CHAPTER 2: X-RAY, NEUTRON, AND ELECTRON

DIFFRACTION IN CRYSTALS

Introduction

• In this chapter we shall discuss the determination of crystal structures. One can determine the structure
of a crystal by studying the diffraction pattern of a beam of radiation incident on the crystal.
• Beam diffraction takes place only in certain specific directions, much as light is diffracted by a grating.
• By measuring the directions (pattern) of the diffraction and the corresponding intensities, one obtains
information concerning the crystal structure responsible for the diffraction.
• Three types of radiation are used: x-rays, neutrons, and electrons. The treatment of these three types is
quite similar; therefore we shall examine in detail only the x-ray case.
GENERATION AND ABSORPTION OF X-RAYS
• X-rays are electromagnetic waves whose wavelengths are in the neighborhood of 1.0 Å. Except for the
fact that their wavelength is so short, they have the same physical properties as other electromagnetic
waves, such as optical waves.
• The wavelength of an x-ray is thus of the same order of magnitude as the lattice constants of crystals,
and it is this which makes x-rays useful in the analysis of crystal structures.
• The energy of an x-ray photon is given by the Einstein relation E = hv, where h is Planck's constant and
v is the frequency (recall that v = c/λ) h = 6.6 x 10-27 erg-s and ), λ = 1Å, one finds an energy
E ≈ 104 eV, which is a typical value.
• The basic experimental arrangement generating an x-ray beam is sketched Fig2.1.

Fig2.1.

• Electrons emitted from the -cathode of a vacuum tube are accelerated by a large potential acting across
the tube.
• The electrons thus acquire high kinetic energy, and when they impinge on a metallic target, forming the
anode at the end of the tube, bursts of x-rays are emitted from the target.
• Some of the x-ray radiation is then extracted from the tube and used for the intended purpose. The
emitted radiation has a wide continuous spectrum, on which is superimposed a series of discrete lines.
• The continuous spectrum is due to emission of radiation by the incident electrons as they are deflected
by the nuclear charges in the target, while the discrete lines are due to the emission by atoms in the
target after they are excited by the incident electrons.
• The maximum frequency of the continuous spectrum vo is related to the accelerating potential by eV :
hvo, since the maximum energy of a photon cannot exceed the kinetic energy of the incident electron.
• When an x-ray beam passes through a material medium it is partially absorbed. The intensity of the
beam is attenuated according to the relation
−α x
I = Io e
• where Io, is the initial intensity at the surface of the medium and x the distancetraveled. The parameter
α is known as the absorption coefficient. The attenuation of the intensity expressed is due to the
scattering and absorption of the beam by the atoms of the medium.
BRAGG'S LAW
• When a monochromatic x-ray beam is incident on the surface of a crystal, it is reflected. However, the
reflection takes place only when the angle of incidence has certain values.
• These values depend on the wavelength and the lattice constants of the crystal.
• In 1912, Laue suggested that a crystal which consisted of a three-dimensional array of regularly spaced
atoms could serve as a grating. The crystal differs from the ordinary grating in the sense that the
diffracting centres in the crystal are not in one plane, i.e. crystal acts as a space grating rather than
plane grating used for the study of light diffraction.
• On the suggestion of Laue, his associates succeeded in diffracting X-rays by passing them through a
thin crystal of Zinc blende. The diffraction pattern obtained by them consists of a central spot and a
series of spots arranged in a definite pattern around the central spot.
• This symmetrical pattern of spots is known as Laue pattern.
• The explanation for this was given by Bragg. According to Bragg, the spots are produced due to the
reflection of some of the incident X-rays from the various sets of parallel crystal planes (called as
Bragg’s planes), which contain a large number of atoms.
• Consider a ray PA reflected at atom A in the direction AR from plane I and another ray QB reflected
at another atom B in the direction BS from plane II(Fig. 2.2).

