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. 2. 3. 4. 5. 6. Glide planes, screw axes Space groups Bravais lattices: sc, bcc, fcc (also, lattice with a basis) Primitive, conventional, and Wigner-Seitz cells Miller indices 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)

 Relativistic effects: every time a charge is accelerated or decelerated: wigglers and undulators in a synchrotron

How do we generate soft X-rays (~1000 eV)?

Image Copyright EPSIM 3D/JF Santarelli, Synchotron Soleil

Diagram explaining the mechanics of a synchrotron removed for copyright reasons. See 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 Bremmstrahlung 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
Re 75 Yb 70 Tb 65 Nd 60 Cs 55 Sn 50 Rh 45 Zr 40 Br 35 Zn 30 Mn 25 Ca 20 P 15 8 10 12 14 16 18 20 22
Frequency (Hz) 1016 M M

L L series

hL = 13.6eV (Z - 7.4)2

1 22
L

1 32
L

n=5
n=4
n=3 L n=2
K n=1 L M N

K K K K

K K series K

Figure by MIT OCW.

hK = 13.6eV (Z - 1)2

1 12

1 3 13.6 (Z -1)2 eV = 22 4

Figure by MIT OCW.

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

How do we generate X-rays?

3 Relative Intensity Intensity I Increase of accelerating voltage

K Characteristic x-rays K X-rays from a molybdenum target at 35 kV

min

Wavelength

X Ray Emission Spectrum

1 Brehmsstrahlung continuum

Intensity I

.02

.04 .06 .08 .10 Wavelength (nm)

.12

Increase of heating voltage

Figure by MIT OCW.

min

Wavelength

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

Diffraction from a grating

(Left-pointing 1st, 2nd, and 3rd order, and all higher order beams not shown.) 0th Order 1st Order 2nd Order 3rd Order

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

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

Reciprocal lattice (I)

Lets start with a Bravais lattice, defined in terms of its primitive lattice vectors

r r a3 a 2 r a1

r r r r R = la1 + ma2 + na3 l , m, n integer numbers 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 lets take a plane wave

r r r (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 = 2n n integer is satisfied by r r r r G = hb1 + ib2 + jb3 with h, i, j integers, provided
r r a2 a3 r b1 = 2 r r r a1 a2 a3

r r a3 a1 r b2 = 2 r r r a1 a2 a3

r r a1a2 r b3 = 2 r r r 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

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

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

First Laue condition

( AB CD ) = a ( cos n cos 0 ) = nx

o a

C A D n B

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 n r r a S0 = a cos 0
So a.So a a.S S
Figure by MIT OCW.

r r r a ( cos n cos 0 ) = a S S0 = nx

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

Second Laue condition

Figure by MIT OCW.

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

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)