FISIKA ZAT PADAT

S.
S. Kennedy
Kennedy et
et al.,
al., Nano
Nano Letters
Letters (2002)
(2002)

Jurusan Fisika
Universitas Negeri Makassar
2019
 III. Diffraction and Crystal Structure

A. Syarat Laue dan Hukum Bragg

B. Perhitungan “The Structure Factor”
C. Detil Eksperimental dari X-ray Diffraction
 Teknik Difraksi

01/20/25 3
 Diffraction
m
sin   m 1, 2, 3, ...
W

01/20/25 4
 Diffraction

01/20/25 5
Commercial X-ray Tube
 Mo 0.07 nm
Cu 0.15 nm
Co 0.18 nm
01/20/25 Cr 0.23 nm 7
Interaction between X-ray & Matter

01/20/25 8
01/20/25 9
 Indexing a powder pattern

Bragg’s Law
n = 2d sin

For cubic crystals

a
d hkl  2
h  k 2  l2
which gives rise to
sin 2 θ 2
2 2 2
 2
 S1 h k l 4a
θ (for front reflections) or which is a constant
2W
  S2 
θ  1  (for back reflections)
2 W
 Photons
Diffraction for Crystals Electrons
Neutrons

Diffraction techniques exploit the

scattering of radiation from large
numbers of sites. We will concentrate
on scattering from atoms, groups of
atoms and molecules, mainly in
crystals.
There are various diffraction
techniques currently employed which
result in diffraction patterns. These
patterns are records of the diffracted
beams produced.
01/20/25 11
 A. Syarat Laue dan Hukum Bragg

In a diffraction grating for visible light, constructive interference

between light rays passing through slits of the grating leads to
light intensity ONLY at certain locations on the screen:

d
n=2
n=1
n=0
n = -1
 n = -2

n d sin 
grating
screen
 Starting Assumptions

For x-rays, electrons, and neutrons incident on a crystal,

diffraction occurs due to interference between waves
scattered elastically from the atoms in the crystal.

If we treat the incident waves as plane waves and the

atoms as ideal point scatterers, the scattered waves are
spherical waves. We will assume they are also isotropic.
 Model Untuk X-ray Scattering
Consider two parallel plane waves scattered elastically from two
nearby atoms A and B in a solid material:

 A P
k 
k detector


O

B

i ( k r  t ) f  
i ( k r  t )
 incident e  scattered  e
r
 
elastic scattering: k   k f = atomic form factor
(scattering power of atom)
 Phase Difference Between the Waves
For the spherical waves scattered from atoms A and B (of the same type):

f  
i ( k r  t ) f  
i ( k r  t   )
A  e B  e
r rB

where: r = position of detector relative to A

rB = position of detector relative to B

 = position of B relative to A
 = phase difference between  A and  B
        
 k   k   (k   k )  k scattering
vector
phase lag phase advance
from O  B from A  P
 Sum of Scattered Waves

So the wave scattered from the jth atom is:

fj  
 
 
i ( k r  t   j k )
j  e
rj

 = position of atom j relative to A
Thus the total scattered wave at the detector is:

fj     fj    

 i ( k r  t ) i (  j k )
e
i ( k r  t ) i (  j k )
 e e  e
all atoms rj R all atoms

For a small sample, the distances rj are all essentially the same
( R). Thus we see that constructive and destructive
interference between the scattered waves that reach the detector
is due to the atomic sum. The

detector location
 is determined
k
by the scattered wave vector and thusk .
 Summing Over All Atoms

c 
Now assume
  
a crystal whose lattice has b
a, b , c
base vectors , with a total number of
atoms along each axis M, N, and P, 
a
respectively:

Thus the amplitude of the total wave at the detector is proportional to:

  M  1 N  1 P 1    
e    e
i (  j k ) i[( ma  nb  pc )k ]

all atoms m 0 n 0 p 0

which can be rearranged to give:

M1 3
  N1   P 1    M1   
  e ima k
e
inb k
e ipc k
  e ima k

m 0 n 0 p 0  m 0 
 Evaluating the Sum
We need  

 
iMa k
only M1   M1  
ia k m 1 e
evaluate the
sum inside
e
m 0
ima k
 e
m 0

1 e
 
ia k

the brackets:

Now the intensity of

I 
2
 * 

1 e
 
 iMa k
1  e 
 
iMa k

1  e 1  e 
the total wave at the    
detector is given by:  ia k ia k

 
which 2 e e
 
 iMa k
 
iMa k
2  2 cos Ma k 
I   
simplifies
to give:
   
2  e  iak  e iak 2  2 cos a k  
 
1  cos Ma k  
I  
1  cos a k  
 The Bottom Line
Now use the familiar identity: cos 2 x cos 2 x  sin 2 x 1  2 sin 2 x

which gives the result:

   

1  cos Ma k 2 1
sin 2 Ma k   
I    
1  cos a k  2 1 

sin 2 a k  
This is the same as the intensity of an M-slit diffraction grating. If M is large (
108 for a macroscopic crystal), it has very narrow, intense peaks where the
denominator goes to zero. In between the peaks the intensity is essentially zero.
Remembering that there are three of these terms in the intensity equation, the peaks
occur when:
     
a k 2n1 b k 2n2 c k 2n3 n1, n2, n3 integers
 A Simpler Formulation
Just one year after von Laue’s work, two British physicists developed a
simpler (and easier to use) expression for the x-ray diffraction condition, and
actually used it to determine the crystal structure of NaCl!
This was a father & son team: William Henry Bragg and William Lawrence
Bragg. The father is shown at left below, along with Max von Laue.

The Braggs’ experimental skill and

their simple equation allowed them to
quickly determine the crystal structure
of many common salts and metals.
Max von Laue and the Braggs received
the Nobel Prize in physics in 1914 and
1915, respectively.
 From Laue to Bragg

Now the magnitude of the scattering vector k depends on the angle
between the incident wave vector and the scattered wave vector:
 
 k 
k k

  k
2
d hkl 
k

Do you see why this angle is 2 ?

  2
Elastic scattering requires: 
k  k k 

So from the wave vector triangle  4 

G 
2
k 2k sin   sin  hkl
d hkl
and the Laue condition we see: 
For each (hkl) family x-rays will
Leaving Bragg’s law:  2d hkl sin 
“diffract” at only one angle 
 A Final Comment
The interplanar distance between (hkl) planes is d hkl . By inspection we
can see that the distance between (nh nk nl) planesd hkl
is / n . This means
that we can write the Bragg condition for these planes as:

 2d hkl / n sin  n 2d hkl sin  n 1, 2, 3,...

However, in practice we need only consider the n = 1 values, since the n = 2

and higher values for the (hkl) planes correspond to the n = 1 value for the
(nh nk nl) planes, and this would be redundant.


k 1 2 
 k
Question: can you see a simple

derivation of Bragg’s law by

requiring constructive interference
d hkl between x-ray paths 1 and 2?
Contoh Diffraktogram
 B. The Structure Factor Shkl
We know that the scattered x-ray intensity is proportional to:
2 2
  M  1 N  1 P 1    
e e
i (  j k ) i[( ma  nb  pc )k ]
I
all atoms m 0 n 0 p 0

where the sum runs over all of the lattice points and we assume that there is
only a single atom at each lattice point.

Laue and Bragg remind us that for

I  0 at the detector:
 
k Ghkl or  2d sin 
BUT if we have a crystal with more than one atom per lattice point (a basis
with two or more atoms), we must sum over all atoms in the basis as well!
 Definisi Faktor Struktur Shkl

    
f
The sum of the scattered i ( k r  t ) i (  j k )
x-rays was found to be:
 e j e
R all atoms

   
f  f
i (  j k ) i (  j Ghkl )
So the amplitude of the A j e j e
sum is proportional to: all atoms lattice basis

Factor struktur S hkl

 
S hkl  f j e
i (  j Ghkl )
The structure factor is a sum over all atoms in
the basis: j

   
Where the position of all atoms in the basis is given by:  j u j a  v j b  w j c
Contoh:
(i) For the simple cubic lattice with a one atom basis [000], ρj = 0:
i (0) 2
S hkl  f e  f  I hkl  S hkl  f 2

