Lecture 2 continued Chapter 2

January 12, 2012

Homework #2 due 1/19 Thursday

Chapter 2 2.1 interplanar spacing 2.2 primitive cell calculations volume, vectors, brillouin zone 2.3 scattered radiation pattern, amplitude and width 2.4 examine scattering linewidth F, K, G 2.5 structure factor

Diffraction
We study the crystal structure using diffraction by electrons, neutrons, X-ray photons.
10
X-ray photon

()

Wavelength

1
Electrons

Neutrons

These particles have appropriate wavelength to resolve atoms

0.1 1

Photon energy, keV Neutron energy, 0.01eV Electron energy, 100eV

10

100 =5000 >> a=5

E-beam elastically scatters from atomic lattice Reflected beams constructive interference

E=hR =hc/P P=hc/E= X-rays: E=10 - 50 keV h ! 6.62x10 34 J s

Scattering Amplitude, F=NS

What do we know already?

Scattering Amplitude
X-Ray diffraction schematic and data

Constructive Interference
Constructive interference occurs when reflected beam path lengths differ by n

d dsin

2dsin =n

Bragg Law

Constructive Interference
Constructive interference occurs when reflected beam path lengths differ by n

d dsin

2dsin =n cos(k(r  d )) ! cos(kr) k(r  d ) ! kr  kd ! kr  2T n kd ! 2TP n d ! nP

Bragg Law

Reciprocal Lattice Vectors

Crystal has 2 lattices
Crystal lattice, vectors have dimensions of [length] Reciprocal lattice, vectors have dimension of [1/length]
every position in Fourier space may have a meaning as a description of a wave

Microscope image is real space a X Diffraction pattern is reciprocal space b

n(x) a a a a x G

2T 4T 4T 2T 0  a a a a

Diffraction Conditions reciprocal space

rsin dV
r

Crystal specimen

X k
Incoming beam ~ eikr
O

X k'
Outgoing beam ~ eikr

vr sin J | Difference in path length over2dV v Difference in phase angle ! T r sin J k  r | P

Diffraction Conditions contd.

For the diffracted wave, the difference in phase angle v v is: (k r ! (N The total difference in phase angle is:

X X X (J ! ( k  k ' ) r X X X Phase factor ! exp[i ( k  k ' ) r ]

X k'
X k

of the wave scattered from dV at r relative to the wave scattered from a volume element at the origin O.

X (k

X X X k  (k ! k '
Scattering vector measures change in wavevector

Diffraction Conditions Ewald Sphere

Ewald sphere determines which lattice planes (represented by the grid points on the reciprocal lattice) will result in a diffracted signal for a given wavelength, , of incident radiation. The incident wave on the crystal has a wave vector Ki =2 / . The diffracted wave has a wave vector Kf. The difference between the wave-vectors of diffracted and incident wave is defined as scattering vector K = Kf Ki. If no energy is gained or lost (it is elastic) then Kf has the same length as Ki. K = 0 Since Ki and Kf have the same length the scattering vector must lie on the surface of a sphere of radius 2 / . This sphere is called the Ewald sphere.

Bragg condition: X X G ! (k

Diffraction Conditions map real to reciprocal

Reciprocal lattice vectors G determines possible reflection We want an expression to relate Bragg Condition to G. Next define G using reciprocal lattice vectors

X X X X G ! v1b1  v2b2  v3b3

X X X 2Ta2 v a3 b1 ! X X X a1 a2 v a3
X X X 2Ta3 v a1 b2 ! X X X a1 a2 v a3 X X X 2Ta1 v a2 b3 ! X X X a1 a2 v a3
Translates reciprocal to real

Diffraction Conditions contd.

Scattering Amplitude:

v v v v F ! dV n( r )exp[i( k  k ') r ] ! NSG 

XX X ! dVn(r ) exp(i(k r )
Integral volume Electron number Phase factor

Specify n(r) for atomic lattice

G dependence

TT X X n(r ) ! nG exp(iG r ) X
G

X XX X F ! dVnG exp[i (G  (k ) r ] X
G

X X For G ! (k

X G: X (k :

Reciprocal lattice vector Scattering vector

X F ! VnG

Diffraction Conditions Ewald Sphere

Now complete the description for diffraction Diffraction conditions
k = incident wave intersect crystal @ lattice point 1 Ewald sphere intersect lattice @ point 2 k is reflected wave G connects 1 2
2

Bragg Law

We want to express these conditions in terms of d vs.

