Fachbereich SciTec

Lab Course Instruction Präzision - Optik - Materialien - Umwelt

Lab Course Physical Materials Diagnostics

X - Ray Powder Diffraction

1. Introduction

The main task of the experiment is the qualitative characterization of unknown

crystalline samples using X-ray diffraction (XRD). The experiments will be performed
on two Bruker D8 diffractometers with different setups. The experiments start with a
sample preparation followed by diffraction measurements. The measured data will be
evaluated based on a database of crystalline materials. The influence of
measurements conditions and sample properties will be studied as well.

2. Basics
2.1. Crystallography

In the experiment: “Crystal Structures & Simulation of Microstructure Analysis

by X-Ray Diffraction” an introduction to the description of crystalline materials is given
already. For the further discussion, some additional information of the
crystallographic classification will be given here. The 14 Bravais lattices represent the
14 possible ways to fill the three-dimensional space with a periodic arrangement of
points fulfilling a translational symmetry. The 14 Bravais lattices can be distinguished
from each other by their different symmetry properties like for example rotation axis.
Combining any possible symmetry of motifs with the 14 Bravais lattices result in 230
space groups. These 230 space groups represent all possible crystal symmetries
fulfilling the requirement of translational symmetry.

2.2. Introduction to X-ray Diffraction

X-ray diffraction is a non-destructive technique to analyse mainly crystalline solids.

However, the method can also be utilized to study amorphous or liquid materials. In
case of X-ray diffraction the wave character of photons is utilized to extract primarily
crystallographic information which can be used to conclude on a number of physical
properties.

2.3. X-ray Tubes & X-ray Emission

X-rays are produced when high speed electrons are decelerated by interaction within
solid matter. Thus to generate X - rays we need:

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 • a source of electrons
• a possibility to accelerate the emitted electrons
• a target to decelerate the electrons to create X-rays

The device for generating X - rays is called an X - ray tube, see figure 2. The
electrons are produced by an electrically heated tungsten filament. The electrons are
accelerated towards the target by applying a large potential difference (voltage)
between the filament and the target.

Figure 1: Schematic cross section of an X - ray tube

The electrons hitting the target(anode) transfer their kinetic by scattering processes.
The transferred energy can excite the solid in various ways, in majority: (i) increase of
temperature (lattice vibrations - phonons); (ii) emission of radiation with different
energies; (iii) inner shell ionization of atoms. The emission of radiation with different
energies results in a continuous spectrum of X-ray radiation, often called as
“Bremsstrahlung” (the German word “Bremsstrahlung” can be translated as “radiation
by braking”). The inner shell ionization of atoms is the starting point for the emission
of characteristic radiation. The inner shell electron vacancy can be filled by another
electron from an electron level higher in energy. The released energy is used up by
the emission of a photon with an energy which is equal to the energy difference
between the two involved electron levels. This type of radiation is known as
characteristic radiation.
Figure 2 displays the typical resulting X-ray spectrum. In the example two sharp
peaks (characteristic radiation) are superimposed on the background radiation
(Bremsstrahlung).

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 Figure 1:
X - ray spectrum of Molybdenum showing Kα and Kβ lines
superimposed by the continuous spectrum. The
wavelengths of the lines are characteristic of the target
element (here Mo)

2.4. X-Ray Diffraction

The interaction of incident X - ray beam with atoms (for example in solids) results in
the scattering of the X-rays. In case of elastic scattering processes (wave length is
not changed) then interference phenomena may occur. The result is a spatial
modulation of the intensity of the scattered radiation. An illustrative representation of
the results of the kinematic scattering theory for ordered arrangements of atoms is
Bragg’s law (Fig 4).

Fig 4:
Illustration of Braggs’s law

2 ⋅ d hkl ⋅ sin θ hkl = n ⋅ λ

The parameter - the lattice spacing - is the distance between a family of planes
with the same Miller index; is the wave length of the X-rays; is the
corresponding diffraction angle and is the order of diffraction. The fulfilment of
Bragg’s law within the experimental parameters is a geometrical prerequisite for the
observation of an interference maximum showing up as maximum intensity.
However, the law gives no information on the absolute value of the intensity which
can be expected for a certain family of planes. The intensity is determined by a

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number of factors from the experimental setup but also by materials properties itself.
The most prominent factor is the structure factor, which summarizes the influence of
the inner structure (motif) of a crystalline lattice. Starting from Bragg’s law it is
possible to discuss different experimental setups using the relationship, for example:
determination of wavelength ( , known) or determination of ( , known).
The most common setup of an X-ray diffraction experiment is the determination of
different lattice spacings for an unknown sample based on the measurement of the
scattered intensity versus diffraction angle at a fixed wavelength .
The measurement result is plotted in a graph where the x-axis is 2 and the y-axis is
the corresponding measured intensity. This figure is called diffractogram or diffraction
pattern. An example for a two-phase material is given in figure 5. The coloured dots
assign the intensity maxima (diffraction peaks) found to -values of the respective
phases.

