X – Ray Diffraction and

Electron Microscopy
 Index
1. Basic Crystallography
2. Symmetry, Point Groups and Space Groups.
3. XRD : Fundamentals and Applications.
4. Stereographic Projection.
5. Reciprocal Space.
6. Ewald Sphere.
7. General Conditions for Electron Diffraction.
8. Transmission Electron Microscopy.
Basics of Crystallography
 Outline of this lecture
• Classification of material based on structure (crystalline, quasi –
crystals and amorphous materials).
• Definition of crystalline materials
• What is a crystal, lattice and motif?
• 14 Bravais Lattices, 7 Crystal Classes.
• Why only 14 Bravais Lattices and 7 Crystal Classes?
• Importance of Symmetry, Symmetry wrt a point, plane and line.
• Choice of unit cell, primitive and non – primitive cells, translation in
1D/2D/3D.
• Miller indices and Miller – Bravais indices for planes/direction.
 Atomic Arrangement
• Solids are classified as crystalline and amorphous
• Crystalline = periodic arrangement of atoms – definite repetitive
pattern – LRO + SRO
• In crystalline materials unit cell is repeated which implies translation
and each atom has identical surrounding – discrete diffraction lines
• Amorphous materials = random arrangement of atoms – no concept
of unit cell – SRO present due to bonds
• Amorphous material have pair distribution function which is used to
probe them – pair distribution function depends on bond length,
bond angle and bond type
 Atomic Arrangement
• Solids can be classified as Amorphous, Quasi – Crystals and Crystalline
based on structure.
• In quasi crystals point group symmetry can be applied as the are
single unit cell
• Quasicrystals have 5 – fold, 7 – fold, 10 – fold, 12 – fold and 14 – fold
symmetry
• Quasicrystals are not fully amorphous.
• The definition of crystalline materials by International Union of
Crystallography (IUCr) = Any material which gives a discrete
diffraction pattern is crystalline.
• Quasicrystal symmetry can be seen in TEM
 Crystals
• A 3D translationally periodic arrangement of atoms/molecules in
space is called a crystal.
 Lattice
• A 3D translationally periodic arrangement of points in space is called
a lattice or space lattice.
 Difference
• Crystals have attributes like mass, density, color, etc. due to the
presence of atoms/molecules.
• Lattice does not have any attributes.
 Relation
• Crystal = Lattice + Motif
• Motif (Basis) = An atom or a group of atoms associated with each
lattice point.
• If symmetry of atoms (basis/motif) > symmetry of lattice = symmetry
of crystal is retained
 Another definition
• Crystal = Space Group (how to repeat) + Asymmetric Unit (Motif, what
to repeat) + Wyckoff positions
• First atom cannot replace another atom = asymmetric atoms (motif)
• No. of atoms in unit cell = Wyckoff positions
• Wyckoff position determines where to put atoms (motif/asymmetric
unit)
• 230 theoretical space groups, out of which 72 are simple space
groups (based on simple definition)
• In many space groups no material exists – mathematical space group
• We can change the crystal structure by changing orientation of basis
 Translation Vector
• Choice of primitive vector is ours.
• The choice of primitive vector does not change the type of crystal
structure.
• Choice of unit cell is also ours.
• Crystal is defined by its inherent symmetry.
• We can have both primitive or non – primitive unit cells and basis
vector.
 Unit Cell of a Lattice
• A unit cell of a lattice is not unique.
• The choice of unit cell does not change the crystal structure of the
material.
• It is just represented in different forms.
• Therefore, unit cell shape CANNOT be the basis for classification of
lattices.
• The choice of unit cell (primitive or non – primitive) does not change
the crystal structure of the material.
Primitive Unit Cell (2D)
Non – Primitive Unit Cells
Bravais Lattices
Non – Bravais Lattices
Planar (2D) Lattices
3D Lattices
Coordinates
Classification of Lattices