• Now, draw two perpendiculars AC and AD from the atom A on QB and BS respectively. The two
reflected rays AR and BS will be in phase or out of phase depending on the path difference.
• When the path difference, CB + BD is a whole wavelength λ, or multiple of whole wavelength (nλ),
then the two rays will reinforce each other and produce an intense spot due to constructive interference.
• So the paths difference between of any two consecutive rays is an integral multiple of the wavelength.
That is,

CB + BD = nλ
CB = BD = d sin θ

• where, θ is the angle between the incident ray and the planes of reflection and called as glancing angle.
• Therefore, we have

2d sin θ = nλ
• where d is the interplanar spacing of planes, i.e. distance between the same set of planes and n=1,2,3. . .
stand for first order, second order, third order maxima respectively.This Equation is known as Bragg’s
Law.
• We must note that the Bragg’s reflection can occur only for λ ≤ 2d. The directions along which the
maxima are observed can be obtained from Bragg’s law, by giving different values of θ;
• i.e., for first maximum, sin θ1 = λ/2d
for second maximum, sin θ2 = 2λ/2d
for third maximum, sin θ3 = 3λ/2d and so on.
• As the order of spectrum increases, the intensity goes on decreasing.
• We must note that the Bragg equation is not limited to atomic planes parallel to the crystal surface. Sets
• of parallel atomic planes can be constructed through the crystal at different angles. The value of the
grating space d is different for each set of parallel planes.
• Reflection rules of X-ray diffraction for common metal structures are summarized in the following
table 2.1.
Crystal
Diffraction does not occur for Diffraction occurs for
structure
• BCC • h + k + l = odd number • h + k + l = even number
• FCC • h, k, l can have both even and odd integer • h, k, l can be all even or
values all odd numbers
• HCP • h + 2k = 3n, l odd (n → integer) • All other cases

BRAGG’S X-RAY SPECTROMETER

• The X-rays from the target T of an X-ray tube pass through two slits S1 and S2 in thick lead sheets (Fig.
2.3). then it fall on the single crystal D mounted on a turn table. The crystal is rotated by means of the
turn-table so as to increase the glancing angle at which X-rays are incident at the exposed face of the
crystal.
• The position of the crystal can be read with the help of the vernier v and a circular scale. An ionization
chamber I is mounted on an arm which can rotate about the same axis as that of the crystal table.
• The ionization chamber or photographic plate is used for measuring the intensities of reflected rays. the
angles, for which reflection intensities are maximum, give the values of θ of equation nλ = 2d sin θ.
one can carry out the process for each plane of the crystal. n = 1 creates the condition for the lowest
angle at which the lowest reflection occurs. n = 2 creates the condition for the next higher angle at
which the maximum reflection occurs and so on.
• Thus, we have
For n=1 λ = 2d sin θ1
n=2 2λ = 2d sin θ2
n=3 3λ = 2d sin θ3 ………etc.
where θ1, θ2 and θ3 are glancing angles for n = 1, 2 and 3 respectively.
Thus sin θ1 : sin θ2 : sin θ3 = 1 : 2 : 3
• Obviously, by measuring glancing angles at which reflection occurs, one can determine the interplanar
spacings knowing the wavelength of X-rays.
 Fig. 2.3. Bragg’s X-ray spectrometer
• The variation of ionization current against glancing angle θ is shown in Fig. 2.4. This curve is obtained
when X-rays from a tube containing a platinum target were reflected by a crystal of rock salt (NaCl).

Fig. 2.4. Variation of ionization current with glancing angle

• The experimental results have shown that the first order reflection maxima occurred at 5.9°, 8.4° and
5.2° for (100), (110) and (111) planes respectively.
• For first order reflection, n = 1 and hence
λ 1
d = ∝
2 sin θ sin θ
1 1 1
• Therefore d 100 : d 110 : d 111 = : :
sin θ1 sin θ2 sin θ3
1 1 1
• or d 100 : d 110 : d 111 = o
: o
: o
= 9.73 : 6.84 : 11.04
sin 5.9 sin 8.4 sin 5.2
 1 2
• d 100 : d 110 : d 111 = 1 : :
√2 √3
• One can follow this procedure for other crystals. Following table summarizes the values of ratios
between interplanar distance of planes (100), (110) and (111) for the cubic structures.

