305-32113A

May 2010

SHIMADZU ENERGY DISPERSIVE

X-RAY FLUORESCENCE SPECTROMETER

EDX SERIES
INSTRUCTION MANUAL
Beginners' Book

Read the instruction manual thoroughly before you use the product.
Keep this instruction manual for future reference.
© 2008-2010 Shimadzu Corporation. All rights reserved.

ii EDX SERIES Beginners' Book

 Contents

1 What Is Fluorescent X-ray Spectroscopy?

1.1 What Are X-Rays?................................................................................................ 1

1.2 Characteristics of X-Rays..................................................................................... 2

1.3 The Energy of X-Rays.......................................................................................... 3

1.4 Principle of Generation of Fluorescent X-Rays..................................................... 4

1.5 Fluorescent X-Ray Spectroscopy......................................................................... 6

1.6 Characteristics and Applications of Fluorescent X‑Ray Spectroscopy................. 7

2 X-ray Fluorescence Spectrometers

2.1 X-Ray Fluorescence Spectrometers..................................................................... 9

2.2 Characteristics of Energy Dispersive X-Ray Spectrometers (EDX).................... 10

2.3 Characteristics of Wavelength Dispersive X-Ray Spectrometers (WDX)........... 10

2.4 Parts that Comprise the Equipment.................................................................... 11

2.4.1 X-Ray Tube........................................................................................................11
2.4.2 Semiconductor Detector....................................................................................13

EDX SERIES Beginners' Book iii

Contents

3 Fluorescent X-ray Spectroscopy

3.1 Types of Fluorescent X-Ray Spectroscopy......................................................... 15

3.2 Qualitative Analysis............................................................................................. 16

3.2.1 Overlap of Spectra.............................................................................................17
3.2.2 Scattered Radiation...........................................................................................18
3.2.3 Escape Peaks and Sum Peaks.........................................................................19
3.2.4 Diffraction Lines.................................................................................................20

3.3 Quantitative Analysis.......................................................................................... 21

3.4 Calibration Curve Method................................................................................... 22

3.4.1 Description.........................................................................................................22
3.4.2 Standard Samples.............................................................................................23

3.5 Quantitative Analysis Using the FP (Fundamental Parameter) Method............. 24

3.5.1 FP Method.........................................................................................................24
3.5.2 Quantitative Calculation Method........................................................................24
3.5.3 Points to Note About Quantitative Analysis Using the FP Method.....................25

iv EDX SERIES Beginners' Book

1 What Is Fluorescent X-ray
Spectroscopy?

1.1 What Are X-Rays?

X-rays are a kind of electromagnetic waves discovered by the German physicist W. C. Röntgen (1845 -
1
1923) in 1895.

W. C. Röntgen, 1845-1923

Photo from: Wikipedia (http://en.wikipedia.org/wiki/Radiology)

When X-rays strike matter, some of them are absorbed by the matter and the rest pass through. The
degree of absorption and penetration depend on the chemical elements that make up the matter as well as
the thickness of the matter.

Penetration

X-rays bearing
element information

Absorbed

Matter
X-ray

In general, the character of X-rays is that they are not easily absorbed by light elements (elements with
a low atomic number) but are easily absorbed by heavy elements (elements with a high atomic number).
Equipments that make use of this difference are medical X-ray machines and equipments used to inspect
hand luggage at airports and elsewhere. The process involved can be likened to the production of shadow
pictures.

X-ray

Equipment That Makes Use of Differences in Absorption

EDX SERIES Beginners' Book 1

1 What Is Fluorescent X-ray Spectroscopy?

As a result of X-rays being absorbed by matter, X-rays are generated that carry information about the
elements in that matter. There is analytical equipment that makes use of this to identify the component
elements of matter. This kind of equipment is called an X-ray fluorescence spectrometer.

? Iron!

Equipment That Makes Use of the X-Rays Generated by Absorption

1.2 Characteristics of X-Rays

X-rays are a kind of light (electromagnetic wave), but they cannot be discerned by the eye like visible
light.

