X-RAY Diffraction

Materials Characterization 2
 Readings/Resources Review
XRD ability and Xray generation principle

XRD Diffraction principle

https://www.youtube.com/watch?v=QHMzFUo0NL8
https://www.youtube.com/watch?v=C1cYJthlBZY

XRD Analysis
Basic: Peak indexing
https://www.youtube.com/watch?v=6IzrOWIw3zQ
Use of Softwares : Xpert, ORIGIN etc

Advanced
FWHM (crystallinity/Crystallite size)
https://www.youtube.com/watch?v=PwCc4ecj2w0
 History: Wilhelm Conrad Röntgen

Wilhelm Conrad Röntgen discovered 1895 the X-rays. 1901 he was

honoured by the Noble prize for physics. In 1995 the German Post
edited a stamp, dedicated to W.C. Röntgen.
X-Ray Tube
The Principle of Generation Bremsstrahlung

Generation of bremsstahlung when decelerating

an electron which interacts with an atom
 The Principle of Generation the
Characteristic Radiation

Photoelectron Emission

M K-Quant

Electron L-Quant

K-Quant
The Generating of X-rays
 The Generating of X-rays
Tube characteristic
Anode (kV) Wavelength  (Angström) Filter
K1 : 0,70926
Zr
Mo K2 : 0,71354
20,0 0,08mm
K1 : 0,63225

K1 : 1,5405
Cu 9,0 Ni
K2 : 1,54434 0,015mm
K1 : 1,39217

K1 : 1,78890
Co 7,7 Fe
K2 : 1,79279
0,012mm
K1 : 1,62073

K1 : 1,93597
Fe 7,1 Mn
K2 : 1,93991
0,011mm
K1 : 1,75654
The Generating of X-rays

Emission Spectrum of a
Molybdenum X-Ray Tube

Bremsstrahlung = continuous spectra

characteristic radiation = line spectra

 History:
Max Theodor Felix von Laue

Max von Laue put forward a(cos-cos0)=h

the conditions for scattering b(cos-cos0)=k
maxima, the Laue equations: c(cosg-cosg0)=l
 Laue’s Experiment in 1912
Single Crystal X-ray Diffraction
 Laue’s Experiment in 1912
Single Crystal X-ray Diffraction
Laue’s Pattern

Displaying cubic symmetry in the mineral

microlite.

Displaying hexagonal symmetry in the

mineral calciotantite.
Pattern for polycrystalline
 History:
W. H. Bragg and W. Lawrence Bragg
W.H. Bragg (father) and William Lawrence. Bragg (son) developed a
simple relation for scattering angles, now call Bragg’s law.

n
d=
2  sin  n = 1, 2, 3, ...
reflection order
More on Bragg law

1st order reflection: λ = 2d sin θ1

2nd order reflection: λ = 2d sin θ2

3rd order reflection: λ = 2d sin θ3

Reflection Planes in a Cubic Lattice
 Crystal Systems

Crystal systems Axes system

cubic a = b = c ,  =  = g = 90°

Tetragonal a = b  c ,  =  = g = 90°

Hexagonal a = b  c ,  =  = 90°, g = 120°

Rhomboedric a = b = c ,  =  = g  90°

Orthorhombic a  b  c ,  =  = g = 90°

Monoclinic a  b  c ,  = g = 90° ,   90°

Triclinic a  b  c ,   g  °
Crystal Systems
 Relationship between d-value and
the Lattice Constants
 = 2 d s in  Bragg´s law
▪ The wavelength is known
▪ Theta is the half value of the peak position
▪ d will be calculated

2 2 2 2 2 2 Equation for the determination of the

1/d = (h + k )/a + l /c d-value of a tetragonal elementary cell
a=b≠c

▪ h,k and l are the Miller indices of the peaks

▪ a and c are lattice parameter of the elementary cell
▪ if a and c are known it is possible to calculate the peak position
▪ if the peak position is known it is possible to calculate the lattice
parameter
http://www.wwnorton.com/college/chemistry/gilbert/tutorials/ch10.htm
XRD System
XRD SYSTEM
 XRD SYSTEM

