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Chem 253, UC, Berkeley

What we will see in XRD of simple


cubic, BCC, FCC?

Position
Intensity

Chem 253, UC, Berkeley

Structure Factor:
adds up all scattered X-ray from each lattice points in
crystal
n
Sk   e
iK d j

j 1

K  ha   kb  lc 
   
d j  x a y b z c

I ( hkl )  S k
2

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Chem 253, UC, Berkeley

X-ray scattered from each primitive


cell interfere constructively when:

e iK R  1
2d sin   n

For n-atom basis:

sum up the X-ray scattered from the whole basis

Chem 253, UC, Berkeley

 
k d
k'

di R dj
 ' 
K  k k
Phase difference: K  (d i  d j )
The amplitude of the two rays differ: iK ( d i  d j )
e

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Chem 253, UC, Berkeley

The amplitude of the rays scattered at d1, d2, d3…. are in

the ratios :
iK d j
e
The net ray scattered by the entire cell:

n
Sk   e
iK d j

j 1

I ( hkl )  S k
2

Chem 253, UC, Berkeley

For simple cubic: (0,0,0)

iK 0
Sk  e 1

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For BCC: (0,0,0), (1/2, ½, ½)…. Two point basis

2 1   
iK  ( x  y  z )
Sk   e
iK d j iK 0
e e 2

j 1

 1  e i ( h  k l )

 1  (1) h  k l

S=2, when h+k+l even


S=0, when h+k+l odd, systematical absence

Chem 253, UC, Berkeley

For BCC: (0,0,0), (1/2, ½, ½)…. Two point basis

S=2, when h+k+l even


S=0, when h+k+l odd, systematical absence

(100): destructive

(200): constructive

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Chem 253, UC, Berkeley

Observable diffraction
peaks

h2  k 2  l 2
Ratio

SC: 1,2,3,4,5,6,8,9,10,11,12..
Simple
cubic BCC: 2,4,6,8,10, 12….

FCC: 3,4,8,11,12,16,19, 24….


a
d hkl 
h2  k 2  l 2
2d sin   n

Chem 253, UC, Berkeley

FCC

S=4 when h+k, k+l, h+l


all even (h,k, l all even/odd)

S=0, otherwise

S k  1  e  i ( h  k )  e  i ( h  l )  e  i ( l  k )

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Chem 253, UC, Berkeley

Observable diffraction
peaks

h k l
2 2 2

Ratio
SC: 1,2,3,4,5,6,8,9,10,11,12..

Simple BCC: 2,4,6,8,10, 12, 14….


cubic (1,2,3,4,5,6,7…)

FCC: 3,4,8,11,12,16,19, 24….


a
d hkl 
h2  k 2  l 2

2d sin   n

Chem 253, UC, Berkeley

Observable diffraction peaks


h2  k 2  l 2
Ratio a
d hkl 
SC: 1,2,3,4,5,6,8,9,10,11,12.. h2  k 2  l 2
BCC: 2,4,6,8,10, 12, 14….
(1,2,3,4,5,6,7…) 2d sin   n
FCC: 3,4,8,11,12,16, 19, 24….
2
sin  
2
2
(h 2  k 2  l 2 )
4a

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Chem 253, UC, Berkeley

What we will see in XRD of simple


cubic, BCC, FCC?
sin 2  A
 0.5 ( BCC );  0.75 ( FCC )
sin 2  B

a
d hkl 
h2  k 2  l 2

Chem 253, UC, Berkeley


Ex: An element, BCC or FCC, shows diffraction
peaks at 2: 40, 58, 73, 86.8,100.4 and 114.7.
Determine:(a) Crystal structure?(b) Lattice constant?
(c) What is the element?
2theta theta sin 2  h2  k 2  l 2 (hkl)
40 20 0.117 1 (110)
58 29 0.235 2 (200)
73 36.5 0.3538 3 (211)
86.8 43.4 0.4721 4 (220)
100.4 50.2 0.5903 5 (310)
114.7 57.35 0.7090 6 (222)

a =3.18 Å, BCC,  W

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Chem 253, UC, Berkeley Reading : West Chapter 5

Polyatomic Structures

K  ha   kb  lc 
n
S k   f j ( k )e
i K d j
   
j 1 d j  x a y b z c

fj: atomic scattering factor


 No. of electrons
n n
Sk   f j e   f j e  2i ( hx  ky lz )
iK d j

j 1 j 1

Chem 253, UC, Berkeley

Simple Cubic Lattice


Caesium Chloride
(CsCl) is primitive
cubic
Cs (0,0,0)
Cl (1/2,1/2,1/2)
S k  f Cs  f Cl e i ( h  k l )

What about CsI?

