Theory of X-ray Structure

Determination
By
Dr HH. Mungondori
 X-Ray
• An electromagnetic wave of high energy and very short wavelength (between ultraviolet light and gamma
rays), which is able to pass through many materials opaque to light.

• Most X-rays have a wavelength ranging from 0.01 to 10 nanometers, corresponding to frequencies in the range 30
petahertz to 30 exahertz (3×1016 Hz to 3×1019 Hz) and energies in the range 100 eV to 100 keV.
 Diffraction
• The process by which a beam of light or other system of waves is spread out as a result of passing
through a narrow aperture or across an edge, typically accompanied by interference between the
wave forms produced.
 X Ray Diffraction
• A technique used to determine the atomic and molecular structure of a crystal, in which the crystalline
atoms cause a beam of incident X-rays to diffract into many specific directions.
• The atomic planes of a crystal cause an incident beam of X-rays to interfere with one another as they
leave the crystal. The phenomenon is called X-ray diffraction.
• A stream of X-rays directed at a crystal diffract and scatter as they encounter atoms. The scattered rays
interfere with each other and produce spots of different intensities that can be recorded on film.

• “ Every crystalline substance gives a pattern; the same substance always gives the same pattern; and
in a mixture of substances each produces its pattern independently of the others”
• The X-ray diffraction pattern of a pure substance is, therefore, like a fingerprint of the substance.
X-rays production process
• The X-rays which are used in almost all laboratory-based diffraction experiments are produced by a
process that leads to monochromatic X-rays.
• A beam of electrons, accelerated through, say, 30 kV, is allowed to strike a metal target, often Cu.
• The incident electrons have sufficient energy to ionise some of the Cu 1s (K shell) electrons.
• An electron in an outer orbital (2p or 3p) immediately drops down to occupy the vacant 1s level and
the energy released in the transition appears as X-radiation.
• The transition energies have fixed values and so a spectrum of characteristic X-rays results.

Kα1
Kα2
White radiation
Kβ
Cut
off

Wavelength (Ȧ)

• For Cu, the 2p→1s transition, called Kα, has a wavelength of 1.5418 Ȧ and the 3p→1s transition,
Kβ, 1.3922 Ȧ.
• The Kα transition occurs much more frequently than the Kβ transition and the more intense Kα
radiation that is produced is used in diffraction experiments.
• In fact, the Kα radiation is a doublet, Kα1=1.54051 Ȧ and Kα2 =1.54433 Ȧ, because the 2p→1s
transition has a slightly different energy for the two possible spin states of the 2p electron which
makes the transition, relative to the spin of the vacant 1s orbital.
Interaction of X-rays with matter

• X-rays can interact with matter in two general ways: by scattering and by absorption.
• If there is no loss of energy on scattering, the scattered X-rays are coherent with the incident X-rays
and these are used for X-ray diffraction experiments.
• Scattered X-rays may also lose some of their energy, in which case they are incoherent and of
longer wavelength than the incident X-rays.
• Incoherent scattering, also known as Compton scattering, is generally a nuisance and contributes to
the background scattering in diffraction patterns.
• X-rays may also be absorbed by matter, leading either to ionisation of electrons or to promotion of
electrons to higher, unoccupied energy levels.
• The latter process generates atoms in excited states, which can then return to their ground state
accompanied by emission of radiation of appropriate energy.
• This energy may also be in the X-ray region when the electrons are ionised from inner shell levels;
the process is known generally as fluorescence.
Essential Parts of the Diffractometer
• X-ray Tube: the source of X Rays
• Incident-beam optics: condition the X-ray beam before it hits the
sample
• The goniometer: the platform that holds and moves the sample,
optics, detector, and/or tube
• The sample & sample holder
• Receiving-side optics: condition the X-ray beam after it has
encountered the sample
• Detector: count the number of X-rays scattered by the sample
Experimental Setup