crystal wave

X k'

X G
k
1

2U X

Elastic Scattering G vector

w w Energy is conserved J ! J '

X X X X X X (k ! G X X k G ! k' k  (k ! k ' X X2 X (k  G ) ! k '2 X X X XX X X X k k  2X X GG ! k ' k ' kG  k 2  2k G  G 2 ! k ' 2 k 2 ! k '2

2T G ! d 2T k ! P

k ! k'

k 2 ! k '2

XX 2 2k G  G ! 0 2 X X G ! G

XX 2 2k G ! G

Express G in terms of d, k in terms of

Where d is distance between (hkl) planes normal to G

XX G d ! 0

Elastic Scattering contd.

X X X X Reciprocal lattice vector: G ! hb1  kb2  lb3 2T d (hkl ) ! Distance between (hkl) planes normal to G: G XX
Rewrite

2T G ! d

2k G ! G 2

2T 2T 2T 2 2 sin U ! ( ) P d d 2T 2T 2 sin U ! P d

2d sin U ! P

Bragg condition

Here we considered diffraction conditions based on reciprocal lattice.

Laue Equations also derive E.S.

Laue equations relate to real lattice to reciprocal lattice Axis vectors of the reciprocal lattice:

X X X 2Ta2 v a3 b1 ! X X X a1 a2 v a3
TT Thus: bi a j ! 2TH ij
T TT b1 B a2 , a3

X X X 2Ta3 v a1 b2 ! X X X a1 a2 v a3
T TT b3 B a1 , a2

X X X 2Ta1 v a2 b3 ! X X X a1 a2 v a3

Each vector is orthogonal to two axis vectors of the crystal lattice:

T TT b2 B a3 , a1

H ij ! 1 if i ! j H ij ! 0 if i { j

Points in the reciprocal lattice are:

T v1 , v2 , v3 are integers, G is a reciprocal lattice vector

T T T T G ! v1b1  v2b2  v3b3

Laue condition contd.

X X XX X Thus G, (k can be rewritten in terms of a1 , a2 , a3

X X X X a1 (v1b1  v2b2  v3b3 ) ! 2Tv1 X X X X a2 (v1b1  v2b2  v3b3 ) ! 2Tv2 X X X X a3 (v1b1  v2b2  v3b3 ) ! 2Tv3
2

X X X X a1 (k ! a1 G

Relates back to Ewald Sphere

U
But why a.G?

X k'

X G
k
1

2U X

Brillouin Zone
XX 2 Provide geometrical, visual interpretation of 2k G ! G
Use Wigner-Seitz primitive cell in reciprocal space.

1. Draw lines to connect central lattice point to surrounding lattice point. 2. Draw new lines (planes) which bisect these connecting lines perpendicularly.

Brillouin Zone contd.

A similar construction describes the diffraction conditions
D
1 2

X X k2 O 1 G C
2

1 X GD 2

X k1
C

X GC O C 1 X GC Normal to plane 1 from O 2 X X GD

k1

Incident vector satisfies * O D

X k 2 Satisfies *

X 1 X 1 X2 k ( G) ! ( G) 2 2

Brillioun Zone Oblique lattice

Brillouin Zone contd.

All incident waves with wave vector k terminating on bisecting plane will satisfy Bragg condition The central square is:
a primitive cell of the reciprocal lattice A Wigner-Seitz cell of the reciprocal lattice The first Brillouin zone the smallest volume entirely enclosed by planes that are the perpendicular bisectors of the reciprocal lattice vectors drawn from the origin.

Reciprocal Lattice to sc Lattice

Reciprocal Lattice to sc Lattice

The primitive translation vectors of a sc lattice: X X X a1 ! ax; a2 ! ay; a3 ! az.

x, y, z are orthogonal vectors of unit length XX X 3 The volume of the cell: V ! a1 a2 v a3 ! a

The primitive translation vectors of the reciprocal lattice:

X X X b1 ! (2T / a ) x; b2 ! (2T / a ) y; b3 ! (2T / a ) z;

The reciprocal lattice is a sc lattice, with lattice constant 2 /a.