Ultraviolet light Visible light Energy

10 10 10 8 10 6 10 4 10 2 1 10 -2 10 -4 10 -6 10 -8 10 -10 10 -12 eV
Radio waves
X-ray
Microwaves Long wave
Infrared
Gamma rays light

10 -15 10 -12 10 -9 10 -6 10 -3 1 10 3 10 6 m
fm pm nm µm mm m km Mm Wavelength

Visible light rays

Medium wave
Short wave
Orange
Yellow
Indigo

Green

Red
Blue

Ultrashort wave
nm 3 4 4 5 5 6 7
8 3 9 5 9 4 8
0 0 0 0 0 0 0

Types of Electromagnetic Wave

2 EDX SERIES Beginners' Book

 1.3 The Energy of X-Rays

1.3 The Energy of X-Rays

X-rays have wave characteristics and particle characteristics. The wave characteristics are expressed
in wave motion with a particular wavelength (λ: specified in nm (nanometer) units). The particle
characteristics are expressed in the form of photons (particles) that have a particular energy (E: specified
in keV (kilo electron volt) units).
The energy is large when the wavelength is short, and becomes smaller as the wavelength increases. 1
@@Note
Wavelength (λ: in nm units) and energy (E: keV units) are inversely proportional to each other, and their
relationship is expressed by the formula below.
hc 1.24
E = hν = =
λ λ
h: Planck's constant (4.14 × 10-18 keV•s)
ν: Frequency
c: The velocity of light (3.00 × 1017 nm/s)

Example: Iron (Fe)

The wavelength of an X-ray generated from an iron atom is 0.194 nm. Converted into energy,
this gives 6.40 keV.
1.24
E= = 6.40 keV
0.194

EDX SERIES Beginners' Book 3

1 What Is Fluorescent X-ray Spectroscopy?

1.4 Principle of Generation of Fluorescent X-Rays

Matter is composed of atoms, and when matter is struck by electrons or X-rays, X-rays of a wavelength
(energy) that is specific to those atoms are generated from the matter. When a material is struck by
electrons or X-rays, it generates new X-rays, called characteristic X-rays. Fluorescent X-rays are
characteristic X-rays produced as a result of a material being struck by X-rays only.

Mechanism for Generation of Fluorescent X-Rays

1) An X-ray collides with an atom.
▼
2) An inner shell electron close to the nucleus of the atom is knocked out, leaving a hole.
▼
3) An outer shell electron drops into this hole.
▼
4) The electron that has dropped from a high-energy orbit (outer shell) to a low-energy orbit (inner
shell) radiates the energy difference as an electromagnetic wave (= fluorescent X-ray).

1) 2) 3) 4)
Fluorescent
X-ray X-ray

Electron Hole An electron drops A fluorescent X-ray

in from an outer shell. is generated.
An X-ray collides The electron is
with an electron. knocked out,
creating a hole.

Fluorescent X-ray Electron

Electron
X-ray
Electron

Electron

Principle of Generation of Fluorescent X-Rays

4 EDX SERIES Beginners' Book

 1.4 Principle of Generation of Fluorescent X-Rays

Atoms have an atomic nucleus at their center, and electrons are arranged in orbits called the K shell, the
L shell, and the M shell (working from inner to outer orbits) with a fixed number of electrons in each
shell. The type of fluorescent X-ray generated differs depending on which electron is knocked out by
the irradiating X-ray and which electron drops in to fill the hole. The X-ray generated when an electron
drops down to fill a hole in the K shell will be a K series fluorescent X-ray, the X-ray generated when
an electron drops down to fill a hole in the L shell will be an L series fluorescent X-ray, and the X-ray
generated when an electron drops down to fill a hole in the M shell will be an M series fluorescent X-ray.
The fluorescent X-ray generated when a hole in the K shell is filled by an electron from the L shell is a
1
Kα ray, and the fluorescent X-ray generated when a hole in the K shell is filled by an electron from the M
shell or N shell is a Kβ ray.
The fluorescent X-ray generated when a hole in the L shell is filled by an electron from the M shell is an
Lα ray, and the fluorescent X-ray generated when a hole in the L shell is filled by an electron from the M
shell or N shell is an Lβ ray.

Sun
Mercury Venus

Rough ratio of fluorescent X-rays Earth Mars

Kα rays : Kβ rays = 100 : 20
Lα rays : Lβ rays = 100 : 70 to 100
The construction of an atom can be
likened to the solar system.
Knocked-out electron
(photoelectron)
Fluorescent X-ray (Kα ray)

N
M
//m
Kβ L
K
Mα
Lα

Lβ

Atomic nucleus

Irradiating X-ray Electron

Hole

Interactions Between X-Rays and Substances and the Mechanism for Generation of Fluorescent X-Rays

EDX SERIES Beginners' Book 5

1 What Is Fluorescent X-ray Spectroscopy?

@@Note
Examples of the energy of fluorescent X-rays
As shown in the table below, fluorescent X-rays have an energy that is specific to the element concerned.