Figure 5: XRD - pattern of a mixture of two crystalline phases

The assignment of the diffraction peaks to a certain material is typically done using a
data base with crystal structure data of solids. Common software packages include
control procedures for the measurement itself but also search instruments to index
the measured diffraction pattern. The most comprehensive data base is the PDF
(Powder Diffraction File) published by the ICDD (International Centre for Diffraction
Data). The data for a crystalline phase are summarized in a data set (PDF card –
historically it was indeed a card with data) including mainly the following data:
• PDF number
• Interplanar spacings and relative intensities of the corresponding reflexes
• Chemical formula
• Chemical name and mineralogical name

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 • Unit cell data (lattice constants & angles; Bravais lattice, space group)
• Quality mark & experimental conditions

Besides the determination of the crystalline structure, hence, the determination of

unknown solids further information can be obtained from the diffractogram. The
detailed evaluation of the peak shape as well as eventual shifts of their expected
position vs. 2θ can be used to get more insight to the real structure of the material
(Fig. 6). A lot of application techniques for various material classes are available,
each reveals its own specific details of the studied sample.

Figure 6: Overview on available information in a powder diffraction pattern

2.5. Methods of X-Ray Diffraction

This chapter describes selected setups and evaluation methods applied in the lab
course.

2.5.1. Bragg-Brentano Geometry

This geometry is dedicated mainly for the analysis of powders and for polycrystalline
bulk samples. The main idea of this geometry is a symmetric alignment of the X-ray
source and detector with respect to the sample (Fig. 7). This geometry is realized by
placing the sample in the middle of a circle – called diffractometer circle – and
situating the detector and the X-ray tube on the circumference of the circle. The
advantage of this geometry is its self-focusing property. The slightly divergent X-ray

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beam (point source on the circumference) is scattered at the sample and all partial
beams fulfilling the Bragg equation are focused back to one point on the
diffractometer circle. In this way the influence of the beam divergence on the
accuracy of the measurement of the scattering angle θ is minimized.
The change of the scattering angle θ is realized either by a movement of the sample
with θ combined with a detector movement of 2θ at the same time (θ-2θ-goniometer)
or by a fixed sample and moving tube and detector, each with θ (θ-θ-goniometer). It
need to be mentioned that in Bragg Brentano only those lattice planes contribute to
the observed intensity which are aligned parallel to the sample surface.

Figure 7: Schematic of X - ray diffractometer with Bragg-Brentano geometry [1]

A compromise has to be taken between a good resolution and a short measuring

time. The following parameters have a rough influence on the resulting diffractogram:

Divergence of the beam

The reduction of beam divergences could be done by apertures or by an
arrangement of parallel metal plates (Soller slit). An example of a combination of a
Soller slit and a slit aperture on the primary side is shown in figure 8 below. To limit
the lateral divergence of the primary beam to values below 1°, a fixed aperture is
used with a typical slit width of about 0.6 mm. This aperture influences the illuminated
area of the sample. Furthermore, the systematic error of the determination of θ is
influenced. Both, the illuminated area as well as the measurement error increases
with increasing aperture width.

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Figure 8: Example for X-ray beam optics [2]

To reduce the axial divergence a Soller slit can be inserted in the beam. The distance
of one plate to the next one is around ten times of the thickness of one plate. The
ratio of the length of a plate and the distance reduce the divergence to around ± 2.5°.
The application of the Soller slit is accompanied by a certain intensity loss, however,
the accuracy within θ will be improved further, resulting in an increased height/width
ratio of the observed diffraction peaks.
A further element improving the measurement results is a monochromator (in fig. 10
implemented on the secondary side). The usage of a curved crystal results in a
second focusing condition which is fulfilled only by Cu Kα lines and beam parts with a
certain limitation of the divergence.

Goniometer - circle:
The distance R of the sample to the tube and the detector entry slit is typical around
30 cm. With decreasing R the resolution turns worse, but the intensity will be
increased.

Detector slit:
It should be as small as possible, but if the slit gets too small, the intensity decreases
further without a change in the resolution.

Sample holder:
The sample can be fixed or rotating. The rotation can improve the statistics of the
measurement. The size of the sample should be in the range of the illuminated area
or larger to avoid diffraction peaks from the sample holder.

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2.5.2. Grazing Incidence Diffraction

This setup is used for the analysis of polycrystalline thin films. In case of grazing
incidence diffraction the incoming beam is running nearly parallel to the sample
surface. The angle between the surface and the beam is typically chosen below 3°.
This angle is kept constant throughout the experiment, only the detector is moving,
refer to figure 9.

substrate

Figure 9: Principle of diffraction in the grazing incidence setup

Because the beam is incident at a small angle, the penetration depth of the beam is
limited to within about 100 nm of the sample surface. The illuminated volume is thus
concentrated to a volume covering a large surface area multiplied by a rather small
depth. Therefore the method is especially suitable for the analysis of thin films. It
needs to be mentioned that in this measurement geometry the normal of lattice
planes contributing to the diffracted intensity change their direction during the
variation of 2θ.

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3. Questions for Preparation of the XRD lab (self study)

3.1. What is the typical range of X-ray wavelengths?

3.2. What is a typical range of atomic plane spacings?
3.3. What is varied and measured in a typical diffraction experiment?
3.4. What are the main parts of an X-ray tube?
3.5. Which beam forming elements do you know?
3.6. What is Bragg’s law?
3.7. How the lattice plane distance for planes is calculated for a cubic crystal
lattice with the lattice constant a?
3.8. What means Bragg-Brentano geometry?
3.9. For which samples grazing incidence diffraction is used?

4. Ressources

Lecture “Physical Materials Analysis”; files in the download area for the lab course

Image Sources:

[1] http://pubs.usgs.gov/of/2001/of01-041/htmldocs/images/xrdschem.jpg
[2] Modified from http://pubs.usgs.gov/of/2001/of01-041/htmldocs/images/xraydiff.jpg
[3] L. Spieß et al.: Moderne Röntgenbeugung.