Analisis Difraksi Sinar- X

Mengapa difraksi sinar-x?

Tujuan menggunakan difraksi sinar-x

Difraktometer yang mana?
Kondisi eksperimen
Pemrosesan data
Alat analisis yang tepat

Tujuan memakai difraktometer

Identifikasi fasa
Penentuan komposisi
Parameter kisi
Regangan-ukuran kristal
Penentuan struktur
kristal

Tegangan
Depth profiling
Penentuan koefisien
ekspansi termal
Fasa lapisan tipis
Preferred orientation
kristal

Kondisi Eksperimen

Ambien
Suhu tinggi/rendah
Tekanan tinggi/rendah
Medan magnet
Tegangan (stress)
dll.

Analisis yang tepat

Apa tujuannya?
Apa alat analisisnya?
Mudah/sukar aksesnya?
Performa
Informasi seputar pemakaian

Left-Hand Side (250mm radius) of the Rigaku Diffractometer

RSM
X-Ray Detector

Diffractometer Circle

DS=Divergence Slit

Sample

SS=Scatter Slit

2Theta

SS
RS

Graphite
Monochromator

Theta

* X-Ray Source
DS

RS= Receiving Slit

RSM= Monochromator
Receiving Slit

Hukum Bragg adalah model

sederhana untuk memahami
difraksi sinar-X

d hkl d hkl

2d hkl sin

Jarak antara bidang-bidang difraksi dari atom menentukan

posisi-posisi puncak
Puncak-puncak intensitas ditentukan oleh atom-atom dalam
bidang difraksi

powder diffractometers
Detector
X-ray
tube

Kristal tunggal akan menghasilkan hanya

satu jenis puncak dalam pola difraksi

At 20.6 2, Braggs law

fulfilled for the (100) planes,
producing a diffraction peak.

The (110) planes would diffract at 29.3

2; however, they are not properly
aligned to produce a diffraction peak
(the perpendicular to those planes
does not bisect the incident and
diffracted beams). Only background is
observed.

The (200) planes are parallel to the (100)

planes. Therefore, they also diffract for this
crystal. Since d200 is d100, they appear at
42 2.

Sampel polikristal mengandung banyak polikristalin. Oleh karena

itu semua pola-pola difraksi akan terobservasi

For every set of planes, there will be a small percentage of crystallites that are properly
oriented to diffract (the plane perpendicular bisects the incident and diffracted beams).
Basic assumptions of powder diffraction are that for every set of planes there is an equal
number of crystallites that will diffract and that there is a statistically relevant number of
crystallites, not just one or two.

constructive interference occurs when the path

difference is n

destructive interference
11

Diffraction from a crystal

Constructive interference
occurs when the path
length the waves travel
differs by some multiple of
the wavelength:

2d sin n

d sin

is the spacing between the planes of atoms

d sin

For diffraction to
occur: d
hence visible light
does not diffract from
crystals
12

In these set of slides we shall consider:

scattering from an electron
scattering from an atom
structure factor calculations (scattering from an unit cell)
the relative intensity of reflections in power patterns

MATERIALS SCIENCE
A Learners Guide

Part of

AALearners
LearnersGuide
Guide

&
AN INTRODUCTORY E-BOOK

ENGINEERING

Anandh Subramaniam & Kantesh Balani

Materials Science and Engineering (MSE)
Indian Institute of Technology, Kanpur- 208016
Email:http://home.iitk.ac.in/~anandh/E-book.htm
anandh@iitk.ac.in, URL: home.iitk.ac.in/~anandh

Elements of X-Ray Diffraction

B.D. Cullity & S.R. Stock

Intensity of the Scattered electrons

Scattering by a crystal

A
Electron Polarization factor

B
Atom Atomic scattering factor (f)

C
Unit cell (uc) Structure factor (F)
Click here to jump to structure factor calculations

Structure Factor

E1 A1 sin 2t 1
E2 A2 sin 2t 2

Vector summation of E1 and E

Structure Factor
i 1
e ix cos x i sin x
Ae i A cos Ai sin
2

Ae i Ae i Ae i A 2 A 2 cos 2 sin 2

Ae i fe 2 i hu kv lw
F f1e 2 i hu1 kv1 lw1 f 2 e 2i hu 2 kv 2 lw2 f 3e 2i hu 3 kv3 lw3 f N e 2i hu N kv N lw N