Element Fluorescent X-Ray Energy

Iron (Fe) Kα ray 6.400 keV

Rhodium (Rh) Kα ray 20.167 keV

Rhodium (Rh) Lα ray 2.699 keV

1.5 Fluorescent X-Ray Spectroscopy

As described in section 1.4, the X-rays that are generated as the result of X-rays striking matter (a
sample) are called fluorescent X-rays. Since these fluorescent X-rays have a specific energy (wavelength)
depending on the element struck, elements can be identified by measuring this energy (wavelengths).
Since the intensity of the fluorescent X-rays is proportional to the quantity of the relevant elements, the
quantity of each element can be estimated by measuring this intensity. This method of analysis using
fluorescent X-rays is called X-ray fluorescence analysis (XRF).

Cr Fe Pb
Fe
Cr
Cr Fe
Pb Cr
Fe
X-ray Cr Pb
Fluorescent Pb
X-ray Cr
Fe
Pb

Matter (sample)

Penetrated X-ray

Generation of Fluorescent X-Rays

6 EDX SERIES Beginners' Book

 1.6 Characteristics and Applications of Fluorescent X‑Ray Spectroscopy

1.6 Characteristics and Applications of Fluorescent

X‑Ray Spectroscopy
Fluorescent X-ray spectroscopy is used for a wide range of applications since it can be used to analyze
samples in various forms, as solids, powders, and liquids, no chemical pre-processing is required and
it is fast and non-destructive. It has been adopted by the Japan Industrial Standards (JIS) as a high-
accuracy method of analysis, particularly in the fields of ceramics, brick making, glassmaking and cement
1
manufacture.

„„Characteristics of Fluorescent X-Ray Spectroscopy

•• It allows analysis of the types and quantities of elements.
•• It is a non-destructive and fast method of analysis.
•• Solid, powder form and liquid samples can be analyzed without chemical pre-processing.
•• A wide range of elements can be analyzed.
•• Accurate analysis is possible over a range from a few ppm to materials entirely (100%) composed of
a single element.
•• No special equipment is required to examine large quantities.

„„Applications
•• Recycling of Resources
To effectively recycle resources, it is important to sort the waste materials that have been collected.
Fluorescent X-ray spectroscopy, which does not require any chemical pre-processing, is used for this
sorting task.

Sorting of waste materials

Analysis

Applications of Fluorescent X-Rays (Recycling of Resources)

EDX SERIES Beginners' Book 7

1 What Is Fluorescent X-ray Spectroscopy?

•• Restoring Cultural Assets

Restoration work is required to maintain cultural assets, such as paintings, that have been designated
national treasures for future generations. When restoring a painting, the same pigments as used by
the artist have to be used. Since it is a fast and non-destruction method of analysis, fluorescent X-ray
spectroscopy is the method used to examine these pigments.
To give an example, although white pigments look the same, they have a variety of different main
components, including lead (Pb), Zinc (Zn) and titanium (Ti). Analyzing the components makes it
possible to pin down the true nature of the original pigments, allowing restoration with the same
pigments.

What pigment has been used?

Ti
Zn
Pb Ti Pb
Zn

Applications of Fluorescent X-Rays (Restoration of Cultural Assets)

•• Screening for Harmful Elements

To ensure that materials and parts used in electrical and electronic equipment and in automobiles
do not include more than the reference quantities of harmful elements such as cadmium (Cd) and
lead (Pb), the European Union regulates their content with the RoHS (Restriction of Hazardous
Substances, i.e. restrictions on use of specific harmful substances in electrical and electronic devices)
and ELV (End of Life Vehicle) directives. In the electrical and electronic devices industry and the
automotive industry, screening that makes use of fluorescent X-ray spectroscopy is widely used as
a means of quickly determining whether the content of these harmful elements exceeds the control
values when purchasing materials and parts, and when shipping assembly parts. Recently, X-ray
fluorescence spectrometers have been used for screening for harmful elements that might be included
in toys.

Cd Hg Pb

Applications of Fluorescent X-Rays (Screening of Harmful Elements)

8 EDX SERIES Beginners' Book

2 X-ray Fluorescence
Spectrometers

2.1 X-Ray Fluorescence Spectrometers

The X-ray fluorescence spectrometers available on the market are divided into two types: energy
dispersive X-ray spectrometers, abbreviated as EDX, and wavelength dispersive X-ray spectrometers,
abbreviated as WDX. 2
Energy Dispersive Type (EDX) and Wave Dispersive Type (WDX)

Energy Dispersive Type (EDX) Wave Dispersive Type (WDX)

Field of Use Industrial Research
Equipment Size Small Large
Compact and inexpensive Large and expensive
Can analyze multiple elements at the same Capable of high resolution, high-accuracy
Characteristics time analysis
Principally analysis in the atmosphere Principally analysis in a vacuum
Short measuring time Long measuring time

Energy-dispersive X-ray spectrometer (EDX) Wavelength-Dispersive X-Ray Spectrometer (WDX)

Types of X-Ray Spectrometer

EDX SERIES Beginners' Book 9

2 X-ray Fluorescence Spectrometers

2.2 Characteristics of Energy Dispersive X-Ray

Spectrometers (EDX)
The fluorescent X-rays generated from the sample enter the semiconductor sensor at the same time. Then,
calculations for each element (each energy) are performed through electric signal processing and the
fluorescent X-ray spectrum is obtained. With EDX, multiple elements can be analyzed at the same time.

