X-Ray diffraction technique: an

interesting tool for studying the matter

in solid state

Difracción de rayos X: una herramienta

interesante para estudiar la materia en
estado sólido

J. CARRIAZO, Dr. Sc.

Departamento de Química, Facultad de Ciencias,
Universidad Nacional de Colombia
Ferrioxalato de potasio (polvo y cristales pequeños)
 Historical Background
• Two experiments are crucial to our discussion:
1) Discovery of X-rays by C. W. Röntgen in 1895.
2) Discovery of X-ray diffraction by Max von Laue in 1912.

• The scientific context of Röntgen’s experiment included the work of

Ampère, Faraday, Franklin, Galvani, Gilbert, Henry, Ohm, and Volta
on electricity; the work of Boyle, Geissler, Hook, and Torricelli on
vacuum pumps; Crookes, Goldstein, Hertz, Hittorf, and Lenard on
cathodic rays; and Maxwell and Helmholtz on theoretical
speculations. All these preceded what Röntgen was about to do.
• Henry Moseley (Periodic Table): 1914

X-ray absorption techniques X-ray fluorescence X-ray diffraction

X-ray radiography X-ray crystallography

Elemental chemical
analysis And structural analysis
Diagnostic methods for medical and
industrial uses.
 Nature and production of X-rays
• X-rays: relatively short-wavelength (between 0,1 and 100 Å, high
energy beams: 0,1-100 keV) electromagnetic radiation. Sinusoidal
oscillating electric field with, at right angles to it, a similarly varying
magnetic field changing with time.
hc
E=
λ
• Production of X-rays: There is three ways to obtain them, for
analytical uses:
1) Bombarding a metallic sample with electrons having high energy.
2) By exposition of a substance to a primary X-ray beam in order to
obtain a secondary X-ray beam (fluorescence).
3) Using a radioactive source.

electrons
High voltage current

X-rays

Tungsten filament

Vacuum
 Kα:
Kα1 = 1,54056 Å

Kβ

0,2 1,4 1,5 Wavelength (Å)

Kβ
∆E =hν
Displacer electron M
Kα
L Electron from K-shell

K Displacer electron at
reduced energy
Nucleus
 FRX
Haz de electrones
e-

Producción de Radiación X

E Kα

EXCITACIÓN EMISIÓN
 FRX
N
Eo M
L
K

Lαβ
K
 Scattered (unchanged wavelength:
coherent scattering = diffraction)
X-ray
transmitted
Heat
Fluorescent characteristic X-rays

sample

X-ray diffraction: It is the result of the scattering of X-radiation,

produced by a regular disposition of the particles, whose spacing
is at the same order of magnitude that the wavelength of such a
radiation.
(amplitude of a wave scattered by the atom in question)
f =
(amplitude of a wave scattered by an electron)
Crystalline materials
F = ∑ ( f n ,θ n )
n
 Crystal structure of solids

Unit cell: the smallest

repeating three-dimensional
structure unit
Crystal structure:
particles are in regular
and repetitive order
 Cubic

Tetragonal

Orthorhombic

Rhombohedral

Hexagonal

Monoclinic

Triclinic
 Miller indices and the reciprocal lattice

Miller indices (h k l) are used to descript the crystallographic

planes in the crystalline solids.
z

β α b y
a γ

x
1 1 1
(a b c) ( ) (h k l)
a b c
(110) (010)

(111) (111)
 Reciprocal lattice: a doubly idealized lattice,
“an abstraction of an abstraction”.
c
d*
d*
l

α k b
β
h γ

Intersections of planes in the reciprocal lattice: in an

orthogonal system, a* = 1/a ; b* = 1/b ; c* = 1/c……d*
= 1/d
 (dhkl*)2 = dhkl*. dhkl*

d*2 = d*. d*

d*2 = (ha* + kb* + lc*). (ha* + kb* + lc*).

d*2 = h2a*2 + k2b*2 + l2c*2 + 2hka*b*cosγ +2hla*c*cosβ +

2klb*c*cosα.

d*2 = h2a*2 + k2b*2 + l2c*2

In the cubic system:
d*2 = a*2 (h2 + k2 + l2)
And so:

(1/d)2 = (1/a)2 (h2 + k2 + l2) dhkl = a/(h2 + k2 + l2)1/2

This equation is useful for indexing operations

Diffraction of X-ray by the crystalline planes

Result of interaction
between the X-rays and
the crystal particles

unchanged wavelength:
coherent scattering

Destructive Wave out of phase

Interference
Constructive Wave in phase

William Henry Bragg and

Bragg’s equation: nλ = 2dsenθ William Lawrence Bragg,
1913.
 λ = 0,154 nm (Cu-Kα)

Remember:
dhkl = a/(h2 + k2 + l2)1/2
1
2 2 2
nλ = 2a/(h2 + k2 + l2)1/2 senθ senθhkl = (λ 2a)(h + k + l ) 2
For indexing:

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

h2 + k2 + l2 1 2 3 4 5 6 8 9 9 10

To determine the cell parameter (a):

For example, in a zeolite (an aluminosilicate with cubic

system cell), we have obtained the following values of angles
to the positions of reflection lines. What is the value of the
cell parameter (a)? The wavelength employed is 1,54Å.