Notes: 11/9/99
pg. 1

Fhkl

f n e 2i hu n kv n lwn

Notes: 11/11/99
pg. 1

 2 ( h x k y l z ) In complex notation
E Aei fei[2 ( h x k y l z )]
If atom B is different from atom A the amplitudes must be
weighed by the respective atomic scattering factors (f)

The resultant amplitude of all the waves scattered by all the atoms
in the UC gives the scattering factor for the unit cell
Scattering by an unit cell = f(position of the atoms, atomic scattering fac
The unit cell scattering factor is called the Structure Factor (F)
F Structure Factor

hkl
n

fj e
j 1

Amplitude of wave scattered by all atoms in uc

Amplitude of wave scattered by an electron

i j

fj e

i[2 ( h xj k y j l z j )]

I F2

For n atoms in the UC

j 1

Structure factor is independent of the shape and size of the unit cell!

If the UC distorts so do the plane

F Fhkl
Note:

e n i (1)n

e n i e n i

n is an integer

Structure factor calculations

Simple Cubic

ni

(1)

e ( odd n ) i 1

Atom at (0,0,0) and equivalent positions

e ( even n ) i 1

e ni e ni
e i e i
Cos ( )
2

F fj e
F f

i j

fj e

ei[2 ( h 0 k 0

l 0)]

i [2 ( h x j k y j l z j )]

f e0 f

are
F 2 f 2 F is independent of the scattering plane (hkAlll)reflections
present

B Atom at (0,0,0) & (, , 0) and equivalent positions

F fj e

i j

fj e

i [2 ( h xj k y j l z j )]

F f ei[2 ( h 0 k 0

l 0)]

i[ 2 (

h k
)]
2

f e0 f e

C- centred Orthorhombic

f e

1
1
i [2 ( h k l 0)]

2
2

f [1 ei ( h k ) ]
Real

2
2
en dd F 2 f
v
e
)
k
F

4
f
+
(h or both o
ven
e
h
t
o
B
e.g. (001), (110), (112); (021), (02
F f [1 e i ( h kM) ]ixtur
e of odd
a
2
(h + k) nd even F 0
F
0
odd

e.g. (100), (101), (102); (031), (03

F is independent of the l index

C Atom at (0,0,0) & (, , ) and equivalent positions

F fj e

i j

fj e

F f ei[2 ( h 0 k 0
f e0 f e

i[ 2 (

Body centred
Orthorhombic

i [2 ( h xj k y j l z j )]

l 0)]

f e

h k l
)]
2

1
1
1
i[2 ( h k l )]
2
2
2

f [1 ei ( h k l ) ]
Real

F 2f

F2 4 f 2

F 0

F 0

even
)
l
+
k
(h +
i ( h k l )
e.g. (110), (200), (211); (220), (02
F f [1 e
] (h
+ k + l) o
dd
2
e.g. (100), (001), (111); (210), (032), (133)
This implies that (h+k+l) even reflections are only present.
The situation is identical in BCC crystals as well.

Face Centred Cubic

D Atom at (0,0,0) & (, , 0) and equivalent positions

F fj e

i j

fj e

i [ 2 ( 0 )]

i [ 2 (

(, , 0), (, 0, ), (0,

i [2 ( h xj k y j l z j )]

hk
)]
2

i [ 2 (

k l
)]
2

i [ 2 (

l h
)]
2

F fe
e
e
e

f [1 e i ( h k ) e i ( k l ) e i ( l h ) ]
Real
F f [1 e i ( h k ) e i ( k l ) e i ( l h ) ]
(h, k, l) unmixed

h,k,l all even or all odd

(h, k, l) mixed

F 4f

F 2 16 f 2

e.g. (111), (200), (220), (333), (42

F 0

Two odd and one even (e.g. 112); two even and one odd (e.g. 122)

F2 0

e.g. (100), (211); (210), (032), (03

Two odd and one even (e.g. 112); two even and one odd (e.g. 122)
Mixed indices

Mixed indices

CASE

CASE A : [1 ei ( e ) ei ( o ) ei ( o ) ] [1 1 1 1] 0
CASE B : [1 ei ( o ) ei (e ) ei ( o ) ] [1 1 1 1] 0

(h, k, l) mixed

F 0

F 0 e.g. (100), (211); (210), (032

2

All odd (e.g. 111); all even (e.g. 222)

Unmixed indices

Unmixed indices CASE

CASE A : [1 ei ( e ) ei ( e ) ei (e ) ] [1 1 1 1] 4
CASE B : [1 ei ( e ) ei ( e ) ei ( e ) ] [1 1 1 1] 4

(h, k, l) unmixed

F 4f

This implies that in FCConly

h,k,l unmixed reflections are
present.

