9/23/2009

ADVANCED NANOMATERIALS CHARACTERIZATION  I

UNIT I I
UNIT X‐RAY
X RAY DIFFRACTION
DIFFRACTION
y X‐ray powder diffraction 
y Single crystal diffraction techniques 
y Determination of accurate lattice parameters
y Nanostructural analysis 
y Profile analysis 
Profile analysis
y Particle size analysis using Scherer formula

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y Characterization of materials requires obtaining detailed 
Characterization of materials requires obtaining detailed
information about the spatial arrangement  of the atoms 
and identifying precisely which atoms occupy which 
particular sites in the structure.

y It often involves measuring some particular electronic or 
optical properties

y Some of the tools that are at our disposal are…..
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Tools 
y Some tools are used like ‘cameras’:
SEM (Scanning Electron
l Microscope)

TEM (Transmission Electron Microscope)

STM ((Scanning Tunneling Microscope)

STM 

HRTEM (High Resolution Transmission Electron Microscope)

igh R

AFM (Atomic Force Microscope) 

LEEM ((Low Energy Electron Microscope)

LEEM 

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More tools 
y Others take pictures in the momentum space or wave‐
p p
vector space rather than in real space:
 XRD (X‐Ray Diffraction)

 LEED (Low Energy Electron Diffraction)

 RHEED (Reflection High Energy Electron Diffraction)

 NEUTRON DIFFRACTION
y As with any camera, information is readily obtained about 
the static structure of the material, although blurriness also 
conveys some dynamical information 

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Some more !
y Additionally ,  there are some other tools also that work in the 
real time and in the frequency variable space
y In the real time, time dependent luminescent studies can be 
, p
used to study the dynamical evolution of the system
y In the frequency space are the optical spectrospcopies:
y IR, VIS and UV Spectroscopies

y Light Scattering, Ellipsometry, IR absorption, Raman Scattering, 

Photoluminescence and Non‐Linear
h l d Opticall Spectroscopy

y EELS (Electron Energy Loss Spectroscopy)

y AES (Auger Electron Spectroscopy)

y INS (Inelastic Neutron Scattering)

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Even more !!
y Techniques in which both electrons and photons play a 
significant role:
™ EXAFS (Extended X‐ray Absorption Fine‐structure Spectroscopy)

™ XPS (X‐ray Photoemission Spectroscopy)

™ UVPS (UV Photoemission Spectroscopy)

™ NMR ((Nuclear Magnetic

g Resonance))

™ ESR (Electron Spin Resonance)

™ NQR (Nuclear Quadrupole Moment )

™ MOSSBAUER EFFECT
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Here we go again!!!

y Using ionic probes some more techniques :
o SIMS (Secondary Ion Mass Spectrometry)

o RBS (Rutherford Back Scattering)

o PAS (Positron Annihilation Spectroscopy)

o µPS/ MPS
PS/ MPS (Muon
(M P
Precession
i Spectroscopy)
S t )

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Wilhelm Conrad 
Röntgen
(1845
1845‐‐1923
1923))

• Wilhelm Conrad Röntgen

discovered the X-rays in
1895.
• In
I 1901 he
h was honoured
h d with
ith
the Nobel prize for physics.
• In 1995 the German Federal
Mail edited a stamp dedicated A modern radiograph
Bertha Röntgen’s Hand
of a hand
8 Nov, 1895
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y Radiographs like the ones in the 
last slide are simply shadowgrams. 
y The X‐rays either pass straight 
through or are stopped by the 
object. 
y The diagram on the upper left 
illustrates the principle and shows 
a perfect shadow.
y In reality, a large fraction of the X‐
rays are not simply absorbed or 
transmitted by the object but are 
scattered. 
d
y The diagram on the bottom left 
illustrates this effect and illustrates 
the fuzzy edge of the object that is 
produced in the image by the 
scattered X‐rays. 
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y The first kind of scatter process to be 
recognised was discovered by                  
Max Theodor Felix von
Max Theodor Felix  von Laue 
y Laue was awarded the Nobel prize for 
physics in 1914 "for his discovery of the 
for his discovery of the 
diffraction of X‐‐rays by crystals
diffraction of X rays by crystals". 
y His collaborators Walter Friedrich and Paul 
Max Theodor Felix von Laue Knipping in 1912, took the picture of  a 
(1897-1960)
characteristic pattern of a crystal (copper 
sulphate in this case) when it scattered a 
beam of  X‐rays.  
y The X‐ray powder diffraction pattern of a 
pure substance is like a fingerprint of the 
substance and is thus ideally suited for 
characterization and identification of 
polycrystalline phases.
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y X rays are invisible, highly penetrating electromagnetic radiation

