ECE8863-Lecture5 - Characterizations Part1

Introduction to Nanoscience
LECTURE 4
Characterization I
Copyright: CRC Press 2009

Agenda
• All kinds of characterization tools

• Electromagnetic methods
• Electronic beam methods
• Scanning probe methods
• Thermodynamic methods

Characterization of Materials
Think of all the different kinds of analytical / characterization
methods you have experienced in your undergraduate career:
GENERAL KINDS (and many more):
UV-visible spectroscopy
FTIR
Calorimetry
HPLC
Gravimetric analysis
Optical microscopy
X-Ray diffraction

Which are Applicable to Nanomaterials?
YES APPLICATIONS
UV-visible spectroscopy Optical absorption of gold colloid solutions
FTIR Quality control of surface engineering
Calorimetry Stability of metastable nano-materials
HPLC Nano-HPLC with “lab-on-a-chip”
Gravimetric analysis Thermal gravimetric analysis (TGA)
Optical microscopy NSOM capable of sub 100 nm resolution
X-Ray diffraction XRD of particles and powders
AND MANY MORE

The Ones That Made Nano and Are Nano
Scanning Electron Microscopy (SEM)
Transmission Electron Microscopy (TEM)
Atomic Force Microscopy (AFM)
Scanning Tunneling Microscopy (STM)
Surface Enhanced Raman Spectroscopy (SERS)
Dynamic Light Scattering (DLS) (nanoparticles)
Ellipsometry (thin films)
Brunauer-Emmett-Teller (BET) (surface area, porosity)
Localized Surface Plasmon Resonance (LSPR)
Mass Spectrometry (MS)
Thermal Analysis (TGA, DSC, DTA)
ELECTRON BEAM METHODS

Particle-Wave Duality
de Broglie’s Relationship (review):
hν h
ρ= =
c λ
2
h h ρ
λe = = and KE = 12 meυ 2 = 2
= eV
ρ€ meυ 2me
h
€ ρ = 2meeV and λe =
2meeV
€ Copyright: CRC Press 2009

Davisson and Germer’s Famous Experiment
h 6.626x10−34 J ⋅ s
λ= = = 0.1669 nm
2meeV 2 ⋅ 9.104x10 kg ⋅1.6022x10 C ⋅ 54V
−31 −19
n⋅λ 1⋅ 0.1669 nm
d= = = 0.0921 nm
2 ⋅ sin θ 2 ⋅ sin65°
€
Relativistic Effects
As the velocity of electrons approach the speed of light,
relativistic effects need to be considered:
h h h υ2
λr = = = 1− 2
ρ γ mυ mυ c
dt 1
γ= =
dτ 1− β 2
€
c 1
= =
c2 − υ 2 1− υ 2 / c2
γ is the Lorentz factor for special
relativity. τ is the “proper time”
€ and t is coordinate time. β = υ/c.
γ equals ca. 22.4 when υ ~ c. and
λr gets shorter.
Example 4.1
Q: At 200 KeV, calculate the relativistic mass mr of an
electron if it is traveling at 0.7000c. Use the Lorentz factor γ.
A: The rest mass of an electron is me = 9.109x10-31 kg.
( )
υ = 0.7000 ⋅ c = 0.7000 ⋅ 2.998x108 m⋅ s−1 = 2.099x10 8 m⋅ s−1
The relativistic mass is:
€ 1 9.109x10−31 kg 9.109x10−31 kg
mr = me ⋅ = = = 1.276x10−30 kg
υ2  2.099x108 m⋅ s−1 2 0.5098
1− 2 1− 
c 8 −1 
 2.998x10 m⋅ s 
The relativistic mass of the electron is nearly 1.4 times

€ (factor of γ) as large as its rest mass.

Example 4.2
Q: What is the wavelength of this electron? How does it
compare to the non-relativistic wavelength? What is the
accelerating voltage required to meet these conditions?
h h 6.626x10-34 J ⋅ s
λr = = = = 0.002474x10 −12
m = 0.00247 nm
ρ mrυ 1.276x10 kg ⋅ 2.099x10 m⋅ s
−30
( 8 −1
)
The regular wavelength of this electron at 200 KeV:
h 6.626x10-34 J ⋅ s
λe = =
2meeV ( )( )( )
2 ⋅ 9.109x10−31 kg ⋅ 1.6022x10−19 C ⋅ 2.000x105 V
= 0.00276x10−12 m = 0.00276 nm
If we use λ = h/meυ, we get a different answer. Why?

