Crystallography

Syllabus
Module 4:
Elementary ideas of crystal structure - lattice, basis, unit cell, Fundamental types of lattices – Bravais
lattice, Simple cubic, f.c.c. and b.c.c. lattices, (use of models in the class during teaching is desirable]
Miller indices and miller planes, Co-ordination number and Atomic packing factor.
X-rays – Origin of Characteristic and Continuous X-ray, Bragg’s law (No derivation), Determination of
lattice constant. 5L

Lecture 1
Solid-state physics, the largest branch of condensed matter physics, is the study of rigid
matter, or solids. The bulk of solid-state physics theory and research is focused on
crystals, largely because the periodicity of atoms in a crystal — its defining characteristic
—facilitates mathematical modeling, and also because crystalline materials often have
electrical, magnetic, optical, or mechanical properties that can be exploited for
engineering purposes.

Categories of Solids Based on the Solid Pack

Solids can be divided into three categories on the basis of how the particles that form the
solid pack.
Crystalline solids are three-dimensional analogs of a brick wall. They have a regular
structure, in which the particles pack in a repeating pattern from one edge of the solid to
the other.
Amorphous solids (literally, "solids without form") have a random structure, with little if
any long-range order.
Polycrystalline solids are an aggregate of a large number of small crystals or grains in
which the structure is regular, but the crystals or grains are arranged in a random fashion.
The extent to which a solid is crystalline has important effects on its physical properties.

Categories of Solids Based on Bonds that Hold the Solid Together

There are a number of different possible bonding mechanisms, which will determine the
atomic arrangements and the physical properties of the resulting solids. If all materials
are made of atoms, whether the material is a solid or a liquid or a vapor depends on
whether the atoms form some relatively rigid bond with respect to their neighboring
atoms or whether that bond is such that the atoms or molecules can move with respect to
each other, yet form a surface (as in a condensed droplet), or whether they behave
independently of each other and can only be contained within a closed volume.
Covalent solids, such as diamond, form crystals that can be viewed as a single giant
molecule made up of an almost endless number of covalent bonds. Each carbon atom in
diamond is covalently bound to four other carbon atoms oriented toward the corners of a
tetrahedron, as shown in the figure below. Because all of the bonds in this structure are
equally strong, covalent solids are often very hard and they are notoriously difficult to
melt. Diamond is the hardest natural substance and it melts at 3550°C.
Ionic solids are salts, such as NaCl, that are held together by the strong force of attraction
between ions of opposite charge. Because this force of attraction depends on the square
of the distance between the positive and negative charges, the strength of an ionic bond
depends on the radii of the ions that form the solid. As these ions become larger, the bond
becomes weaker.
The force of attraction between atoms in metallic solids, such as copper and aluminum,
or alloys, such as brass and bronze, are metallic bonds. Metal atoms don't have enough
electrons to fill their valence shells by sharing electrons with their immediate neighbors.
Therefore many atoms, instead of just two, share electrons in the valence shell.

Note:
• All ionic solids and most covalent solids are crystalline.
• All solid metals, under normal circumstances, are crystalline.
• The ideal crystal has an infinite 3D repetition of identical units, which may be
atoms or molecules.

Differences between Solids and Crystals

The term "liquid crystal" seems, at first glance, to be a contradiction, as we are
accustomed to equating crystals with solids. There are some important differences
between solids and crystals, however. In a crystal, molecules are ordered, but not
necessarily held rigidly in place. In a crystal, molecules are ordered, but not necessarily
held rigidly in place. In contrast, in solids the orientation and positions of the atoms, ions
or molecules are fixed, but not necessarily ordered with respect to each other. Often, both
of these properties coincide in the same material to give rise to a crystalline solid.