PHA
Semiconductor Pulse Height
Detector Analyzer

X-ray tube Semiconductor X-ray Fe

Fe
Detector Fe Amplifier Fe Fe 3
Cr Pb
Cr
Cr Cr 2
Fluorescent Pb
X-ray Fe Pb Pb 2
Sample

Principle of Energy-Dispersive X-Ray Spectrometers (EDX)

2.3 Characteristics of Wavelength Dispersive X-Ray

Spectrometers (WDX)
The fluorescent X-rays generated from the sample pass through a slit into a monochromator. The
monochromator and detector are linked to each other while maintaining the relationship indicated by q,
2q in the figure below. Only fluorescent X-rays of the wavelength that satisfies this relationship enter the
detector. Since the wavelength of the fluorescent X-rays that can be extracted depends on q, a fluorescent
X-ray spectrum can be obtained by continuously changing q.

X-ray tube

Monochromator
Monochromator θ 2θ

Fluorescent
X-ray

Primary X-rays Slit

(1)

Sample (2) Detector

(1) (2)

Pb
Cr

Detector
In this example lead (Pb) is extracted. Detector
In this example chromium (Cr) is extracted.
Principle of Wavelength-Dispersive X-Ray Spectrometers (WDX)

10 EDX SERIES Beginners' Book

 2.4 Parts that Comprise the Equipment

2.4 Parts that Comprise the Equipment

Among the parts that comprise X-ray spectrometers, the X-ray tube and semiconductor detector, which
are particularly important, are described here.

2.4.1 X-Ray Tube

The X-ray tube is a vacuum tube that is provided with a filament and target. When a current flows through
the filament it is heated up and thermoelectrons are generated. On applying a high voltage between
the filament and the target these thermoelectrons are accelerated and they are attracted to the target 2
and collide with it. The collisions generate X-rays. The X-rays are radiated outside the tube through a
beryllium window. A schematic diagram of an X-ray tube is given below.

High voltage

Target
Current
Electron
Filament

Beryllium window X-ray (photon)

Construction of an X-Ray Tube

The proportion of thermoelectrons that collide with the target which generate X-rays is extremely low, a
mere 0.1% to 1%. The remainder convert to heat, so the target reaches a very high temperature.
Because of this, the X-ray tubes in X-ray spectrometers are forcibly cooled by air cooling and water
cooling systems.
Apart from the characteristic X-rays generated from the elements that comprise the target material, as
described in section 1.4, the X-rays from an X-ray tube also include "continuous X-rays".

EDX SERIES Beginners' Book 11

2 X-ray Fluorescence Spectrometers

„„Continuous X-Rays
Electrons collide with matter in many ways, and one of these ways was described in section 1.4. In
addition to this way, an irradiating electron may be influenced by the attractive and repulsive forces of the
surrounding nucleus and electrons without colliding with any of the electrons that comprise the atom, so
that its course is altered and/or it slows down. When an electron changes course and/or slows down, an
X-ray is emitted. This is called "bremsstrahlung" (= braking radiation) and the X-rays that are generated
by this phenomenon are called continuous X-rays. Since the manner of deflection and/or degree of
deceleration of an electron will differ depending on where it enters an atom, the continuous X-rays that
are generated by bremsstrahlung have a variety of energies.

Continuous X-ray
Electron

Atomic
nucleus

Electron
Continuous X-ray Electron

Mechanism for Generation of Continuous X-Rays

The X-rays generated from the X-ray tube when the target material is rhodium (Rh) are continuous X-rays
and the X-rays specific to rhodium. If we plot the energy of these X-rays on the horizontal axis and their
intensity on the vertical axis, the distribution is as shown in the figure below.
X-ray intensity

Characteristic X-ray
Rh-Kα

Continuous X-ray

Rh-Lα Rh-Lβ Rh-Kβ

2.697 20.17 Energy (keV)

Continuous X-Rays and X-Rays Characteristic of Rhodium

@@Note
Target material
The material used for the target is generally rhodium, for the following reasons.
•• The K-rays from rhodium can generate fluorescent X-rays from heavy elements (elements with a high
atomic number) efficiently, and the L-rays from rhodium can generate fluorescent X-rays from light
elements (elements with a low atomic number) efficiently.
•• It is rare that rhodium itself is the subject of analysis.
Since the efficiency of generation of the fluorescent X-rays of an element varies depending on the energy of
the specific X-rays, X-rays tubes with a target material other than rhodium may be used in order to increase
the efficiency of generation of the fluorescent X-rays of a specific element.