€ h 6.626x10-34 J ⋅ s
λe = = = 3.46x10 −12
m = 0.00345 nm
meυ ( −31
)( 8
9.109x10 kg ⋅ 2.099x10 m⋅ s −1
)
Imaging Superiority
Resolution, depth-of-field and depth-of-focus significantly

better for SEMs than for optical microscopes

Scanning Electron Microscopy
Basic Principles:
• Imaging by scanning (rastering) a high energy focused
electron beam over sample surface to generate a variety
of signals
• Analytical value? surface topography, electrical

conductivity and composition (via EDX)
• Analytical signal consists of secondary electrons, back-

scattered electrons, characteristic x-rays, cathodo-
luminescence, specimen current and transmitted
electrons if the sample is thin enough.
• Resolving power of average instruments is in the 1 to 5

nm range
Limitations of SEM
• Sample must fit into chamber (rather large specimens on

the order of 10 cm. vertical dimension limited to ca. 40 mm.
• Samples must be able to withstand high vacuum (10-6

torr).. i.e. no out-gassing or humid samples
• Most EDX detectors cannot detect light elements H, He, Li
• Electrically conducting coating applied to insulating

samples in older instruments
• Over-estimation of particle size

Electron Interactions with Matter
THICK SAMPLES for SEM:
Inelastic Interactions: Ionizations

(for EELS), secondary electrons,
characteristic x-rays and auger
electrons; phonons created from
heating the sample; plasmons that
decay into phonons or photons; and
Cathodoluminescence, common in
semiconductor materials.
Energy loss electrons from 1° e
Elastic Interactions:
Backscattered electrons and
elastically scattered electrons

Interaction Volume
The size of the interaction volume teardrop” depends on the

energy of the 1° electron, the atomic number Z of the atoms
in the sample and the density of the sample material.
The size ranges from several tens of nm to ca. 5 or more µm

in depth.

Secondary Electrons
Secondary electrons are low energy electrons released in high
yield that are primarily used for topographical information.
Secondary electrons are produced
by the 1° source that knocks loose
a K shell electron. The K shell
electron loses energy (via inelastic
collisions) as it makes its way to the
surface. If it has enough energy to
overcome the work function of the
material, a 2°e (SE) is released for
detection.
2°e are of low energy (5 < 50 eV)

and are sensitive to the topography
of the surface, atomic number
(higher the better) and the angle of
incidence. 2°e have a mean-free-
path of less than 1 nm…. therefore,
they originate near the surface of
the specimen.
Secondary Electron Detection
Secondary electrons are detected with an Everhart-Thornley
detector (1960)– a scintillator-photomultiplier system.
Components include a scintillator inside of a Faraday cage. A

Faraday cage is a mesh made of conducting materials with the
purpose of attracting electrons (or EM shielding in other
applications).
Faraday Grid
Cage at Bias to
Photomultiplier Attract Electrons
Electron Beam
Scintillator
Sample

Backscattered Electrons
BSE reveal compositional information about the sample by
varying contrast depending on atomic number and interaction
volume.
BSE are produced when 1° beam

electrons at nearly normal incidence
are deflected (with high deflection ~
180°) by the specimen’s atomic
nuclei. The larger the Z, the larger
the deflection. BSE are produced
without additional electrons.
The kinetic energy of BSE are on par

with the 1° excitation source
electrons. BSE arise from greater
depths (10 to 1 to 500 nm)
penetration depth is greater than that
for SE.

Backscattered Electron Detection
Backscattered electron detectors are found in the proximity of
the electron beam. BSE are high energy elastically scattered
electron. the donut configuration maximizes interaction with
the solid angle collection of BSE. Detectors can be
scintillation or semiconductor type. Electron Beam
BSE detectors can establish

atomic number contrast in a
sample. They are also used to Bottom-Up View
map topography if an BSE Detector
asymmetrical arrangement is
used.
Backscattered
Semiconductor Detector Electrons
A p/n-jxn Sample
Bias Gold Film

Auger Electrons
Auger electrons are characteristic of the material from which
they emanate.
Following ejection of the K electron
(e.g. the 2° electron event), a higher
level electron drops into the K-shell
vacancy (usually an L1 or L2 e).
Enough energy is released during
this event to excite a low energy
electron near the surface (<1 to 3
nm) to overcome the work function
of the material.
Incident Auger electrons are used primarily

Electron for surface chemical analysis.
Intensity, % composition of
elements (including low Z) are
evaluated from the KE of the ejected
electron.
Energy Loss
Electron
Auger Electron Detection
Auger electrons, because they are less intense than SE and

BSE, require more intense electron 1°e excitation. This
usually results in larger beam diameter. Resolution is ca. 10
nm. The kinetic energy and the quantity of Auger electrons
are the analytical contribution. Auger (surface, ~ 4 nm)
complements x-ray microanalysis (~ 3 µm).
One kind of Auger detector is called the cylindrical mirror

analyzer. It is comprised of two co-axial cylinders that bend
the path of the electron. A uniform electric field deflects the
path of the e into a curved trajectory.