Difference between Amorphous Solids and Crystalline Solids

Amorphous Solids Crystalline Solids

Solids that don't have definite They have characteristic geometrical shape
geometrical shape.
Amorphous solids don't have particular They have sharp melting point
melting point. They melt over a wide range
of temperature.
Physical properties of amorphous solids are Physical properties of crystalline solids are
same in different direction, i.e. amorphous generally different in different directions.
solids are isotropic This phenomenon is known as Anisotropy.
Amorphous solids are asymmetrical When crystalline solids are rotated about an
axis, their appearance does not change.
This shows that they are symmetrical
Amorphous solids don't break at Crystalline solids cleavage along particular
fixed cleavage planes. direction at fixed cleavage planes.

2
The Crystal, Lattice and Atomic Basis
A crystal is a three-dimensional body, which consists of a single atom or a group of
atoms arranged as a periodic array.
The mathematical construction, the lattice, gives the array its periodic nature. Attaching
an atom or a group of atoms to each lattice point produces the crystal.

Lattice: A physical crystal receives its periodic structure from a lattice, which is a
mathematical object. In general, the three-dimensional lattices are referred as space
lattices. And it is defined as an infinite array of points in three dimensions, in which
every point has an identical environment as any other point in the array. These individual
points are called lattice points or lattice sites.

The mathematical definition for the lattice:

r r r
Given three non-coplanar vectors a1 , a 2 , a3 , we define the lattice to be the collection of
r r r r
points given by r = n1 a1 + n 2 a 2 + n 3 a 3 for all integers ni (positive or negative).
r r r
As an important note, the primitive vectors a1 , a 2 , a3 in the definition need be neither
unit vectors nor orthogonal.

Basis: The crystal consists of an atomic basis (or atomic cluster) attached to the lattice
points. The “basis” can be a single atom or a group of atoms attached to each lattice
point. Each lattice point receives an identical basis (or cluster). The (infinite) crystal
consists of the collection of these regularly arranged clusters.

3
Unit cells: Unit cells consist of small regions of space that, when duplicated, can be
translated to fill the entire volume of the crystal. We briefly consider the primitive unit
cell and the conventional unit cell. The primitive unit cell contains exactly a single lattice
point and a single cluster. The primitive cell has boundaries made of the primitive
vectors, which are the shortest vectors that span the lattice. Therefore, translating the
primitive unit cell through every possible integer combination of primitive vectors covers
the entire crystal. The above figure shows two equally valid primitive unit cells. In both
r r
cases, the two vectors a1 , a 2 span a region of space that contains only one lattice point or
atomic cluster as is obviously true for the primitive cell in the bottom of the figure. The
upper unit cell contains exactly one point and one unit cluster since the sides of the
parallelepiped cut through the points and clusters in such a way that the sum of the pieces
adds up to a single unit. Although primitive unit cells might appear to be the simplest for
calculation purposes, it is sometime more convenient to work with non-primitive unit
cells.
The conventional unit cell does not necessarily contain exactly one lattice point and one
atomic cluster. For the convenience in calculations, we usually choose orthogonal
spanning vectors to define this unit cell. Translating the conventional unit cell by all
integer combinations of spanning vectors covers the entire crystal. The next section lists
the most typical examples of conventional unit cells.

Important Note: For a particular lattice structure, more than one set of primitive vectors
is possible.

