Single crystal X-ray diffraction

Zsolt Kovács

based on the Hungarian version of the Laue lab description which was written by
Levente Balogh, Jenő Gubicza and Lehel Zsoldos

INTRODUCTION

X-ray diffraction is a key and diverse test method used in all aspects of the modern natural sciences.
Different X-ray diffraction methods exist for the investigation of crystalline and amorphous solids,
liquids and gases. X-ray diffraction procedures are used in the case of crystalline materials for both
polycrystalline and single crystal samples, however the methods used in these two groups are
significantly different. In polycrystalline or powder diffraction, a monochromatic X-ray beam interacts
with large number of crystallites with different spatial orientation. Therefore, quite a lot of crystal
orientation meet with the conditions of diffraction and several diffraction maxima (reflections) become
measurable. The powder diffraction techniques can be effectively used in the following cases:
• (I) Phase analysis: identification one or more crystalline phases from polycrystalline or
powdered sample.
• (II) Determination of lattice parameters: very accurate lattice parameters of a known crystal
structure is measured.
• (III) Microstructure examination: diffraction line shape (line profile analysis) of polycrystalline
sample is determined to determine crystallite size distribution and type of crystal defects in the
sample.
The powder diffraction methods maybe used for the determination of unknown crystal structures (e.g.
Rietveld methods), but they are not so effective as single crystal diffraction methods.

Single crystals diffraction methods are suitable for single crystal samples in which the crystalline order
of the atoms does not change in the whole tested volume of the material. For example, crystal
microdiffraction is also single crystal diffraction method, if the beam size is smaller than the crystallite
size and only one crystallite is illuminated simultaneously.
The single-crystal diffraction techniques can be effectively used in the following cases:
• (I) Structure determination when an unknown structure or atoms arrangement of a single crystal
to be determined. Nowadays, this method is used intensively for structure determination of
proteins. Whereas, the unknown structure of crystallized protein is determined very precisely
from X-ray diffraction allowing the determination of atomic structure of the protein molecule
itself.
• (II) Determination of lattice defects in single crystal. (Crystals often contain lattice defects due
to crystal preparation or deformation.) The amount and type of the dislocations in a single
crystal can be determined from the shape of the diffraction peaks.
• (III) Determination of the orientation of single crystals, i.e. the orientation of the
crystallographic axes of a single crystal in the coordinate system of the lab. This method is
useful when the single crystal is to be machined or cut parallel to particular crystal planes.
Completion of lattice defect analysis (test II) also requires the knowledge of crystal orientation.

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In the following description and also in the laboratory experiment, we will deal with the details of the
orientation determination method for single crystals by the Laue method.

DESCRIPTION OF THE THEORY OF LAUE METHOD

The Laue diffraction methods was the first developed single crystals diffraction method. Additionally, it
is the simplest and most famous single crystals examination procedure, which is commonly used for
crystals orientation determination. The method leads to about 1 deg accuracy using relative simple
measurement setups. In Laue diffraction, a thin sample is illuminated by a few tenths of a millimeter
diameter continuous spectrum X-ray beam and the diffraction image is recorded onto a planar or
cylindrical surface with film, imaging plate or CCD detector. In the lab tests an imaging plate detector
will be used.
Mostly, the recording media has a planar surface and it is perpendicular to the primary beam. If the
surface is placed in the 2θ <90° range, the detector is in front reflection position (Figure 1), and if it is
in the 2θ> 90° range, the detector is in rear reflexion position. Due to the continuous X-ray spectrum,
all crystal plane (with adequate crystal plane distance) have a specific λ wavelength components, which
meets with the conditions of the Bragg's equation [1],

2d hkl sin (θhkl )=λ (1)

where hkl are the Miller indices for a given crystal plane, dhkl is the corresponding distance of the
crystal planes and θ is a fix Bragg angle determined by the setup. Therefore, the different hkl planes
reflect sharp intensity maxima in different directions with the matchinh λ wavelengths.

Figure 1: The Laue-geometry. S - indicates the sample. (arrows indicate only the direction of the
different vectors).