12 EDX SERIES Beginners' Book

 2.4 Parts that Comprise the Equipment

2.4.2 Semiconductor Detector

The semiconductor detector electrically processes the fluorescent X-rays generated from the sample
and extracts them as signals. The semiconductor detector is connected to an amplifier that amplifies the
extracted signals and a PHA that sorts the extracted signals into fluorescent X-ray signals for each energy.
The figure below shows a schematic diagram of the semiconductor detector system.

Semiconductor Detector
2
Sample

X-ray tube

Amplifier PHA

Semiconductor Detector System

Since the signals from the semiconductor detector are extremely small, they are amplified using an
amplifier.

EDX SERIES Beginners' Book 13

2 X-ray Fluorescence Spectrometers

„„Relationship Between the PHA (Pulse Height Analyzer) and Spectrum

The PHA classifies the signals input from the semiconductor detector into fluorescent X-ray signals for
each energy. This function is illustrated by analogy in the figure below. Signals from the amplifier are
successively sent to the PHA, and the PHA classifies these signals. The signals are also put in order as
information that shows which types of signal are represented in what volumes. This information tells us
what volumes of fluorescent X-rays of which energies have been counted, and this is shown in the form
of a spectrum with energy plotted on the horizontal axis and intensity plotted on the vertical axis.
A variety of analyses are performed using this fluorescent X-ray spectrum.

Br

Fe
Br Ca
Br
Fe Category
Ca
Br
Br
Fe
Fe

Ca
Number Intensity

Br Br

Fe Fe

Ca Ca

Type Energy

Principle of the Pulse Height Analyzer

14 EDX SERIES Beginners' Book

3 Fluorescent X-ray
Spectroscopy

3.1 Types of Fluorescent X-Ray Spectroscopy

Fluorescent X-ray spectroscopy is divided into qualitative analysis and quantitative analysis.

Types of Analysis

Qualitative Analysis Quantitative Analysis

Purpose
Determines the types of element contained
in a sample
Determines how much of each element is
in the sample.
3
Not specified
Element Element specified in advance
All elements analyzed together

Qualitative analysis Quantitative analysis

How many of each group

Who is here? are here?
Three
Two of us of us

We are! Fe Fe Fe
Cr Cr

Fe Zn
Cr
Zn One of me

Qualitative Analysis and Quantitative Analysis

EDX SERIES Beginners' Book 15

3 Fluorescent X-ray Spectroscopy

3.2 Qualitative Analysis

Qualitative analysis means determining which elements are contained in a sample. An example of
qualitative analysis is given below. The horizontal axis plots the energy of fluorescent X-rays (units: keV)
and the vertical axis plots the intensity (unit: counts, cps, cps/µA, etc.)
The energy of fluorescent X-rays is peculiar to each element, and by measuring these energies we can
determine which elements are present.

Find the peaks to identify

the elements.

X-ray intensity
X-ray intensity

6.4 11.9 Energy, keV

Fe-Kα Br-Kα

The energies are determined

by the elements.
Energy

Example of a Qualitative Analysis Spectrum

@@Note
Units for intensity of fluorescent X-rays
counts: This is the number of fluorescent X-rays detected within the measuring time.
cps: This stands for "counts per second" and is the number of fluorescent X-rays detected in one
second.
cps/μA: This is the abbreviation of "cps per micro ampere" and it indicates the number of fluorescent
X-rays detected per unit of current in one second.

The intensity is proportional to the quantity of an element contained in the sample. Analysis that makes use
of intensity is explained in section 3.3 "Quantitative Analysis".

In qualitative analysis the elements that are associated with each peak position in the spectrum are
identified, making it the simplest method of analysis. However, as described in section 1.4, multiple
fluorescent X-rays – such as Kα, Kβ, Lα and Lβ – are obtained from a single element. In addition, a
sample is generally composed of more than one element. Consequently, the spectra obtained show peaks
at many locations. Depending on the element, different fluorescent X-rays with energies very close to
each other may be generated or peaks may actually coincide. Peaks that are not related to the fluorescent
X-rays generated from the sample may also be produced. The possibility that these problems may occur
must be understood to correctly determine the component elements in a sample through qualitative
analysis.