4
Lecture 2
The Crystal Systems
On the basis of the lengths and directions of the axes of the symmetry, all the crystals
may be classified into the following seven systems. Here instead of using primitive
r r r
vectors a1 , a 2 and a3 we consider the lengths (a, b and c) and the angles (α between
r r r r r r
a 2 and a3 , β between a3 and a1 , γ between a1 and a 2 )
(i) Triclinic crystal: This is the most general structure, where lengths of the unit cell
are different and all three angles are unequal ( a ≠ b ≠ c and α ≠ β ≠ γ ≠ 90 0 ).
(ii) Monoclinic crystals: In this crystal the lengths of the unit cells are different and
only two of the angles are right angles ( a ≠ b ≠ c and α = β = 90 0 ≠ γ ).
(iii) Orthorhombic crystal: Here the lengths of the unit cell are different, while the three
axes are perpendicular to each other ( a ≠ b ≠ c and α = β = γ = 90 0 ).
(iv) Tetragonal crystal: In this case two of the three lengths of the unit cell are equal
and the angles are right angles ( a = b ≠ c and α = β = γ = 90 0 ).
(v) Rhombohedral (Trigonal) crystal: In this crystal all the three lengths are equal and
so are the angles but not 90o ( a = b = c and α = β = γ ≠ 90 0 ).
(vi) Hexagonal crystal: In this case a = b ≠ c and α = β = 90 0 , γ = 120 0 .
(vii) Cubic (Isometric) crystal: In this case, as expected, a = b = c and α = β = γ = 90 0 .

Bravais lattice
There are number of ways in which atoms or molecules are arranged together and huge
number of crystal structures are formed. But the crystal lattice associated with each of the
structures has some fundamental pattern. In 1848 Auguste Bravais showed that there are
only fourteen ways of arranging points in space so that the environment look the same
from each point. These fourteen types of space lattices are known as Bravais lattices.
Development of the Bravais lattices: The 14 Bravais lattices are arrived at by combining
one of the seven crystal systems (or axial systems) with one of the lattice centering. Each
Bravais lattice refers a distinct lattice type.
The lattice centerings are:
• Primitive centering (P): lattice points on the cell corners only
• Body centered (I): one additional lattice point at the center of the cell
• Face centered (F): one additional lattice point at center of each of the faces of the
cell
• Centered on a single face (A, B or C centering): one additional lattice point at the
center of one of the cell faces.
Though there are in total 7 × 6 = 42 combinations, but it can be shown that several of
these are in fact equivalent to each other. For example, the monoclinic I lattice can be
described by a monoclinic C lattice by different choice of crystal axes. Similarly, all A-
or B-centered lattices can be described either by a C- or a P-centering. This reduces the
number of combinations to 14 conventional Bravais lattices, shown in the table below.

5
Crystal system Bravais lattices
P

Triclinic

P C

Monoclinic

P C I F

Orthorhombic

P I

Tetragonal

Rhombohedral
(Trigonal)

Hexagonal

P I F

Cubic

6
Some important fundamental parameters related to crystal structure
Atomic radius (r): In a crystal system of pure element (i.e. single atomic basis), half of
the distance between the nearest neighboring atoms is considered as the atomic radius.

Nearest neighbor distance (2r): The distance between the centers of any two nearest
neighboring atoms is called nearest neighbor distance. The nearest neighbor distance is 2r
if the atomic radius is r.

Coordination number (n): The number of equidistant nearest neighboring atoms with
respect to any particular atom in a given crystal is known as coordination number. This is
also termed as number of first neighbors.

Atomic packing factor (APF): The ratio of the volume occupied by the atoms in a unit
cell to the volume of the unit cell is termed as atomic packing factor or simply packing
factor. It is also known as packing fraction or packing efficiency or packing density of the
system. So, if V is the volume of the unit cell and v is the volume of one atom, then
nv
APF = , where n is the coordination number.
V
Note: Larger is the coordination number; higher is the value of APF and more closely
packed will be the crystal structure.

Now we will study the simple cubic structure (sc), the body centered cubic (bcc) structure
and the face centered cubic (fcc) structure in some details, because it is easy to
understand the cubic crystal system than the other.
(i) Simple cubic (sc) structure: This is the simplest structure of the crystal
system. The unit cell is described by three edge lengths a = b = c = 2r (r is
the host atom radius), and the angles between the edges, α = β = γ = 90 0 . In
simple cubic system there is one lattice point at each corner of a cubic unit
cell. Each corner point is shared by eight adjacent unit cells. So, the
contribution of each lattice point is 1/8. Therefore eight lattice points at all the
corners sum up to only one lattice point. Simple cubic structure is a primitive
cell.

