All you want to know about

powder x-ray diffraction

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Introduction

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 What are x-rays?
• Electromagnetic wave
• Discovered by Wilhelm Conrad Röntgen (Roentgen)
on Nov. 8, 1895
 Wilhelm Conrad Röntgen (1845 – 1923, Germany)
 Nobel Prize in Physics in 1901

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 X-rays as electromagnetic wave
• Wavelength 100 – 0.1 Å (10 – 0.01 nm)
 Longer than gamma rays, shorter than ultraviolet rays
 Invisible to the human eye

• Energy 120 eV – 120 keV

 High penetration power
 Could damage cells and cause a burn and cancer
 Widely used for medical and industrial radiography and airport
security luggage scanning

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 Why x-rays?
~10 Å
~5 Å
λ ~ 1.54 Å

Cu Kα wavelength
Quartz unit cell

Buckyball λ ~ 475 nm
Blue

λ ~ 510 nm
Green

λ ~ 650 nm
Red

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 X-ray & materials interaction

Scattered x-rays
(XRD, XRR, SAXS)
Fluorescent x-rays
X-rays (XRF)
Transmission x-rays
(EXAFS, XANES)

Electrons (XPS)

Heat
Analysis techniques using x-rays as the incident beam

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X-ray scattering by atoms

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Diffraction by periodic structure

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Diffraction condition

Diffraction condition (Bragg’s law)

2d sin θ = nλ
d: Spacing between lattice planes, θ: Diffraction angle
λ: Wavelength, n: integer

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 X-ray diffraction patterns

Gas Liquid / amorphous Powder / polycrystalline Single crystal

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Powder x-ray diffraction patterns

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Phase identification

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Advanced analyses

Whole pattern  Phase identification, quantitative analysis

Peak position  Lattice parameters

Peak width  Crystallite size & strain

Diffraction %Crystallinity
Amorphous scattering

Background

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Instrumentation

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 Geometries
XG
RS Detector
DS SS DS PSA
XG
Detector
Mirror
Sample Sample

Focusing geometry Parallel beam geometry

Cause of Flat sample
systematic Axial divergence Axial divergence
errors Sample absorption
Sample displacement
Calibration Internal (preferred) External
Int & res High / high Medium / medium
When to use Trace phases, peak overlap Curved/rough surface samples, thin
films, structure analysis, in-situ

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 X-ray generators

Filament: W
Target: Cr, Co, Cu, Mo etc.
X-ray generation efficiency
ε = 1.1×10-9 ZV ~ 0.1 % for Cu 50 kV
Z: Atomic number of the target material
V: Applied voltage

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 Sealed tube and rotating anode

Sealed tube Rotating anode

Cooling water
Anode
Cathode Anode

Cathode

Cooling water

• MiniFlex II (0.45 kW), Ultima IV (3 • TTRAX III (18 kV), SmartLab (9 kW)
kW), SmartLab (3 kW)

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 X-ray spectrum
Kβ Kα 50kV

W
40kV

35kV

Mo 30kV
Cr 25kV
20kV

Intensity of characteristic x-rays Intensity of continuous x-rays

I ∝ i x (V - V0)n I ∝ i x V2Z
n = 2 (V ～ 2 - 3V0) Shortest wavelength
n = 1 (V > 3V0) λ [Å] = 12.4 /V [kV]
V: Applied voltage, V0: Excitation voltage Z: Atomic number of the target material

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 Characteristic x-rays
M-shell

L-shell Kβ
K-shell Kα1
Kα2

Lα1

Kicked out electron

Kicked out electron

Electrons from the filament

Energy level gap and wavelength

En - Ek = hνk = h(c/λk)
Ex: Energy level of X-shell, λx: Wavelength of X characteristic x-rays
h: Planck’s constant, c: Light speed

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 X-ray absorption
Elastic scattered x-rays

Inelastic scattered x-rays

X-rays (I0) Transmitted x-rays (I)

μ/ρ Electrons

t Heat

The incident x-ray intensity, I0, decreases as the x-rays go through a material.
I = I0exp(-μt)
μ [1/cm]: Linear absorption coefficient
(μ/ρ [cm2/g]: Mass absorption coefficient, ρ [g/cm3]: Density)
t [cm]: Thickness

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 X-ray absorption edge
Ni K absorption edge

The Ni K absorption edge is used as Kβ filter for Cu radiation.

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 Target materials

Target Wavelength [Å] Absorption Excitation

Material Z Kα1 Kα2 Kβ edge [Å] [keV]
Cr 24 2.294 2.260 2.085 2.070 6.0
Fe 26 1.940 1.936 1.757 1.743 7.1
Co 27 1.793 1.789 1.621 1.608 7.7
Cu 29 1.544 1.541 1.392 1.380 8.9
Mo 42 0.714 0.709 0.632 0.620 20.0

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 X-ray detectors (scintillation counter)

Dynodes
Photocathode Anode

X-ray photon Light

Electrons Signal

Be window High voltage

Scintillator (NaI (Tl)) Photomultiplier ( x 105 ~ 107)

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PHA, Kβ filter, and monochromator
Kα1+2
Kβ filter
Kβ
Scintillation counter
Pulse height analyzer

Monochromator

Kα1+2

Continuous
Kβ

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Crystal structure

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 What are crystals?

Unit cell

A crystal is an anisotropic, homogeneous body consisting of a

three-dimensional periodic ordering of atoms, ions, or molecules.

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Lattice parameters

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 Miller index

(111)

(110)

( ) plane

(010)

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 High and low symmetries

Molybdenum
S.G.= 229 Im-3m
Cubic / a = 3.1 Å

Crundum
S.G.= 167 R-3c
Hexagonal / a = 4.7 Å, c= 12.9 Å

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Examples

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 ZnO, MgO, Al2O3 mixture

Bragg-Brentano (Rietveld analysis)

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 CaCO3  CaO phase transition
Bragg-Brentano, HT1500 + high speed detector (2 min/scan)

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 BaTiO3 phase transition
Parallel beam

Cubic

Pseudo-cubic

Tetragonal

Pseudo-cubic

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