Uppsala University

Department of Physics and Astronomy

Laboratory exercise

X-ray spectroscopy:
Experimental studies of Moseley’s law (K-line x-ray fluorescence)
and x-ray material’s composition determination

Summary of exercise:

1. Record the Kα and the Kβ lines emitted from different metals and
make an energy calibration of the spectra.
2. Determine the energies of the observed K lines.
3. Verify Moseley’s law in a diagram.
4. Measure the x-ray spectrum of an unknown material.
5. Determine the material’s elemental composition from measured K, L, or M lines.
6. Make an oral report on the results.

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 Laboratory exercise in Quantum Physics

X-ray spectroscopy
Author/date: Lage Hedin, Filip Heijkensköld /2008-04-18/ 2011-09-22
1. Introduction

Vacancies in inner shells (electron holes) of an atom can be created by absorption of x-ray
radiation or by collisions with energetic particles. The atom ionised in this way then has an electron
hole, which rapidly will be filled with an electron from other, less strongly bound shells of the
atom. E.g., a vacancy in the K-shell can be filled by the transition of an electron from the L-shell.
Such a transition is connected with the emission of a photon. This radiation has only particular
discrete photon energies corresponding to the energy difference of the levels involved and it is
characteristic for every chemical element. Radiation like this is called x-ray fluorescence.
In the laboratory exercise the radiation to be investigated is emitted from some different metals in
which vacancies are created in K shells using the radiation from an x-ray tube equipped with a
molybdenum (Mo) anode.
The designations of the characteristic x-ray lines are a combination of the symbol for the electron
shell (K, L, M, etc) and a Greek letter α, β, γ, etc). The electron shell being referred to is the one
where a vacancy was created before the transition of an electron from an outer shell.

Preparatory exercises and questions

1. Formulate Moseley’s law? What are characteristic x-rays?

2. Draw an energy level diagram, with level terms, e.g., for copper. Mark allowed
transitions in the diagram and label the terms for corresponding emission lines.

3. Calculate the cut-off limit of the bremsstrahlung from a molybdenum anode in an x-

ray tube with an accelerating voltage of 35 kV.

4. What is the lowest possible voltage over the tube which still generates molybdenum’s
Kα radiation?

2. Theory

2.1 Characteristic radiation

In the present laboratory exercise characteristic Kα and Kβ x-ray fluorescence (see explanation of
designations in the section “Moseley’s law”) from some different metals will be investigated. The
process may be described in the following way, where the atom is represented by its electron
configuration and a 1s electron is assumed to be emitted from the atom with a kinetic energy of
free
E kin

e-( E inkin ) + 1s2 2s2 2p6 3s2 3p6 3d10 4s → e-( E out 5 2 6 10 - free
kin ) + 1s 2s 2p 3s 3p 3d 4s + e ( E kin )
1 2

In the metal the outer electron shells aren’t strictly atomic, but form valence and conduction

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bands. The other electrons can, however, be considered to be primarily atomic.
By the interaction, a vacancy in the 1s-shell in a copper atom will be created. Due to the selection
rule Δl = ±1, only electrons from the 2p and 3p shell come into consideration in the case of copper.
The former give rise to the Kα radiation, and the latter to the Kβ radiation (see lecture notes). The
energies of these radiation components can be calculated from the binding energies for different
electrons. These energies are tabulated below:

Orbital 1s 2s 2p½ 2p3/2 3s 3p½ 3p3/2

Energy (eV) 8979 1096,7 952,3 932,5 122,5 77,3 75,1

Thus, an energy of at least 8979 eV to release a 1s electron, has to be supplied e.g. by means of x-
ray photons. The energy of the state has been raised with the same value.
For example, when the 1s vacancy is filled by an electron from the 2p shell, the following
configuration appears:

1s2 2s2 2p5 3s2 3p6 3d10 4s

This state has an energy of about 942 eV higher than the ground state energy (mean value of the
two spin-orbit components). The difference in energy is:

ΔE = 8979 - 942 = 8037 eV

If the electron relaxation is followed by the emission of a photon, then the photon will have the
energy 8037 eV. (Another possibility is that an electron leaves the system in a so-called Auger
process.)
If we calculate this energy more accurately, taking the spin-orbit interaction into account, we will
actually get two transitions with the energies 8047 eV (Cu Kα1 ) and 8027 eV (Cu Kα2 ). These
components are close in energy, and are difficult to resolve in the used x-ray spectrometer.

2.2 Moseley’s law

The designations of the characteristic x-ray lines are a combination of the symbol for the electron
shell and a Greek letter. The electron shell being referred to is the one where a vacancy is created
before the electron transition. For example, the designation Kα -line describes the transition from
the L-shell into the K-shell, Kβ -line refers to the transition from the M-shell to the K-shell. The Lα -
and Lβ -lines refer to the transitions from the M-shell and the N-shell, respectively, to the L-shell.

For the energies E of the characteristic lines Moseley found in 1913 the following relations.