Lattices

7 Crystal
Structures

14 Bravais
Lattices
 Cubic
• 𝑎𝑎 = 𝑏𝑏 = 𝑐𝑐, 𝛼𝛼 = 𝛽𝛽 = 𝛾𝛾 = 90°
• A minimum of four 3 – fold axis of rotation.
• Axis of rotation = body diagonals.
 Tetragonal
• 𝑎𝑎 = 𝑏𝑏 ≠ 𝑐𝑐, 𝛼𝛼 = 𝛽𝛽 = 𝛾𝛾 = 90°
• A minimum of one 4 – fold axis of rotation.
 Orthorhombic
• 𝑎𝑎 ≠ 𝑏𝑏 ≠ 𝑐𝑐, 𝛼𝛼 = 𝛽𝛽 = 𝛾𝛾 = 90°
• Three perpendicular 2 – fold axis of rotation.
 Hexagonal
• 𝑎𝑎 = 𝑏𝑏 ≠ 𝑐𝑐, 𝛼𝛼 = 𝛽𝛽 = 90°, 𝛾𝛾 = 120°
• One 6 – fold axis of rotation.
 Trigonal
• 𝑎𝑎 = 𝑏𝑏 = 𝑐𝑐, 𝛼𝛼 = 𝛽𝛽 = 𝛾𝛾 ≠ 90°
• One 3 – fold axis of rotation.
 Monoclinic
• 𝑎𝑎 ≠ 𝑏𝑏 ≠ 𝑐𝑐, 𝛼𝛼 = 𝛾𝛾 = 90° ≠ 𝛽𝛽
• One 2 – fold axis of rotation.
 Triclinic
• 𝑎𝑎 ≠ 𝑏𝑏 ≠ 𝑐𝑐
• 𝛼𝛼 ≠ 𝛽𝛽 ≠ 𝛾𝛾 ≠ 90°
• No Symetry
 Important Points
• The crystal attains the symmetry of the lowest symmetry element.
• Lattices are classified on the basis of their symmetry.
 Symmetry
• A geometrical or other regularity that is possessed by a mathematical
object and is characterized by the operations that leave the object
invariant.
• In general, if an object is brought into self coincidence after a certain
operation or initial and final positions are indistinguishable from each
other, it is said have symmetry.
• Finite symmetry operations are :
1. Point (Inversion)
2. Line (Rotation)
3. Plane (Reflection)
4. Combination of the above
 Symmetry
• In addition, lattices/crystals also have infinite symmetry operator i.e.
translational symmetry.
• Finite Symmetry Operators give rise to point groups.
• Finite + Infinite Symmetry Operators give rise to space groups.
 Rotational Symmetry
• If you rotate an object around a line passing through its center or
away from it and the object seems to remain unchanged, then the
object is said to have rotational symmetry.
• The line around which it is rotated is called the rotation axis and the
smallest angle you rotate is called angle of rotation.
 Crystallographic Restriction Theorem
• Why only 1,2,3,4, and 6 – fold rotation?
• Crystals are built by regular stacking of unit cells that are translated.
• In other words, crystals have translation.
• All the symmetry operations must be compatible with each other
(internal as well as external).
• Translational symmetry operator should be compatible with rotation
symmetry operator.
• This results in limitation on combination of symmetry elements that
are compatible with each other.
 Crystallographic Restriction Theorem
• Rotation operators acting on points A & A’ generate points B & B’.
• For B & B’ to be valid lattice points, the distance between them (t’)
must be an integral number (m) of the translation vector(t).
• Therefore, t’ = mt.
 Symmetry of Lattices
• Lattices have:
1. Translational Symmetry
2. Rotational Symmetry
3. Reflection Symmetry
 Point Group and Space Group
• The group of all symmetry elements of a crystal except translation
(rotation, reflection, inversion and their combinations) passing
through a single point is called its POINT GROUP. Any point group
symmetry operation leaves this point invariant. They relate internal
symmetry to external symmetry of crystal.
• The complete group of all symmetry elements including translations
of a crystal is called its SPACE GROUP. It describes how all symmetry
elements are arranged relative to one another. There are 17 Space
Groups in 2D and 230 in 3D.
 Classification of Lattices
• Crystal systems and Bravais Lattices
• Based on the point group symmetry – i.e. excluding translational
symmetry – 7 types of lattices = 7 types of crystal systems.
• Based on space group symmetry – point group + translational
symmetry – 14 types of lattices = 14 Bravais lattices
Symmetry Elements
7 Crystal Systems
 Hexagonal Close Packed (HCP) Lattice does
not exist!!
• Only hexagonal lattice is simple hexagonal lattice.
• HCP Crystal = …ABAB… stacking of close packed layers.
• A & B are not translationally equal.
• HCP Crystal = Hexagonal P lattice + 2 atom motif (1A & 1B).
Miller Indices, Cubic Lattices
Equivalent Planes and Directions
Interplanar Spacing
 Hexagonal Unit Cell
• Non – orthogonal, requires slightly different system.
• The unit cell is defined as two coplanar vectors 𝑎𝑎1 , 𝑎𝑎2 120° 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 ,
and 𝑐𝑐 at right angles.
• A third vector 𝑎𝑎3 120° 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑡𝑡𝑡𝑡 𝑡𝑡𝑡𝑡𝑡 𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 𝑡𝑡𝑡𝑡𝑡𝑡 is also used.
• Miller Bravais System – 𝑎𝑎1 , 𝑎𝑎2 , 𝑎𝑎3 , 𝑐𝑐 − for hexagonal system.
• Miller Bravais indices for a plane ℎ𝑘𝑘𝑘𝑘𝑘𝑘 , where ℎ + 𝑘𝑘 = −𝑖𝑖.
• The three indices is needed to show the symmetry inherent in the
system.
• 1010 , 0110 , 1100 , 0110 − same family of planes.
 Hexagonal Unit Cell
• Directions are best described in terms of the three basis vectors
𝑈𝑈𝑈𝑈𝑈𝑈 .
• The four indices system using four vectors 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 is also used and
can be calculated in terms of the three – vector system.
•U=u–t u = (2U – V)/3
•V=v–t v = (2V – U)/3
•W=w t = – (u + v) = – (U + V)/3
• w=W
• {hkil}
• <uvtw>
 Bravais Lattice
• The no. of atoms per unit cell = N
• The indices i, f, and c stands for internal, face and corner atoms.
𝑁𝑁𝑓𝑓 𝑁𝑁𝑐𝑐
• 𝑁𝑁 = 𝑁𝑁𝑖𝑖 + +
2 8
 Weiss Zone Law
• Condition for a direction [uvw] to be parallel to a plane or lie in the
plane (hkl).
• hu + kv + lw = 0
• hU + kV + iT + lW =0
• True for all crystal systems.
 Cubic Crystals
• Angle between two directions ℎ1 𝑘𝑘1 𝑙𝑙1 𝑎𝑎𝑎𝑎𝑎𝑎 ℎ2 𝑘𝑘2 𝑙𝑙2 .
ℎ1 ℎ2 +𝑘𝑘1 𝑘𝑘2 +𝑙𝑙1 𝑙𝑙2
• cos 𝜃𝜃 =
ℎ12 +𝑘𝑘12 +𝑙𝑙12 ℎ22 +𝑘𝑘22 +𝑙𝑙22
Examples of Structures
 Simple Cubic
• E.g.: 84 – Po (a = 3.35 𝐴𝐴0 )
• (0,0,0)
• One atom per unit cell.
• CN = 6
 BCC
• Two atoms per unit cell.
1 1 1
• 0,0,0 , , ,
2 2 2
• Cr, Fe, Mo
 FCC
• Four atoms per unit cell.
1 1 1 1 1 1
• 0,0,0 , , ,0 , , 0, , 0, ,
2 2 2 2 2 2
• Cu, Ag, Au
 Diamond Structure
• C, Si, Ge
1 1 1
• FCC lattice + 2 atom basis – 0,0,0 𝑎𝑎𝑎𝑎𝑎𝑎 , ,
4 4 4
11 1 1 11 111 331 313 133
• C= 000, 0, 0 , 0 , , , ,
22 2 2 22 444 444 444 444
• 100% Covalent bonding.
• Total internal reflection is possible.
 CsCl Structure
• 2 atoms per unit cell
• CsCl, CsI
111
• SC + 2 atom basis (000 , )
222
• 𝐶𝐶𝐶𝐶 + = 000 (bigger)
− 111
• 𝐶𝐶𝐶𝐶 = (smaller)
222
 NaCl Structure
• NaCl, KBr, CaO
111
• FCC + 2 atom basis (000, )
222
• CN = 6 – not a closed packed structure
• 100% ionic bonding
• 8 atoms per unit cell
+ 11 1 1 11
• 𝑁𝑁𝑁𝑁 = 000, 0, 0 , 0
22 2 2 22
− 111 1 1 1 111 1 1 1
• 𝐶𝐶𝐶𝐶 = , 11 , 1 1, 11 = , 00 , 0 0, 00
222 2 2 2 222 2 2 2
• Octahedral structure
 Zinc Blend Structure
• ZnS, GaAs, SiC
111
• FCC + 2 atom basis 000,
444
• 8 atoms per unit cell
2+ 11 1 1 11
• 𝑍𝑍𝑍𝑍 = 000, 0, 0 , 0
22 2 2 22
2− 111 331 313 133
• 𝑆𝑆 = , , ,
444 444 444 444
• CN = 4
 Important Points
• Hexagons + Pentagons are required to create spherical structure
(Bucky Balls/Fullerene).
• Frequency of Rotation at Room Temperature is very high.
• 𝐶𝐶60
• Atoms are associated with lattice points.
• It is not necessary that atoms must be present at the lattice points,
atoms may or may not be present on the lattice points.
Symmetry, Point Groups and
Space Groups
 Definition
• Crystal = Space Group (how to repeat) + Asymmetric Unit (Motif, what
to repeat) + Wyckoff positions
• First atom cannot replace another atom = asymmetric atoms (motif)
• No. of atoms in unit cell = Wyckoff positions
• Wyckoff position determines where to put atoms (motif/asymmetric
unit)
• 230 theoretical space groups, out of which 72 are simple space
groups (based on simple definition)
• In many space groups no material exists – mathematical space group
• We can change the crystal structure by changing orientation of basis
 Point Group and Space Group
• The group of all symmetry elements of a crystal except translation
(rotation, reflection, inversion and their combinations) passing
through a single point is called its POINT GROUP. Any point group
symmetry operation leaves this point invariant. They relate internal
symmetry to external symmetry of crystal. 32 point groups in 3D.
• The complete group of all symmetry elements including translations
of a crystal is called its SPACE GROUP. It describes how all symmetry
elements are arranged relative to one another. There are 17 Space
Groups in 2D and 230 in 3D. (219 without chirals, 230 with chirals)
 External Symmetry
• An object that consists of a systematic repetition of identical features
is said to have symmetry.
 Types of External (Macroscopic) Symmetry
1. Symmetry with respect to a plane (mirror)
2D + 3D
2. Symmetry with respect to a line (axis)
3. Symmetry with respect to a point (inversion center) – 3D only
 Four Macroscopic Symmetry Operations
1. Reflection (mirror plane)
2. Rotation Axis (1,2,3,4 and 6 fold)
3. Inversion Center
4. Roto – inversion (combination of rotation and inversion)
 Crystallographic Restriction Theorem
• Why only 1,2,3,4, and 6 – fold rotation?
• Crystals are built by regular stacking of unit cells that are translated.
• In other words, crystals have translation.
• All the symmetry operations must be compatible with each other
(internal as well as external).
• Translational symmetry operator should be compatible with rotation
symmetry operator.
• This results in limitation on combination of symmetry elements that
are compatible with each other.
 Crystallographic Restriction Theorem
• Rotation operators acting on points A & A’ generate points B & B’.
• For B & B’ to be valid lattice points, the distance between them (t’)
must be an integral number (m) of the translation vector(t).
• Therefore, t’ = mt.
Symmetry with respect to a line
 Symmetry with respect to a point
• Symmetry w.r.t a point signifies that equidistant from this point in
opposite directions identical features will always be encountered.
 Kind of Symmetry Operations
• The geometric movement necessary to bring a given point 𝑎𝑎1 into
coincidence with a symmetrically equivalent point 𝑎𝑎2 is called
symmetry operation.
• FIRST KIND OPERATIONS: These operations generate additional
left/right hand. 1,2,3,4, and 6 fold axes represent the operations of
first kind and called proper axes.
• SECOND KIND OPERATIONS: These operations produce a change of
hand and are called improper axes. These include (1) Plane of
symmetry (reflection), (2) Centre of symmetry (inversion) and
(3) Roto – inversion i.e. rotation followed by inversion.
Symmetry Operators associated with the five
improper axes or inversion axes
Review of the 10 – point groups
Symmetry Representation
 Mathematical Group
• A nonempty set G and a binary operation * on G such that the
operation obeys the following axioms.
• A1, Closure : a*b is in G
• A2, Associativity : (a*b)*c = a*(b*c)
• A3, Identity : a*𝐼𝐼 = 𝐼𝐼*a
• A4, Inverse : For each a in G, there exists an inverse element 𝑥𝑥 in G
such that 𝑎𝑎*𝑥𝑥 = 𝑥𝑥*a = 𝐼𝐼
 Combination of Symmetry Elements
• 10 basic symmetry elements (5 proper axes and 5 improper axes) or
combinations in which 3 or more of these pass through the center of
a crystal are sufficient to describe the external symmetry of any
crystal in the universe.
• In addition to 10 basic elements(6, 4, 3, 2, 1, 6� , 4� , 3� , 2� (= m), and 1�
( = i)), only 22 possible combinations of them can pass through a
central point in a crystal.
• 2 and only 2 symmetry axes intersecting at a point is an impossibility.
If 2 such axes intersect, at least a third axis must also pass through
their common point.
 Combination of Rotations
• Axes of rotation can only be combined in symmetrically consistent
way such that an infinite set of axes is not generated.
• All symmetry axes must intersect at a point such that it remains
unchanged by the operations.
• Furthermore, many combinations are impossible in crystals because
the symmetry elements would react repeatedly on each other to
produce an infinite multiplicity of these elements.
 Combination of Rotations
• To illustrate, two 6-fold axes, 𝑎𝑎1 and b in Figure 1 – 8, cannot pass
through a common point p in a crystal and be compatible with its
symmetry.
• Thus the operation of axis b on 𝑎𝑎1 requires five additional 6 – fold
axes at 𝑎𝑎2 , 𝑎𝑎3 , 𝑎𝑎4 , 𝑎𝑎5 , 𝑎𝑎6 . These then operate at b, on 𝑎𝑎1 , and on each
other require still more 6 – fold axes which, in turn, interact with each
other (and those already established). The process would continue ad
infinitum until 6 – fold axes extended outwards from 𝑝𝑝 in an infinite
variety of directions.
 Combination of Rotations
• Such an infinite multiplicity of symmetry axes extending outwards
from a single point is compatible only with the external symmetry of a
perfect sphere, a geometric shape alien to all crystals. (However, all
crystals do possess an infinite number of 1 – fold axes, that is, axes of
nonsymmetry; these represent all the directions in the crystal that do
not coincide with 2 –, 3 –, 4 –, 6 –, 1� − , 2� − , 3� − , 4� − , 𝑜𝑜𝑜𝑜 6� − fold
axes).
Rule of Spherical Triangles
Mirror Plane Perpendicular to Even Fold Axis
• 2/m
• 4/m
• 6/m
• Inversion Center is created at the intersection of the even fold axis
and the mirror plane.
• Point groups seen till now are = 1, 2, 3, 4, 6, 1� 𝑖𝑖 , 2� 𝑚𝑚 , �3, �4, 6� ,
2 4 6
222, 322, 422, 622, 233, 432, , , 𝑎𝑎𝑎𝑎𝑎𝑎 (Total of 19 point
𝑚𝑚 𝑚𝑚 𝑚𝑚
groups).
 Mirror Plane Perpendicular to Each Axis
2 2 2
• 222°𝑖𝑖 = = 𝑚𝑚𝑚𝑚𝑚𝑚 = Point group of Orthorhombic Structure =
𝑚𝑚 𝑚𝑚 𝑚𝑚
3 perpendicular 2 – fold axis and 3 perpendicular mirrors intersecting
each other.
4 2 2
• 422°𝑖𝑖 = = 𝑜𝑜𝑜𝑜𝑜𝑜 4 − 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 + 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 2 − 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 +
𝑚𝑚 𝑚𝑚 𝑚𝑚
5 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚.
2 2
• 322°𝑖𝑖 = 3 �
𝑚𝑚 𝑚𝑚
6 2 2
• 622°𝑖𝑖 =
𝑚𝑚 𝑚𝑚 𝑚𝑚
 Mirror Plane Perpendicular to Each Axis
2 2
• 233°𝑖𝑖 = 3� 3� = 3�
𝑚𝑚 𝑚𝑚
• 3 perpendicular mirror planes + 3 perpendicular 2 – fold axis + four 3�
axis in 233°𝑖𝑖.
4 2
�
• 432°𝑖𝑖 = 3 = 𝑚𝑚3� 𝑚𝑚 = ℎ𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔
𝑚𝑚 𝑚𝑚
• 𝑚𝑚3� 𝑚𝑚 = cubic (SC+BCC+FCC)
• In 𝑚𝑚3� 𝑚𝑚 𝑖𝑖𝑖𝑖 𝐼𝐼 put an atom at (0,0,0) – then we will get 8 atoms at 8
corners by symmetry.
• If I put an atom in 𝑚𝑚3� 𝑚𝑚 at any general point 𝑥𝑥, 𝑦𝑦, 𝑧𝑧 and not at any
special point (mirror, axis, inversion center) then we can generate 48
equivalent positions and the structure will still be cubic if symmetry is
followed.
 622°𝑖𝑖
322°𝑖𝑖
• No two mirror planes can intersect without
having an axis passing through their junction.
 32 Point Groups
1. 1
2. 2
3. 3
4. 4
5. 6
6. 1� = 𝑖𝑖
7. 2� = 𝑚𝑚
8. 3�
 32 Point Groups
9. 4�
3
10. 6� = 𝑚𝑚
11. 222
12. 322
13. 422
14. 622
15. 233
16. 432
 32 Point Groups
2
17. 𝑚𝑚
4
18. 𝑚𝑚
6
19. 𝑚𝑚
2 2 2
20. 222°𝑖𝑖 = 𝑚𝑚 𝑚𝑚 𝑚𝑚
= 𝑚𝑚𝑚𝑚𝑚𝑚
21. 322°𝑖𝑖 = �3 2 2
𝑚𝑚 𝑚𝑚
4 2 2
22. 422°𝑖𝑖 = 𝑚𝑚 𝑚𝑚 𝑚𝑚
 32 Point Groups
6 2 2
23. 622°𝑖𝑖 = 𝑚𝑚 𝑚𝑚 𝑚𝑚
2
24. 233°𝑖𝑖 = �33� = 2 3�
𝑚𝑚 𝑚𝑚
4
25. 432°𝑖𝑖 = �3 2 = 𝑚𝑚3� 𝑚𝑚
𝑚𝑚 𝑚𝑚
26. 22� 2� = 2𝑚𝑚𝑚𝑚
27. 32� 2� = 3𝑚𝑚𝑚𝑚
28. 42� 2� = 4𝑚𝑚𝑚𝑚
29. 62� 2� = 6𝑚𝑚𝑚𝑚
 32 Point Groups
30. 4� 32� = 4� 3𝑚𝑚
31. 6� 2� 2 = 6� 𝑚𝑚𝑚
32. 4� 22� = 4� 2𝑚𝑚 = 4� 𝑚𝑚𝑚
 Screw Axis and Glide Planes
• Rotation, Reflection planes, Inversion lead to 32 point groups – No
translations.
• We need to minimize mean free volume of structures
• When translation interact with symmetry operators it results in the
two final symmetry operators.
• Screw Axis = Rotation + Translation (21 , 31 , 32 , 41 , 42 , 43 , 61 , 62 , 63 , 64 ,
65 ).
• Glide Planes = Mirror Plane + Translation (a, b, c, n, d).
 Glide Planes
• Reflection + Translation
• When going from a space group to parent point group, all a’s , b’s , c’s,
n’s and d’s are converted back into m’s.
 Screw Axis
• Rotation + Translation
• n – fold rotation followed by a translation parallel to the rotation axis.
• Each and every point in the crystal should have identical
surroundings.
• 𝑛𝑛𝑚𝑚 = Screw Axis
𝑚𝑚
• 𝑛𝑛𝑚𝑚 → 𝑡𝑡 = 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑜𝑜𝑜𝑜 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 = 𝑃𝑃,
𝑛𝑛
• P = Lattice Translation Vector
1
• 42 = 𝑃𝑃
2
 Some Other Points
• 41 𝑎𝑎𝑎𝑎𝑎𝑎 43 𝑎𝑎𝑎𝑎𝑎𝑎 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
• 31 𝑎𝑎𝑎𝑎𝑎𝑎 32 𝑎𝑎𝑎𝑎𝑎𝑎 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
• 61 𝑎𝑎𝑎𝑎𝑎𝑎 65 𝑎𝑎𝑎𝑎𝑎𝑎 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
• 62 𝑎𝑎𝑎𝑎𝑎𝑎 64 𝑎𝑎𝑎𝑎𝑎𝑎 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
• 42 𝑎𝑎𝑎𝑎𝑎𝑎 63 𝑎𝑎𝑎𝑎𝑎𝑎 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
• Combination of 32 point groups with 14 Bravais Lattices results in 72
simple space groups under 7 crystal systems.
• In a cubic crystal system the P, 𝐼𝐼, F types of lattices exists for all 5
point groups giving a total of 15 space groups.
 Some Other Points
• Combination of 32 point groups with screw axis and glide planes
results in remaining 158 space groups.
• Total 230 space groups. Any crystal has to be one of these 230
combinations.
 Some facts about point groups
• Diffraction Pattern is always centro – symmetric.
• Centro – symmetry = even though inversion center is present the
diffraction pattern will say it is not present.
32 Point Groups

𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 − 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 11 Laue Classes
𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑖𝑖𝑖𝑖 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑

𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 6 Laue Classes

• Most of the 32-point groups are distinguished by Convergent Beam Electron

Diffraction (CBED) , Low Order Laue Zones (LOLZ) , High Order Laue Zones (HOLZ)
– TEM techniques.
Space Groups
 Space Groups
• 𝐼𝐼 41 22
• 41 22 = generator = used to produce identity points.
• General point in cubic = generates 48 points – for 𝐹𝐹𝐹𝐹3� 𝑚𝑚 − (000),
11 1 1 11
0 , 0 , 0 = 48 × 3 = 192 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 − 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝐹𝐹𝐹𝐹𝐹𝐹.
22 2 2 22
• A prototype (i.e. structure type) is provided for each phase.
• Pearson symbol and space group tell us about Bravais Lattice, Basis,
and Symmetry.
• Atoms, Point Set, (xyz) and Occ (Occupancy) are the Wykoff
generating sites.
 Occupancy
• For pure Cu structure = occupancy of Cu = 1.
• For CuZn (𝛽𝛽 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵) = occupancy of Cu = 0.5, occupancy of Zn = 0.5.
 Space Groups
• These are the sites of specific atoms in the crystal structure that the
space group symmetry operators act on.
• We find these sites in the International Tables for Crystallography,
Volume A, Space Group Symmetry.
Mathematical Representation of
Rotation, Reflection and Inversion
 One Step Operations
2D Pattern Change of Sense
Translation Of no coordinate
Reflection Of one coordinate
Rotation Of two coordinate