16 EDX SERIES Beginners' Book

 3.2 Qualitative Analysis

3.2.1 Overlap of Spectra

When the energies of the fluorescent X-rays of different elements are close to each other, their peaks
overlap, changing the peak profile. Provided that the apices of each of the peaks are still visible,
qualitative analysis is still possible even in such cases. However, there are some different elements whose
fluorescent X-ray energies almost coincide (for example Pb-Lα and As-Kα). In cases like this the peaks
are stacked together in a single spike and correct qualitative analysis is not possible. To make distinctions
in these cases, we check for the presence of energies (peaks) of other fluorescent X-rays for the same
elements.
If Kβ (Lβ) is present, it is certain that Kα (Lα) will also be present. And since the ratio of the intensities
of Kα - Kβ and Lα - Lβ is more or less fixed (see section 1.4), a ratio that differs from what is expected
means that there is an overlap with another element.

Pb-Lα?
As-Kα?
3
Pb-Lα
Bi-Lα

10.5 10.8 Energy (keV) 10.5 Energy (keV)

Even if they overlap the individual peaks Since only one peak can be seen, we can tell
can be checked, so qualitative analysis whether it is a peak for a single element or
is possible. a peak for multiple elements.

Pb-Lα
and
As-Kα
Pb-Lβ
Since the other peaks for the relevant
As-Kβ elements can be seen, we can tell
that the 10.5 keV peak is the result of
the overlap of Pb-Lα and As-Kα.

Energy (keV)
10.5 11.7 12.6

Overlapping of Spectra

EDX SERIES Beginners' Book 17

3 Fluorescent X-ray Spectroscopy

3.2.2 Scattered Radiation

This gives peaks that differ from those of the fluorescent X-rays from the sample. Some of the X-rays
from the X-ray tube don't generate fluorescent X-rays when they strike the sample but instead are
scattered within the sample and enter the semiconductor detector. These X-rays are called scattered
X-rays. Some of these scattered X-rays are generated directly by the scattering of X-rays when they
strike the sample, while others are generated as residual energy when an X-ray loses part of its energy
on being scattered inside the sample. The former kind are called Compton scattered radiation and the
latter kind are called Rayleigh scattered radiation. When a rhodium (Rh) X-ray tube is used, the scattered
radiation caused by characteristic X-rays is quite pronounced, and Rh-Kα (20.17 keV) and Rh-Kβ (22.73
keV) become Rayleigh scattered radiation. A slightly wider peak that appears at the left of each peak is
Compton scattered radiation. The intensity of Compton scattered radiation varies greatly depending on
the sample material.

Rays that are scattered with some energy loss when

the characteristic X-rays of the target metal of the
X-ray tube, which is rhodium, strike the material
(Compton scattered radiation)
X-ray intensity

Energy

Rays that are scattered without any energy change

when the characteristic X-rays of the target metal of
the X-ray tube, which is rhodium, strike the material
(Rayleigh scattered radiation)

Example of a Spectrum with Scattered Radiation

18 EDX SERIES Beginners' Book

 3.2 Qualitative Analysis

3.2.3 Escape Peaks and Sum Peaks

These are peaks that are generated in the detection process of the semiconductor detector and are not
related to the fluorescent X-rays from the sample. They are generated when a high peak intensity has been
obtained. They are classified into the following two types depending on how they are detected.
•• Escape Peak
A peak that appears at the position obtained by subtracting 1.74 keV (energy of the Si-Kα fluorescent
X-ray) from the detected peak energy.
•• Sum Peak
A peak that appears at twice the detected peak energy. For example, if Fe-Kα (6.4 keV) is detected,
the peak appears at the position that is twice this value, i.e. 12.8 keV. Note also that when multiple
high peaks have been detected, another peak appears at the position obtained by adding the energies
of each of these peaks together. 3
Escape peaks
Escape peak Sum peaks

X-ray intensity
X-ray intensity

Sum peak
Rh-Kα Rh-Kα
Cu-Kα
Fe-Kα Fe-Kα (Fe+Cu)
FeSUM FeSUM SUM CuSUM
Cu-Kβ

Fe-Kβ
Rh-Kβ CuESC Fe-Kβ Rh-Kβ
FeESC FeESC

4.66 6.4 12.8 Energy keV 4.66 6.2 6.4 8.0 12.8 14.4 16.0 Energy keV
(6.4 − 1.74) (6.4 + 6.4) (8.0 − 1.74) (8.0 + 6.4)
When there is a single peak When there are multiple peaks