 E
Ry
=  Z − 
 
1 1
−
n12 n 22
(1)

with the atomic number Z, the screening constant σ, the constant Ry=me e 4 / 8 e 20 h 2 = 13,6 eV and
the principal quantum numbers n1 and n2 for the electron shells involved ( n1 <n 2 ). This equation
can be rewritten as

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 E=RyZ 2eff
 1 1
−
n12 n 22  where Z eff =Z − (2)

which is the Bohr model applied to many-electron atoms. Like the Schrödinger equation it gives the
energies of the emitted photons.

3. The x-ray spectrometer

When high-energy electrons hit the anode of the x-ray tube two different processes may take
place leading to x-ray emission. On the one hand, electrons can be decelerated by the anode atoms,
and radiation emitted as bremsstrahlung. This radiation is continuous and the onset of the
distribution occurs at maximum kinetic energy of the electron. On the other hand, vacancies can be
created in inner shells and filled by electrons from outer shells. Transitions of this kind lead to
emission of characteristic radiation (the wavelengths are characteristic of the anode material).

The experimental set-up is shown on the front page and in figure 1 and 2. The essential
components are an x-ray tube equipped with a molybdenum anode and a hot cathode, a goniometer
and a cooled detector which directly gives the energy of each incoming photon. The anode is seated
in a copper block to dissipate heat. The voltage across the x-ray tube should, in these experiments,
be adjusted to 35 kV and the emission current should be adjusted to 1 mA.
The goniometer is used for mounting the target and setting it at proper angles. The apparatus is
equipped with two independently controllable stepping motors, which move the detector and target
arms. Do not block the target arm and sensor arm of the goniometer and do not use force to
move them.

4. Procedures
4.1 Start up procedure
Turn on computer and log in as a student without password. Turn on the x-ray apparatus.
Push the sensor button (see figure 2) and adjust to 90°. Be careful and do not override the
angle. The equipment has no automatic stop.
Push the target button (see figure 2) and adjust to 45°.
Open the sliding glass window to access the target compartment.
Start the Cassy lab program in the computer by double-clicking the icon on the desktop.
Click in the middle lower figure in the context menu on the screen to select a new diagram.
A green LED on the detector and the Cassy interface shows that they are ready to be used.
Change the setting on in the “Measuring Parameters”. Set number of channels to 1024 and
set pulse height to -2000 mV.
4.2 Calibration procedure
Load the sample holder with an iron sample. Close all sliding glass windows. Turn on the
high voltage for the x-ray tube, set it to 35 kV. Adjust the current to 1.0 mA. Use F9 on the
computer to start the measurement. After the measurement is ready turn off high voltage,
open windows and change to a molybdenum sample. Use F9 on the computer to start the
measurement.
4.2.1 Open in the context menu of the diagram (right-click mouse button) the Energy
calibration, select global energy calibration and enter on the right-hand side the energies
of the Fe Kα-line (6.40 keV) and of the Mo Kα-line (17.48 keV). Do not close the
Energy calibration window.

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4.2.2 In the context menu of the diagram select under Other evaluations use Calculate peak
center, mark the Fe Kα-line and enter the result in the left-hand side of the energy
calibration (e.g., with drag & drop from status line). Then determine the center of the Mo Kα
-line and also enter the result on the left-hand side.
4.2.3 Close the Energy calibration window. The scale of the x-axis is now in keV!
4.3 Measurement of other samples
4.3.1 Replace the sample with the next sample, close all windows, turn on high voltage
and push the F9 button at the computer to start a new measurement.
Repeat the measurements for other remaining known (marked) samples.
Measure the characteristic energy for unknown samples and try to identify the elements the
samples contain.
4.4 Evaluation
As the atomic number Z increases the energy of the characteristic lines also increases and so does
the separation between the α- and the β- component in the K spectral series. For a quantitative
analysis, the energies of the individual Kα -line can be determined. Click on top of the lines to
determine the energy and read the energy of the peak positions from the status line and enter them
together with the atomic numbers Z of the different metals.
Make a diagram by using Excel for the energies E  Z −1 2 , i.e. the x-ray energy as a function of
the square the effective charge. Add a linear regression line with the equation for the regression line
to the graph.
4.5 Investigation of the unknown samples
Your task is to find out what elements the other samples are made from. Look for L- or M- lines
when you suspect heavy elements.

4.6 Examination
You are expected to work in groups of two students, to be prepared and be present in the laboratory
at your allocated time. You have to print out the instructions and read the instructions before going
to the lab. Bring your own copy of the instructions with you.

You have to make a short oral presentation of your experiment and of the results of your laboration
on x-ray spectroscopy. This presentation you will present at the allocated time the day after your
lab. You do your presentation together with your group partner.

Your report has to contain the answer to the following questions:

How does the energy of the measured emission lines correspond to what you get from energy
tables? Specify the amount of deviation. Why is it necessary to use the screening constant σ in the
calculation of the energy of the characteristic radiation? Have you verified Moseley’s law with your
measurement and calculation? What are the elements you detected in your unknown sample, and
how did you establish this?

You have to hand in your presentation in electronic form by uploading it in pdf format to your
folder in the Studentportalen. Each student has to upload his/her material into her/his personal
folder. The name of the file has to be the same as yours and your lab-partner's name, e.g.,
Anna_Sevedsson_Hezekiel_Hansson.pdf could do.

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 Sensor

Target

Figure 1: Sample compartment with x-ray detector.

Figure 2: Control panel.