3D Pattern Change of Sense

Translation Of no coordinate
Reflection Of one coordinate
Rotation Of two coordinate
Inversion Of three coordinate
Rotation about z - axis
 Properties of Rotation Matrices
• Square, 2 × 2 𝑜𝑜𝑜𝑜 3 × 3.
• The product of any two rotation matrices is a rotation matrix.
• The inverse equals the transpose, 𝑅𝑅 −1 = 𝑅𝑅 𝑇𝑇 .
• Orthogonality,
1. The dot product of any row or column with itself is one.
2. The dot product of any row or column with a different row or
column is zero.
• 𝑥𝑥 equals 𝑅𝑅𝑅𝑅 , for any rotation R.
 Rotation
cos 𝜃𝜃 − sin 𝜃𝜃 0 𝑥𝑥 𝑥𝑥′
• sin 𝜃𝜃 cos 𝜃𝜃 0 𝑦𝑦 = 𝑦𝑦𝑦
0 0 1 𝑧𝑧 𝑧𝑧𝑧
 2 – Fold Rotation
−1 0 0 𝑥𝑥 −𝑥𝑥
• 0 −1 0 𝑦𝑦 = −𝑦𝑦
0 0 1 𝑧𝑧 𝑧𝑧
• Equivalent Positions = (xyz), 𝑥𝑥̅ 𝑦𝑦𝑧𝑧
�
 4 – fold rotation
0 −1 0 𝑥𝑥 −𝑦𝑦
• 1 0 0 𝑦𝑦 = 𝑥𝑥
0 0 1 𝑧𝑧 𝑧𝑧
• Equivalent Positions = (xyz), 𝑦𝑦𝑥𝑥𝑥𝑥
� , 𝑥𝑥̅ 𝑦𝑦𝑧𝑧
� , 𝑦𝑦𝑥𝑥𝑧𝑧
̅
 Mirror Plane
1 0 0 𝑥𝑥 𝑥𝑥
• 0 1 0 𝑦𝑦 = 𝑦𝑦
0 0 −1 𝑧𝑧 −𝑧𝑧
 Point of Inversion
−1 0 0 𝑥𝑥 𝑥𝑥̅
• 0 −1 0 𝑦𝑦 = 𝑦𝑦�
0 0 −1 𝑧𝑧 𝑧𝑧̅
 Glide Plane
1 0 0 𝑥𝑥 1⁄2 𝑥𝑥 + 1/2
• 0 1 0 𝑦𝑦 + 0 = 𝑦𝑦
0 0 −1 𝑧𝑧 0 𝑧𝑧̅
 A 3D Rotation Matrix
• Is the product of 2D rotation matrices.
cos 𝛽𝛽 − sin 𝛽𝛽 0 cos 𝛾𝛾 0 sin 𝛾𝛾
• sin 𝛽𝛽 cos 𝛽𝛽 0 0 1 0 =
0 0 1 sin 𝛾𝛾 0 cos 𝛾𝛾

cos 𝛽𝛽 cos 𝛾𝛾 − sin 𝛽𝛽 cos 𝛽𝛽

sin 𝛽𝛽 cos 𝛾𝛾 cos 𝛽𝛽 − sin 𝛽𝛽 sin 𝛾𝛾
sin 𝛾𝛾 0 cos 𝛾𝛾
XRD : Fundamentals and
Applications
 XRD Applications
1. Powder Diffraction = Phase Identification/Quantification (Rietveld
Method).
2. Phase Transformation (High Temperature XRD).
3. Texture in Materials.
4. Thin film (GIXRD) and X – Ray Reflectivity (Polycrystalline, Epitaxial
and Amorphous Films).
5. Residual Stresses.
6. Small Angle X – Ray Scattering (Nano Size Distribution).
7. Size – Strain Analysis (Size Distribution and defect density – WH,
WA, MWH, MWA analysis).
8. X – Ray Tomography.
 Basics of XRD
• Interaction of X – Rays with Matter (Fluorescence and Diffraction).
• Bragg’s Law.
• Powdered vs. Bulk Sample, Sample Preparation.
• Relative Intensity and Parameters Affecting Diffracted Intensity in
Single Phase Materials, Multiphase Materials.
• Typical Diffractometers (Intensity vs. 2𝜃𝜃) for SC, BCC and FCC
materials.
• Finally how to do phase analysis and crystallite size analysis?
Qualitative and Quantitative).
 Interaction of X – Rays with a Material
• When an incident monochromatic beam of X – rays of intensity 𝐼𝐼0 is
incident on a material several phenomena occur like:
1. Beam Attenuation (Intensity of Transmitted Beam = 𝐼𝐼)
2. Elastic Scattering ℎ𝜈𝜈
3. Inelastic Scattering ℎ𝜈𝜈𝜈
4. Photo – electrons are emitted 𝐸𝐸
5. Auger electrons are emitted 𝐸𝐸𝐴𝐴
6. Fluorescence ℎ𝜐𝜐𝑓𝑓
 Interaction of X – Rays with a Material
• Transmitted beam is 95% of the incident beam.
𝐼𝐼
• 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 =
𝐼𝐼0
• Constructive Interference of Elastically Scattered waves in a particular
direction given by Bragg’s Law is called Diffraction.
 X – Ray and Atom
• An X – Ray photon (wave) interacts with electrons – electronic
phenomenon.
• Nucleus is considered to be very heavy, so it does not take part in the
interaction.
• Electrons are scattering centers.
• Frequency of oscillation of electrons = frequency of oscillation of
incoming radiation.
• X – Ray beam interacts with each individual electron and gets
scattered in other directions in 3D.
 X – Ray and Atom
• These scattering centers (electrons) depend on the crystal structure
of the material.
• Beams will interact with each other depending on the phase
difference between them in certain directions. The directions are
given by Bragg’s Law. This gives rise to constructive interference.
 Fluorescence
• Emission at a different wavelength (Non – Elastic).
 Scattering
• Emission at same wavelength (Elastic).
• Dipole oscillations of electrons.
• When X – Rays are incident on any Single Crystal in any orientation,
the maximum intensity is of the transmitted beam.
• If we are using X – Rays of 5 𝜇𝜇𝑚𝑚 diameter then the spot has a
diameter of 4 𝜇𝜇𝑚𝑚.
• If inversion center is present in the point group of that material it is
present at the center of the spot and gets masked due to the very
intense transmitted radiation, so we get only 11 Laue Patterns instead
of the 32 Point Groups in XRD.
 Inversion Center = masked by the
Sample coarse spot due to the
transmission beam

Incident Beam Transmitted Beam

Coarse Spot due to the

transmission beam
 Diffraction = Sum of Scattering
• Scattered X – Rays adding together in phase to give a diffracted beam
(interference).
• Bragg’s Law is followed.
 Scattering Centers in Material
• Any material is a mass of scattering center as if it has a homogeneous
electric field distribution.
• At GB – no specific arrangement of atoms – imperfection – no order –
inhomogeneous elastic field distribution – so when probing GB we get
destructive interference i.e. scattered intensity.
• Where any length scale is repeated sufficiently often there will be
enhanced scattering intensity in some directions due to
homogeneous electric field distribution.
 Scattering Centers in Material
• Random distribution of bond lengths in amorphous solids and liquids
(SRO and no LRO) gives an amorphous hump and information about
the average SRO of the material is obtained.
• If the scattering centers are very ordered and periodic the peaks in
scattered intensity form a diffraction pattern.
• Crystals have homogeneous electric field distribution and periodic
array, so they show discreet diffraction pattern.
• X – Ray studies are done for solids (mostly for crystalline solids).
 Diffraction from Crystals
• How to simplify diffraction from 3D array of atoms.
• Principle (Laue/Ewald) : Add scattering from every individual
scattering center.
𝑆𝑆−𝑆𝑆0
• =ℎ
𝜆𝜆
𝑆𝑆−𝑆𝑆0
• = 𝑘𝑘 Laue Conditions
𝜆𝜆
𝑆𝑆−𝑆𝑆0
• = 𝑙𝑙
𝜆𝜆
• 𝑆𝑆 = original intensity, 𝑆𝑆0 = scattered intensity
 Diffraction from Crystals
• Simplification : Bragg’s Law : Describes a crystal as set of planes
• Universal Law
• 𝑛𝑛𝜆𝜆 = 2𝑑𝑑 sin 𝜃𝜃
• 𝑑𝑑 = 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
 Compton Experiment (1922)
′ ℏ
• 𝜆𝜆 = 𝜆𝜆 +
𝑚𝑚𝑚𝑚
• 𝜆𝜆′ = 𝜆𝜆 + 𝜆𝜆𝐶𝐶 1 − cos 𝜃𝜃
• 𝜆𝜆𝐶𝐶 = 0.002426 𝐴𝐴̇ (𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊)
• Elastic Interaction:
1. Coherent (Thomson Scattering)
2. Incoherent (Compton Scattering) – dependent on angle
′ 𝐸𝐸 (𝑘𝑘𝑘𝑘𝑘𝑘)
• 𝐸𝐸 𝑘𝑘𝑘𝑘𝑘𝑘 =
1+0.001957𝐸𝐸 1−cos 𝜃𝜃
• XRD is elastic coherent scattering.
 Scattering of X – Rays from an Electron
Thomson Scattering Compton Scattering
𝜈𝜈 ′ = 𝜈𝜈 𝜈𝜈′ ≠ 𝜈𝜈
Elastic (“coherent”, “unmodified”) Inelastic (“incoherent”, “modified”)
Free electron = Classical Treatment Free Electron = Quantum Treatment
Electrons in atom = tightly bounded Electrons in atom = Loosely bounded
 Bragg’s Law
• Conditions for the validity of Bragg’s Law :
1. Incident Beam, Scattered Beam and Plane Normal should be
coplanar.
𝜆𝜆
2. sin 𝜃𝜃 = 2𝑑𝑑
< 1 → 𝜆𝜆 < 2𝑑𝑑
3. Angle of incidence = Angle of Reflection (Symmetry)
• Constructive interference causes amplitude to be increased at Bragg’s
Angle.
• Destructive Interference causes amplitude to be decreased to zero at
non – Bragg’s angle (if crystal is infinitely thick perpendicular to the
said plane).
 Bragg’s Law
• 𝑛𝑛𝜆𝜆 = 2𝑑𝑑 sin 𝜃𝜃
• The width could be indicative of thickness (size) of the crystal in that
direction.
Bragg’s Law gives information only about lattice planes (Bravais Lattice)

