

(1)To know how Probe-based microscope works

(2)To understand the differences between STM
and AFM
(3) To know the difference operating modes for
AFM and STM as well as their Pros and Cons
(4) To know the differences between STM and
AFM probe and who they can be fabricated
(5) To understand AFM force curves
Scanning Probe Microscopy
 Scanning Probe Microscopy
• Monitor the interactions
between a probe and a
sample surface
• What we “see” is really an
image
• Two types of microscopy
we will look at:
– Scanning Tunneling
Microscope (STM)
– Atomic Force
Microscope (AFM)
 Quantum mechanical tunneling

Quantum mechanics allows a small particle, such as an electron, t o

overcome a potential barrier larger than its kinetic energy.

Tunneling is possible because of the wave-like properties of matter.

Transmission Probability: T ≈ 16ε(1 – ε)e -2κL

 Basic Principles of STM

Bias voltage:
d~6
mV – V range
Å

Electrons tunnel between the tip and sample, a small current I is

generated (10 pA to 1 nA).

I proportional to e-2kd, I decreases by a factor of 10 when d is

increased by 1 Å.
 STM

STM
– steady current
(tunneling current)
maintained
between
microscope probe
and specimen
– up and down
movement of probe
as it maintains
current is detected
and used to create
image of surface of
specimen
 Conductive Substrate

tunneling of electrons through

piezo- air between probe and surface
element
e-
e-
nA e-
e-
probe
R e- e- < 1nm
e-
e-
e-

x-y stage

only conducting material

 STM Tips

• How do you
make an STM
Let’s Zoom In!
tip “one atom”
sharp?

e-

x 10 6 x 10 8 x 10 8

Source: http://www.chem.qmw.ac.uk/surfaces/scc/scat7_
http://www.chem.qmw.ac.uk/surfaces/scc/scat7_6.htm
 Two Modes of Scanning

Constant
Height Mode

Constant
Current Mode
Image from an STM

Iron atoms on the surface of Cu(111)

 Challenges of the STM

• Works primarily with conducting materials

• Vibrational interference
• Contamination
– Physical (dust and other pollutants in the air)
– Chemical (chemical reactivity)
 References
G. Binnig and H. Rohrer. "Scanning Tunneling Microscopy", IBM J
Carbon Res. Develop., 30:355, 1986.
Monoxide
Man G. Binnig, H. Rohrer, “Scanning Tunneling Microscopy - From
Birth t o Adolescence”, Nobel lecture, December 8, 1986.

Tit-Wah Hui, “Scanning Tunneling Microscopy - A Tutorial”,

http://www.chembio.uoguelph.ca/educmat/chm729/STMpage/
stmtutor.htm

Wikipedia, “Scanning Tunneling Microscope”,

http://en.wikipedia.org/wiki/Scanning_tunneling_microscope

Nobel e-Museum, “The Scanning Tunneling Microscope”,

http://www.nobel.se/physics/educational/microscopes/
scanning/index.html
Carbon Monoxide on Platinum (111)
Pictures from http://www.almaden.ibm.com/vis/stm/blue.html
 Family of SPM

• STM scanning tunneling microscope

• AFM Atomic force microscope
• FFM (or LFM) (Lateral or Friction) force microscope
• SEFM Scanning electrostatic force microscope
• SFAM scanning force acoustic microscope
• AFAM atomic force acoustic microscope
• SMM scanning magnetic microscope
• MFM magnetic force microscope
• SNOM scanning near field optical microscope
• SThM scanning thermal microscope
• SEcM scanning electrochemical microscope
• SKpM scanning Kelvin Probe microscope
• SCPM scanning chemical potential microscope
• SICM scanning ion conductance microscope
• SCM scanning capacitance microscope