The normal direction of the reflecting planes (this is the g diffraction vector) can be determined from
the directions of reflections and that of the the primary beam as shown in Figure 1. The Bragg equation
can be reformulated to reflect the relationship between the g diffraction vector and the primary beams
and the scattered k0 and k wave vectors,

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 k −k 0=g . (2)

Based on Eq 2., the vector g is in the plane which is spanned by k and k0 vectors. A characteristic
feature of Laue image is that if the crystal along an axis of symmetry is illuminated the Laue pattern of
the diffraction image will show this symmetry, as shown in Figure 2.

Figure 2: Laue image of a quartz single crystal. The incident beam is parallel to the c axis of the
hexagonal crystal, so that diffraction image has a three fold symmetry.

Therefore, directions of the symmetry axis can be recognized without further investigation, even
without the knowledge of parameters of the crystal unit cell.
The crystal planes, which are parallel to a common direction form a zone. The common
direction of the planes is called zone axis (see Figure 3a). The vector of the zone axis, Auvw, can be
expressed as a linear combination of the vectors of the unit cell,

Auvw=ua 1+ va 2 +wa 3 , (3)

where u, v and w are integers and a1, a2 and a3 are the vectors of the unit cell. An hkl plane is parallel to
the axis if Auvw vector of the zone axis is normal to the Hhkl vector of the plane, so that scalar product of
the zone axis and the vector of the plane is zero,

Auvw H hkl =0 , (4)

From the theory of diffraction we know that the ghkl diffraction vector of a hkl plane is parallel to the
normal vector of the reflecting plane. Thus, these reflections belongs to a zone,

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 Auvw g hkl =0 , (5)

where

g hkl =hb1 +kb 2 +lb 3 , (6)

and b1, b2 and b3 are the vectors of the reciprocal lattice. Because the vectors of the crystal's unit cell
and the vectors of the reciprocal lattice are defined to meet the aibj=δij relationship, the zone law can be
calculated from Eq. 3, Eq. 6 and Eq 5,

hu +kv + lw=0 , (7)

(a) (b)

Figure 3: (a) The Auvw zone axis and schematic hkl planes of the given zone. The Hhkl is the normal
vector of the planes and it is normal to the zone axis. (b) The planes belongs to a common zone axis
reflect radiation along a cone.

Let s and s0 are the unit vectors of incident and the reflected beams on a particular hkl plane,
respectively. They are λ times the k and k0 vectors. From the Bragg's equation of Eq. 2

s−s0 =λ g hlk , (8)

Let multiply both side of Eq. 8 by the zone axis vector, Auvw,

sAuvw −s 0 Auvw =λ g hlk Auvw . (9)

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 (a) (b)

Figure 4: (a) Laue image of an aluminum oxide single crystal in front position. (b) Laue image of
silicon single crystal rear position.

If we select hlk planes from a uvw zone, than the rhs. of Eq. 9 will be zero based on Eq. 5. This means
that the angle between the direction of the incident beam and the zone axis equal to the angle between
the direction of the reflected beam and the zone axis for all the hlk planes of a selected uvw zone,

sAuvw=s 0 Auvw , (10)

Therefore, the s reflection vectors which are related to planes of a given zone axis are placed along a
cone with φ0 half angle (see Fig 3b) and the intensity maxima recorded onto a plane are placed along
cone-sections. These cone-sections are ellipses in the front reflection position while they are hyperbolas
in the rear reflection positions (see in Figures 4a and 4b).

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SHORT DESCRIPTION OF THE EXPERIMENTAL PROCEDURE TO BE PERFORMED IN THE
LAUE LAB

1. Single crystal samples will be selected for orientation determination (students can also bring
their samples).
2. Sample will be attached to an adequate goniometer to position and rotate the single crystal
samples in the Laue diffractometer.
3. Laue diffraction image will be captured in the diffractometer using imaging plates and it will be
recorded and digitalized by an imaging plate reader.
4. Laue diffraction image will be analyzed and orientation of the crystal sample will be determined
by using unit cell parameters of the crystal and the experimental parameters in a specific
program.
5. Crystal orientation will be presented in an stereographic projection and rotation angles between
the calculated orientation and a selected crystal orientation will be determined.

Please, know and understand, the following expressions when you participate in the Laue Lab:
Bragg-equation, unit cell and unit cell parameters, stereographic projection, zone axis, Miller-indices