Source: http://pruffle.mit.edu/atomiccontrol/education/xray/xray_diff.php
 How Does It Work

Crystal (regular array of atoms) is

mounted on a Goniometer
Source: http://en.wikipedia.org/wiki/File:X_ray_diffraction.png

Bombarded with X-Ray while

rotating

Production of diffraction pattern

of regularly spaced spots

The 2-D images taken at different

rotation are converted to 3-D
models of the electron density map
by the method of Fourier
Transform
Bragg’s law
• Bragg’s law is a simplistic model to understand what conditions are required for diffraction.
• The Bragg approach to diffraction is to regard crystals as built up in layers or planes such that each acts
as a semi-transparent mirror.
• Some of the X-rays are reflected off a plane with an angle of reflection equal to the angle of incidence, but
the rest are transmitted to be subsequently reflected by succeeding planes.
• The derivation of Bragg’s law is shown in the Figure below. Two X-ray beams, 1 and 2, are reflected from
adjacent planes, A and B, within the crystal and we wish to know under what conditions the reflected
beams 1 and 2 are in-phase.
• Beam 22 has to travel an extra distance xyz compared with beam 11 ; for 1 and 2 to be in-phase, the
distance xyz must equal a whole number of wavelengths.
• The perpendicular distance between pairs of adjacent planes, the d-spacing, d, and the angle of
incidence, or Bragg angle, θ , are related to the distance xy by
• xy = yz = d sin θ
•
• Hence, xyz = 2d sin θ
• However, xyz = nλ
• and therefore 2d sinθ = nλ: Bragg’s law
• When Bragg’s law is satisfied, the reflected beams are in-phase and interfere constructively.
• At angles of incidence other than the Bragg angle, reflected beams are out-of-phase and destructive
interference or cancellation occurs.
 l  2d hkl sin q q q

dhkl dhkl
• For parallel planes of atoms, with a space dhkl between the planes, constructive
interference only occurs when Bragg’s law is satisfied.
– In our diffractometers, the X-ray wavelength l is fixed.
– Consequently, a family of planes produces a diffraction peak only at a specific angle q.
– Additionally, the plane normal must be parallel to the diffraction vector
• Plane normal: the direction perpendicular to a plane of atoms
• Diffraction vector: the vector that bisects the angle between the incident and diffracted beam
• The space between diffracting planes of atoms determines peak positions.
• The peak intensity is determined by what atoms are in the diffracting plane.
X-ray Diffraction Methods
• When reduced to basic essentials, the X-ray diffraction experiment, requires an X-ray source, the
sample under investigation and a detector to pick up the diffracted X-rays.
• Within this broad framework, three variables govern the different X-ray techniques:

(a) radiation – monochromatic or of variable λ;

(b) sample – single crystal, powder or a solid piece;
(c) detector – radiation counter or photographic film.

X-ray diffraction methods are generally used for investigating the internal structures.

• Laue photographic method

• Braggs X-Ray spectrometer
• Rotating crystal method
• Powder method
 Laue photographic method
• In his first experiments, Max von Laue (Nobel Prize in Physics in 1914) used continuous radiation (with all
possible wavelengths) to impact on a stationary crystal.
• With this procedure the crystal generates a set of diffracted beams that show the internal symmetry of the
crystal.
• In these circumstances, and taking into account Bragg's Law, the experimental constants are the interplanar
spacings d and the crystal position referred to the incident beam.
• The variables are the wavelength λ and the integer number n:
nλ = 2dhkl sin θnh,nk,nl

• Thus, the diffraction pattern will contain (for the same spacing d) the diffracted beams corresponding to the
first order of diffraction (n=1) of a certain wavelength, the second order (n=2) of half the wavelength (λ/2), the
third order (n=3) with wavelength λ/3, etc.
• Therefore, the Laue diagram is simply a stereographic projection of the crystal
Laue diagram of a crystal
 What is X-ray Powder Diffraction (XRD)
• X-ray powder diffraction (XRD) is a rapid analytical
technique primarily used for phase identification of a
crystalline material and can provide information on
unit cell dimensions.