Escape Peaks and Sum Peaks

EDX SERIES Beginners' Book 19

3 Fluorescent X-ray Spectroscopy

3.2.4 Diffraction Lines

In the measurement of a sample comprising specified metals, peaks that resemble fluorescent X-ray peaks
may appear at unspecified positions. These peaks are called diffraction lines.
The likelihood of generation of diffraction lines increases together with the degree of crystalline
orientation of the sample (the regularity of the arrangement of atoms). They are often generated in
samples that are so-called monocrystals in which the atoms are arranged in the same way in a fixed
direction, an example being silicon wafers, which are composed entirely of silicon (Si).
Since diffraction lines appear at unspecified positions, they may appear at the same position as a
fluorescent X-ray peak, or at a position where fluorescent X-ray peaks are not generated.
If an unknown peak that cannot be identified, or a peak for an element that is very unlikely to be present
in the sample appears in the spectrum, there is a possibility that it is a diffraction line.
The positions at which diffraction lines appear differ according to how the sample is placed. When a peak
that is thought to be a diffraction line appears, it can be identified as either a fluorescent X-ray peak or a
diffraction line by changing the orientation of the sample and measuring again.

Diffraction line
X-ray intensity

Energy

By changing the way that the Zinc (Zn) plate sample is

placed, the diffraction lines indicated in the figure are
affected but the fluorescent X-ray peaks are unaffected.

Diffraction Lines

20 EDX SERIES Beginners' Book

 3.3 Quantitative Analysis

3.3 Quantitative Analysis

Quantitative analysis means determining how much of each element is contained in the sample.
In qualitative analysis our purpose was to read the horizontal axis (energy) of the spectrum, but in
quantitative analysis our purpose is to read the vertical axis (intensity).
The vertical axis data obtained from an X-ray fluorescence spectrometer is the number of fluorescent
X-rays that are detected by the semiconductor detector. Let's take an example where the result of analysis
of the sample in terms of numbers of fluorescent X-rays (counts) is 100 for iron (Fe), 30 for chromium (Cr),
50 for nickel (Ni), and 5 for copper (Cu). When this information is shown in a spectrum, data other than
this counts information may be used, i.e., the number of fluorescent X-rays detected in one second (counts
per second: cps), or the number of fluorescent X-rays per 1 μA of tube current per second (cps per micro

3
ampere: cps/μA).
So we see that it is not possible to derive content information directly from the count information
obtained from the spectrometer. For this purpose we need a scale that relates counts to content (as ppm or
percentages).
This "scale" is used a little differently from one for everyday applications. On the scales used in
fluorescent X-ray spectroscopy, the width of the graduations differs for each element. The widths of
the graduations on the scale for chromium and the scale for cadmium are different. Even for the same
element, the scale has graduations of different widths depending on whether the sample is plastic or
metal. To give an example, the difference between the chromium and cadmium scales applied to plastic
samples in terms of the width of a graduation is a factor of about 1.5, while the difference between the
chromium and cadmium scales applied to metal samples in terms of the width of a graduation is a factor
of 20.
Consequently, correct analysis is not possible without using the appropriate scale for the element and the
sample material concerned. In the next section we explain mechanism for these scales.

Cd 1
Cr 1
tal
Me
tal Cd
Me Cr
ppm
100
pm
ppm 50 p
200 1 pp
m
ppm
100
m
1 pp
Cd 1 stic
Pla Cd
Cr 1
c
sti Cr
Pla
m m
4 pp 5 pp
m m
ppm
2 pp 3 pp
1500
ppm
1000 m
500
ppm 1 pp
m
1 pp

EDX SERIES Beginners' Book 21

3 Fluorescent X-ray Spectroscopy

3.4 Calibration Curve Method

3.4.1 Description
This is a method of estimation based on scales created for each element and the sample material as
described in the previous section. A calibration curve is a curve plotted to show the relationship between
the content, on the horizontal axis, and the intensity of fluorescent X-rays, on the vertical axis. This is
taken as the "scale". A sample whose content is already known is used to show this relationship. This
kind of sample is called a "standard sample", and can either be made in-house or purchased on the
market. By measuring the standard sample and finding the intensity of the fluorescent X-rays, we obtain
the relationship between the X-ray intensity and the content. We can ascertain this relationship with
one standard sample, but the general practice is to determine an accurate relationship based on several
standard samples with different contents.

Standard sample
Prepare standard samples with known contents.
▼

X-ray intensity, I
Unknown sample
Measure the fluorescent X-ray intensities of these standard
samples.
Calibration curve
▼
Create the calibration curve based on the contents of the
standard samples and the measured intensities.
▼
Measure the fluorescent X-ray intensities of an unknown sample
and determine its content by using the calibration curve.
0 Content, W (%)

Mechanism of the Calibration Method

22 EDX SERIES Beginners' Book

 3.4 Calibration Curve Method

3.4.2 Standard Samples

As explained in the previous section, the first step for quantitative analysis using the calibration method is
to prepare standard samples. In fields where fluorescent X-ray spectroscopy is used as method for check
analysis of products, such as the steel industry, non-ferrous metals (copper alloys, aluminum alloys,
etc.), and the ceramics, brickmaking, glassmaking and cement manufacture fields, standard samples are
available on the market. They are used in combination with samples whose component elements and
content ranges are unknown.

