Lecture 3

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X-RAY DIFFRACTION

The Diffraction Phenomenon

Diffraction occurs when a wave encounters a series of regularly spaced obstacles

that (1) are capable of scattering the wave, and (2) have spacings that are comparable in
magnitude to the wavelength. Furthermore, diffraction is a consequence of specific
phase relationships established between two or more waves that have been scattered by
the obstacles.
Consider waves 1 and 2 in Figure 1, which have the same wavelength (λ) and are
in phase at point O – 𝑶′ .

Figure 1: (a) Two waves (1 and 2) that have the same wavelength λ remain in phase
after a scattering event (constructively interfere). (b) Two waves (3 and 4) that have the
same wavelength become out of phase after a scattering event (destructively interfere).

Now, suppose that both waves are scattered in such a way that they traverse
different paths. The phase relationship between the scattered waves, which depends
upon the difference in path length, is important. One possibility results when this path

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length difference is an integral number of wavelengths. As noted in Figure 1(a), these

scattered waves (labelled 1' and 2') are still in phase. They are said to mutually
reinforce or constructively interfere with one another (Figure 2 (a)); when amplitudes
are added, the wave shown on the right side of the figure 1 (a) results. This is a
manifestation of diffraction, and we refer to a diffracted beam as one composed of a
large number of scattered waves that mutually reinforce one another.

Other phase relationships are possible between scattered waves that will not lead
to this mutual reinforcement. The other extreme is that demonstrated in Figure 1(b), in
which the path length difference after scattering is some integral number of half-
wavelengths. The scattered waves are out of phase (Figure 2 (b) - that is,
corresponding amplitudes cancel one another, or destructively interfere (i.e., the
resultant wave has zero amplitude), as indicated on the right side of the figure. Of
course, phase relationships intermediate between these two extremes exist, resulting in
only partial reinforcement.

a b

Figure 2: (a) Reinforcing interactions between x-rays and the crystalline material
(b) Destructive and.

X-Ray Diffraction and Bragg’s Law

X-rays are a form of electromagnetic radiation that have high energies and short
wavelengths (wavelengths on the order of the atomic spacings for solids). When a beam
of x-rays strikes a solid material, a portion of this beam is scattered in all directions.

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Let us now examine the necessary conditions for diffraction of x-rays by a periodic
arrangement of atoms.

Consider the two parallel planes of atoms A–A' and B–B' in Figure 3, which have the
same h, k, and l Miller indices and are separated by the interplanar spacing dhkl.

Figure 3: Diffraction of x-rays by planes of atoms (A–A' and B–B').

Now assume that a parallel, monochromatic, and coherent (in-phase) beam of x-

rays of wavelength λ is incident on these two planes at an angle θ. Two rays in this
beam, labelled 1 and 2, are scattered by atoms P and Q. Constructive interference of the
scattered rays 1' and 2' occurs also at an angle θ to the planes if the path length
difference between 1–P–1' and 2–Q–2' (i.e., SQ + QT) is equal to a whole number, (n),
of wavelengths- that is, the condition for diffraction is

Bragg’s law

The above equation is known as Bragg’s law, where n is the order of reflection, which
may be any integer (1, 2, 3, . . .) consistent with sin θ not exceeding unity. Thus, we
have a simple expression relating the x-ray wavelength and interatomic spacing to the
angle of the diffracted beam. The x-rays are diffracted (the beam is reinforced) when
conditions satisfy Bragg’s law. If Bragg’s law is not satisfied, then the interference will
be nonconstructive so as to yield a very low-intensity diffracted beam.

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Interplanar Spacing

The magnitude of the distance between two adjacent and parallel planes of
atoms (the interplanar spacing dhkl) is a function of the Miller indices (h, k, and l) as
well as the lattice parameter(s). For example, for crystal structures those have cubic
symmetry, in which a is the lattice parameter (unit cell edge length)

The interplanar spacings for non-cubic materials are given by more complex
expressions.

Specific sets of crystallographic planes that do not produce diffracted beams

depend on crystal structure. For the BCC crystal structure, h + k + l must be even if
diffraction is to occur, whereas for FCC structure, h, k, and l must all be either odd or
even; diffracted beams for all sets of crystallographic planes are present for the simple
cubic crystal structure (SC). These restrictions, called reflection rules, are summarized
in Table 1.