of much shorter wavelength (higher frequency) than visible light

y The
h wavelength
l h range for
f X rays is from
f about
b 10‐88 m to about
b
10‐11 m and the corresponding frequency range is from about
3 × 1016 Hz to about 3 × 1019 Hz

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X-RAY ENERGY
y Electromagnetic radiation is described as having packets of
energy, or photons
y The energy of the photon is related to its frequency by the
following formula
E= h
E= hνν
and
hc ν = c/
c/λλ
E=
λ

λ=Wavelength , 
=Wavelength , νν= Frequency ,  c = Velocity of light

E = hc
E = hc//λ
λx‐ray ≈ 10‐10 ≈ 1A° E ≈ 104 eV
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X-RAY TUBE
| X rays can be produced in a highly evacuated glass bulb,
called an X‐ray tube, that contains essentially two
electrodes—an anode made of platinum, tungsten, or
another heavy metal of high melting point, and a cathode.
| When a high voltage is applied between the electrodes,
streams of electrons (cathode rays) are accelerated from the
cathode to the anode and produce X‐rays as they strike the
anode.
Evacuated glass bulb 

Anode Cathode

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K-shell knockout
y The free electron collides with the tungsten atom, knocking an electron out
of a lower orbital.
y An electron in a higher orbital immediately falls to the lower energy level,
releasing its extra energy in the form of a photon. It's a big drop, so the
photon has a high energy level; it is an X-ray
X ray photon.

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Monochromatic and Broad Spectrum of X-rays

y For X-rays to be generated, electrons of high energy (> 104)
are required.

y Some of these electrons may excite electrons from the core

states in the target metal, which then recombine, producing
highly monochromatic X-rays. These are referred to as
characteristic X-ray lines.

y Other electrons, which are decelerated by the periodic

potential of the metal, produce a broad spectrum of X-ray
f
frequencies
i (Bremsstrahlung
(B
B
Bremsstrahlung-
t hl stopping
t i potential).
t ti l)

y Depending on the diffraction experiment, either or both of

these X-ray spectra can be used.

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Continuous Radiation (Bremsstrahlung
Bremsstrahlung)

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Characteristic Radiation

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X‐ray Spectrum

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Characteristic Radiation

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Absorption of X-rays
y The atoms that make up your body tissue absorb
visible light photons very well. The energy level of
the photon fits with various energy differences
between electron positions.

y Radio waves don't have enough energy to move

electrons between orbitals in larger atoms, so they
pass through most stuff.
...something you won't see 
y X-ray photons also pass through most things, but very often (Visible light)
for the opposite reason: They have too much
energy.
X‐ray
y The absorption of X-rays
X rays is given by
I (λ
(λ) = Io (λ) exp ((µρ µρx x)
Where, µ – absorption coefficient of the material
ρ – density of the material
x – distance travelled by the X-
X-rays through the material
Note that mass absorption coefficients are additive functions of
the weights fractions of elements.
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Absorption of X-rays
y A larger atom is more likely to absorb an X‐ray photon in
this way, because larger atoms have greater energy
differences between orbitals ‐‐ the energy level more closely
matches the energy of the photon.
y Smaller atoms
atoms, where the electron orbitals are separated by
relatively low jumps in energy, are less likely to absorb X‐ray
photons.
photons
y The soft tissue in your body is composed of smaller atoms,
and so does not absorb X‐ray photons particularly well.
y The calcium atoms that make up your bones are much larger,
so they are better at absorbing X‐ray photons.

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