You can easily find out the coordination number and atomic packing factor for
this structure. – So, this is an assignment.

7
(ii) Body centered cubic (bcc) structure: In this lattice structure the unit cell is a
cube with one lattice point at each of its eight corners and an additional one at
the center of each cell.

So, effective number lattice points in a bcc unit cell are 2. Thus bcc unit cell is
a non-primitive cell.

Packing density for bcc:

Let us consider, spherical atoms of radius r are placed at the eight corners and
one additional at the center of a cubic structure of side a. Understandably, the
central atom are in touch with rest of the atoms. Which means the body
diagonal must be four times the radius of the atomic spheres.
i.e. d = 4r

The body diagonal is given by:

d 2 = a2 + a2 + a2
d = 3a
hence,
3
d = 3 a=4r; r= a
4
Now the cube will contain two whole atoms.
The volume of two of these atoms is given by:
3
4 8 ⎛ 3 ⎞ 3π 3
V = 2 × π r 3 = π ⎜⎜ a⎟ = a ≈ 0.68 a 3
3 3 ⎝ 4 ⎟⎠ 8
The atoms occupy 68% of the cube.

8
(iii) Face centered cubic (fcc) structure: In case of fcc crystal structure, the unit
cell is a cube with one atom at each of its eight corners and one atom at the
center of each six faces.

So, the atom at the center of the face of a cell is shared by two unit cells.
Therefore, the effective number of atoms in a unit cell is (1 + 3 =) 4. Thus bcc
unit cell is also a non-primitive cell.

Packing density for fcc

Fitting the same size spheres along the face diagonal, the face diagonal must
be four times the radius of the spheres.
i.e. d = 4r
The face diagonal (from Pythagoras) is given by:
d 2 = a2 + a2
d= 2a
hence
d = 2 a=4r;
2
r= a
4
Now the cube will contain four whole atoms.
The volume of four of these atoms is given by:
3
4 16 ⎛ 2 ⎞
V = 4 × π r 3 = π ⎜⎜ a⎟
3 3 ⎝ 4 ⎟⎠
π
= a 3 ≈ 0.74 a 3
3 2
The atoms occupy 74% of the cube.

9
Characteristics of cubic crystals

Simple Body-centered Face-centered

Volume of conventional cell a3 a3 a3
Lattice points per cell 1 2 4
Volume of primitive cell a3 1 3
a
1 3
a
2 4
Lattice points per unit volume 1 2 4
a3 a3 a3
Co-ordination number 6 8 12
Nearest neighbor distance a 3 1
a ≈ 0.866 a a ≈ 0.707 a
2 2
Packing factor π π 3 π 2
≈ 0.52 ≈ 0.68 ≈ 0.74
6 8 6

Important Note:
bcc lattice
The primitive cell of a bcc lattice is
3
rhombohedral with edge = a ≈ 0.866 a
2
and angle between adjacent edges =
109o28/ as shown in this figure.

The primitive cell of an fcc lattice is also

rhombohedral, with each side =
1
a ≈ 0.707 a and angle between
2
adjacent edges = 60o.

10
Relation between mass-density of a crystal and its lattice constant
Let us consider a cubic lattice with lattice constant a and density of crystalline material
be ρ.
Since, the volume of a cubic unit cell is a 3 , the mass of each unit cell = ρ a 3 .

If n be the number of molecules (or atoms, in case of single atomic crystal) per unit cell
and M be the gram molecular weight (or atomic weight), then M N A is the mass of each
molecule (atom), where NA is the Avogadro number (6.023 × 1023).
So, in this way, the mass of each unit cell = n M N A .
Equating the mass of one unit cell calculated in the above two methods, we can find,
nM
a3 =
ρ NA

nM
or, ρ=
a3 N A

This is the relation between the lattice constant and the density of a cubic crystalline
material

11
Lecture 3
Lattice planes/Miller planes/crystal faces in a crystal lattice
Crystal faces develop along planes defined by the points in the lattice. In other words, all
crystal faces must intersect atoms or molecules that make up the points. These parallel
planes are called lattice planes / Miller planes / crystal faces. A face is more commonly
developed in a crystal if it intersects a larger number of lattice points.
For example, in the plane lattice
shown at the right, faces will be
more common if they develop along
the lattice planes labeled 1,
somewhat common if they develop
along those labeled 2, and less and
less common if they develop along
planes labeled 3, 4, and 5.