Lattice Type can be determined

Information available only about GRID

 Bragg’s Law
• What about BASIS??
• Crystal Structure = Space Lattice + BASIS
 Properties of X – Rays Required in XRD
• Narrow line width (~0.6 𝑒𝑒𝑒𝑒 𝑎𝑎𝑎𝑎 ~1𝑘𝑘𝑘𝑘𝑘𝑘).
• Monochromatic Radiation.
• Perfectly Parallel Beam.
• High Intensities (>100 times the background).
• Cooling is warranted as only 1% of the KE is converted into X – Rays.
• Several modes of excitation, by electrons, photons and ions.
• Excitation of ionizing K, L, M, …. Electrons.
• Several modes of relaxation like Fluorescence, Auger Electrons, etc.
 Production of X - Rays
• A 45 keV bias is generated between the cathode (W – filament) and
the anode (target metal).
• Fluorescence occurs i.e. 𝐾𝐾𝛼𝛼 , 𝐾𝐾𝛽𝛽 , 𝐿𝐿𝛼𝛼 , 𝐿𝐿𝛽𝛽 wavelength radiations are
emitted.
• These are the 4 strongest radiations.
• The Be window is at 6° to the target metal plate as the maximum
efficiency of X – Rays generation is obtained at this angle i.e. the
maximum output of X – Rays is obtained.
• The Be window absorbs the 𝐿𝐿𝛼𝛼 , 𝐿𝐿𝛽𝛽 wavelengths or they can be
removed electronically.
 Production of X - Rays
• The source is linear filament .
• Both Linear Focus and Point Focus is possible.
• Line Focus is used in XRD.
• Point Focus is used for calculating Residual Stresses, Texture, etc.
• Water at 23℃ is used to cool the target metal as 99% of the KE goes
as heat.
• Conventional XRD: 45 keV and 40 mA.
• Rotating Anode Generator – Anode is continuously rotating – we can
afford to have higher current as target metal will not melt – 45 keV
and 300 mA – as current and voltage increase the intensity increases.
 X – Ray Source
• The Probing Dimension should match the wavelength of the probe.
• 𝜆𝜆 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑑𝑑ℎ𝑘𝑘𝑘𝑘 .
• Diffraction Grating must have spacing comparable to the wavelength
of the diffracted radiation.
• X – Rays are produced when any electrically charged particles of
sufficient kinetic energy is rapidly deaccelerated.
• Electrons are normally used for this purpose they are emitted due to
thermionic emission.
• X – Rays are produced at the point of impact and radiate in all
directions.
 X – Ray Source
1
• 𝐾𝐾𝐾𝐾 = 𝑒𝑒𝑒𝑒 = 𝑚𝑚𝑒𝑒 𝑣𝑣 2
2
• Most of the Kinetic Energy of the electrons are converted into X –
Rays.
• Only less than 1% being converted into X – Rays .
• X – Rays coming from the target have a mixture of different
wavelengths.
• The intensity is zero up to a certain wavelength called the Short
Wavelength Limit (SWL).
 X – Ray Source
• Smooth Curves are called Heterochromatic, Continuous or White
Radiation.
• Continuous Spectrum is due to deceleration of Electrons.
• There is a threshold voltage which only triggers the release of
Characteristic X – Rays.
• As the Accelerating Voltage Increases then the Intensity increases,
and the wavelength of the peak intensity reduces.
 The Continuous Spectrum
• Due to deceleration of Electrons.
• Any decelerated charge emits energy.
• The electrons which are stopped in one impact will give rise to
photons of maximum energy, i.e. X – Rays of minimum wavelength,
for such transition we may write.
• 𝑒𝑒𝑒𝑒 = ℎ𝜐𝜐𝑚𝑚𝑚𝑚𝑚𝑚
𝑐𝑐 ℎ𝑐𝑐 12.39×103
• 𝜆𝜆𝑆𝑆𝑆𝑆𝑆𝑆 = 𝜆𝜆𝑚𝑚𝑚𝑚𝑚𝑚 = = = (𝑖𝑖𝑖𝑖 𝐴𝐴0 )
𝜈𝜈𝑚𝑚𝑚𝑚𝑚𝑚 𝑒𝑒𝑒𝑒 𝑉𝑉
0
• This equation gives SWL in 𝐴𝐴 as a function of applied voltage.
 The Continuous Spectrum
• The total X – Ray energy emitted per second, which is proportional to
the area under one of the curves, which also depends upon Atomic
Number of the target Z, tube current ‘𝑖𝑖’, the later being the measure
of number of electrons per second striking the target.
• The total X – Ray intensity is given by:
• 𝐼𝐼𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 (𝑐𝑐𝑐𝑐) = 𝐴𝐴𝐴𝐴𝐴𝐴𝑉𝑉 𝑚𝑚
• 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤, 𝐴𝐴 𝑖𝑖𝑖𝑖 𝑡𝑡𝑡𝑡𝑡 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑎𝑎𝑎𝑎𝑎𝑎 𝑚𝑚 𝑖𝑖𝑖𝑖 𝑎𝑎 constant
with a value of about 2.
• W and Ag are used as targets in XRF as they have Z and will produce
high intensity white radiation (fluorescence) – high 𝑖𝑖.
 The Characteristic Spectrum
• When the voltage is raised above a certain critical value, which is a
characteristic of a target metal then sharp intensity maxima appears
at certain wavelengths superimposed on the continuous spectrum.
• These lines are narrow and since their wavelengths are characteristics
of the target metal used, they are called characteristic lines.
• The 𝐿𝐿𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝐿𝐿𝛽𝛽 𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙 are removed using a Be windows or
electronically.
• Only K lines are useful in XRD as the longer wavelength line being
easily absorbed.
 The Characteristic Spectrum
• The above Figure is of spectrum of Mo at 35 kV, resolved doublet
peak
• 𝐾𝐾𝛼𝛼1 = 0.709 𝐴𝐴0
• 𝐾𝐾𝛼𝛼2 = 0.714 𝐴𝐴0
• 𝐾𝐾𝛽𝛽1 = 0.632 𝐴𝐴0
• The intensity of the characteristic radiation depends on the tube
current i, applied voltage V and excitation voltage 𝑉𝑉𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 .
• 𝐼𝐼𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = 𝐵𝐵𝐵𝐵 𝑉𝑉 − 𝑉𝑉𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑛𝑛
• 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤, 𝑛𝑛 = 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 1.5 𝑎𝑎𝑎𝑎𝑎𝑎 𝐵𝐵 = 𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
 The Characteristic Spectrum
• The critical excitation voltage necessary for Cu target is 25 keV.
• 𝜈𝜈 = 𝐶𝐶 𝑍𝑍 − 𝜎𝜎 → 𝑇𝑇𝑇𝑇𝑇𝑇𝑇 𝑖𝑖𝑖𝑖 𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑦𝑦 ′ 𝑠𝑠 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅.
• The wavelength of any particular line decreases as the Z of the
emitter increases. Where C and 𝜎𝜎 are constants.
 Possible Electron Transitions
• The difference in the two shell energies equals the energy of the
characteristic X – Ray.
• K excitation voltage is necessary to excite K characteristic radiation.
• An increase in the voltage above the critical voltage, increases the
intensity of the characteristic lines relative to the continuous
spectrum but wavelength remains same.
• Given below is the curve for Mosley’s Relation between frequency
and atomic number (Z) of two characteristic lines.
 Possible Electron Transitions
• The above figure shows that L lines are not always of long
wavelength, here the 𝐿𝐿𝛼𝛼1 line of a heavy metal like W has about the
same wavelength as the 𝐾𝐾𝛼𝛼1 line of Cu, namely 1.5 𝐴𝐴.̇
• Critical excitation voltage is required for characteristic radiation.
• For example, K radiation cannot be excited unless the tube voltage is
such that the bombarding electrons have enough energy to knock an
electron out off K shell of atom.
• The work required to remove a K electron, then the necessary KE of
the electron is given by:
1
• 𝑊𝑊𝐾𝐾 = 𝑚𝑚𝑣𝑣 2
2
 Possible Electron Transitions
• Intensity of 𝐾𝐾𝛼𝛼1 = 2 × 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝑜𝑜𝑜𝑜 𝐾𝐾𝛼𝛼𝛼
 Absorption
• When X – Rays encounter any form of matter they are partly
absorbed and partly transmitted.
• The fractional decrease in the intensity 𝐼𝐼 of an X – Ray beam as it
passes through any homogenous substance is proportional to the
distance traveled.
𝑑𝑑𝑑𝑑
• − = 𝜇𝜇𝜇𝜇𝜇𝜇
𝐼𝐼
• 𝜇𝜇 = Linear Absorption Coefficient and depends on the substance, its
density and on the wavelength of the X – Rays.
 Absorption
• 𝐼𝐼𝑥𝑥 = 𝐼𝐼0 𝑒𝑒 −𝜇𝜇𝜇𝜇
• 𝐼𝐼0 = 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝑜𝑜𝑜𝑜 𝑡𝑡𝑡𝑡𝑡 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵
• 𝐼𝐼𝑥𝑥 = 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝑜𝑜𝑜𝑜 𝑡𝑡𝑡𝑡𝑡 𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵
• 𝑥𝑥 = 𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇
• 𝜇𝜇 is directly proportional to 𝜌𝜌.
𝜇𝜇
• So = Constant of a material and is independent of physical state and
𝜌𝜌
is called mass absorption coefficient.
𝜇𝜇
−𝜌𝜌 𝑥𝑥
• 𝐼𝐼𝑥𝑥 = 𝐼𝐼0 𝑒𝑒 𝜌𝜌
 Absorption
• Whether the substance is a mechanical mixture, a solution or a
chemical compound and whether it is solid, liquid or gaseous. Its
𝜇𝜇
mass absorption coefficient is simply the weighted average of the
𝜌𝜌
of its constituent elements.
𝜇𝜇 𝜇𝜇 𝜇𝜇
• = 𝑤𝑤1 + 𝑤𝑤2 +……….
𝜌𝜌 𝜌𝜌 1 𝜌𝜌 2
• 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤, w1 , w2 ,…. Are the wt. fractions of the elements
• The way in which the absorption coefficient varies with wavelength
gives the clue about the interaction of X – Rays and atoms.
 Absorption
• Two similar branches separated by a sharp discontinuity called
Absorption Edge.
• Along each branch the absorption coefficient varies with wavelength
approximately according to the form:
𝜇𝜇
• = 𝑘𝑘𝜆𝜆3 𝑍𝑍 3
𝜌𝜌
• k = a constant, with a different value for each branch of the curve
• Z = Atomic number of Absorber
• Short Wavelength of X – Rays = Hard X – Rays
• Long Wavelength of X – Rays = Soft X - Rays
 Filters
• We need to filter out the 𝐾𝐾𝛽𝛽 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑡𝑡𝑡𝑡𝑡 𝐾𝐾𝛼𝛼 .
• So we use a filter of a material having high mass absorption
coefficient for the 𝐾𝐾𝛽𝛽 wavelength of the target material.
• This filter absorbs the incident 𝐾𝐾𝛽𝛽 wavelength and causes
fluorescence in itself.
• Normally for a target plate of material having an Atomic Number Z,
the filter is of a material having an Atomic Number (Z – 1).
• So for Cu target a Ni filter is used to filter out the 𝐾𝐾𝛽𝛽 , similarly for Mo
target Zr filter is used.
 Filters
• The intensity of the 𝐾𝐾𝛼𝛼 line also decreases on using a filter, but we
can achieve a desired 𝐾𝐾𝛼𝛼 𝑡𝑡𝑡𝑡 𝐾𝐾𝛽𝛽 ratio – (250:1 to 350:1).
• We cannot separate 𝐾𝐾𝛼𝛼2 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝐾𝐾𝛼𝛼1 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓.
 High Resolution Diffractometer
• In High Resolution Diffractometer we use optics to separate 𝐾𝐾𝛼𝛼1 from
𝐾𝐾𝛼𝛼2 .
• The optics is like the optics that we use in WDS to separate the
different wavelengths.
• In a conventional diffractometer we cannot see the effect of
tetragonality as the ratio and position of the 𝐾𝐾𝛼𝛼1 𝑎𝑎𝑎𝑎𝑎𝑎 𝐾𝐾𝛼𝛼𝛼 peaks is
same as that of the 𝐾𝐾𝛼𝛼1 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑓𝑓𝑓𝑓𝑓𝑓 𝑎𝑎 𝑎𝑎𝑎𝑎𝑎𝑎 𝐾𝐾𝛼𝛼𝛼 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑓𝑓𝑓𝑓𝑓𝑓 𝑐𝑐 in case of
martensite and for electronic materials like BaTiO3.
• The tetragonality is 0.2 for martensite.
 High Resolution Diffractometer
• So we need to use High Resolution Diffractometer to observe
tetragonality, microstrain, etc.
• This is because the High – Resolution Diffractometer has a least count
of 0.002°.
 Diffraction Intensity
• Bragg’s Law of Diffraction merely refers to the direction of diffraction
and does not refer to the intensity of the diffracted beam.
• The intensity of the diffracted beam depends on several factors like
the atoms involved, the type of the crystal structure, the no. and type
of the reflecting planes involved, the geometry of the diffraction
method used, the temperature during diffraction, etc.
• So it is possible that even though Bragg’s Law is satisfied, the
diffraction intensity may be negligible or zero if the factors mentioned
are not favourable.
 Factors Affecting Peak Intensity
1. Structure Factor (Form Factor)
2. Multiplicity
3. Lorentz Factor
4. Polarization Factor
5. Temperature Factor or Atomic Displacement
6. Absorption
7. Preferred Orientation
8. Extinction Coefficients
 Diffraction Intensity
• In such conditions the diffracted beam may not practically exist.
• In other words, it is not necessary that diffraction should occur
whenever Bragg’s Law is satisfied.
• But, if Bragg’s law is not satisfied, the diffraction can never occur.
• 𝐼𝐼 = 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 2 × 𝑝𝑝 × 𝐿𝐿𝐿𝐿𝐿𝐿 × 𝐴𝐴𝐴𝐴 × 𝑇𝑇𝑇𝑇
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 = 𝑓𝑓(𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝑖𝑖. 𝑒𝑒. 𝑓𝑓)
• 𝑝𝑝 = 𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀
• 𝐿𝐿𝐿𝐿𝐿𝐿 = 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 − 𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹
• 𝐴𝐴𝐴𝐴 = 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹
• 𝑇𝑇𝑇𝑇 = 𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹
 Atomic Scattering Factor
• When X – Rays beam strikes an atom, coherent (Thomson) scattering
takes place from all the bound electrons of the atom in accordance
with the Thomson Equation.
• Nucleus of the atom is not able to take part in scattering since it
cannot be made to oscillate to an appreciable extent due to its
extremely large mass relative to an electron.
• Thomson Equation shows that the scattering intensity is inversely
proportional to the square of the mass of the scattering particle and
the intensity scattered by the nucleus is therefore negligible due to its
large mass.
 Atomic Scattering Factor
• In the Fig. Path Difference between the two scattered rays from the
two electrons = CB – AD
• This value is small compared to the wavelength of X – Rays used for
the purpose of diffraction, destructive interference takes place, the
extent of which depends on the angle 2𝜃𝜃.
• The scattered rays in the forward direction (2𝜃𝜃 = 0°) are completely
in phase with each other whereas the rays scattered in all other
directions are out of phase to different extents.
• As the angle 2𝜃𝜃 increases, the path difference increases between the
scattered rays and the intensity consequently decreases, because of
increased “out – of – phaseness”.
 Atomic Scattering Factor
• The atomic scattering factor ‘f’ is defined as the ratio of the amplitude
of the X – Ray wave scattered by an atom (i.e. by all the electrons in
the atom) to that scattered by a single electron
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑜𝑜𝑜𝑜 𝑡𝑡𝑡𝑡𝑡 𝑋𝑋−𝑅𝑅𝑅𝑅𝑅𝑅 𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴
• 𝑓𝑓 =
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑜𝑜𝑜𝑜 𝑡𝑡𝑡𝑡𝑡 𝑋𝑋−𝑅𝑅𝑅𝑅𝑅𝑅 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑏𝑏𝑏𝑏 𝑜𝑜𝑜𝑜𝑜𝑜 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒
• The factor f = Z, for an atom scattering the forward in the forward
direction (2𝜃𝜃 = 0°) as Z is the atomic number indicating the number
of electrons in a given atom.
• As 2𝜃𝜃 increases, the factor ‘f’ keeps on decreasing because of
increasing amount of destructive interference.
 Atomic Scattering Factor
• As the wavelength ‘𝜆𝜆′, of the incident beam, decreases, the ‘out – of –
phaseness’ (with respect to 𝜆𝜆) of the scattered beam increase, for the
same path difference (i.e., for a fixed 2𝜃𝜃) and consequently, the factor
f decreases.
sin 𝜃𝜃
• Factor ‘f’ = 𝑓𝑓
𝜆𝜆
 Structure Factor (𝐹𝐹ℎ𝑘𝑘𝑘𝑘 )
• Diffraction by a unit cell of a crystal structure is the resultant of the
waves scattered by all the atoms of the unit cell.
• The resultant wave can be obtained by summing up of the waves
scattered by atoms present in the unit cell with due respect to their
individual positions and the amplitudes.
• It has been already noted that the direction in which the diffraction
takes place should satisfy Bragg’s Law.
 Structure Factor (𝐹𝐹ℎ𝑘𝑘𝑘𝑘 )
• The waves scattered by the atoms in the unit cell may have different
phase angles and different amplitudes depending on their fractional
coordinates (xyz) and atomic scattering factor (f).
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = ∑𝑛𝑛1 𝑓𝑓𝑛𝑛 𝑒𝑒 2𝜋𝜋𝜋𝜋 ℎ𝑥𝑥+𝑘𝑘𝑘𝑘+𝑙𝑙𝑙𝑙
• 𝑒𝑒 𝑛𝑛𝜋𝜋𝜋𝜋 = −1 (𝑖𝑖𝑖𝑖 𝑛𝑛 = 𝑜𝑜𝑜𝑜𝑜𝑜)
• 𝑒𝑒 𝑛𝑛𝜋𝜋𝜋𝜋 = 1 (𝑖𝑖𝑖𝑖 𝑛𝑛 = 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒)
• 𝑓𝑓 = 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹
• 𝑒𝑒 2𝜋𝜋𝜋𝜋 = 𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷
• 𝑛𝑛 = 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 𝑜𝑜𝑜𝑜 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑖𝑖𝑖𝑖 𝑡𝑡𝑡𝑡𝑡 𝑈𝑈𝑈𝑈𝑈𝑈𝑈𝑈 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
 Structure Factor (𝐹𝐹ℎ𝑘𝑘𝑘𝑘 )
• The diffracted beam intensity is proportional to the 𝐹𝐹 2 since the
intensity of a wave is proportional to the square of its amplitude.
• 𝐼𝐼ℎ𝑘𝑘𝑘𝑘 ∝ 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 2
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑜𝑜𝑜𝑜 𝑡𝑡𝑡𝑡𝑡 𝑋𝑋−𝑅𝑅𝑅𝑅𝑅𝑅 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑜𝑜𝑜𝑜 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
• 𝐹𝐹 =
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑜𝑜𝑜𝑜 𝑡𝑡𝑡𝑡𝑡 𝑋𝑋−𝑅𝑅𝑅𝑅𝑅𝑅 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑏𝑏𝑏𝑏 𝑜𝑜𝑜𝑜𝑜𝑜 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒
 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 𝑓𝑓𝑓𝑓𝑓𝑓 𝑆𝑆𝑆𝑆 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
• 𝑛𝑛 = 1
• Position of Atom = (0,0,0)
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝑛𝑛 𝑒𝑒 2𝜋𝜋𝜋𝜋(ℎ×0+𝑘𝑘×0+𝑙𝑙×0)
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝑛𝑛
• Peaks of all planes can be observed as there is no hkl dependence as
long as the plane satisfies Bragg’s Law
 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 𝑓𝑓𝑓𝑓𝑓𝑓 𝐵𝐵𝐵𝐵𝐵𝐵 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
• 𝑛𝑛 = 2
1 1 1
2𝜋𝜋𝜋𝜋 ℎ× + 𝑘𝑘× + 𝑙𝑙×
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝑛𝑛 𝑒𝑒 2𝜋𝜋𝜋𝜋 ℎ×0+𝑘𝑘×0+𝑙𝑙×0
+ 𝑓𝑓𝑛𝑛 𝑒𝑒 2 2 2

• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝑛𝑛 + 𝑓𝑓𝑛𝑛 𝑒𝑒 𝜋𝜋𝜋𝜋 ℎ+𝑘𝑘+𝑙𝑙

• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝑛𝑛 1 + 𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ+𝑘𝑘+𝑙𝑙)

• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 0 𝑖𝑖𝑖𝑖 ℎ + 𝑘𝑘 + 𝑙𝑙 = 𝑜𝑜𝑜𝑜𝑜𝑜 𝑖𝑖. 𝑒𝑒. 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 2𝑓𝑓𝑛𝑛 (𝑖𝑖𝑖𝑖 ℎ + 𝑘𝑘 + 𝑙𝑙 = 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒)
• Only Peaks of Planes having (h + k + l) = even, will be visible in the
Diffraction Peak Pattern for BCC Crystal Structure
 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 𝑓𝑓𝑓𝑓𝑓𝑓 𝐹𝐹𝐹𝐹𝐹𝐹 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝑛𝑛 + 𝑓𝑓𝑛𝑛 𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ+𝑘𝑘) + 𝑓𝑓𝑛𝑛 𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ+𝑙𝑙) + 𝑓𝑓𝑛𝑛 𝑒𝑒 𝜋𝜋𝜋𝜋(𝑙𝑙+𝑘𝑘)
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝑛𝑛 1 + 𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ+𝑘𝑘) + 𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ+𝑙𝑙) + 𝑒𝑒 𝜋𝜋𝜋𝜋(𝑙𝑙+𝑘𝑘)
• For (1) (100) – Fhkl = 0, (2) (110) – Fhkl = 0, (3) (111) – Fhkl = 4fn ,
(4) (200) – Fhkl = 4fn , (5) (210) – Fhkl = 0 , (6) (211) – Fhkl = 0 ,
(7) (220) – Fhkl = 4fn , (8) (221) – Fhkl = 0 , (9) (222) – Fhkl = 4fn
• Constructive Interference will occur only if hkl = all odd or all even
(unmixed)
• If hkl = mixed, then Complete Destructive Interference
 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 𝑓𝑓𝑓𝑓𝑓𝑓 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
+ − 1 1 1
• 𝑆𝑆𝑆𝑆 + 𝐶𝐶𝐶𝐶 𝑎𝑎𝑎𝑎 0,0,0 𝑎𝑎𝑎𝑎𝑎𝑎 𝐶𝐶𝐶𝐶 𝑎𝑎𝑎𝑎 , ,
2 2 2
• 2 atoms/unit cell
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝐶𝐶𝐶𝐶+ + 𝑓𝑓𝐶𝐶𝐶𝐶− 𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ+𝑘𝑘+𝑙𝑙)
• 𝐼𝐼𝐼𝐼 ℎ + 𝑘𝑘 + 𝑙𝑙 = 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒, 𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝐶𝐶𝐶𝐶+ + 𝑓𝑓𝐶𝐶𝐶𝐶−
• 𝐼𝐼𝐼𝐼 ℎ + 𝑘𝑘 + 𝑙𝑙 = 𝑜𝑜𝑜𝑜𝑜𝑜, 𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝐶𝐶𝐶𝐶+ − 𝑓𝑓𝐶𝐶𝐶𝐶−
• If h + k + l = even, then slight increase in intensity and if h + k + l =
odd, then slight decrease in intensity.
• All peaks visible in SC are observed
 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 𝑓𝑓𝑓𝑓𝑓𝑓 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
• 𝐹𝐹𝐹𝐹𝐹𝐹
• 8 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑝𝑝𝑝𝑝𝑝𝑝 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
+ 1 1 1 1 1 1
• 𝑁𝑁𝑁𝑁 𝑎𝑎𝑎𝑎 0,0,0 , , , 0 , , 0, , 0, ,
2 2 2 2 2 2
− 1 1 1 1 1 1
• 𝐶𝐶𝐶𝐶 𝑎𝑎𝑎𝑎 , , , 1,1, , 1, , 1 , , 1,1
2 2 2 2 2 2
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = (𝑓𝑓𝑁𝑁𝑁𝑁+ + 𝑓𝑓𝐶𝐶𝐶𝐶− 𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ+𝑘𝑘+𝑙𝑙) ) 1 + 𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ+𝑘𝑘)
+ 𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ+𝑙𝑙) + 𝑒𝑒 𝜋𝜋𝜋𝜋(𝑙𝑙+𝑘𝑘)
• All peaks of FCC will be present, but their intensities will be different
 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 𝑓𝑓𝑓𝑓𝑓𝑓 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
• FCC + 2 atom basis of C
• 8 atoms per unit cell
11 1 1 11 111 331 313 133
• C at 000 , 0 , 0 , 0 , , , ,( )
22 2 2 22 444 444 444 444
ℎ 𝑘𝑘 𝑙𝑙
𝜋𝜋𝜋𝜋 + +
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝐶𝐶 1 + 𝑒𝑒 1 + 𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ+𝑘𝑘) + 𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ+𝑙𝑙) + 𝑒𝑒 𝜋𝜋𝜋𝜋(𝑘𝑘+𝑙𝑙)
2 2 2