So the x-ray intensity is nonzero for all values of (hkl), subject to the Bragg
condition, which can be expressed .
 2d hkl sin 

a
Now we know for cubic lattices: d hkl 
h 2 2
k l 
2 1/ 2

2
Substituting and squaring both sides: sin 2  
4a 2
h 2
 k2 l2 
 Another example
Consider the body-centered cubic 
lattice with a one atom basis. This is i (0) i ( a2 iˆ  b2 ˆj  c kˆ )Ghkl
equivalent to the simple cubic lattice S hkl  f e  fe 2

with a two atom basis, with atoms at

[000] and [½½½]:

Remembering that the base vectors      

in direct and reciprocal space are Ghkl a 2h Ghkl b 2k Ghkl c 2l
related by:

We obtain:
  
S hkl  f 1  e i (h k l )  f 1  e i ( h k l ) 
Now by inspection (or trial and error) 2f if h+k+l is even
we can see that there are only two S hkl 
possible values for the structure factor: 0 if h+k+l is odd
 The result
So for a crystal with the bcc lattice and a one atom basis, the x-ray intensity
is nonzero for all planes (hkl), subject to the Bragg condition, except for the
planes where h+k+l is odd. Thus, diffraction peaks will be observed for the
following planes:
(100) (110) (111) (200) (210) (211) (220) (221) (300) …

Just as before, if we are given or can

sin 2 
measure the angles at which each
diffraction peak occurs, we can
graphically determine a for the lattice!
h2  k 2  l 2

A similar analysis can be done for a crystal with the fcc lattice and a one atom
basis, or in other words for the simple cubic lattice with a four atom basis. A
slightly different rule for the values of (hkl) is generated.
Bidang Bidang difraksi
Kubus
{hkl}
h2  k 2  l 2  2 2
(h  k  l ) 2
Kubus (hkl)
FCC BCC
{100} 12  0 2  0 2 1 …

{110} 12  12  0 2 2 … 110

{111} 12  12  12 3 111

{200} 22  02  02 4 200 200

{210} 2 2  12  0 2 5 … …

{211} 2 2  12  12 6 … 211

…
{220} 22  22  02 8 220 220

{221} 2 2  2 2  12 9

{310} 3 2  12  0 2 10 … 310
Analisis struktur dari PbO2
 But how can we determine the lattice type?

Typically all we know is the angles at which diffraction peaks are found. If we
suspect a cubic lattice, how can we determine whether it is sc, bcc, or fcc? This
is your assignment.

Once you make a plot for each lattice

sin 
2
type and see which one is linear, you will
know the lattice type and can then find
the lattice constant a.

h2  k 2  l 2
 KISI RESIPROK
Salah satu cara untuk merepresentasikan kisi kristal yakni dengan
konsep kisi resiprok. Konsep ini dipakai di dalam difraksi sinar-X
dan difraksi elektron. Misalkan

vektor basis dalam ruang nyata
 
diungkapkan sebagai a , b , dan c

Kisi dalam ruang nyata Kisi resiprok

Gbr.1
 Real space Reciprocal space

Crystal Lattice Reciprocal Lattice

Crystal structure Diffraction pattern

Unit cell content Structure factor

x’
y y’

x’
x y’
Real
Real space
space lattice
lattice -- basis
basis vectors
vectors

a
Kisi dalam ruang nyata Kisi resiprok

Gbr.2
Real
Real space
space lattice
lattice -- choose
choose set
set of
of planes
planes

(100)
planes

n100
Real
Real space
space lattice
lattice -- interplanar
interplanar spacing
spacing dd

(100)
planes
d100

1/d100
n100
Real
Real space
space lattice
lattice ––>
––> the
the (100)
(100) recip
recip lattice
lattice pt
pt

(100)
planes
d100

n100

(100)
The
The (010)
(010) recip
recip lattice
lattice pt
pt

n010
(100)
planes

d010

(010)

(100)
The
The (020)
(020) recip
recip lattice
lattice pt
pt

n020
(100)
planes

(010) (020) d020

(100)
(100)
planes

(010) (020)

(100)
The
The (110)
(110) recip
recip lattice
lattice pt
pt

(100)
planes n110
d110

(010) (020)

(100) (110)
Still
Still more
more recip
recip lattice
lattice pts
pts

(100)
planes

(010) (020)