Miller Indices (hkl)

The orientation of a surface or a crystal plane may be defined by considering how the
plane (or indeed any parallel plane) intersects the main crystallographic axes of the solid.
The application of a set of rules leads to the assignment of the Miller Indices, (hkl); a set
of numbers which quantify the intercepts and thus may be used to uniquely identify the
plane or surface. The following treatment of the procedure used to assign the Miller
Indices is a simplified one (it may be best if you simply regard it as a "recipe") and only a
cubic crystal system (one having a cubic unit cell with dimensions a × a × a) will be
considered.

Step 1: Identify the intercepts on the x, y and z axes

In this case the intercept on the x-axis is at x = a [at the point (a, 0, 0)], but the surface is
parallel to the y and z-axes - strictly therefore there is no intercept on these two axes but

12
we shall consider the intercept to be at infinity (∞) for the special case where the plane is
parallel to an axis. The intercepts on the x, y and z-axes are thus
Intercepts: a, ∞, ∞

Step 2: Specify the intercepts in fractional co-ordinates

Co-ordinates are converted to fractional co-ordinates by dividing by the respective cell-
dimension, e.g. a point (x, y, z) in a unit cell of dimensions a × b × c has fractional co-
ordinates of (x/a, y/b, z/c). In the case of a cubic unit cell each co-ordinate will simply be
divided by the cubic cell constant, a. This gives
Fractional Intercepts: a/a, ∞/a, ∞/a i.e. 1, ∞, ∞

Step 3: Take the reciprocals of the fractional intercepts

This final manipulation generates the Miller Indices that (by convention) should then be
specified without being separated by any commas or other symbols. The Miller Indices
are also enclosed within standard brackets (….) when one is specifying a unique surface
such as that being considered here.
The reciprocals of 1 and ∞ are 1 and 0 respectively, thus yielding
Miller Indices: (100)
So the surface/plane illustrated is the (100) plane of the cubic crystal.
Other Examples

1. The (110) surface

Assignment

Hints:

Intercepts: a, a, ∞

Fractional intercepts: 1, 1, ∞

Miller Indices: (110)

2. The (111) surface

Another assignment

Hints:

Intercepts: a, a, a

Fractional intercepts: 1, 1, 1

Miller Indices: (111)

13
The (100), (110) and (111) surfaces considered above are the so-called low index surfaces
of a cubic crystal system (the "low" refers to the Miller indices being small numbers - 0
or 1 in this case). These surfaces have a particular importance but there an infinite
number of other planes that may be defined using Miller index notation. We shall just
look at one more …

1. The (210) surface

Assignment

Hints:

Intercepts: 1
2 a , a, ∞

Fractional intercepts: 1
2 , 1, ∞

Miller indices: (210)

Further notes:
(i) In some instances the Miller indices are best multiplied or divided through by
a common number in order to simplify them by, for example, removing a
common factor. This operation of multiplication simply generates a parallel
plane, which is at a different distance from the origin of the particular unit cell
being considered.
For example, (200) is transformed to (100) by dividing through by 2.

(ii) If any of the intercepts are at negative values on the axes then the negative
sign will carry through into the Miller indices; in such cases the negative sign
is actually denoted by over striking the relevant number.
For example, (00 -1) is instead denoted by (00 1 ) .