• All peaks of FCC are obtained but their intensities are different.
 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 𝑓𝑓𝑓𝑓𝑓𝑓 𝑍𝑍𝑍𝑍𝑍𝑍 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
• FCC + 2 atom basis.
• 8 atoms per unit cell.
2+ 11 1 1 11
• 𝑍𝑍𝑍𝑍 = 000 , 0 , 0 , 0
22 2 2 22
2− 111 331 313 133
• 𝑆𝑆 = , , ,
444 444 444 444
ℎ 𝑘𝑘 𝑙𝑙
𝜋𝜋𝜋𝜋 + +
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝑍𝑍𝑍𝑍2+ + 𝑓𝑓𝑆𝑆 2− 𝑒𝑒 2 2 2 1 + 𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ+𝑘𝑘) + 𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ+𝑙𝑙) + 𝑒𝑒 𝜋𝜋𝜋𝜋(𝑘𝑘+𝑙𝑙)
Cannot be
expressed as
h2+k2+l2
 Multiplicity (p)
• Relative portion of hkl planes contributing to the same reflection
enters the intensity equation as a quantity p
• In a powder there are 6 to 7 equivalent orientations
• But (111) plane is 8/6 times stronger than (100) plane
• Also (110) plane is 2 times stronger than (100) plane
• So we need to normalize the intensities
 How distortions affect multiplicity
• Cubic ((100), M = 6) → Tetragonal (((100), M = 4) + ((001), M = 2))
• Cubic ((110), M = 12) → Tetragonal (((110), M = 4) + ((101), M = 8))
• Cubic ((111), M = 8) → Tetragonal ((111), M = 8) but peak is shifted.
• For most tetragonal materials, the degree of tetragonality is 5 to 10%
therefore we need to use HRXRD as in conventional XRD the peak
overlap will be substantial.
 Lorentz Factor
• LF = Lorentz Factor = Geometry
1 1
• 𝐿𝐿𝐿𝐿 = ×
4 𝑠𝑠𝑠𝑠𝑠𝑠2 𝜃𝜃 cos 𝜃𝜃
• The LF is a measure of the amount of time that a point of reciprocal
lattice remains on the sphere of reflection during the measuring
process.
• Small deviations from Braggs Law depends on 1/ sin 2𝜃𝜃.
• Orientation of crystals depends on cos 𝜃𝜃.
• Fraction of the diffraction cone that intercepts the detector –
depends on 1/ sin 2𝜃𝜃.
 Polarization Factor
1+𝑐𝑐𝑐𝑐𝑐𝑐 2 2𝜃𝜃
• 𝑃𝑃𝑃𝑃 =
2
• 𝐿𝐿𝐿𝐿𝐿𝐿 = 𝐿𝐿𝐿𝐿 × 𝑃𝑃𝑃𝑃
1
• Neglecting the constant term
8
1+𝑐𝑐𝑐𝑐𝑐𝑐 2 2𝜃𝜃
• 𝐿𝐿𝐿𝐿𝐿𝐿 =
𝑠𝑠𝑠𝑠𝑠𝑠2 𝜃𝜃 cos 𝜃𝜃
1
• If a monochromator is used, the PF is 1 + 𝑐𝑐𝑐𝑐𝑐𝑐 2 (2𝜃𝜃)𝑐𝑐𝑐𝑐𝑐𝑐 2 (2𝜃𝜃𝑀𝑀 )
2
where 𝜃𝜃𝑀𝑀 = Bragg angle for the monochromator.
• For neutron diffraction, polarization is a constant
 Absorption Factor (AF)
• It is the number by which the calculated intensity is to be multiplied
to allow for absorption.
• In Lab – AF = 1 – interaction volume is same
• If 𝜃𝜃 increases, depth of interaction volume increases but width of
interaction volume decreases, so interaction volume remains same
• Using Debye – Scherer Camera – AF ≠ 1
• Using Debye – Scherer Camera - 𝐴𝐴𝐴𝐴 = 𝑓𝑓 𝜃𝜃
 Temperature Factor (TF)
• 𝑇𝑇𝑇𝑇 = 𝑒𝑒 −2𝑀𝑀
sin 𝜃𝜃 2
• 𝑀𝑀 = 𝐵𝐵
𝜆𝜆
2
• 𝐵𝐵 = 8𝜋𝜋𝜇𝜇̅
• 𝑀𝑀 = 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹
• 𝜇𝜇̅ = 𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑜𝑜𝑜𝑜 𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉 𝑜𝑜𝑜𝑜 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑎𝑎𝑎𝑎 𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇
• B – Isotropic or Anisotropic
 Temperature Factor (TF)
• At Higher Temperatures, Background goes on increasing as 2𝜃𝜃
increases i.e. as Interplanar Spacing decreases
• At Room Temperature interference is less
• At Higher Temperatures, the atom start vibrating and loose phase
difference, so the intensity of the peaks decreases
• So at Higher Temperatures there may be some intensities at Non –
Bragg Angles
• As d increases – less interference and background decreases
• At higher d – more interference so more background
 Extinction
• Destructive interference from re – reflections within the crystals. The
strong peaks appear weaker. The solution is to grind the powdered
sample more to the optimum particle size.
• Optimum particle size = 0.1 microns – this avoids extinction.
• Below optimum particle size = size effect is observed.
 The Concept of Powder
• An ideal powder is a polycrystalline sample (a true powder or a bulk
specimen) such that for every possible orientation a sufficiently high
number of grains (grain statics) has atomic planes in Bragg Condition
(Random Orientation).
• If preferred orientation (texture) are present, suitable models are
necessary, to account for the ‘non – ideal’ conditions.
• A polycrystalline sample should contain thousands of crystallites.
Therefore, all possible diffraction peaks should be observed.
 The Concept of Powder
• For every set of planes, there will be a small percentage of crystallites
that are properly oriented to diffract (the plane perpendicular bisects
the incident and diffracted beams).
• Basic assumptions of powder diffraction are that for every set of
planes there is an equal number of crystallites that will diffract and
that there is a statistically relevant number of crystallites, not just one
or two.
• A single crystal specimen in a Bragg – Brentano diffractometer would
produce only one family of peaks in diffraction pattern.
 In Conclusion about XRD
• The diffraction pattern is like a fingerprint of the crystal structure:
1. 𝑑𝑑 values reflect the unit cell parameters (grid).
2. Intensities reflect the atoms/molecules (building blocks).
 Amorphous Content
• Amorphous content produces hump.
• Ratio of area under amorphous hump to the crystallite peaks gives
amorphous content.
Sample Types and Characterization by XRD
Optics – Components of BB(Bragg – Brentano)
Diffractometer
• The Components of a Bragg – Brentano Diffractometer are:
1. X – Ray Tube
2. Soller Slit – to make the beam perfectly parallel
3. Divergence Slit
4. Sample
5. Anti Scatter Slit
6. Receiving Slit
7. Soller Slit
8. Secondary Monochromator
9. Detector
 Bragg – Brentano Diffractometer
• In powder diffraction, we need high resolution, as a shift which is
greater than 0.03° is considered a large shift and is unwanted as the
peak positions will change
• In case of BB Diffractometer if we change the sample position up and
down, even a little we will get change in peak position
• It has high resolution
• So cannot be used for Fractured Specimens or specimens having
uneven surface
 Parallel Beam Diffractometer
• We use Parallel Beam Diffractometer for Fractured Specimens
• In Parallel Beam Diffractometer we use a parabolic mirror to make the
incident beam parallel
• The divergence in case of Parallel Beam Diffractometer is 0.3°
• It gives lower resolution
• But if we shift the sample position up and down it has no effect on
peak positions
 Debye – Scherrer Camera
• In Debye – Scherrer Camera the sample is kept in a capillary
• It is used to obtain the exact lattice parameter measurements
• We need to use high angle peaks i.e. peaks with 2𝜃𝜃 > 100°
• But in BB Diffractometer the maximum 2𝜃𝜃 possible is 145°
 Point Detectors
• The types of Point Detectors are:
1. Gas Filled Detector – Zenon Filled Detector – The Gas is Ionized due
to the incident photons – As the intensity of diffracted beam
increases the no. of photons increases – voltage generated
increases
2. Scintillator Counter
• When we use point detector, we need to specify the step size – as the
step size increases the quality of data decreases – data degrades
• Time required for detection is very high – so quality of data is good
• Background is small
 Line Detector
• A semiconducting detector is a line detector
• On the linear chips acts as multiple detectors (multiple channels)
• It can capture the entire range of 2° 𝑡𝑡𝑡𝑡 2.5° at once making the
detector very fast
• Background is high
• To determine dislocation density we need to analyze the background
– how is the tail decaying and what is the scatter – line detector is
useful
• As Receiving Slit Width Increases the Resolution will decrease.
There is also an AREA DETECTOR
 Effect of Fluorescence in XRD
• When we use a Cu target for obtaining an XRD Pattern of Fe we get
fluorescence and less diffraction
• We get more background in the XRD Pattern
• It is not a problem for stronger peaks but is a problem for weaker
peaks
• So for Fe samples we use a Co target
• Resolution in XRD is the ability of the instrument to distinguish
between 𝐾𝐾𝛼𝛼1 𝑎𝑎𝑎𝑎𝑎𝑎 𝐾𝐾𝛼𝛼𝛼 for a fully recrystallized material.
 Effect of Fluorescence in XRD
• As Slit Thickness increases the resolution of XRD decreases i.e. the
peak shape changes
• If we cannot change the target and fluorescence is occurring, use a
Secondary Monochromator but the monochromator reduces the
intensity 10 times.
 Symmetry and Structure Factor
𝑁𝑁/2
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑗𝑗=1 𝑓𝑓𝑗𝑗 𝑒𝑒 2𝜋𝜋𝜋𝜋(ℎ𝑥𝑥+𝑘𝑘𝑘𝑘+𝑙𝑙𝑙𝑙)
∑
• ℎ𝑥𝑥 + 𝑘𝑘𝑘𝑘 + 𝑙𝑙𝑙𝑙 = 𝑔𝑔. 𝑟𝑟𝑗𝑗
• Symmetry also gives rise to extinction like structure.
I. Inversion:
• 𝑟𝑟 = −𝑟𝑟
• If N atoms.
𝑁𝑁/2 2𝜋𝜋𝜋𝜋𝜋𝜋.𝑟𝑟𝑗𝑗 −2𝜋𝜋𝜋𝜋𝜋𝜋.𝑟𝑟𝑗𝑗 𝑁𝑁/2
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 ∑
= 𝑗𝑗=1 𝑓𝑓𝑗𝑗 𝑒𝑒 + 𝑒𝑒 ∑
= 2 𝑗𝑗=1 𝑓𝑓𝑗𝑗 cos 2𝜋𝜋𝜋𝜋. 𝑟𝑟𝑗𝑗
• Structure factor for a material with inversion center is always real.
 Symmetry and Structure Factor
II. Screw Axis:
• Consider 41 axis parallel to 𝑐𝑐 − 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 through (0,0,0).
1
• For an atom at 𝑟𝑟 = 𝑥𝑥, 𝑦𝑦, 𝑧𝑧 , there will be atoms at −𝑦𝑦, 𝑥𝑥, 𝑧𝑧 + ,
4
1 3
−𝑥𝑥, −𝑦𝑦, 𝑧𝑧 + , 𝑎𝑎𝑎𝑎𝑎𝑎 𝑦𝑦, −𝑥𝑥, 𝑧𝑧 + .
2 4
1
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = ∑4𝑗𝑗=1 𝑓𝑓𝑗𝑗 �𝑒𝑒 𝜋𝜋𝜋𝜋(ℎ𝑥𝑥+𝑘𝑘𝑘𝑘+𝑙𝑙𝑙𝑙) + 𝑒𝑒
𝜋𝜋𝜋𝜋 −ℎ𝑦𝑦+𝑘𝑘𝑘𝑘+𝑙𝑙 𝑧𝑧+
4 +
1 3
𝑒𝑒
𝜋𝜋𝜋𝜋 −ℎ𝑥𝑥−𝑘𝑘𝑘𝑘+𝑙𝑙 𝑧𝑧+
+ 𝑒𝑒
2
𝜋𝜋𝜋𝜋 ℎ𝑦𝑦−𝑘𝑘𝑘𝑘+𝑙𝑙 𝑧𝑧+
4 �
• For (00l) type reflections.
 Symmetry and Structure Factor
1 1 3
• 𝐹𝐹00𝑙𝑙 = ∑𝑁𝑁/4
𝑗𝑗=1 𝑒𝑒 2𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋 + 𝑒𝑒
2𝜋𝜋𝜋𝜋𝜋𝜋 𝑧𝑧+
4 + 𝑒𝑒
2𝜋𝜋𝜋𝜋𝜋𝜋 𝑧𝑧+
2 + 𝑒𝑒
2𝜋𝜋𝜋𝜋𝜋𝜋 𝑧𝑧+
4

𝑠𝑠𝑠𝑠
• 𝐹𝐹00𝑙𝑙 = ∑3𝑠𝑠=0 𝑒𝑒 𝜋𝜋𝜋𝜋
2 ∑𝑁𝑁/4
𝑗𝑗=1 𝑒𝑒 2𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋

• For 𝑙𝑙 = 4𝑛𝑛, denominator becomes zero with n integers

1−𝑒𝑒 2𝜋𝜋𝜋𝜋𝜋𝜋
lim = 4𝑒𝑒 6𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋 = 4
𝑙𝑙→4𝑛𝑛 1−𝑒𝑒 𝜋𝜋𝜋𝜋𝜋𝜋/2
• For 00𝑙𝑙 reflection and for 𝑙𝑙 ≠ 4𝑛𝑛 absent if present parallel to c –
axis, similar conditions can be derived for others.
• If 41 screw present (00𝑙𝑙) will be absent if 𝑙𝑙 ≠ 4𝑛𝑛.
 Symmetry and Structure Factor
III. Glide Plane Symmetry:
11
• 𝑛𝑛 glide planes parallel to 00𝑙𝑙 going through origin with 𝜏𝜏 = 0 .
22
• Consider an atom (𝑥𝑥, 𝑦𝑦, 𝑧𝑧) have equivalent atoms at positions
1 1
corresponding to 𝑥𝑥 + , 𝑦𝑦 + , 𝑧𝑧̅ .
2 2
1 1
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = ∑𝑁𝑁/2
𝑗𝑗=1 𝑓𝑓𝑗𝑗 𝑒𝑒 2𝜋𝜋𝜋𝜋(ℎ𝑥𝑥+𝑘𝑘𝑘𝑘+𝑙𝑙𝑙𝑙) + 𝑒𝑒
2𝜋𝜋𝜋𝜋 ℎ 𝑥𝑥+ +𝑘𝑘 𝑦𝑦+ −𝑙𝑙𝑙𝑙
2 2

ℎ+𝑘𝑘
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = ∑𝑁𝑁/2 𝑓𝑓
𝑗𝑗=1 𝑗𝑗 𝑒𝑒 2𝜋𝜋𝑖𝑖(ℎ𝑥𝑥+𝑘𝑘𝑘𝑘)
𝑒𝑒 2𝜋𝜋𝜋𝜋𝜋𝜋𝜋𝜋 + 𝑒𝑒
2𝜋𝜋𝜋𝜋
2
−𝑙𝑙𝑙𝑙
 Symmetry and Structure Factor
• For (ℎ𝑘𝑘𝑘) planes
ℎ+𝑘𝑘
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = ∑𝑁𝑁/2
𝑗𝑗=1 𝑓𝑓𝑗𝑗 𝑒𝑒 2𝜋𝜋𝜋𝜋(ℎ𝑥𝑥+𝑘𝑘𝑘𝑘) 1 + 𝑒𝑒
2𝜋𝜋𝜋𝜋
2

• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 0; 𝑤𝑤𝑤𝑤𝑤𝑤𝑤 ℎ + 𝑘𝑘 = 2𝑛𝑛 + 1

• Reflections of type (ℎ𝑘𝑘𝑘) are absent when glide plane (00𝑙𝑙) passing
1 1
through origin is present with 𝜏𝜏 = , , 0 and ℎ + 𝑘𝑘 = 2𝑛𝑛 + 1.
2 2
Identification of an Unknown
(Single Phase)
 Identification of an Unknown (Single Phase)
1. Collect XRD Pattern and Index it and determine the d – spacing of
each reflection.

