Basics of X – ray Diffraction

Velaga. Srihari.

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 One can use XRD to determine
• Phase Composition of a Sample
- Quantitative Phase Analysis: determine the relative amounts of phases in a mixture
by referencing the relative peak intensities
• Unit cell lattice parameters and Bravais lattice symmetry
- Index peak positions
• Crystal Structure
- By Rietveld refinement of the entire diffraction pattern
• Texture/Orientation
• Crystallite Size and Residual Strain (macrostrain)
- Indicated by peak broadening
- Other defects (stacking faults, etc.) can be measured by analysis of peak shapes and
peak width

• in-situ capabilities, (evaluate all properties above as a function of time, temperature,

pressure and gas environment)

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Information one can get from the Diffraction

• Peak position

• Integrated intensity

o The space between diffracting planes of atoms determines peak positions.

o The peak intensity is determined by atoms in the diffracting plane.

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Underlying Principle (peak position)

• Braggs law:

θ θ

dhkl dhkl
n  2d hkl sin 

various instrumental and specimen features may affect the observed positions of
Bragg peaks. ~ ∆2θ.
∆2θobs = 2θcalc + ∆2θ

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Intensity of Diffraction lines

o Electrons set into oscillations by the electric field of the EM waves(X-rays).

2 2
    e 
2
I  I     sin  (Thomson equation)
 4   mr 

Where: Io - incident intensity

α – angle between scattering direction and direction of acceleration of e–.

XSCGS/MSD/IGCAR Syllabus discussions – 1 11-07-2008

 Factors effecting the relative intensities of the diffraction lines

 Polarization factor,
 Structure factor,
 Multiplicity factor,
 Lorentz factor,
 Absorption factor,
 Temperature factor.

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Polarization factor

 1  B cos 2 2 
K  
 1 B 

Where: B – constant depends on the quality of the monochromater crystal

for an ideally perfect crystal B = 1

 1  cos 2  2
K  
 2 

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Structure factor/form factor

Atomic scattering factor f

 ampl.scatt.wave by an atom 
f  _ 
 ampl .scatt .wave by one e 

Atomic scattering factor f = Z in the forward direction


f 
sin 

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 scattering by unit cell

o Situation is similar to that of an atom

o Phase difference depends on the arrangement of atoms

  2 (hu  kv  lw)
x y z
where : u  ,v  ,w 
a b c

o Amplitude differ if atoms are of different types

F   f je
2 i ( hu j  kv j  lw j )

j
Where j varies over all the atoms in the hkl plane

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Multiplicity factor (P)
#. Of different planes having same d spacing contribute to same reflection

Lorentz factor

• finite size of reciprocal lattice points and finite thickness of the Ewald's sphere
1

sin 
• variable radii of the Debye rings (constant size of receiving slit)
1

sin 2

 1 
L  
 sin  sin 2 

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

  1 
 L  
 cos  sin 2
 
Lorentz – polarization factor

 1  cos 2 2 
 L.P   
 cos  sin  
2

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Absorption factor (A)

A depends on geometry of the diffraction method

In case of Debye-Scherrer cameras: A ∝ 2θ (negligible)

In case of Diffractrometers A independent of θ.

constant for all 2θ values.

 t
Ae

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Temperature factor

Thermal vibrations cause:

- unit cell expansion
- gradual decrease in diffraction line intensity
- increase in background scattering with 2θ.

Temperature & absorption effects in cylindrical specimens varies in

opposite ways cancels each other
Theoretically, thermal vibrations cause an increase in FWHM
but experimentally no evidence

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Intensity of powder pattern lines

Total scattering intensity

2
2  1  cos 2 
2
 K
I  Io N   tAP F  
 sin  cos  
2
 r 

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Cases of Background

• Air Scattering.
• Specimen fluorescence.
• Compton scattering.
• Non-X-ray background.
• Beam obstructions.
• Electronic troubles.
• Thermal diffuse scattering.

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 X-ray Generators

• X-ray production results from bombarding a metallic target with electrons.

- retarding / accelerating the electrons.
• Requirements:
- high energy e- beam
- metal target with high thermal conductivity

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 sealed tube X-ray Generator

– linear focal spot: 10 × 0.1 mm;

– point focal spot: 1 × 1 mm.

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Rotating anode X-ray Generator

XSCGS/MSD/IGCAR Syllabus discussions – 1 11-07-2008

 Windows

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Synchrotron radiation

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008
 Monochromatization

• Filters:
e-μt
where μ - the linear absorption coefficient
& t - is thickness
best choice: element very close in periodic table
• Monochromator Crystals:
Single crystals (mosaic)
bent monochromators
channel cut crystal
• Pulse height selection using a proportional
counter
• Energy resolution using a solid-state detector

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Monochromator

Selective diffraction by a single crystal

curved crystal monochromator (Johann)

channel cut crystal

cylindrical cut monochromator

Multi-layered monochromators or mirrors
(Johansson)
XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008
 Detectors
• Photographic film
• Gas detectors:
Ionization chambers
Proportional counters
Geiger-Müller counters
• Solid detectors
Semiconductor detectors
• Direct observation of light photons
Fluorescent screens
CCD cameras

• Scintillation detectors
• Indirect method: the imaging plate

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Diffractometers for powder or bulk polycrystalline
samples

Debye-Scherrer and Hull diffractometer

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008
 Debye-Scherrer diffractometer equipped with a position sensitive detector

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Focusing diffractometers: Seeman and Bohlin diffractometer

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Bragg-Brentano diffractometer

θ -2θ Bragg-Brentano diffractometers θ -θ Bragg-Brentano diffractometers

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Graphite
SS Monochromator

DS

X-Ray Source *
RS

Theta

2Theta

Sample
X-Ray Detector

Diffractometer Circle

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008

 Determination of crystal structure
Crystal structure Diffraction pattern
Unit cell line position

Atom positions Line intensities

• Shape & size of unit cell from angular positions of diffraction lines
- Assumption of correct crystal structure
- Indexing the pattern
- determination of unit cell size from position and miller indices

• #. of atoms per unit cell from: shape & size, chemical composition & measured density

• Positions of atoms in unit cell from relative intensities.

XSCGS/MSD/IGCAR Syllabus discussions - 1 11-07-2008