X-ray diffraction (XRD)

It is the experimental method for the determination of the atomic and molecular structure of a crystal. By
measuring the angles and intensities of the diffracted X-ray beams, a three-dimensional picture of the
density of electrons within the crystal can be derived. From this electron density, the mean positions of
the atoms in the crystal and the types of their chemical bonds can be obtained.

Interference is a phenomenon in which two waves superpose to form a resultant wave of greater, lower,
or the same amplitude.

Constructive interference: If two waves are in phase (their maxima and minima occur at exactly the
same positions), the waves will interfere with one another and their amplitudes will add together to
produce a resultant wave that has higher amplitude.

Destructive interference: If the waves are out of phase, being off by a non-integer number of
wavelengths, then destructive interference will occur and the amplitude of the waves will be reduced. In
an extreme case, if the waves are out of phase by an odd multiple of ½ λ, the resultant wave will have no
amplitude and thus be completely destroyed.

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Crystals are regular arrays of atoms. The electron cloud of each atom scatters X-ray waves producing
spherical waves. Although these waves cancel one another out in most directions through destructive
interference, they add constructively in a few specific directions, determined by Bragg's law:

Where d is the distance between atomic layers in a crystal,  is the wavelength of the incident X-ray
beam; n is an integer and ϑ is the incident angle.

The lower ray travels an extra path as compared to the upper ray.
The path difference between them = 2d sin

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Basics of crystallography

Unit cell: the smallest repeating unit having the full symmetry of the crystal structure.

Seven crystal systems

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Diffraction peak appears when the plane normal [hkl] is parallel to the diffraction vector (s)
– Plane normal [hkl]: the direction perpendicular to a plane of atoms
– Diffraction vector (s): the vector that bisects the angle between the incident and diffracted beam

Indexing directions (plane normal) and planes

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Generation of X-rays
X-rays are produced generally by either synchrotron radiation or x-ray tubes.

Synchrotron radiation is the electromagnetic radiation emitted when charged particles travel in curved
paths. Electrons or positrons travelling at near light speed in a circular storage ring emit thousands to
millions of times more intense X-ray radiation than laboratory x-ray tubes.

X-ray tube is evacuated electron tube that produces X rays by accelerating electrons to a high velocity
with a high-voltage field and causing them to collide with a target, the anode plate.

If the bombarding electrons have sufficient energy, they can knock an electron out of an inner shell of the
target metal atoms. Then, electrons from higher states drop down to fill the vacancy emitting x-ray
photons with precise energies determined by the electron energy levels. These x-rays are called
characteristic x-rays. The anode material determines the wavelengths of characteristic radiation. X-rays
exit the tube through X-ray transparent beryllium windows. Optics are used to limit divergence of the X-
ray beam and to remove unwanted wavelengths.

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 X-rays are produced when the electrons are
suddenly decelerated upon collision with the
metal target. These x-rays are commonly
called brehmsstrahlung or "braking radiation".
When the energy of the bombarding electrons
is high enough, the radiation is in the x-ray
region of the electromagnetic spectrum. It is
characterized by a continuous distribution of
radiation energy which becomes more intense
and shifts toward higher frequencies when the
energy of the bombarding electrons is
increased. The curves above originate from the
bombardment of tungsten target with electrons
of four different energies.

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X-ray Single Crystal Diffraction
Used to determine:
 crystal structure
 orientation
 degree of crystalline perfection

Sample is illuminated with monochromatic radiation. Sample is rotated to bring different planes into
diffracting condition. Diffraction spots are produced in a sphere around the crystal. The distribution of
diffraction spots is dependent on the crystal structure and the orientation of the crystal in the
diffractometer. It is easier to determine the crystal structure because the diffraction peaks are uniquely
resolved.

X-rays are used to produce the diffraction pattern because their wavelength λ is typically the same order
of magnitude (0.1–10 nm) as the spacing (d) between planes in the crystal. The atomic nuclei, which are
much heavier than an electron, contribute negligibly to the scattered X-rays.

1. The first-and often most difficult-step is to obtain an adequate crystal of the material under study. The
crystal should be sufficiently large (typically larger than 0.1 mm in all dimensions), pure in composition
and regular in structure, with no significant internal imperfections such as cracks or twinning. The precise
position of each atom in a molecule can only be determined if the compound is crystallized.

2. The crystal is placed in an intense beam of X-rays, usually of a single wavelength (monochromatic X-
rays), producing the regular pattern of reflections. As the crystal is gradually rotated, previous reflections
disappear and new ones appear; the intensity of every spot is recorded at every orientation of the crystal.

3. The integrated intensities of the diffraction peaks are used to reconstruct the electron density map
within the unit cell in the crystal. (Unit cell is the smallest repeating unit having the full symmetry of the
crystal structure.) The data is then processed by a computer to refine a model of the arrangement of atoms
within the crystal and the structure of the molecule is visualized.

Powder diffraction data consists of a record of photon intensity versus detector angle 2θ.

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X-ray Powder Diffraction (XRPD)
A powder is a polycrystalline material in which there are all possible orientations of the crystals so that
similar planes in different crystals will scatter in different directions. 0.1m < particle size < 40 m
All possible diffraction peaks can be observed in a measurement.
Assumptions:
Every diffraction peak is the product of X-rays scattering from an equal number of crystallites
There are statistically relevant number of crystallites.
Inefficient method:
A small fraction of the crystallites in the sample contributes to the measured diffraction pattern

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Every crystalline substance produces a unique diffraction pattern, which is a fingerprint of the material.

Phases with the same chemical composition can have drastically different diffraction patterns. The three
crystalline form of TiO2 (anatase, brookite and rutile) can be distinguished.

In polycrystalline materials each phase produces its pattern independently of the others. The diffraction
pattern of a mixture is a simple sum of the scattering from each component.

X-ray diffraction analysis is thus ideally suited for characterization and identification of various phases.

The relative amounts of phases cannot be determined based only on the relative intensities of the
diffraction peaks because various materials diffract X-rays with different efficiency. Proper calibration is
needed.

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Effect of lattice strain: uniform strain causes peak shift but no change in peak shape,
non-uniform strain results in peak broadening

Crystallite size smaller than ~120 nm also creates broadening of diffraction peaks, which can be used to
quantify the average crystallite size of nanoparticles.

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