Characteristic X-Rays
Auger electrons are characteristic of the material from which
they emanate.
Following ejection of an inner core
electron, usually a K electron,
creating a vacancy. This hole is
quickly filled by electrons cascading
down from higher levels. In the
process, x-rays are emitted that are
characteristic of the element.
X-rays originating from the K, L and

M shells are element specific.
Bremsstrahlung contributes to the

broad x-ray spectrum formed by
inelastic collisions of electrons that
release a broad range of energy in
the x-ray region of the EM spectrum.
They form a continuous background
spectrum superimposed upon the
characteristic x-ray peaks.
X-Ray Analysis
There are two general categories: energy dispersive (EDS,

EDX or EDXRF) and wavelength dispersive (WDS).
EDS: Process related to XRF (x-ray fluorescence

spectroscopy). Analysis is by collection of characteristic x-
rays.
WDS: Utilizes diffraction patterns following interaction with a

sample and single x-ray wavelength at specific angles
(Bragg’s Law).

EDS-WDS Comparison
EDS WDS
Input Lower energy electron beam Higher energy electron beam
Requirement
Count Pulse pileup, overlaps Can handle high count rates
Resolution Worse (tenths of a percent) Better– examines specific
areas of x-ray spectrum
Efficiency of Better: < 2%, sample closer to Worse: < 0.2%
Collection detector
X-Rays that 100% counted;
Make it to Z < 5 difficult 30% counted
the Detector
Stray electrons and x-rays cause
Spectral distortions that produce peak More clean
Artifacts distortion, broadening, escape peaks,
absorption & fluorescence
Spot Size Smaller beam diameter: 2 µm - 0.05 Requires larger spot size: 10
µm µm
Data Rapid – analyses of numerous Slower – analysis of one
Acquisition elements simultaneously element at a time
Instrument SEM, TEM EPMA

Production of Electrons
There are a few types of electron guns: thermionic and field
emission (FEG).
Thermionic Electron gun emits electrons from a conducting

cathode by applying heat until outer orbital electrons obtain
enough energy to overcome the work function barrier of the
conducting material.
Field Emission guns apply sufficient electric field strong

enough to induce tunneling of electron through a barrier.
FEGs can be enhanced by applying some thermal energy so
that electrons are able to tunnel easier.
Schottky Emitters: Thermal filed emitters enhanced by

doped surfaces that reduce the work function of the combined
material.
Thermionic Electron Gun
Electrons leave filament with energy ~ kBT
Filament (8.62·10-5 eV·K-1). At 2700 K, E ~ 0.23 eV.
The e needs to overcome work function of
material governed by Richardson-Dushman
equation:
Wehnelt 2 −φ / k B T
Grid Cup J = AT e
where A is a material constant (60 A·cm-2·K-2
for tungsten, φ is the work function of the
material (4.5 eV for tungsten).
Electron Potential
Beam Δ € As the filament emits electrons, an emission
current begins to flow from the filament
towards the grid cup. The electrons are then
collimated and drawn from the cathode
Anode + towards the positively charged anode.
The beam is aligned and focused down the

column by a series of magnetic lenses.

Field Emission Electron Gun
Field emission tip is usually single crystal tungsten sharpened

by electrolytic etching down to 100 to 10 nm diameter at
several kilovolts negative potential.
The principle of emission also depends on the work function

of the metal used in the filament.

Production of Electrons
Properties Tungsten LaB6 F.E.G.
Work Function (eV) 4.5 2.4 4.5
Temperature (K) 2700 2000 1800
Energy Range (eV) 3–4 1.5 – 3 0.4 – 1.5
Source Size (nm) 30,000 5,000 < 10
Max. Current (nA) 1000 500 300

Brightness (A·cm-2sr)* 1 20 - 50 1013
Lifetime (h) 100 500 100 - 1000
Vacuum Required 10-5 Torr 10-6 Torr 10-9 Torr
Source: Swiss federal Institute of Technology, Zurich, ETH, www.microscopy.ethz.ch/generation.htm

*sr = steradian

Typical
SEM
Source: Swiss Federal Institute of Technology at Zurich www.micronano.ethz.ch/.../Salts-tem-SEM.jpg
Transmission Electron Microscopy
THIN SAMPLES for TEM:
Inelastic Interactions: Secondary

electrons, phonons, characteristic x-
rays and auger electrons.
Kakuchi lines.
Elastic Interactions:
Backscattered electrons, elastically
scattered electrons, transmitted
electrons and electron diffraction.

