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Moseley’s Law
The law states that “the wavelength of any particular line decreased as the
atomic number of the emitter is increased”

A linear relationship exists between the square root of the line frequency ν
and the atomic number Z

𝜈 = 𝐶(𝑍 − 𝜎)

Where C and σ are constants,

Z is atomic number of emitter

• Lα lines are not always of long

wavelength
• Lα1 of Tungsten has about
same wavelength as Kα lines of
copper (K lines have smaller
wavelengths) Fig. Moseley’s relation between, 𝜈 and
Dr. Mohsin Ali Raza
Z for two characteristic lines

Energy Dispersive X-ray Spectroscopy (EDX or EDS)

• EDS makes use of x-ray spectrum emitted by solid sample

when bombarded with a focused beam of electrons to obtain
localised chemical analysis.

• By principle all elements from atomic number 4 to 92 can be

detected (difficult for light elements such as O, H) (Na
onwards)

• Qualitative analysis involves identification of lines in the

spectrum (simple and straight forward)

• Quantitative analysis measure line intensities of each

element in the sample and for the same elements in
Calibration standards of known composition

• Elements maps or element distribution images can also be

produced

• X-ray spectrometer is attached with electron microscopes.

Dr. Mohsin Ali Raza

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Energy Dispersive X-ray Spectroscopy (EDX or EDS)

Dr. Mohsin Ali Raza

Energy Dispersive X-ray Spectroscopy (EDX or EDS)

Microanalysis technique

Dr. Mohsin Ali Raza

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Energy Dispersive X-ray Spectroscopy (EDX or EDS)

Schematic of inner atomic electron shells

Dr. Mohsin Ali Raza

Energy Dispersive X-ray Spectroscopy (EDX or EDS)

Energy difference of x-ray

photon is equal to energy
difference between the levels
concerned

E1-E2= hν

In the case of Kα1

hνα1= Wk- WLIII
ℎ𝜈𝐾𝛼1 = ℎ𝜈𝐾 − ℎ𝜈𝐿𝐼𝐼𝐼

1 1 1
𝜆𝐾𝛼1 = 𝜆𝜅 − 𝜆𝐿𝐼𝐼𝐼

Energy level diagram for Ag showing transitions responsible

Dr. Mohsin Ali Raza for K and L emission lines

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Energy Dispersive X-ray Spectroscopy (EDX or EDS)

The incident electrons must have energy greater than Eo called critical
excitation energy to produce K or L shell vacancy.
Mosely’s law is basis of element identification in EDS

Fig. Energies of principal characteristic lines and their excitation energies

Dr. Mohsin Ali Raza

Energy Dispersive X-ray Spectroscopy (EDX or EDS)

Dr. Mohsin Ali Raza

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Energy Dispersive X-ray Spectroscopy (EDX or EDS)

Dr. Mohsin Ali Raza

Energy Dispersive X-ray Spectroscopy (EDX or EDS)

x-rays are treated as photons possessing specific energy (E)

Eλ= 12396

Where E is eV, λ= Å

ℎ𝑐
𝑒𝑉𝑘 = 𝑊𝑘 = ℎ𝜈𝑘 =
𝜆𝑘

12.40 × 103
𝑉𝑘 = 𝐸𝑘 =
𝜆𝑘

Dr. Mohsin Ali Raza

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Energy Dispersive X-ray Spectroscopy (EDX or EDS)

Typical K spectra

Electron bombardment not only produces characteristic x-ray lines but

also continuous x-ray spectrum ( “continuum” Covering energy from 0
to E0)
Dr. Mohsin Ali Raza

Energy Dispersive X-ray Spectroscopy (EDX or EDS)

Peak to Background Ratio

Highest P/B would occur at the highest accelerating voltages

Dr. Mohsin Ali Raza

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Energy Dispersive X-ray Spectroscopy (EDX or EDS)

Typical K spectra

Dr. Mohsin Ali Raza

Energy Dispersive X-ray Spectroscopy (EDX or EDS)

Typical L spectra

Dr. Mohsin Ali Raza

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Energy Dispersive X-ray Spectroscopy (EDX or EDS)

Element mapping

Dr. Mohsin Ali Raza

Energy Dispersive X-ray Spectroscopy (EDX or EDS)

Components of EDS system

• X-ray detector

• Pulse processor

• Multi channel analyser

Sample preparation: Flat and polished sample should be used for high accuracy.
Powders can also be used.
Dr. Mohsin Ali Raza

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XRF (X-ray Fluorescence Spectroscopy)

• The emission of characteristic "secondary" (or
fluorescent) X-rays from a material that has been
excited by bombarding with high-energy X-rays or gamma
rays.

• XRF is used for elemental analysis in almost every field

(mineralogy, geology, metallurgy, biotechnology, forensic
etc)

• XRF is used for general chemical analysis

• XRF is fast, accurate, non destructive, and usually

requires minimal sample preparation.