F 2 16 f 2
e.g. (111), (200), (220), (333), (420)

+
E Na at (0,0,0) + Face Centering Translations (, , 0), (, 0, ), (0, ,
Cl at (, 0, 0) + FCT (0, , 0), (0, 0, ), (, , ) NaCl:
i[ 2 ( 0)] i[ 2 ( h 2 k )] i[ 2 ( k 2l )] i[ 2 ( l 2h )] Face Centred Cu

F f Na e
e
e
e

i[ 2 ( h2 )] i[ 2 ( k2 )] i[ 2 ( 2l )] i[ 2 ( h 2k l )]
f Cl e
e
e
e

F f Na [1 e i ( h k ) e i ( k l ) e i ( l h ) ]
f Cl [e i ( h ) e i ( k ) e i ( l ) e i ( h k l ) ]
F f Na [1 e i ( h k ) e i ( k l ) e i ( l h ) ]
f Cl e i ( h k l ) [e i ( k l ) e i ( l h ) e i ( h k ) 1]

F [ f Na f Cl e i ( h k l ) ][1 e i ( h k ) e i ( k l ) e i ( l h ) ]

F [ f Na f Cl e i ( h k l ) ][1 e i ( h k ) e i ( k l ) e i ( l h ) ]
F [Term 1][Term 2]
Mixed indices

Mixed indices

Zero for mixed indices

CASE

CASE A : Term 2 [1 e i ( e ) e i ( o ) e i ( o ) ] [1 1 1 1] 0
CASE B : Term 2 [1 e i ( o ) e i ( e ) e i ( o ) ] [1 1 1 1] 0

(h, k, l) mixed

F 0

F 2 0 e.g. (100), (211); (210), (032

Unmixed indices

Unmixed indices CASE

CASE A : Term 2 [1 e i ( e ) e i ( e ) e i ( e ) ] [1 1 1 1] 4
CASE B : Term 2 [1 e i ( e ) e i ( e ) e i ( e ) ] [1 1 1 1] 4

(h, k, l) unmixed

F 4[ f Na f Cl e i ( h k l ) ]

h,k,l all even or all odd

F 4[ f Na f Cl ]

e.g. (111), (222); (133), (244)

If (h + k + l) is even

F 2 16[ f Na f Cl ]2

e.g. (222),(24

F 4[ f Na f Cl ]

If (h + k + l) is odd

F 2 16[ f Na f Cl ]2

e.g. (111), (13

NiAl: Simple Cubic (B2- ordered struc

Al at (0, 0, 0)
Ni at (, , )

F f Al ei[2 ( h 0 k 0
f Al e0 f Ni e

Click here to know more about ordered structures

l 0)]

i[ 2 (

f Ni e

h k l
)]
2

1
1
1
i[2 ( h k l )]
2
2
2

f Al f Ni ei [ h k l ]
Real

F f Al f Ni

F f Al f Ni ei [ h k l ]

(h + k +
(h + k +

l) even

l) odd

SC
F 2 ( f Al f Ni ) 2

e.g. (110), (200), (211), (220), (310

F f Al f Ni

F 2 ( f Al f Ni ) 2

e.g. (100), (111), (210), (032), (13

When the central atom is identical to the corner ones we have the BCC case.
This implies that (h+k+l) even reflections are only present in BCC.

This term is zero for BCC

Click here to know more about

Reciprocal lattice/crystal of NiAl

e.g. (110), (200), (211); (220), (310)

I ( f Al f Ni ) 2

I ( f Al f Ni ) 2

e.g. (100), (111), (210), (032), (133)

Click
Click here
here to
to know
know more
more about
about ordered
ordered structures
structures

Al Atom at (0,0,0)

G Ni atom at (, , 0) and equivalent positions

F f Al e

i[2 (

hk
)]
2

i[2 (

f Ni e
e

f Al f Ni [ei ( h k ) ei ( k l ) ei ( l h ) ]
i [2 ( 0)]

k l
)]
2

i[2 (

Simple Cubic (L12 ordered structure)

(, , 0), (, 0, ), (0, ,

l h
)]
2

Real

Ni

Al

F f Al f Ni [ei ( h k ) ei ( k l ) ei ( l h ) ]

(h, k, l) unmixed

F f Al 3 f Ni

h,k,l all even or all odd

(h, k, l) mixed

F 2 ( f Al 3 f Ni ) 2

e.g. (111), (200), (220), (333), (42

F f Al f Ni

Two odd and one even (e.g. 112); two even and one odd (e.g. 122)

F 2 ( f Al f Ni ) 2

e.g. (100), (211); (210), (032), (03

Selection / Extinction Rules

Bravais Lattice

Reflections which may

be present

Reflections necessarily
absent

Simple

all

None

Body centred

(h + k + l) even

(h + k + l) odd

Face centred

h, k and l unmixed

h, k and l mixed

End centred

h and k unmixed
C centred

h and k mixed
C centred

Bravais Lattice

Allowed Reflections

SC

All

BCC

(h + k + l) even

FCC

h, k and l unmixed

DC

h, k and l are all odd

Or
all are even
& (h + k + l) divisible by 4

h2 + k2 + l2

SC

FCC

100

110

111

111

200

200

210

211

BCC

DC

110
111
200
211

7
8

220

220

300, 221

10

310

11

311

311

12

222

222

13

320

14

321

220

220

310
311
222
321

15
16

400

17

410, 322

18

411, 330

19

331

400

400

400

411, 330
331

331

Identifying structure from a powder pattern (-2) measurement

A typical x-ray
trace. We see
several peaks. In
order to identify
the structure we
have to know the
wavelength of
radiation and the
angles (half the 2
values).
Cu= 0.154 nm
31

CsCl diffraction: effect of the source on -2 scans

Intensit y (%)

2d hkl sin

1, 1, 0
(30.64, 100. 0)

100

90

80

70

60

CuK=0.154 nm

50

1, 0, 0

40

(21. 54,37.0)

2, 1, 1
(54. 47, 32. 4)

30

20
1,1,1

2,0, 0
2, 1, 0
(43. 88, 16.
7) 39, 15. 9)
(49.

3, 2, 1

3, 1, 0

(88. 70,13.5)

2, 2, 0
43, 12. 3)
3, 0,(72.
0
2, 2, 1
(63. 80,9.4)
(68.18,6. 9)
3, 1, 1

(37. 76, 11.8)

10

2, 2, 2 3, 2, 0
(76.58,(80.66,
3. 8)
(84.
2. 9)69, 2. 8)

4, 1, 1
3, 3, 0
4, 1, 0
4,2,0
86, 7.6)
3, 2,(104.
2
3, 3,(113.
1
34, 4. 9)
4, 0,(100.
0
76, 3. 8)
(109. 05, 1.8)
(96. 71, 1. 4)

0
0

10

15

20

25

30

35

40

Intensity (%)

45

50

55

60

65

70

75

80

85

90

95

100

105

110

115
116

1, 1,0
(46.24, 100. 0)

100

90

80

CrK=0.229 nm

70

60

50
1, 0, 0
(32. 24,39. 1)

40

2, 1, 1
(85.71, 33.2)

30

2, 0, 0

2, 1,0

(67. 47,15. 8)

(76. 76, 15. 3)

20
1, 1, 1

3, 0, 0
2, 2, 1

2,2, 0
(103. 51, 12. 8)

(57.49, 11.4)

(112.82, 11.7)

10

0
0

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

105

110

115
116

120

32

Identifying structure from a powder pattern (-2) measurement

- A typical XRD trace... X-ray intensity v. 2
- Several peaks - diagnostic of the material
- Each corresponds to an {hkl} for which Braggs Law is satisfied.

2dsin = n

Cu= 1.54

- In order to identify the structure of the material we need to know the

wavelength of radiation and the angles (i.e., half the 2 values).

33

2dsin = n
Cu= 1.54
- assume an order of refraction (n) of 1.

- Once you have the angles for each reflection, you can calculate the d values.
- Remember were measuring 2 but were using !

d = interplanar spacings for each

allowed h, k, l
34

Allowed ???

Additional Considerations:
- The set of all possible hkl that will actually diffract is limited by the particular
Bravais Lattice and the atomic positions.
- i.e., not all reflections will be observed in an XRD experiment
- Consider the cubic structures

The BCC and FCC cubic space lattices have more than one atom per unit cell
and there are extra interferences that can occur off of these atoms.
- This leads to the cancellation of peaks that youd otherwise expect to be there.
- Only certain reflections are allowed.

35

Allowed Reflections for Cubic Space Lattices

Recall

36

Allowable Reflections
Simple Cubic
Body-Centered Cubic
Face-Centered Cubic
Plane
(100)
(110)
(111)
(200)
(210)
(211)
(220)
(300)
(310)
(311)
(222)
(320)
(321)

(400)
(331)

(h2 + k2 + l2)
1
2
3
4
5
6
8
9
10
11
12
13
14

16
19

Constraints on (h2 + k2 + l2)

all values of (h2 + k2 + l2)
(h2 + k2 + l2) = even number
h, k, and l either all even or all odd
SC
1
2
3
4
5
6
8
9
10
11
12
13
14

16
19

BC
2
4
6
8
10
12
14

16
-

FCC
3
4
8
11
12

16
19

37

Back to the story:

- Weve calculated the d spacings for each value of We want to get a.

d = interplanar spacings for each

allowed {hkl}

- Now we need to determine the type of crystal structure (i.e., SC, BCC, or FCC)
and formulate a set of Miller Indices to assign to each line in the data set.
- Were assuming a cubic structure. Recall that
- Interplanar spacing d is related to Miller Indices h, k, and l and the lattice parameters by:

So 38

and

So for for two different {hkl}s:

d2h

1k1l1

d2h

2k2l2

So

sin2
sin
2

sin2
sin2

2dsin = n

(e.g., h1k1l1 and h2k2l2)

(h22 + k22 + l22)

(h12 + k12 + l12)

(h22 + k22 + l22)

(h12 + k12 + l12)

So you calculate sin2values from each value of obtained from the XRD trace
Then the ratio of the sin2values should equal the ratio of the (h22 + k22 + l22)
values (that we determined earlier) for allowable reflections for each structure.
We can then determine the structure (i.e., SC, BCC, or FCC).
39

Once we find a structure, we can assign the correct Miller Indices to each peak in the data.

So from before
ratio
0.75
0.50
0.72
0.92
0.75
0.84
SC
1
2
3
4
5
6
8
9
10
11
12
13
14

16
19

0.50
0.67
0.75
0.80

BC
2
0.50
4
0.67
6
0.75
8
10
12
14

16
-

(h2 + k2 + l2)
1
2
3
4
5
6
8
9
10
11
12
13
14

16
19

Plane
(100)
(110)
(111)
(200)
(210)
(211)
(220)
(300)
(310)
(311)
(222)
(320)
(321)

(400)
(331)

FCC
3
0.75
4
0.50
8
0.73
11
12 0.92
0.75

16
0.84
19

sin2
sin
2

(h22 + k22 + l22)

(h12 + k12 + l12)

The ratios of sin2values are

consistent with the ratios of
the allowed (h22 + k22 + l22) for
the FCC structure only
40

- We can now assign Miller Indices to each peak in the XRD trace
(111)
(200)

(220)

(311)
(331)
(222)
(400)

Plane
(100)
(110)
(111)
(200)
(210)
(211)
(220)
(300)
(310)
(311)
(222)
(320)
(321)

(400)
(331)

(h2 + k2 + l2)
1
2
3
4
5
6
8
9
10
11
12
13
14

16
19

- Once a structure is assigned, we can go back

and determine the lattice parameter for this
material

FCC
3
4
8
11
12

16
19

41

- Once a structure is found, we can go back and

determine the lattice parameter for this
material:
or

a2 = d2hkl(h2 + k2 + l2)

- We can determine the lattice parameter for each line and

average to get the most accurate measurement...

aavg = 3.522

The FCC structure and the lattice parameter identify this metal as Ni.
42

43

That was the description of perfect crystals

What are real crystals and materials
like?
In real crystals there are errors in the crystal:
Point errors

missing atoms, extra atoms, impurities,

Line errors

dislocations (columns of missing atoms)

Planar errors stacking faults (missing or extra planes of atoms)

These types of defects will; give rise to the processes of
Solid-state diffusion, phase transformations, strength of
materials, the mechanical behavior of materials
44