• The analyzed material is finely ground, homogenized,

and average bulk composition is determined.
Fundamental Principles of X-ray Powder Diffraction (XRD)

• Max von Laue, in 1912, discovered that crystalline substances act as three-
dimensional diffraction gratings for X-ray wavelengths similar to the spacing of
planes in a crystal lattice.

• X-ray diffraction is now a common technique for the study of crystal structures
and atomic spacing.

• X-ray diffraction is based on constructive interference of monochromatic X-rays

and a crystalline sample.

• These X-rays are generated by a cathode ray tube, filtered to produce

monochromatic radiation, collimated to concentrate, and directed toward the
sample.
• The interaction of the incident rays with the sample produces constructive
interference (and a diffracted ray) when conditions satisfy Bragg's Law (nλ=2d
sin θ).
• This law relates the wavelength of electromagnetic radiation to the diffraction
angle and the lattice spacing in a crystalline sample.

• These diffracted X-rays are then detected, processed and counted.

• By scanning the sample through a range of 2θ angles, all possible diffraction

directions of the lattice should be attained due to the random orientation of the
powdered material.

• Conversion of the diffraction peaks to d-spacings allows identification of the

mineral because each mineral has a set of unique d-spacings.

• Typically, this is achieved by comparison of d-spacings with standard reference

patterns.
• All diffraction methods are based on generation of X-rays in an X-ray tube.

• These X-rays are directed at the sample, and the diffracted rays are collected.

• A key component of all diffraction is the angle between the incident and diffracted rays.

• Powder and single crystal diffraction vary in instrumentation.

Why only x-rays are used?

• Because x-rays have wavelengths of about the same magnitude as the distance between
the atoms or molecules of a crystal.
Applications of XRD
• XRD is a nondestructive technique

• To identify crystalline phases and orientation

• To determine structural properties:

• Lattice parameters, strain, grain size, epitaxy, phase composition, preferred orientation (Laue)
order-disorder transformation, thermal expansion

• To measure thickness of thin films and multi-layers

• To determine atomic arrangement

Applications
• X-ray powder diffraction is most widely used for the identification of unknown
crystalline materials (e.g. minerals, inorganic compounds).

• Determination of unknown solids is critical to studies in geology, environmental

science, material science, engineering and biology.

• Other applications include:

• characterization of crystalline materials

• identification of fine-grained minerals such as clays and mixed layer clays that
are difficult to determine optically

• determination of unit cell dimensions measurement of sample purity

With specialized techniques, XRD can be used to:

• determine crystal structures using Rietveld refinement

• determine of modal amounts of minerals (quantitative analysis)

• make textural measurements, such as the orientation of grains, in a polycrystalline sample

• characterize thin films samples by:

 determining lattice mismatch between film and substrate and to inferring stress and strain

 determining dislocation density and quality of the film by rocking curve measurements

 measuring super-lattices in multilayered epitaxial structures

 determining the thickness, roughness and density of the film using glancing incidence X-ray
reflectivity measurements
Strengths and Limitations of X-ray Powder Diffraction (XRD)?

Strengths

 Powerful and rapid (< 20 min) technique for identification of an unknown mineral

 In most cases, it provides an unambiguous mineral determination

Minimal sample preparation is required

 XRD units are widely available

 Data interpretation is relatively straight forward

Limitations

 Homogeneous and single phase material is best for identification of an unknown

 Must have access to a standard reference file of inorganic compounds (d-spacings, hkls)

 Requires tenths of a gram of material which must be ground into a powder

 For mixed materials, detection limit is ~ 2% of sample

For unit cell determinations, indexing of patterns for non-isometric crystal systems is complicated

 Peak overlay may occur and worsens for high angle 'reflections'