Typical
TEM

The Charge Coupled Device (CCD) Camera
Closely spaced array of gated metal oxide semiconductor
(MOS) capacitors or silicon diode photosensor (a.k.a. a pixel,
1” x 1” or 1024 pixels square) in the photoactive region is
coupled to a charge storage domain (transmission region)
connected to an amplifier. Use “Bucket Brigade” analogy:
Rain = Electrons
Conveyor Belt
to Amplifier
Conveyor Belts
Contents
Measured
Buckets (CCD Pixels)
Source: F. Ruddell, Technology for CCD Imagers, N. ireland Semiconductor Research Centre, School of
Electrical and Electronic Engineering, Queen’s University, Belfast
The Charge Coupled Device (Continued)
Three Phases:
• Image read by clocking charge through vertical

registers
• Output via horizontal serial register
• Charge converted to voltage
All based on charge generation, collection, transfer and

measurement.
Charge transfer efficiency near 100%

TEM Sample Preparation
• Embed biological or inorganic sample into polymer matrix
and section with a microtome (thickness via interference
color)— staining with heavy metals improves contrast
• Mechanically cut and grind sample to desired thinness (a

few nm)
diamond saw
grind and polish
dimpler treatment (lapping)
• Erode sample by ion milling
• Place in sample holder in TEM

Generic Summary
TEM, SEM and EPMA rely on electron beams accelerated to
high voltages
Relativistic effects need to be considered if acceleration

voltages are large
Many kinds of electrons are produced for analysis
SEM and TEM have EDX capability to identify elements
CCD cameras replaced the old fashioned Polaroid films

Nano Summary
• Electron beams have nanometer or less wavelength
• Resolution improves as wavelength is decreased
• TEM and SEM are workhorses of nanoscience and

nanotechnology

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Introduction to Nanoscience

Copyright: CRC Press 2009

• All kinds of characterization tools

Copyright: CRC Press 2009

Copyright: CRC Press 2009

FTIR Quality control of surface engineering

Calorimetry Stability of metastable nano-materials

HPLC Nano-HPLC with “lab-on-a-chip”

Gravimetric analysis Thermal gravimetric analysis (TGA)

Optical microscopy NSOM capable of sub 100 nm resolution

X-Ray diffraction XRD of particles and powders

AND MANY MORE

Copyright: CRC Press 2009

€ Copyright: CRC Press 2009

The relativistic mass is:

The relativistic mass of the electron is nearly 1.4 times

Copyright: CRC Press 2009

If we use λ = h/meυ, we get a different answer. Why?

Resolution, depth-of-field and depth-of-focus significantly

Copyright: CRC Press 2009

• Analytical value? surface topography, electrical

• Analytical signal consists of secondary electrons, back-

• Resolving power of average instruments is in the 1 to 5

• Sample must fit into chamber (rather large specimens on

• Samples must be able to withstand high vacuum (10-6

• Most EDX detectors cannot detect light elements H, He, Li

• Electrically conducting coating applied to insulating

• Over-estimation of particle size

Copyright: CRC Press 2009

THICK SAMPLES for SEM:

Inelastic Interactions: Ionizations

Energy loss electrons from 1° e

Copyright: CRC Press 2009

The size of the interaction volume teardrop” depends on the

The size ranges from several tens of nm to ca. 5 or more µm

Copyright: CRC Press 2009

2°e are of low energy (5 < 50 eV)

Components include a scintillator inside of a Faraday cage. A

Copyright: CRC Press 2009

BSE are produced when 1° beam

The kinetic energy of BSE are on par

Copyright: CRC Press 2009

BSE detectors can establish

Bias Gold Film

Incident Auger electrons are used primarily

Auger electrons, because they are less intense than SE and

One kind of Auger detector is called the cylindrical mirror

Copyright: CRC Press 2009

X-rays originating from the K, L and

Bremsstrahlung contributes to the

There are two general categories: energy dispersive (EDS,

EDS: Process related to XRF (x-ray fluorescence

WDS: Utilizes diffraction patterns following interaction with a

Copyright: CRC Press 2009

Copyright: CRC Press 2009

Thermionic Electron gun emits electrons from a conducting

Field Emission guns apply sufficient electric field strong

Schottky Emitters: Thermal filed emitters enhanced by

The beam is aligned and focused down the

Copyright: CRC Press 2009

Field emission tip is usually single crystal tungsten sharpened

The principle of emission also depends on the work function

Copyright: CRC Press 2009