The first Brillouin zone of sc crystal lattice is a cube of edge 2 /a and of volume (2 /a)3

BCC Real and Reciprocal

J !J' w w k ! k'
k 2 ! k '2

v a2 

v a3 

v a1 

b2

b1
b3

Reciprocal Lattice to bcc Lattice

The primitive translation vectors of a bcc lattice: X 1 1 X 1  y  z ); a3 ! a ( x  y  z ); X a1 ! a ( x  y  z ); a2 ! a( x 2 2 2 a is the side of the conventional cube x, y, z are orthogonal vectors of unit length
XX X 1 3 The volume of the cell: V ! a1 a2 v a3 ! a 2

The primitive translation vectors of the reciprocal lattice:

X X X b1 ! (2T / a )( y  z ); b2 ! (2T / a )( x  z ); b3 ! (2T / a )( x  y );
The reciprocal lattice is a fcc lattice.

The general reciprocal lattice vector is: X X X X G ! v1b1  v2b2  v3b3 ! (2T / a )[(v2  v3 ) x  (v1  v3 ) y  (v1  v2 ) z ];

Reciprocal Lattice to fcc Lattice

The primitive translation vectors of a fcc lattice: X 1 X 1 X 1  z ); a1 ! a ( y  z ); a2 ! a ( x a3 ! a( x  y ); 2 2 2 a is the side of the conventional cube x, y, z are orthogonal vectors of unit length
XX X 1 3 The volume of the cell: V ! a1 a2 v a3 ! a 4

The primitive translation vectors of the reciprocal lattice:

X 2T v 2T ( x  y  z ); b1 ! ( x  y  z ); b2 ! a a 
The reciprocal lattice is a bcc lattice.

X 2T b3 ! ( x  y  z ); a

The volume of the primitive cell:

v v v 2T 3 a V ! b1 b2 v b3 ! 4 

FCC Real and Reciprocal

Fourier Analysis of Basis

Integrated contribution of electron density (over V) to scattering amplitude: XX X X X FG ! N dVn(r ) exp(iG r ) ! NSG
cell

Structure factor
Number of cells Amplitude Phase relation between crystal and scattering beam

Note that F and S include both real and reciprocal information. Where n(r) is a superposition of electron concentrations nj from atom j in a cell

X XX n(r ) ! n j (r  r j )
s j 1

X rj
O

Single cell

s: number of atoms in cell

X r

Real Space!!

Structure Factor
XX XX Structure factor S G ! dVn j (r  r j ) exp(iG r )
j

XX XX X ! exp(iG rj ) dVn j ( V ) exp(iG V ) j X X X V ! r  rj where XX X Atomic form factor f j ! dVn j ( V ) exp( iG V ) XX Structure factor of the basis SG ! f j exp(iG rj ) j X X X X rj ! x j a1  y j a2  z j a3 X X X XX X X X G rj ! (v1b1  v2b2  v3b3 ) ( x j a1  y j a2  z j a3 ) ! 2T (v1 x j  v2 y j  v3 z j )
Describes a specific reflection condition Describes crystal in real space
X S G (v1v2 v3 ) ! f j exp[i 2T (v1 x j  v2 y j  v3 z j )] j

so

Scattered intensity

wS

X G

X SG can be complex

What does SG indicate? - it identifies crystal symmetries

SG for bcc lattice

bcc basis has identical atoms at
X X X X r1 ! x1a1  y1a2  z1a3 X X X X r2 ! x2 a1  y2 a2  z2 a3

( x1 , y1 , z1 ) ! (000) 111 ( x2 , y 2 , z 2 ) ! ( ) 222

X r2
j=1 O

j=2

S G (v1v2 v3 ) !

exp[i 2T (v1 x j  v2 y j  v3 z j )] j !1, 2 1 1 1 ! f1 1  f 2 exp[i 2T (v1  v2  v3 )] 2 2 2

j

S G ! f {1  exp[iT (v1  v2  v3 )]}

For bcc basis SG=0 when the exponential = -1

f1=f2 identical atoms

SG ! 0 SG ! 2 f

when v1  v2  v3 ! odd integer;  J ! T when v1  v2  v3 ! even integer;  ! 2T VJ

SG for bcc lattice contd.

Total Phase difference 2 (100), (200) 1st plane 2nd plane (100) a

Constructive interference:

(J ! 2T

XX k k ' ! 2T

3rd plane

In bcc, second atomic plane causes

phase difference => destructive

SG(001) ! f {1 exp[iT (v3 ! 1)] ! 1 1} ! 0

Consider metallic Na bcc basis The diffraction pattern DOES NOT include
Not (100), (300), (111), (221), Has (110), (200),
How do we analyze a crystal grown on the (001) crystal plane?

SG for fcc lattice