Crystallographic direction
In the field of crystallography, it is essential to locate different directions and planes for
crystal analysis. In two-dimension (fig a) the directions are denoted by the coordinated
expressed in form of integer of the first point through which each of the direction line
passes. In case of three-dimension (fig b) the direction is denoted by square bracket
within which coordinates are placed without comma.

Final important note: in the cubic system the vector [hkl] is normal to the (hkl) plane.
However, this characteristic is unique to the cubic crystal.

14
Cleavage plane of a crystal
Crystals often contain planes of atoms along which the bonding between the atoms is
weaker than along other planes. In such a case, if the mineral is struck with a hard object,
it will tend to break along these planes. This property of breaking along specific planes is
termed cleavage. Because cleavage occurs along planes in the crystal lattice, it can be
described in the same manner that crystal forms are described. For example if a mineral
has cleavage along {100} it will break easily along planes parallel to the (100) crystal
face, and any other planes that are related to it by symmetry.

What are symmetry-equivalent surfaces?

In the following diagram the three highlighted surfaces are related by the symmetry
elements of the cubic crystal - they are entirely equivalent.

In fact there are a total of 6 faces related by the symmetry elements and equivalent to the
(100) surface – any surface belonging to this set of symmetry related surfaces may be
denoted by the more general notation {100} where the Miller indices of one of the
surfaces is instead enclosed in curly-brackets.

15
Separation between successive planes in a cubic crystal
Let us consider a crystal plane of Miller indices (hkl) in a cubic crystal of lattice constant
a. The perpendicular distance of this plane from any lattice point of nearest parallel plane,
considered as the origin, is OM (dhkl). OM makes angle α, β and γ with coordinate axes
X, Y and Z respectively. (These angles are different from interfacial angles.) The
intercepts of the plane on the three axes are:
a a a
OA = , OB = , OC = K (1)
h k l

Since OM is perpendicular to the crystal plane ABC, therefore,

d d d
cos α = hkl , cos β = hkl , cos γ = hkl K ( 2)
OA OB OC
Again, from fig b,
(OM )2 = (OD ) 2 + (OE ) 2 + (OF ) 2
2
d hkl [
= (d hkl cosα ) + (d hkl cos β ) + (d hkl cos γ )
2 2 2
]
or,
= d hkl
2
(
cos 2 α + cos 2 β + cos 2 γ )
Therefore,
cos 2 α + cos 2 β + cos 2 γ =1 K (3)
Now, using equations (1) and (2), one can write from (3),
2 2 2
⎛ d hkl h ⎞ ⎛ d hkl k ⎞ ⎛ d hkl l ⎞
⎜ ⎟ +⎜ ⎟ +⎜ ⎟ =1
⎝ a ⎠ ⎝ a ⎠ ⎝ a ⎠
Simplifying this equation, we can get the distance between two adjacent planes with
Miller indices (hkl), as:
a
d hkl = K (4)
(h +k +l
2 2
)2

16
Lecture 4
X-Rays
The X-rays could pass through most substances, including the soft tissues of the body,
but left the bones and most metals visible. One of his earliest photographic plates from
his experiments was that of a film of his wife, Bertha's hand with a ring. Roentgen named
the invisible radiations as X-rays (or unknown rays).

Bertha’s hand with a ring

Detailed experiments showed that when cathode rays or electrons are stopped, X-rays are
emitted. The kinetic energy of the electrons is transferred to the anode material of the
discharge tube. The atoms of the anode emit X-rays. When the cathode rays strike the
atoms in the anode, the electrons of these atoms jump to higher excited orbits. When the
electrons jump back to their original orbits, they emit X-rays. These are called
characteristic X-rays. X-rays are electromagnetic radiations and have energies of the
order of a few eV to a few tens of keV.

Production of X-rays
X-rays are produced by modified discharge tubes that are called Coolidge tubes. Cathode
is in the form of a filament, which emits electrons on heating. Anode is made up of solid
copper, molybdenum or any other material whose X-ray energies are useful for further
applications. Anode is also called the target. A high potential difference between the
cathode and anode is maintained by an external high voltage source. A separate battery
that supplies high current heats the cathode filament. The filament is generally made out
of tungsten and is coiled to provide high resistance to the passing current.