(100)
the reciprocal lattice
(230)
Reciprocal
Reciprocal lattice
lattice notation
notation
Hexagonal
Hexagonal real
real space
space lattice
lattice
Hexagonal
Hexagonal real
real space
space lattice
lattice
Hexagonal
Hexagonal real
real space
space lattice
lattice
Hexagonal
Hexagonal real
real space
space lattice
lattice
Definisi kisi resiprok
 

a* 2 
b c
 

a  (b c )
 

b * 2 
c a 
 
b  (c a )
 
 ( a b )
c * 2   

c  a b 
Beberapa hal tentang kisi resiprok:
a. Berdimensi L-1 atau sama dengan dimensi bilangan
gelombang
b. Besaran a* tegak lurus dengan bidang (b,c) demikian pula
permutasi sikliknya
c. Bahwa a.(bxc) = b.(cxa) = c.(axb) menyatakan volume kisi.
Vektor basis yang baru tersebut digunakan untuk membentuk kisi
baru yang memenuhi vektor berikut ini:
   
G n n1 a * n 2 b * n 3 c *,
n1 , n 2 , n 3 sebagai bil. bulat

Berdasarkan sifat vektor ortogonal,

     
a *  a 2 ; a * b * a *  c * 0

Dapat ditunjukkan bahwa;

 

a 2 

b * c *
 

a *  (b * c *)
 Indeks Miller & Kisi Resiprok
Kaitan antara indeks Miller (hkl) dan titik potong dengan
sumbu X, Y dan Z dapat dijelaskan sebagai berikut:
Z 1 1 1
( h kl )  ( , , )
X Y Z

 v Ungkapan untuk vektor
c  u  

 b u  x a  y b
a
Y
 Ungkapan untuk vektor v
u 
 
X v yb  z c
Gbr.3

Jadi u dan v membataskan bidang (hkl)

 Kisi Resiprok untuk SC, FCC and BCC
Direct lattice Reciprocal lattice Volume
SC
 a1 ax  b1 2 / a x
 
a 2 ay b 2 2 / a y 2 / a 3
 a az  b 2 / a z
 3  3
FCC
 a1 1 ax  y  b1  2  x  y  z 
2  a
 2  x  y  z 
a 2  2 ay  z 
1 b 
 2 a 22 / a 3
a 1 az  x  b  2 x  y  z 
BCC  3 2  3 a
a1 1 ax  y  z   b1  2 y  z 
2  a

a 2  2 a x  y  z 
1 2  x  z 
b
 2 a 42 / a 3
a 1 ax  y  z  b  2 x  y 
 3 2  3 a
 
Vektor kisi resiprok dinyatakan sebagai Ghkl
   
Ghkl h a * k b * l c *
   

 
 
u  Ghkl  x a  y b  h a * k b * l c * 
2  x h  y k 

1 1 1
Karena ( hkl )  ( , , ) maka x h  y k  0
X Y Z
 
Jadi u  G hkl 0

 
Demikian pula: v  Ghkl 0

Hasil ini menunjukkan bahwa vektor kisi resiprok Ghkl tegak lurus dengan
bidang kisi (hkl)
 
Selanjutnya akan dicari hubungan antara dhkl dengan Ghkl
Dari Gbr. 3 tampak bahwa dhkl sama besar dengan proyeksi vektor xa,
atau yb, atau zc pada garis normal
 terhadap bidang (hkl). Garis normal
tersebut dinyatakan sebagai n hkl
 
Jadi, Ghkl Ghkl nhkl
 
  x a  Ghkl
Oleh karena itu, d hkl  x a  n hkl 
Ghkl
  Gbr.4

Tetapi, a  G 
  

hkl a  ha * kb * lc * 2h

Sehingga 2 h x 2
d hkl   , karena h x 1
G hkl G hkl

Tampak jelas bahwa 2 

d hkl  atau d hkl  G hkl 2
G hkl
 Drawing Brillouin ZonesWigner–Seitz cell

The BZ is the
fundamental unit cell
in the space defined
by reciprocal lattice
vectors.

01/20/25 57
 Drawing Brillouin Zones

01/20/25 58
 TUGAS 2, Charles Kittel, Bab 2.
1

2
3