Standard Samples

Points to Note When Using Standard Samples

•• You must use a standard sample made of a material that is very similar to the unknown sample.
You have to match the main component and the content ranges of the elements present.
•• If you make the standard sample yourself, the method of pre-processing and the sample
manufacturing method must be the same as those for the unknown sample.
•• To assure the reliability of the calibration curve, a minimum of three standard samples with different
contents must be prepared (if possible, five or more).

EDX SERIES Beginners' Book 23

3 Fluorescent X-ray Spectroscopy

3.5 Quantitative Analysis Using the FP (Fundamental

Parameter) Method

3.5.1 FP Method
In the previous section we explained how to make scales using standard samples and perform analyses.
There is a method for making something similar to these scales by calculation, without using standard
samples. Used correctly, this method can provide a "universal scale" that can be used with any elements
and any sample material. This is useful in cases where it is not possible to make a scale using the
calibration method.
This is called the FP method. Provided information about the spectrometer and about the sample is
known, this information can be used as parameters, allowing the intensities in fluorescent X-ray spectra
to be found by calculation. The information for a sample can be obtained by comparing the spectrum
intensities obtained from the spectrometer with the spectrum intensities obtained by calculation.

Measured intensity

Exactly right!

Tin (calculation 4)
Sn: 97%
Pb: 2000 ppm
Tin
cal(
cul
atio
n1
)
Sn:
Pb

.
Sn: ...
..

2)
..

lculation Pb
Tin (ca Tin (c
alculati
on 3)
Sn:
....
Pb

Outline of the FP Method

3.5.2 Quantitative Calculation Method

In the FP method, calculations are performed so that the total of the contents of all the components
that make up the sample is 100%. For example, when analyzing the quantity of Pb in Fe, the total of
the contents of Pb and Fe is made 100%. After that the fluorescent X-ray intensities for Pb and Fe are
compared with the calculation results and applied to the densities of each element. So while with the
calibration method the content can be determined provided there is a scale for Pb, with the FP method
Fe (the main component) has to be looked at in addition to Pb. All of the sample information must be
reflected in the spectrum to correctly find contents using the FP method.

24 EDX SERIES Beginners' Book

 3.5 Quantitative Analysis Using the FP (Fundamental Parameter) Method

3.5.3 Points to Note About Quantitative Analysis Using the FP Method

In the last item we learned that in order to find the contents of a sample using the FP method all the
sample information has to be reflected in the spectrum obtained from the spectrometer, but in some cases
a sample has information that cannot be expressed in the spectrum obtained from the spectrometer. In
cases like this, this information must be provided in advance in the spectrum through calculation. If the
information that cannot be expressed in the spectrum is not in the calculation parameters, the content
values obtained will be completely different, so care is required.
The following samples have information that cannot be expressed in the spectrum, so it is necessary to
provide sample information in advance in the form of calculation parameters.
•• Plastic Samples
With an energy dispersive X-ray spectrometer (EDX), carbon (C), hydrogen (H) and oxygen
(O), which are the main components of plastics, cannot be detected as peaks. This is because the
fluorescent X-ray energies of these elements are so very weak that they are absorbed by the air
3
before they reach the semiconductor detector. In other words, despite the fact that they are the main
components they do not appear in the spectrum. The fact that elements that cannot be detected are
contained as the main components has to be provided as information. This information is called
"balance components". If we take the example of a sample that contains 1000 ppm (= 0.1%) of Pb
within plastic, the Pb peak will appear in the spectrum, but the main component information will
not. In this situation, the calculations are done on the assumption that everything other than Pb is the
main components (i.e., the content of the balance components is 100% (all contents) minus 0.1% (the
content of Pb) = 99.9%).
•• Thin Film Samples
An X-ray fluorescence spectrometer measures the number of elements contained in a sample. If, for
example, we thinly slice a very thick sample that contains 1000 ppm of Pb, these slices should have
the same Pb content of 1000 ppm, but since the number of elements in the slice is lower the result of
measurement is not 1000 ppm. To give another example, when a sample that is a thin chromium film
is laid on a steel plate is measured, the information from the underlying steel plate, which is Fe, is
detected in the spectrum in addition to Cr. This is because X-rays have passed through the thin film
and picked up information from the substrate too. In a case like this it is not possible to judge just by
examining the spectrum whether the sample is a steel plate that contains some chromium or a steel
plate with a thin film of chromium placed on it. In such circumstances information on the layers has
to be provided as parameters.

EDX SERIES Beginners' Book 25