The electrons emitted from the filament, experience the potential difference and are
accelerated towards the anode. Thus the electrons gain energy. When such electrons hit

17
on the anode surface, they are stopped. They transfer their kinetic energy to the electrons
of the anode material. These then give rise to the X-rays.
The intensity of the X-rays depends on the number of electrons striking the anode or the
intensity of the electron beam. High energy X-rays are called hard X-rays and they have
very high penetrating power. Low energy X-rays are called soft X-rays and they have low
penetration powers.

Properties of X-rays
• X-rays are invisible electromagnetic radiations. Their wavelength is less than that
of the visible light photons and is larger than the γ-ray photons. They are
generally of the order of a few tens of nano-meters.
• X-rays posses all properties of visible light photons, such as, reflection,
diffraction, rectilinear propagation etc. Refraction of X-rays is not yet seen.
• Being electromagnetic waves, they travel at the speed of light 3 × 108 m/s.
• Since they are not charged particles, they are not affected by either electric or
magnetic fields.
• X-rays can ionize materials through which they pass such as gases. X-rays like –
rays produce fluorescence and affect photographic plates.
• X-rays are highly penetrating. They can easily pass through thin sheets of paper,
metal foils, tissues etc.
• High-density materials such as lead, bones, etc can stop X-rays.

Uses of X-rays
1. Medical uses: X-rays are widely used by radiologists to see if the bones
are broken or not. They can be used to see if a foreign object such as a
bullet has lodged in a body, if there are any other defects such as kidney or
gall bladder stone is present or not. X-rays are also used to test the density
of the bones.
2. Industrial uses: Hard X-rays are routinely used to see if there are any
faults deeper in any structure such as pipes, machine parts, airplane
bodies, etc. X-rays are used to see the characteristic qualities of
gemstones, the genuineness and purity of precious metals such as gold,
silver, etc. X-rays are also used to detect the percentage of certain
elements in an ore before the ore is taken for commercial mining.
3. Scientific uses: X-rays undergo diffraction. This is useful in studying the
nature of the crystal and the arrangements of atoms within the crystal. X-
rays are also extensively used to study the way chemical reactions occur.
Characteristic X-rays give information about the structure of atoms.
4. Engineering uses: They are employed to investigate flaws and gas
pockets in casting, causing weakness in its structure.
5. Police uses: X-rays are used by custom department to detect any
unwanted object inside sealed baggage. They are also used to distinguish
real diamonds or other gems from artificial one, real document from
forged one etc.

18
X-ray spectrum and its origin
The dependence of intensity of X-rays emitted from a target material on wavelength or
frequency is called X-ray spectrum. It is found that the x-ray spectrum emitted by all
target material has two portions – Continuous spectrum and Characteristic spectrum.

Continuous X-ray spectrum

Continuous X-rays are produced by the phenomenon known as Bremsstrahlung (breaking
radiation). Highly energetic electron when hit a target material of high atomic number
their kinetic energy change due to this collision.
Let us consider the velocity of incident electron decreases from vi and vf. If no energy lost
at the time of interaction other than in form of radiation of frequency ν, then we can write
1 1
m vi2 − m v 2f = hν K (5)
2 2
where, h is the Planck’s constant.

Lowest wavelength limit

According to classical theory, the continuous spectrum of X-ray should have all
wavelengths extended from zero to infinity. But quantum theory explains the existence of
minimum wavelength limit for continuous X-ray spectrum. In equation (5) if we put vf =
0 (i.e. electron’s velocity becomes zero due to electrostatic interaction with the target
material)
1
hν max = m vi2 = e V {Since electron is accelerated by the potential difference, V)
2
c 2ch h c
or, λmin = = =
ν max m vi2 e V
using the values of the constants, h, c and e, we can find,
12420
λmin = Å …(6)
V
This relation is known as Duana-Hunt law and this minimum wavelength is called
continuous spectrum boundary.