Table 1: XRD Reflection Rules and Reflection Indices for BCC, FCC, and SC
structures.

Diffraction Techniques

When the material is prepared in the form of a fine powder, there are always at
least some powder particles (crystals) with planes (hkl) oriented at the proper θ angle to
satisfy Bragg’s law. Therefore, a diffracted beam, making an angle of 2θ with the
incident beam, is produced. In a diffractometer, a moving x-ray detector records the 2θ
angles at which the beam is diffracted, giving a characteristic diffraction pattern as

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shown in Figure 4. If we know the wavelength of the x-rays, we can determine the
interplanar spacings and, eventually, the identity of the planes that cause the diffraction.

Figure 4: (a) Diagram of a diffractometer, showing powder sample, incident and

diffracted beams. (b) The diffraction pattern obtained from a sample of gold powder.

Identification of Crystal Structure

One of the primary uses of x-ray diffractometry is for the determination of

crystal structure. The unit cell size and geometry may be resolved from the angular
positions of the diffraction peaks, whereas the arrangement of atoms within the unit cell
is associated with the relative intensities of these peaks.

To identify the crystal structure of a cubic material, we note the pattern of the
diffracted lines- typically by creating a table of sin2θ values. By combining Bragg’s law
with equation of the interplanar spacing, we find that:

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In simple cubic(SC) metals, all possible planes will diffract, giving an h2 + k2 + l2

pattern of 1, 2, 3, 4, 5, 6, 8, . . . . In BCC metals, diffraction occurs only from planes
having an even h2 + k2 + l2 sum of 2, 4, 6, 8, 10, 12, 14, 16, . . . . For FCC metals, more
destructive interference occurs, and planes having h2 + k2 + l2 sums of 3, 4, 8, 11, 12,
16, . . . will diffract. By calculating the values of sin2θ and then finding the appropriate
pattern, the crystal structure can be determined for metals having one of these simple
structures.

Example:

The results of an x-ray diffraction experiment using x-rays with λ= 0.7107 Å

(molybdenum (Mo) target) show that diffracted peaks occur at the following 2θ angles:

Determine the crystal structure, the indices of the plane producing each peak, and the
lattice parameter of the material.

Solution

We can first determine the sin2θ value for each peak, then divide through by the lowest
denominator.

When we do this, we find a pattern of sin2θ /0.0308 values of 1, 2, 3, 4, 5, 6, 7, and 8. If

the material were simple cubic, the 7 would not be present, because no planes have an
h2 + k2 + l2 value of 7. Therefore, the pattern must really be 2, 4, 6, 8, 10, 12, 14, 16, . . .

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and the material must be body-centred cubic (BCC). The (hkl) values listed give these
required h2 + k2 + l2 values.

We could then use 2θ values for any of the peaks to calculate the interplanar spacing
and thus the lattice parameter. Picking peak 8:

This is the lattice parameter for BCC iron (Fe).

Example

For BCC iron, compute

(a) the interplanar spacing, and

(b) the diffraction angle for the (220) set of planes.

The lattice parameter for Fe is 0.2866 nm. Assume that monochromatic radiation having
a wavelength of 0.1790 nm is used, and the order of reflection is 1.

Solution

(a) The value of the interplanar spacing dhkl is determined using the relevant equation,
with a = 0.2866 nm, and h = 2, k = 2, and l = 0 because we are considering the (220)
planes. Therefore,

(b) The value of θ may now be computed using Bragg’s law, with n = 1 because this is
a first order reflection:

The diffraction angle is 2θ,

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Example

Figure below shows an XRD pattern for lead (Pb) taken using a diffractometer and
monochromatic x-radiation having a wavelength of 0.1542 nm; each diffraction peak on
the pattern has been indexed. Compute the interplanar spacing for each set of planes
indexed; also, determine the lattice parameter of Pb for each of the peaks. For all peaks,
assume the order of diffraction is 1.

Peak Index 2θ
111 31.3
200 36.3
220 52.6
311 62.5
222 65.5

Solution

Similar computations are made for the next four peaks; the results are tabulated below: