3.

012 Fund of Mat Sci: Structure – Lecture 17

X-RAY DIFFRACTION
Image of a spiral sea shell (left) and Rosalyn Franklin's original picture of a DNA Alpha Helix (right).
Images removed for copyright reasons.

A beautiful spiral, and … an even more beautiful one

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Homework for Wed Nov 9
• Read: Prof Wuensch Lecture Notes

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Last time:
1. Glide planes, screw axes
2. Space groups
3. Bravais lattices: sc, bcc, fcc (also, lattice with a basis)
4. Primitive, conventional, and Wigner-Seitz cells
5. Miller indices
6. Diamond, zincblend, perovskites, rocksalt, CsCl

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Probing with radiation
• Wavelength need to be smaller than typical
interatomic distances
• Beams of photon (X-rays), electrons, neutrons
• We look at coherent (all same atoms behave in the
same way), elastic (no energy is lost) scattering
• Elastic: diffraction. Inelastic: spectroscopies
• We “interrogate” long-range order with coherent
elastic scattering

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
Examples: http://imagers.gsfc.nasa.gov/ems/ems.html
3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
Energy of an accelerated electron

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
How do we generate soft X-rays (~1000 eV)?
• Relativistic effects: every time a charge is
accelerated or decelerated: wigglers and
undulators in a synchrotron

Image Copyright
© EPSIM 3D/JF
Diagram explaining the mechanics of a synchrotron
Santarelli,
removed for copyright reasons. See
Synchotron Soleil
http://geographyfieldwork.com/SynchrotronWorks.htm
3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
How do we generate soft X-rays?

• In the lab: beam of electrons striking a

metal target
– Electrons are decelerated, and they emit
radiation on a broad spectrum of
frequencies. This is called Bremsstrahlung
– In addition, we excite core electrons, that
decay back emitting radiation at K, L, M
lines

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Moseley law
Moseley Plot of Characteristic X-Rays
1 1
hυLα = 13.6eV (Z - 7.4)2
22 32
Re 75
Lα
Yb 70
Tb 65 L series n=5
n=4
Nd 60 Kδ
Lγ n=3
Cs 55 Lβ
Lα n=2 Kγ
Sn 50 K Kβ
Rh 45 Kα
n=1
Kα L
Zr 40 Mα
M
Br 35 K series Mβ
Zn 30 N

Mn 25 Kβ
Ca 20
P 15
8 10 12 14 16 18 20 22 Figure by MIT OCW.
1 1 3 13.6 (Z -1)2 eV
hυKα = 13.6eV (Z - 1)2
Frequency (Hz)
1016 =
12 22 4

Figure by MIT OCW.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 How do we generate X-rays?

Increase of

Intensity I
accelerating
voltage
3
Kα
Relative Intensity

Characteristic
x-rays λmin Wavelength λ
2
Kβ
X-rays from a X Ray Emission Spectrum
molybdenum
1 Brehmsstrahlung target at 35 kV
continuum

Intensity I
0 Increase of
.02 .04 .06 .08 .10 .12
heating voltage
Wavelength (nm)

Figure by MIT OCW.

λmin Wavelength λ

Figure by MIT OCW.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 The Laue experiment

X-ray photograph of zinc blende from the Laue experiment removed for copyright reasons.
See http://capsicum.me.utexas.edu/ChE386K/html/laue_experiment.htm.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
How does a crystal diffract ?

Figure by MIT OCW.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Diffraction
(wave-like instead of particle-like)

Source: Wikipedia

Figure by MIT OCW.

Figure by MIT OCW.
3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Diffraction from a grating
(Left-pointing 1st, 2nd, and 0th Order
3rd order, and all higher order 1st Order
beams not shown.) 2nd Order
3rd Order

Groove

Incident Plane Wave (Lambda = 2/11 * Grating Pitch)

Diffraction Grating

Figure by MIT OCW.

 Reciprocal lattice (I)
• Let’s start with a Bravais lattice, defined in
terms of its primitive lattice vectors…

r r r r r r
a3 a R = la1 + ma2 + na3
2

r l , m, n integer numbers
a1 r
R = ( l , m, n )

Figure by MIT OCW.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Reciprocal lattice (II)
• …and then let’s take a plane wave

r r r
Ψ (r ) = A exp[i (k ⋅ r )]

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Reciprocal lattice (III)
• What are the wavevectors for which our
plane wave has the same amplitude at all
lattice points ?

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Reciprocal lattice (IV)
r r
k ⋅ R = 2nπ n integer is satisfied by
r r r r
G = hb1 + ib2 + jb3 with h, i, j integers,
r r r r r r
r a 2 ×a3 r a3 ×a1 r a 1×a2
provided b1 = 2π r r r b2 = 2 π r r r b3 = 2π r r r
a1⋅ a2 ×a3( ) a1⋅ a2 ×a3 ( ) (
a1⋅ a2 ×a3 )

r
G = ( h, i, j ) are the reciprocal-lattice vectors

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 Examples of reciprocal lattices

r r r
Direct lattice Reciprocal lattice a2 × a3
b1 = 2π r r r
a1 ⋅ ( a2 × a3 )
Simple cubic Simple cubic
FCC BCC
BCC FCC
Orthorhombic Orthorhombic

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
 First Laue condition
( AB − CD ) = a ( cos α n − cos α 0 ) = nx λ

αo C
A D

a αn

Figure by MIT OCW.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
First Laue condition (vector form)
r r
a ⋅ S = a cos α n
r r
a ⋅ S0 = a cos α 0
S0
r r r
a.S0
a ( cos α n − cos α 0 ) = a ⋅ S − S0 = nx λ ( )
a
a.S
S

Figure by MIT OCW.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
Second Laue condition

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005) Figure by MIT OCW.
Third Laue condition

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)
Back-reflection and transmission Laue

Diagrams of the Laue Method removed for copyright reasons.

See the images at http://www.matter.org.uk/diffraction/x-ray/laue_method.htm.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)