• XRF is a reference method, standards are required for

quantitative results.
Dr. Mohsin Ali Raza

XRF (X-ray Fluorescence Spectroscopy)

X-ray Fluorescence Spectrometry
– Wavelength Dispersive XRF
– Energy Dispersive XRF - Portable, Transportable
(Benchtop)
– Total Reflection XRF

Conventional XRF (The angle of

incidence is greater than the
critical angle and the primary
radiation penetrates into the
sample)

TXRF (the incidence angle is

smaller than critical angle and
the primary radiation is reflected
Dr. Mohsin Ali Razaoff of the surface of sample)

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XRF (X-ray Fluorescence Spectroscopy)

Dr. Mohsin Ali Raza

XRF (X-ray Fluorescence Spectroscopy)

Dr. Mohsin Ali Raza

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XRF (X-ray Fluorescence Spectroscopy)

Measurement ranges

Dr. Mohsin Ali Raza

XRF (X-ray Fluorescence Spectroscopy)

XRF Instrumentation

• Source

• Sample

• Detection system

The source irradiates sample, and the detector measures

fluorescence radiation emitted from sample

Dr. Mohsin Ali Raza

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XRF (X-ray Fluorescence Spectroscopy)

Dr. Mohsin Ali Raza

XRF (X-ray Fluorescence Spectroscopy)

XRF radiation sources

• Conventional X-ray tube (End window or side window)

• Radioisotopes (Gamma rays sealed sources such

Americium-241, Co-57)

End
Window
X-ray tube

Dr. Mohsin Ali Raza

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XRF (X-ray Fluorescence Spectroscopy)

XRF Detector Principles

• Detector is a semi conducting or non-conducting material

between two charged electrodes

• X-ray radiation ionises the detector material causing to become

conductive, momentarily

• The newly freed electrons are accelerated toward the detector

anode to produce output pulse

• An ionised semi-conductor produces electron-hole pairs, the

number of pairs produces is proportional to the X-ray photon
energy

𝑬
• 𝒏 = 𝒆 , where n = number of electron-hole pairs produced, E = X-
ray photon energy, and e= 3.8 eV for Silicon at liquid nitrogen
temperature. Dr. Mohsin Ali Raza

XRF (X-ray Fluorescence Spectroscopy)

Types of Detectors

• Si(Li) detector

• Proportional counter

• Scintillation detector

Dr. Mohsin Ali Raza

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XRF (X-ray Fluorescence Spectroscopy)

Types of Detectors

• Proportional Counter

Ideal for measurement of longer wavelength, but it is insensitive to wavelengths shorter

than 0.15 nm
Dr. Mohsin Ali Raza

XRF (X-ray Fluorescence Spectroscopy)

Types of Detectors

• Si(Li) detector

Dr. Mohsin Ali Raza

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XRF (X-ray Fluorescence Spectroscopy)

Types of Detectors
Tl doped

• Scintillator detector

Ce-sb

• Blue photons with wavelengths 410 nm are produced

• No of blue photon is related to energy of incident x-ray photon
• Photons produce electrons and current produced by PMT is converted to voltage
Dr. Mohsin Ali Raza
pulse

XRF (X-ray Fluorescence Spectroscopy)

WDXRF

• Relatively inefficient, operated at much higher power than EDXRF

• Diffraction devices are also temperature
Dr. Mohsin Ali Raza sensitive

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XRF (X-ray Fluorescence Spectroscopy)

WDXRF
Czerny-Turner monochromator

• The diffraction grating disperses light by diffracting different wavelengths at

different angles.
• The particular wavelength that passes through the monochromator is
selected by rotating the angle of Dr.
the grating.
Mohsin Ali Raza

XRF (X-ray Fluorescence Spectroscopy)

Multilayers

While the crystal spacing is based on the natural atomic spacing,

at a given orientation the multilayer uses a series of thin film
layers of dissimilar elements to do the same thing.

Dr. Mohsin Ali Raza

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XRF (X-ray Fluorescence Spectroscopy)

EDXRF

Dr. Mohsin Ali Raza

XRF (X-ray Fluorescence Spectroscopy)

EDXRF

The height of pulse produced is proportional to the energy of the

respective incoming X-ray

Dr. Mohsin Ali Raza

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XRF (X-ray Fluorescence Spectroscopy)

Multichannel Analyser

The height of pulse produced is proportional to the energy of the

respective incoming X-ray

Dr. Mohsin Ali Raza

XRF (X-ray Fluorescence Spectroscopy)

Rayleigh Scattering

If the energy of the photon is the same before and after scattering, the
process is called elastic or Rayleigh scattering. Elastic scattering takes
place between photons and bound electrons and forms the basis of X-ray
diffraction.

Rayleigh scattering appears as

source peak in the spectrum

Dr. Mohsin Ali Raza

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XRF (X-ray Fluorescence Spectroscopy)

Compton Scattering

If the photon loses some of its energy, the process is called inelastic or
Compton scattering.

Compton scatter appears

slightly less in energy than
Rayleigh Scatter.

Dr. Mohsin Ali Raza

XRF (X-ray Fluorescence Spectroscopy)

Example

file:///E:/CEET/Materials%20Characterisation/XRF%20fun
damentals%20complete%20transitions.pdf

Dr. Mohsin Ali Raza

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XRF (X-ray Fluorescence Spectroscopy)

Sample Preparation

Dr. Mohsin Ali Raza

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