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Chem 253, UC, Berkeley

(hkl) CsCl CsI


(100) 
(110)  
(111) 
(200)  
(210) 
(211)  
(220)  
(221) 
(300) 
(310)  
(311) 

Chem 253, UC, Berkeley

FCC Lattices
Sodium Chloride
(NaCl)

Na: (0,0,0)(0,1/2,1/2)(1/2,0,1/2)(1/2,1/2,0)

Add (1/2,1/2,1/2)

Cl: (1/2,1/2,1/2) (1/2,0,0)(0,1/2,0)(0,0,1/2)

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Chem 253, UC, Berkeley

S k  [ f Na  f Cl e  i ( h  k l ) ][1  e i ( h  k )  e i ( h l )  e  i (l  k ) ]

S=4 (fNa +fCl) when h, k, l, all even;


S=4(fNa-fCl) when h, k, l all odd
S=0, otherwise

Chem 253, UC, Berkeley

(hkl) NaCl KCl


(100)
(110)
(111) 
(200)  
(210)
(211)
(220)  
(221)
(300)
(310)
(311) 

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Chem 253, UC, Berkeley

Chem 253, UC, Berkeley

Diamond Lattice

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Chem 253, UC, Berkeley S fcc  1  e  i ( h  k )  e  i ( h  l )  e  i ( l  k )
FCC:
Diamond Lattice S=4 when h+k, k+l, h+l
all even (h,k, l all
even/odd)
SSi(hkl)=Sfcc(hkl)[1+exp(i/2)(h+k+l)].
S=0, otherwise

SSi(hkl) will be zero


if the sum (h+k+l) is equal to 2 times an odd integer, such
as (200), (222). [h+k+l=2(2n+1)]

SSi(hkl) will be non-zero if


(1)(h,k,l) contains only even numbers and
(2) the sum (h+k+l) is equal to 4 times an integer.
[h+k+l=4n]
Shkl will be non-zero if h,k, l all odd: 4( f  if )
si si

Chem 253, UC, Berkeley

Silicon Diffraction pattern

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Chem 253, UC, Berkeley

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Chem 253, UC, Berkeley

Chem 253, UC, Berkeley

Bond charges in covalent solid


(1/8,1/8,1/8), (3/8,3/8,1/8),(1/8,3/8,3/8) and (3/8,1/8,3/8).
Bond charges form a "crystal" with a fcc lattice with 4
"atoms" per unit cell.
origin : (1/8,1/8,1/8).
Bond charge position: (0,0,0), (1/4,1/4,0),(0,1/4,1/4) and (1/4,0,1/4).
Sbond-charge(hkl) =
Sfcc(hkl)[1+exp(i/2)(h+k)+exp(i/2)(k+l)+exp(i/2)(h+l)].

For h=k=l=2:
Sbond-charge(222)=Sfcc(222)[1+3exp(i/2)4]=4Sfcc(222) non-zero!

n n
Sk   f j e   f j e  2i ( hx  ky lz )
iK d j

j 1 j 1

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Chem 253, UC, Berkeley

Nanocrystal X-ray Diffraction

Chem 253, UC, Berkeley

Finite Size Effect

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Bragg angle: B
in phase, constructive

For 1   B
1
2 Phase lag between two planes:
  
3
4

j-1
j At j+1 th plane:

j+1
Phase lag:
   j    2
2j-1
2j

2j planes: net diffraction at 1:0

Chem 253, UC, Berkeley

Bragg angle: B
in phase, constructive

For 2  B
1
2 Phase lag between two planes:

  
3
4
5

j-1 At j+1 th plane:



j
Phase lag:
   j    2
j+1

2j-1
2j

2j planes: net diffraction at 2 :0

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Chem 253, UC, Berkeley

How particle size influence the peak


width of the diffraction beam.

Full width half maximum (FWHM)

Chem 253, UC, Berkeley

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Chem 253, UC, Berkeley

The width of the diffraction peak is governed by # of


crystal planes 2j. i.e. crystal thickness/size

Scherrer Formula:

0 .9 
t
B cos  B B 2  BM2  BS2

BM: Measured peak width at half peak intensity (in radians)


BS: Corresponding width for standard bulk materials (large
grain size >200 nm)

Readily applied for crystal size of 5-50 nm.

Chem 253, UC, Berkeley

• Suppose =1.5 Å, d=1.0 Å, and =49°. Then for a crystal


1 mm in diameter, the breath B, due to the small crystal
effect alone, would be about 2x10-7 radian (10-5 degree),
or too small to be observable. Such a crystal would
contain some 107 parallel lattice planes of the spacing
assumed above.

• However, if the crystal were only 500 Å thick, it would


contain only 500 planes, and the diffraction curve would
be relatively broad, namely about 4x10-3 radian (0.2°),
which is easily measurable.

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