A very common x-ray measurement is the -2

measurement where the sample is rotated at an
angle  with respect to the incident beam. To keep
the incident and exit beam at the same angle to the
sample normal, the detector has to move twice as
fast or 2. The measurement is in 2.
 Inside Goniometer
The Bragg-Brentano Geometry

Mono-
chromator
Divergence slit Antiscatter-
slit

Detector-
slit
Tube

Sample
 Inside Goniometer
“Grazing Incidence Diffraction” with Göbel Mirror

Measurement circle
Scintillation
counter

Göbel Mirror
Soller slit

Sample

X-ray Source
 Comparison Bragg-Brentano Geometry versus
Parallel Beam Geometry

Motorized Slit

X-ray Source

Sample

Bragg-Brentano Parallel Beam Geometry

Geometry generated by Göbel Mirrors
 Pattern and Structure

• The d-spacings of lattice planes depend on the size of the elementary

cell and determine the position of the peaks.
• The intensity of each peak is caused by the crystallographic structure,
the position of the atoms within the elementary cell and their thermal
vibration.
• The line width and shape of the peaks may be derived from
conditions of measuring and properties - like particle size - of the
sample material.
http://www.doitpoms.ac.uk/tlplib/xray-diffraction/powder.php
Comparing unknown sample
with database
Identifying structure from a powder
pattern (-2) measurement
Cu= 0.154 nm

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

- Once you have the angles for each reflection, you can calculate the ‘d’ values.
- Remember we’re measuring 2 but we’re using  !

d = interplanar spacings for each

allowed h, k, l

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 you’d otherwise expect

to be there.
•Only certain reflections are ‘allowed’.
“Allowed Reflections” for Cubic Space Lattices
Constraints on (h2 + k2 + l2)
Simple Cubic all values of (h2 + k2 + l2)
Body-Centered Cubic (h2 + k2 + l2) = even number
Face-Centered Cubic h, k, and l either all even or all odd

Plane (h2 + k2 + l2) SC BC FCC

(100) 1 1 - -
(110) 2 2 2 -
(111) 3 3 - 3
(200) 4 4 4 4
(210) 5 5 - -
(211) 6 6 6 -
(220) 8 8 8 8
(300) 9 9 - -
(310) 10 10 10 -
(311) 11 11 - 11
(222) 12 12 12 12
(320) 13 13 - -
(321) 14 14 14 -
… … … … …
(400) 16 16 16 16
(331) 19 19 - 19
 Back to the story:
- We’ve 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.

- We’re assuming a cubic structure. Recall that…

- Interplanar spacing ‘d’ is related to Miller Indices h, k, and l and the lattice parameters by:

1 (h2+k2+l2)
=
d2hkl a2
So…
 1 (h2+k2+l2)
= and 2dsin = n
d2hkl a2

So… for for two different {hkl}s: (e.g., h1k1l1 and h2k2l2)

d2h1k1l1 sin22 (h22 + k22 + l22)

= =
d2h2k2l2 sin21 (h12 + k12 + l12)

So… sin22 (h22 + k22 + l22)

=
sin2 1 (h12 + k12 + l12)

So… you calculate sin2 values from each value of  obtained from the XRD trace

Then… the ratio of the sin2 values 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).

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

sin22 (h22 + k22 + l22)

=
sin2 1 (h12 + k12 + l12)

The ratios of sin2 values are

consistent with the ratios of
the allowed (h22 + k22 + l22) for
the FCC structure only…
- We can now assign Miller Indices to each peak in the XRD trace…

(111)

Plane (h2 + k2 + l2) FCC

(200)
(100) 1 -
(110) 2 -
(111) 3 3
(220) (311) (200) 4 4
(210) 5 -
(211) 6 -
(331) (220) 8 8
(300) 9 -
(222) (310) 10 -
(311) 11 11
(400) (222) 12 12
(320) 13 -
(321) 14 -
… … …
(400) 16 16
(331) 19 19

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

determine the lattice parameter for this material…
36
- Once a structure is found, we can go back and determine
the lattice parameter for this material:

1 (h2+k2+l2) or a2 = d2hkl(h2 + k2 + l2)

=
d2hkl a2

- We can determine the lattice parameter for each line and

average to get the most accurate measurement...

aavg = 3.522 Å

The FCC structure and the lattice parameter identify this metal as Ni.
Comparing unknown sample
with database
THANK YOU