X-ray Diffraction
atomic spacing to produce interference, and hence
X-ray diffraction has acted as the cornerstone of
twentieth-century science. Its development has cata-
lyzed the developments of all of the rest of solid-state
science and much of our understanding of chemical
bonding. X-ray powder diffraction (XRPD) plays a
critical role in materials research and development
because many materials and minerals are not readily
available in single-crystal form. Some 10 000–20 000
powder diffractometers are in use worldwide, and of
the order of 160 000 powder patterns are available in
the Powder Diffraction File (PDF) electronic data-
base. Although the technique is termed ‘‘powder
diffraction,’’ any polycrystalline specimen may be
studied using the technique, including mono-
lithic solids, thin films, and powders. Among the
applications of powder diffraction are:
$ Qualitative identification of the phases present in
a specimen using the powder pattern as a ‘‘fingerprint’’
of the phase which may be compared to known powder
patterns stored in a database.
$ Quantitative analysis of the concentrations of
each phase present in a multiphase specimen can be
carried out.
$ The unit cell metrics, i.e., the size and shape of the
unit cell, of any crystalline material can be determined,
and then refined to very high accuracy. Because the
lattice parameters of a material change with chemical
composition, XRPD finds widespread use in solid
solution analysis, phase diagram work, and for
measuring the true density of materials.
$ Full orientation distribution functions that de-
scribe the crystallite orientation in polycrystalline
materials can be determined.
$ Residual and applied stress can be determined
by measuring the strain present in the crystallites
composing a monolithic body.
$ Microstructural features of a polycrystalline
material including the crystallite size, microstrain
within crystallites, and defect densities may be
determined.
$ In situ techniques under controlled gaseous
atmosphere, temperature, pressure, field, and mech-
anical loading provide a means of determining phase
diagrams and reaction kinetics, and provide a means
of tracking changes in materials during synthesis and
processing.
$ Full structure solution from powders.
The applications listed above are strictly for poly-
crystalline materials. It is important to note, however,
that powder diffractometers may be equipped to study
thin films using x-ray reflectivity and high-resolution
diffraction.
1. Origins of X-ray Powder Patterns
X rays are relatively short wavelength, high-energy
electromagnetic radiation. Diffraction experiments
require x-ray wavelengths of the order of the inter-
typical wavelength ranges are 0.07–0.2 nm. The most
common radiation used in the laboratory is Cu Kα
radiation with λ l 0.15406 nm.
A typical x-ray powder diffraction pattern is shown
in Fig. 1 and consists of diffraction peaks, or ‘‘lines,’’
as a function of the diffraction angle, 2θ. Diffraction
occurs when waves scattering from an object con-
structively and destructively interfere with each other.
The diffraction peaks in Fig. 1 are a result of con-
structive interference of waves scattered from the
atoms or ions composing a crystal. M. von Laue in
1912 first determined that x rays diffract from the peri-
odic arrangement of atoms in a crystal, exactly analo-
gous to the diffraction of visible light from a grating.
Based on the work of von Laue, W. H. and W. L.
Bragg showed in 1913 that diffraction from a crystal is
described by the equation now known as Bragg’s law:
λ l 2dhkt sin θ (1)
This equation allows one to measure the perpendicular
distance (dhkl) between imaginary planes which form
parallel families and which intersect the repeating unit
cell filled with atoms in a way described by the Miller
indices (hkl ). X rays of wavelength λ may be thought
of as reflecting from these imaginary planes at the
measurable angle θ, where θ is one-half of the
diffraction angle as shown in Fig. 1. A powder pattern
therefore contains a set of diffraction peaks at 2θ
positions that correspond to the interplanar spacings
in the crystal. Although dhkl may be calculated for any
set of (hkl ) planes in any unit cell using geometry, the
interplanar spacings are most easily calculated in
reciprocal space. P. P. Ewald developed what is by far
the most useful method for describing diffraction
phenomena using reciprocal space.
Ewald in 1913 showed that a reciprocal lattice can
be constructed by using the reciprocals of all of the
distances in a real unit cell. The reciprocal lattice has
the same symmetry as the real crystal lattice, but the
points in the reciprocal lattice are equally spaced and
hence simple to manipulate. In an orthogonal lattice
(cubic, tetragonal, orthorhombic), all distances are the
reciprocals of the real space distances. a*, b*, and c*
are the reciprocal lattice parameters, while the inter-
axial angles are α*, β*, and γ*, where the reciprocal of
an angle is defined as the complement or 180m minus
the angle. Likewise, the reciprocal of dhkl is d*hkl. In the
nonorthogonal systems, one must account for the
interaxial angles when calculating the reciprocal lattice
parameters.
The convenience of using reciprocal space is demon-
strated when calculating the d*hkl values. Since the
length of d*hkl is simply related to the real space d-
spacing, one simply uses the d*hkl# equation:
# l h#a*#jk#b*#jl #c*#j2hka*b* cos γ*
d*hkl
j2hla*c* cos β*j2kl b*c*cosα* (2)