In the above figure, the intensity of the X-ray spectrum for different potential difference
applied between cathode and target is shown. Some important characteristics of the graph
are listed below:

19
 (i) λmin is independent of the target material.
(ii) λmin decreases with increase in potential difference.
(iii) The intensity distribution has a maximum at a certain wavelength (λm) after
which it gradually decreases.
(iv) The intensity of all wavelengths increases with applied potential.
(v) λm shifts to lower wavelength side with the increase in applied potential.
(vi) At a particular potential difference (here 70 kV), sharp lines appear over the
continuous spectrum. They are the characteristic spectrum, which depend on
the target material.

Characteristic X-ray spectrum

Characteristic X-ray spectrum consists of sharp peaks, which are superimposed on
continuous spectrum. It is highly monochromatic and its intensity is very high with
respect to continuous spectrum.
An atom can be treated as a sphere consisting of a central nucleus with protons and
neutrons; and a suitable number of electrons revolving around the nucleus in different
orbits viz. K, L, M, N etc., where, K-shell electrons are most tightly bound to the nucleus.
When a highly energetic electron hits the target material it can dislodge one of the K-
shell electron it its energy surpluses the K-shell binding energy. Then the created vacancy
is filled by one of the electrons from higher levels emitting a radiation of frequency
proportional to the energy difference of the two levels involve in the electron transition.
All of these transition forms K-series. Similarly L-series, M-series can be grouped.
For a particular target material, the wavelength of K-series is less than that of the L-
series, L-series is less than that of the M-series and so on. And, for the same series, the
wavelength radiated by a target material with high atomic weight is less than that of a
material with lower atomic weight.

Bragg’s Law
After Röntgen discovered X-rays, people started to shine them on crystals. Since the
wavelengths of X-rays are comparable to the spacing between atoms in crystals,
interesting interference effects can be anticipated.

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W. L. Bragg that there is a simple way to understand the effects of the X-rays passing
through the crystals. He suggested that the Miller planes act as mirrors that reflect the X-
rays and that the condition for reflection is constructive interference, which depends on
the wavelength of the X-rays (λ), the angle at which they fell upon the crystal (θ) and the
distance dhkl between nearest neighbor (hkl) planes. He performed experiments with his
father, W. H. Bragg, and they suggested the law:
2d hkl sin θ = n λ K (7)
where, θ is the glancing angle or Bragg’s angle of the incident X-ray of wavelength
λ falling on (hkl) plane of a crystal and n is the order number of constructive interference.
So by acquiring X-ray diffraction data on a crystalline system, it is possible to measure
the distances between crystal planes and this provides us information on the structure.
We know that the maximum possible value of sinθ is 1, thus
λ ≤ 2d
This imposes the limitation on wavelength. The typical interatomic spacing in crystalline
materials is 2-3 Å. Therefore the wavelength of incident radiation should be of the same
order, which corresponds to X-rays.

Absorption of X-ray by a material

When X-ray passes through material, the intensity is reduced. The reduction depends on
the nature of the material and the frequency of the X-ray. Soft X-rays are absorbed easily
by a material than hard X-rays.
The intensity of X-ray beam at any point is defined as the amount of energy passing
through a unit area, perpendicular to the direction of propagation of X-ray, per unit time.
If Io is the incident X-ray intensity and I is the intensity after covering a distance x within
the material, then rate of reduction in intensity = – dI/dx, which eventually is
dI
proportional to the intensity at that point. Therefore, − ∝ I
dx
dI
or, = − µI (8)
dx
where, µ is known as linear absorption coefficient of the material.
Solving equation (8) we get,
I = I 0 exp(− µx)
So, the intensity of the incident X-ray falls of exponentially while passing through a
material.

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