METHODS OF DETERMINING CRYSTAL STRUCTURE

• The following methods are widely used for determining crystal structure
(i) X-ray diffraction: (a) Bragg’s spectrometer method
(b) Laue’s method
(c) Powder method
(ii) Electron diffraction and
(iii) Neutron diffraction
• We have already discussed Bragg’s method. Now, we will discuss other methods.
(b) Laue’s Method
• This is one of the principal method to study X-ray diffraction and to determine crystal structure. In this
• method, a single crystal is placed in the path of X-rays beam and the glancing angle θ is kept constant.
• A white radiation having wide range of wavelengths is allowed to fall on the crystal. Each set of crystal
plane selects appropriate value of wavelength, satisfying Bragg’s law.
• Obviously, each set of plane will produce a spot which fulfills Bragg’s law. A beam of polychromatic
X-rays strike at 90° on the plane of the crystal (Fig. 2.5.).

Fig. 2.5. Laue’s Method

• The rays, while passing through the crystal meet Bragg’s planes having different interplanar spacings d.
• These different sets of planes make different angles θ with the direction of X-rays beam. We can see
that certain combinations of θ and d satisfy the Bragg’s condition, with the result that the intensity of
diffracted X-rays increase.
• Laue’s method is quite useful for single large size crystal.
(c) Powder Method
• This method is quite useful when single crystals of large size are not available. Method is used to
determine the structure of crystalline solids.
• The sample used is in the form of a fine powder containing a large number of tiny crystalline’s with
random orientations. It is prepared by crushing the commonly available polycrystalline material, thus
eliminating the tedious process of growing the single crystals.
• The powder is placed in a capillary tube or pasted on a thin wire or pressed and cemented into a thin
spindle. This powder specimen is mounted at the center around which a strip of circular photographic
film is positioned (Fig. 2.6).

Fig. 2.6 Powder method (a) Photographic film position (b) Flattened photographic film after developing
and indexing of different lines.
• A collimated beam of monochromatic X-rays is produced by passing the X-ray through a filter and a
collimator. This is allowed to strike the specimen (in capillary tube or wire or spindle) through a small
hole.
• The specimen (spindle etc.) is slowly revolved inside the specially constructed powder camera. The X-
ray beam enters through hole a, passes through the specimen and the unused part of beam exit through
hole b.
• Let us consider that the incident beam make an angle q with a set of parallel crystal plane. If Bragg
condition is satisfied, then there will be reflection. Since there are a large number of randomly oriented
crystals in the powder sample and hence there are several possible orientations of this set of planes of
same angle θ.
• The experimental arrangement of powder method consists of a cylindrical camera, called the Debye-
cherrer Camera , whose length is small as compared to the diameter.
ELECTRON AND NEUTRON DIFFRACTION
• Since waves are diffracted by a crystal, we can also use electrons and neutrons instead of X-rays,
provided the wavelengths of matter waves associates with these particles are in the range of 1 to 10 Å.
• Wavelength for neutron

• Thus the energy of a neutron of wavelength of 1 Å is ≈ 0.08 eV. The thermal neutrons in a atomic
reactor have the energy ≈ 0.08 eV and hence can be used for the study of crystal diffraction.
• The thermal neutrons from the nuclear reactors have a large spread in energy and therefore we have to
monochromatize them.
• These neutrons are allowed to fall on a crystal and a particular reflected beam is selected. This is
allowed to fall on the test sample under examination. The intensity of the scattered beam is measured
through a counter.
• We must note that though the neutron diffraction studies are very similar to those of X-rays, there are
many differences. X-rays are scattered by electrons, whereas neutrons are scattered by nuclei. Using
this property of neutrons, one can study many low atomic weight elements by neutron diffraction where
X-rays are incapable of giving precise results.
• We know that a neutron possesses a magnetic moment and hence has an additional scattering due to
magnetic ordering. Obviously, neutron diffraction studies have become important in magnetic structure
determinations,
• X-ray or electron diffraction studies do not reveal this structure. One can also study lattice vibrations
using neutron diffraction technique.

• Wavelength for electron

• Like X-rays or neutrons, electrons can also be used. However, the electrons are much more easily
scattered and hence the penetration depth is small.
• This is why electron diffraction method is used in surface studies-bonds, defects, energy states, etc.
• A comparison of X-rays and neutron diffraction techniques is made in Table 2.3. We can see that the
essential difference between the two techniques lies in the magnetic order and isotope detection by
neutron technique.
• On the other hand, X-rays are easier to produce as compared to neutrons which require a nuclear
reactor.

Table 2.3 A comparative study of X-ray and neutron diffraction techniques

•