θ
°2θ 7,144 10,121 12,405 14,302 16,005 17,563 20,300

Solution
1
2 2 2
senθ hkl = (λ 2a )(h + k + l ) 2
1
2 2 2
senθ hkl = A(h + k + l ) 2
sen 2θ hkl = A2 (h 2 + k 2 + l 2 )
 2,4% Pt/ZY
Intensidad (u. a.)

0,8% Pt/ZY

0,3% Pt/ZY

Zeolita Y

0 10 20 30 40 50 60
2 theta
 Sen2 θ/(3,88E-03)
2θ θ Sen θ Sen2 θ = (h2 + k2 + l2) (hkl)
7,144 3,572 0,062 3,88E-03 1,00 (100)
10,121 5,061 0,088 7,78E-03 2,00 (110)
12,405 6,203 0,108 1,17E-02 3,01 (111)
14,302 7,151 0,124 1,55E-02 3,99 (200)
16,005 8,003 0,139 1,94E-02 4,99 …
17,563 8,782 0,153 2,33E-02 6,01 …
20,300 10,150 0,176 3,11E-02 8,00 …

Then,
A2 = (λ/2a)2 = (3,88E-03)
(λ/2a) = 0,062
a = 1,54Å/(0,124) = 12,42Å
Experimental approach
 X-Ray Diffractometer
(XRD) Siemens D-500
L θ θ

R
 Intensidad (u.a)

crystal cell.

0
10
Hume-Rothery rules.

20
H (012), d=3,89Å

C
B

30
H (104), d=2,80Å

C
H (110), d=2,54Å
B

2 theta
40
H (113), d=2,13Å

H (024), d=1,95Å
C
B

H (116), d=1,88Å

50
H (018), d=1,65Å
C

H (214), d=1,54Å
60
H (300), d=1,51Å
H , d=1,49Å
H (208), d=1,46Å
H (119), d=1, 40Å
B
On the isomorphic substitution

70

H (220), d=1,30Å
X-ray diffraction confirms the substitution of an atom into the
For the prediction of a possible solid solution, we employ the
 B

B
B
H
H C
C H
Intensidad (u.a)

H H C
C H
H H B
C H
C H

0 10 20 30 40 50 60 70

2 theta
Comparison of the d values of the hematite phase and those obtained from literature

Hematite in the Hematite (reference) a Hematite

solid Al-Ce-Fe JCPDSb
d (Å) d (Å) Intensidad Plano (hkl) d (Å)
3,89 3,67 35 (012) 3,68
2,80 2,69 100 (104) 2,70
2,54 2,51 75 (110) 2,52
2,13 2,20 25 (113) 2,20
1,95 1,84 30 (024) 1,84
1,88 1,69 45 (116) 1,69
1,65 1,60 15 (018) 1,60
1,54 1,48 20 (214) 1,48
1,51 1,45 25 (300) 1,45
1,46 1,35 6 (208) 1,35
1,40 1,31 10 (119) 1,31
1,30 1,26 8 (220) 1,26

a Besoain, 1985.
b JCPDS data file (73-2234)- International Centre for Diffraction Data (ICDD).
 Some computational programs and database
information
• EVA: a computational program for indexing and mineral
identification.
• X-Pert
• Crystal Diffract for Windows XP
• Crystal Maker
• Single Crystal
• ORTEP: Oak Ridge Thermal Ellipsoid Program
• Powder X
• www.icdd.com :International Centre for Diffraction Data (ICDD).
• www.surface.com
 Some conclusions
• X-ray diffraction: powerful technique to elucidate crystalline solid
structures.
• XRD provides information about the inter-planar distances, cell
parameter, and so on the possible structural variations in crystalline
materials.
• XRD allows differentiating between a mechanical mixture and a solid
solution in crystalline materials.
• XRD may be used on sample in: single crystal, powder, oriented film.
• Sample preparations for XRD are very easy: no complex treatments
are necessary.