2. Identify the 3 most intense

peaks and label them. d1 is the
most intense peak, d2 is the
second most intense peaks
and d3 is the third most
intense peak
 Identification of an Unknown (Single Phase)
3. Locate proper d1 group in the Hanawalt (Numerical) Search Manual
– Group 2.29 – 2.23 ±1
4. Match d1; look to match d2; repeat for d3
5. Once all three match, compare relative intensities with tabulated
values
6. When the experimental d – spacings and intensities for the most
intense reflections match those in the Hanawalt Manual, get the
ICDD Card and compare for all reflections. Once all agree, you will
have matched the pattern and identified the unknown.
Identification of a Multiphase
Specimen
 Identification of a Multiphase Specimen
1. Collect XRD Pattern and Index it and determine the d – spacing of
each reflection
2. Identify the 3 most intense peaks and label them – d1 , d2 and d3
 𝟐𝟐𝜽𝜽(°) 𝑰𝑰 (𝒄𝒄𝒄𝒄𝒄𝒄) 𝑰𝑰⁄𝑰𝑰𝟎𝟎 𝒅𝒅 𝑨𝑨𝟎𝟎
34.96 89558.4 100 2.57
38.52 70211.3 78.4 2.34
40.59 55128.3 61.6 2.22
55.61 11353.3 12.7 1.65
58.75 33939.3 37.9 1.57
69.69 21387.7 23.9 1.35
70.23 31522.6 35.2 1.34
73.85 10494.4 11.7 1.28
82.56 6292.7 7.0 1.17
87.85 4734.2 5.3 1.11
95.05 8962.5 10.0 1.04
98.22 12845.8 14.3 1.02
101.72 14293.5 16.0 0.99
107.80 2534.4 2.8 0.95
116.35 13242.4 14.8 0,.91
 Identification of a Multiphase Specimen
3. Use 2.57 – 2.51 (±0.01) Group in Search Manual

4. Note that only two possible matches are possible on our identified
d1 and d2:
1. ThTc2
2. GeHf2
 Identification of a Multiphase Specimen
5. However, neither as these has 2.22 as the third most intense
reflection. In addition, the intensity of our second more intense
peak does not match with the patterns for ThTc2 or GeHf2 (from
subscripts in search manual). Thus it is likely that our second and/or
third reflections belong to another phase.
6. Let us search again treating the third most intense peak as d2 and
our fourth most intense peak as d3
• d1 = 2.57 𝐴𝐴0 (𝐼𝐼 ⁄𝐼𝐼0 = 100)
• d2 = 2.22 𝐴𝐴0 (𝐼𝐼 ⁄𝐼𝐼0 ≈ 80)
• d3 = 1.57 𝐴𝐴0 (𝐼𝐼 ⁄𝐼𝐼0 ≈ 40)
 Identification of a Multiphase Specimen

7. Use the 2.57 – 2.51 ±0.01 Group in Search Manual

8. On the basis of our new d1 , d2 and d3 and their relative intensities
(taking into account the ±0.01 𝐴𝐴0 error in the tables), the only
possible match appears to be TaC
 Identification of a Multiphase Specimen
9. The only other phase that is close is TiH1.924 , however its peak
intensities do not match the experimental pattern.
10. Compare with ICDD/JCPDS Card
 Identification of a Multiphase Specimen
11. Take Second Set of peaks and normalize intensities with respect to
the remaining unidentified peaks

𝟐𝟐𝜽𝜽 ° 𝑰𝑰 𝒄𝒄𝒄𝒄𝒄𝒄 𝑰𝑰⁄𝑰𝑰𝟎𝟎 𝒅𝒅 𝑨𝑨𝟎𝟎

38.52 70211.3 100 2.34
55.61 11353.3 16 1.65
69.69 21387.7 30 1.35
82.56 6292.7 9 1.17
95.05 8962.5 13 1.04
107.80 2534.4 4 0.95
 Identification of a Multiphase Specimen
12. Let’s search again treating the most intense peak as d1 , the second
most intense peak as d2 and the third most intense peak as d3
• d1 = 2.34 𝐴𝐴0 (𝐼𝐼 ⁄𝐼𝐼0 = 100)
• d2 = 1.35 𝐴𝐴0 (𝐼𝐼 ⁄𝐼𝐼0 ≈ 30)
• d3 = 1.65 𝐴𝐴0 (𝐼𝐼 ⁄𝐼𝐼0 ≈ 20)
13. Use 2.36 – 2.30 ±0.01 Group in Search Manual
 Identification of a Multiphase Specimen
14. On the basis of our new d1 , d2 and d3 , their relative intensities, and
taking into account the ±0.01 𝐴𝐴0 error in the tables, the only
possible match appears to be Ta (card # 4 – 0788)
15. Compare with ICDD/JCPDS Card
 Identification of a Multiphase Specimen
16. Based on the above analysis the unknown multiphase specimen is
composed of Ta and TaC
 Quantitative Analysis Using XRD
• The qualitative analysis using XRD is very easy but quantitative is not
so easy
• Before quantitative analysis exact phase determination is possible
• When we know all the phases present, we need to simulate the XRD
pattern of a mixture of the phases in various proportions which are
needed to be varied.
• When we get a pattern using simulation that exactly matches the
experimental pattern. Then only we get to know the exact quantities
of each phase
• This Method is called Rietveld Analysis or Nonlinear Least Square
Analysis
 Grain Size, Subgrain Size, Crystallite Size and
Coherently Diffracting Grain Size
• Take an example of Fe sample.
• Each of the grain is of Fe – BCC Structure.

1 2 Fe

• Fe1 and Fe2 – are different – they have different basis vectors.
• Fe1 – basis vectors = a1 , b1 , c1.
• Fe2 – basis vectors = a2 , b2 , c2.
 Grain Size, Subgrain Size, Crystallite Size and
Coherently Diffracting Grain Size
• The basis vectors 𝑎𝑎1 𝑏𝑏1 𝑐𝑐1 and 𝑎𝑎2 𝑏𝑏2 𝑐𝑐2 have an axis common to
both of them as Fe1 and Fe2 are adjacent grains.
• So one of the basis vectors can be rotated around the common axis
by a minimum angle 𝑥𝑥° to coincide with the other basis vectors.
• This is called axis/angle combination.
• All adjacent grains have an axis/angle combination.
• This minimum angle of rotation is called angle of misorientation.
• If the angle of misorientation > 15° → High Angle GB (HAGB).
• If the angle of misorientation > 1° 𝑎𝑎𝑎𝑎𝑎𝑎 < 15° → Low Angle GB
(LAGB).
 Grain Size, Subgrain Size, Crystallite Size and
Coherently Diffracting Grain Size
• The structure is grain structure if it is bounded by HAGB. It can be
seen by OM by etching the sample.
• HAGB have High Energies.
• In each grain there is a sub – structure which is bounded by LAGB –
we get sub grain size.
• Crystallite Size – no definition – measured by XRD, TEM, EBSD.
• Subgrains are formed during recovery.
• Structures having misorientation less than 1°/2° are called coherently
diffracting domains.
 Grain Size, Subgrain Size, Crystallite Size and
Coherently Diffracting Grain Size
• The coherently diffracting domains are nearly perfect – gives perfectly
coherent elastic scattering.
• Particle Size = for powders – Laser Diffraction.
• Grain Size/Sub – Grain Size = Bulk Materials/Non – Powders.
• Coherently Diffracting Domain Size = Powders and Bulk Materials.
• Laser Diffraction – As particle size decreases the angle of scattering
increases.
• Particles are used as probes – we can find particle size distribution.
• Particles can have multiple coherently diffracting domain size.
• We get coherently diffracting domain size by X-Ray Diffraction.
 Particle

𝜃𝜃
 Instrument Broadening
• Source = 𝐾𝐾𝛼𝛼1 𝑎𝑎𝑎𝑎𝑎𝑎 𝐾𝐾𝛼𝛼𝛼 .
• Instrument broadening 𝛽𝛽𝑖𝑖 is due to Optics, Source, Detector,
Measurement Time, and Step Size.
• Instrument Broadening = 𝛽𝛽 = 𝛽𝛽𝑖𝑖 + 𝛽𝛽𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 .
• To fix instrument broadening we need to fix optics, source, detector,
measurement time and step size.
• We neglect 𝐾𝐾𝛼𝛼2 .
• Standard Sample = Stress and Strain Free, Powdered Sample, Multiple
Peaks, Particle Size = 0.1 𝑡𝑡𝑡𝑡 0.5 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚.
 Instrument Broadening
• Plot (FWHM)2 as a function of 2𝜃𝜃, 𝜃𝜃, 𝑑𝑑.
• And Fit the curve.
• 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 − 𝐻𝐻 2 = 𝑢𝑢𝑡𝑡𝑡𝑡𝑡𝑡2 𝜃𝜃 + 𝑣𝑣 tan 𝜃𝜃 + 𝑤𝑤
• 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵 𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 = 𝑢𝑢, 𝑣𝑣, 𝑤𝑤
• National Institute of Standards and Technology (NIST) – standard
sample – LaB6 600 – certificate – to characterize instrumental
broadening 𝛽𝛽𝑖𝑖 .
• Ball milling – reduces size and increases strain.
• To get sample parameters we need to remove 𝐾𝐾𝛼𝛼1 , 𝐾𝐾𝛼𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝛽𝛽𝑖𝑖 .
 Determination of Coherently Diffracting
Domain Size and Micro – Size
• Bulk and Nanocrystalline Samples of same material show different
peak widths.
• Different instruments show different profiles of peaks.
• When evaluating peak broadening, the instrument profile must be
considered.
• Residual Stress – 𝑑𝑑 = 𝑑𝑑0 ± ∆𝑑𝑑 − Plastic Deformation – Peak Shift.
• Non Uniform Deformation – In some cases 𝑑𝑑 = 𝑑𝑑0 + ∆𝑑𝑑 , and in
other cases 𝑑𝑑 = 𝑑𝑑0 − ∆𝑑𝑑 − Peak Broadening – Convolution of Peaks.
 Quantitative Analysis
PEAK SHAPE : FITTING
• Peak Fit:
1. Gaussian
2. Lorentzian
3. Pearson – VII (Sharp Peaks)
4. Pseudo – Voigt (Round Peaks)
 Quantitative Analysis
PEAK SHAPE : FITTING
• Information from fit:
1. Position
2. Width (FWHM)
3. Area
4. Deconvolution
5. Skewness
 Quantitative Analysis
PEAK SHAPE : FITTING
• Bragg’s Law assumes that ideal conditions are maintained during
diffraction – The crystal is perfect and the X – Ray beam is collimated
and monochromatic
• In practice, this condition never exists.
• With powder XRD, the ideal particle size depends on the “relative”
perfection of the polycrystalline sample. Usually from 0.5 − 10 𝜇𝜇𝜇𝜇.
 Quantitative Analysis
PEAK SHAPE : FITTING
• Domain Size:
1. Domains are the parts of an XRD specimen that diffracts X – Rays
coherently. They form “substructure”.
2. Domains are usually regions that are misoriented relative to one
another (usually by < 1°)
3. Subgrain boundaries, Tilt Boundaries, etc.
 Quantitative Analysis
PEAK SHAPE : FITTING
• Grain Size: Single Crystal regions separated by large misoriented
angles.
• Crystals (or crystallite) size: Often used interchangeably with grain
size. Refer to regions separated by large misorientation angles.
• We must first determine the individual contributions to peak
broadening.
• Peak Broadening = Instrumental Component + Strain/Particle Size
• Corrections for instrumental broadening
 Quantitative Analysis
PEAK SHAPE : FITTING
• Let 𝛽𝛽 = 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤
• 𝛽𝛽𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 = 𝛽𝛽𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 + 𝛽𝛽𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 & 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 or 𝛽𝛽𝑜𝑜 = 𝛽𝛽𝑖𝑖 + 𝛽𝛽𝑟𝑟
• 𝛽𝛽𝑜𝑜 is usually determined using well – annealed powders
• Rewrite equation for lattice strain and particle size effects
• 𝛽𝛽𝑟𝑟 = 𝛽𝛽𝑜𝑜 − 𝛽𝛽𝑖𝑖
• This expression holds for Lorentzian peak profile, however, many
peaks have a Gaussian Profile
 Quantitative Analysis
PEAK SHAPE : FITTING
• 𝛽𝛽𝑟𝑟2 = 𝛽𝛽𝑜𝑜2 − 𝛽𝛽𝑖𝑖2 − most texts use this expression for simplicity
• When in doubt, however, use:

• 𝛽𝛽𝑟𝑟 = 𝛽𝛽𝑜𝑜 − 𝛽𝛽𝑖𝑖 𝛽𝛽𝑜𝑜2 − 𝛽𝛽𝑖𝑖2

 Quantitative Analysis
PEAK SHAPE : FITTING
• Broadening due to crystallite size:
𝑘𝑘𝜆𝜆 𝑘𝑘𝑘𝑘
Scherrer Formula: 𝐷𝐷 = → 𝛽𝛽 =
𝛽𝛽 cos 𝜃𝜃 𝐷𝐷 cos 𝜃𝜃
𝐷𝐷 = 𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
𝛽𝛽 = Peak Width in radians at FWHM after correcting for instrumental
broadening
𝑘𝑘 = 0.9 to 1.0 depending upon grain shape
Equation applies for particle/grain size down into the 𝑛𝑛𝑛𝑛 range.
Works best for particles in the range of 2 𝑡𝑡𝑡𝑡 300 𝑛𝑛𝑛𝑛.
 Quantitative Analysis
PEAK SHAPE : FITTING
• Broadening due to strain:
Deformation causes local changes in atomic spacing.
This causes local changes in the 2𝜃𝜃 positions for diffracted X – Rays.
Lattice Strain causes peak broadening.
Broadening due to strain can be represented by the relationship
(Wilson’s Formula) :
𝛽𝛽𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 = 𝜂𝜂 tan 𝜃𝜃 , 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 𝜂𝜂 = 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑖𝑖𝑖𝑖 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚
 Quantitative Analysis
PEAK SHAPE : FITTING
• Variation with Bragg Angle:
Williamson – Hall Formula.
Amount of peak broadening increases with Bragg Angle 𝜃𝜃 .
Most materials exhibit broadening due to crystal size and strain.
Must use low 𝜃𝜃 peaks to separate effects.
Width of diffraction peak after subtracting instrument effects equals
the sum of the widths due to lattice strain and crystal size
𝛽𝛽𝑟𝑟 = 𝛽𝛽𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 + 𝛽𝛽𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
 Quantitative Analysis
PEAK SHAPE : FITTING
Substituting appropriate equation yields:
𝑘𝑘𝜆𝜆 𝑘𝑘𝑘𝑘
𝛽𝛽𝑟𝑟 = + 𝜂𝜂 tan 𝜃𝜃 → 𝛽𝛽𝑟𝑟 cos 𝜃𝜃 = + 𝜂𝜂 sin 𝜃𝜃
𝐷𝐷 cos 𝜃𝜃 𝐷𝐷
This equation can be written in the form of 𝑦𝑦 = 𝑚𝑚𝑚𝑚 + 𝑐𝑐
Basically, the larger the intercept, the smaller the particle size.
The method works best for smaller crystals.
Remember, there will be no peak broadening for extremely large
crystals.
 Quantitative Analysis
PEAK SHAPE : FITTING
• Steps:
1. Collect and Index Diffraction Patterns
A: Well Annealed Specimen
B : Deformed Specimen
2. In well annealed specimen, calculate FWHM for each reflection and
determine instrumental broadening to get 𝛽𝛽𝑖𝑖
3. Repeat calculations for experimental (i.e. deformed) specimen to
get 𝛽𝛽𝑜𝑜
 Quantitative Analysis
PEAK SHAPE : FITTING
4. Determine 𝛽𝛽𝑟𝑟 (true width after subtracting instrumental
broadening) – 𝛽𝛽𝑟𝑟 = 𝛽𝛽𝑜𝑜2 − 𝛽𝛽𝑖𝑖2
5. Calculate 𝛽𝛽𝑟𝑟 cos 𝜃𝜃 and plot versus sin 𝜃𝜃
 Quantitative Analysis
PEAK SHAPE : SIZE AND STRAIN
𝑘𝑘𝑘𝑘
• Scherrer Formula 𝛽𝛽 2𝜃𝜃 =
𝐿𝐿 cos 𝜃𝜃
• Peak Width 𝛽𝛽 is inversely proportional to crystallite size (L)
• 𝑘𝑘 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 ≈ 0.94 𝑡𝑡𝑡𝑡 1 for spherical crystals
• Micro – Strain Broadening
sin 𝜃𝜃
• 𝛽𝛽 2𝜃𝜃 = 4𝜀𝜀
cos 𝜃𝜃
• Peak Broadening = Instrumental + Size + Strain
Quantitative Analysis
PEAK SHAPE : GRAIN SIZE
 Quantitative Analysis
• Measurement time does not affect the results much.
• So measurement time can change from standard sample to specimen.
• But optics need to remain the same.
• In our lab – we have point detectors and array detectors.
• Detector also causes broadening as it has its own resolution.
 Quantitative Phase Analysis of a Powdered
Mixture (Direct Comparison Method)
• Direct Comparison Method does not require any external standard
unlike the RIR (Reference Intensity Ratio) Method.
• It applies for two phases.
• Example :
1. Retained Austenite (RA) in Steels
2. Al – Si Alloys (Si is not miscible in Al)
• Here powdered or randomly oriented material is required.
• Randomly Oriented Material – RA in steel – martensite structure is
randomly oriented structure at room temperature.
 Quantitative Phase Analysis of a Powdered
Mixture (Direct Comparison Method)
• 𝐼𝐼 ∝ 𝐹𝐹 2 . 𝑝𝑝. 𝐿𝐿𝐿𝐿𝐿𝐿. 𝑇𝑇𝑇𝑇. 𝐴𝐴𝐴𝐴
𝐼𝐼0 𝐴𝐴𝜆𝜆3 𝜇𝜇0 2 𝑒𝑒 4 1 2 1+𝑐𝑐𝑐𝑐𝑐𝑐 2 2𝜃𝜃 𝑒𝑒 −2𝑀𝑀
• 𝐼𝐼ℎ𝑘𝑘𝑘𝑘 = 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 . 𝑝𝑝.
32𝜋𝜋𝜋𝜋 4𝜋𝜋 𝑚𝑚2 𝑉𝑉 2 𝑠𝑠𝑠𝑠𝑠𝑠2 𝜃𝜃 cos 𝜃𝜃 2𝜇𝜇
• 𝐼𝐼ℎ𝑘𝑘𝑘𝑘 = 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼
• 𝐼𝐼0 = 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝑜𝑜𝑜𝑜 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵
• 𝜆𝜆 = 𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊
• 𝑟𝑟 = 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝑜𝑜𝑜𝑜 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
• 𝜇𝜇0 = 4𝜋𝜋 × 10−7
• 𝐴𝐴 = 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑜𝑜𝑜𝑜 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵
 Quantitative Phase Analysis of a Powdered
Mixture (Direct Comparison Method)
• 𝑒𝑒 = 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑜𝑜𝑜𝑜 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒
• 𝑚𝑚 = 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒
• 𝑉𝑉 = 𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉 𝑜𝑜𝑜𝑜 𝑈𝑈𝑈𝑈𝑈𝑈𝑈𝑈 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
• We calculate volume of unit cell from diffraction peak values, do not
take the theoretical values.
• Calculate precise lattice parameter by Nelson – Reilly Method or
Cohen’s Method.
𝐼𝐼0 𝐴𝐴𝐴𝐴 𝜇𝜇0 2 𝑒𝑒 4
• In the above equation, let 𝐾𝐾2 =
32𝜋𝜋𝜋𝜋 4𝜋𝜋 𝑚𝑚2
 Quantitative Phase Analysis of a Powdered
Mixture (Direct Comparison Method)
1 2 1+𝑐𝑐𝑐𝑐𝑐𝑐 2 2𝜃𝜃
• 𝑅𝑅 = 2 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 . 𝑝𝑝. 𝑒𝑒 −2𝑀𝑀
𝑉𝑉 𝑠𝑠𝑠𝑠𝑠𝑠2 𝜃𝜃 cos 𝜃𝜃
𝐾𝐾2 𝑅𝑅
• 𝐼𝐼 =
2𝜇𝜇
• 𝜇𝜇 = 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
• 𝜇𝜇𝑚𝑚𝑚𝑚𝑚𝑚 = 𝜇𝜇1 𝜌𝜌1 + 𝜇𝜇2 𝜌𝜌2
• 𝐿𝐿𝐿𝐿𝐿𝐿 𝑢𝑢𝑢𝑢 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑡𝑡𝑡𝑡𝑡𝑡 𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝛽𝛽
𝐾𝐾2 .𝑅𝑅𝛼𝛼 .𝐶𝐶𝛼𝛼
• 𝐼𝐼𝛼𝛼 =
2𝜇𝜇𝑚𝑚𝑚𝑚𝑚𝑚
𝐾𝐾2 .𝑅𝑅𝛽𝛽 .𝐶𝐶𝛽𝛽
• 𝐼𝐼𝛽𝛽 =
2𝜇𝜇𝑚𝑚𝑚𝑚𝑚𝑚
 Quantitative Phase Analysis of a Powdered
Mixture (Direct Comparison Method)
𝐼𝐼𝛼𝛼 𝑅𝑅𝛼𝛼 𝐶𝐶𝛼𝛼
• = .
𝐼𝐼𝛽𝛽 𝑅𝑅𝛽𝛽 𝐶𝐶𝛽𝛽
• 𝐶𝐶𝛼𝛼 + 𝐶𝐶𝛽𝛽 = 1
• 𝐶𝐶 = 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
• Calculate 𝐶𝐶𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝐶𝐶𝛽𝛽 for various peaks and take the mean of them to
get 𝐶𝐶𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝐶𝐶𝛽𝛽 .
• In Direct Comparison Method we need to calculate R for all peaks and
all phases.
• Only possible for 2 or 3 phases.
 Quantitative Phase Analysis of a Powdered
Mixture (Direct Comparison Method)
• One of the most used methods to determine RA in Steel.
• Overlapping peaks are not to be considered.
Reference Intensity Ratio (RIR)
Method
 Reference Intensity Ratio (RIR)

• The Reference Intensity Ratio (RIR) is a method used for

Quantitative Analysis by Powder Diffraction.
• The RIR method is based upon scaling all diffraction data to the
diffraction of standard reference materials.
Reference Intensity Ratio (RIR)

• The intensity of a diffraction peak profile is a convolution of many

factors, only one of which is the concentration of the analyte
(species being measured).
• By using the RIR method, ratios scaled to a common reference, are
used in the experiment. The assumption is that all the factors,
except concentration, of the analyte are ratioed and reduced to a
constant.
• By using ratios and measuring peak areas, the RIR method can be
used to determine concentrations.
 Reference Intensity Ratio (RIR)
• The RIR method scales all diffraction data to a standard.
• By convention, corundum is used as the international reference and
the scale factor is defined by:
• Intensity Analyte / Intensity Corundum = 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶
• 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 can be experimentally derived by adding a known weight
fraction of corundum to a pure specimen of the analyte of interest.
• 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 can also be calculated if the atomic parameters of analyte
are known because the atomic parameters of corundum have been
determined.
• In PDF-4+, 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 has been experimentally determined for close to
10,000 materials and has been calculated for >170,000 materials.
 Overview of the Method
To understand how to use I/Ic values for quantitative analysis with
the PDF-4+ database, a short description of the method is provided
in the following slides.
 Reference Intensity Ratio (RIR)

• RIR, as used in the Powder Diffraction File, is I/Ic (reference to

corundum).
• I/Ic can be determined, experimentally or calculated, from a crystal
structure, both methods are used in the PDF-4+ database.
• Experimentally, I/Ic can be determined by taking
the ratio of the strongest line of the pattern to the intensity of the
strongest line of corundum in a 50/50 weight mixture.
• If we know the crystal structure, we can calculate I/Ic as shown in
the following slide.
 Reference Intensity Ratio (RIR)
• All calculated patterns have I/Ic.
𝐼𝐼 𝜇𝜇𝜇𝜇𝜌𝜌𝐶𝐶
• =
𝐼𝐼𝐶𝐶 𝜇𝜇𝐶𝐶 𝛾𝛾𝐶𝐶 𝜌𝜌
• µ = Linear attenuation coefficient
• γ = Absolute scale factor
• ρ = Density
• (Subscript “c” corresponds to corundum)
• Single crystal determinations have all the data necessary to calculate
the variables in the above equation from atomic parameters and the
unit cell parameters with the use of atomic scattering factors and
published constants. These are used by the ICDD to calculate 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 for
these entries.
 Reference Intensity Ratio (RIR)
• Calculated 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 values often significantly differ from experimental 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶
values.
• Natural products, minerals, and biomaterials often contain trace
impurities, anion/cation substitution in the lattice, or naturally
produced vacancies, and/or defects in the crystalline state. These
physical phenomena are well known to influence peak intensities and
peak profiles that will change the 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 value. This value can be
significantly different from one calculated from a perfect crystalline
pure material.
• If you are using 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 to quantitate a synthetic mixture, you may want
to use a calculated value. If you are using 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 to quantitate a natural
product or mineral sample, you may prefer experimental values.
 Quantitative Analysis

Main equation for quantitative analysis

Kia contains structure factor,

multiplicity, Lorentz-polarization
factor, temperature factor +
scale factor for reflection i of
phase a
Iia = intensity of Xa = wt fraction of
reflection i of KiaXa phase a (want this!!)
phase a Iia =
ρa µ

µ = Linear attenuation coefficient

ρa is density
of phase a
 Quantitative Analysis

Xa = wt fraction of
Measure KiaXa phase a (want this!!)
this!! Iia =
ρa µ
 Quantitative Analysis
Reference Intensity Ratios
KaXa KcXc
For Ia = For
analyte Ic =
ρa µ corundum ρc µ

KaXa
Ia =
ρa µ Ia KaXaρc Xa
= = K
KcXc Ic KcXcρa Xc
Ic =
ρc µ

For 50-50 mixture of analyte with corundum

Ia
= K …..denoted (I/Ic)a
Ic
Quantitative Analysis
Reference Intensity Ratios
Ia KaXaρc Xa
= = K
Ic KcXcρa Xc

For any a + b mixture

Ka ρ c

(Ia/Ic) Kc ρ a
=
(Ib/Ic) Kb ρ c
Kc ρ b
Ka

Ia ρa µ Xa
= =
Ib Kb Xb
ρb µ
 Reference Intensity Ratio (RIR)
Practical Considerations
• The RIR method uses simultaneous equations to solve analyte
concentrations in a multicomponent mixture.
• Many vendor programs interface to PDF-4+ to automatically
extract I/Ic and peak areas from the experimental data for
automated quantitative analysis.
• Automated programs assume that the combination of all
phases identified account for all observed scattering and 100%
of the specimen. Significant errors can occur, if there are non-
crystalline phases or unidentified materials present in the
specimen.
 Finding 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 Search

Start at the main

Search Page

Go to the
Miscellaneous
Tab
 Finding 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 for a Material

1) Perform a Search
2) Select the Preferences Tab
3) Select I/Ic to display Values
Finding 𝐼𝐼⁄𝐼𝐼𝐶𝐶 for a Material

TiO2’s
and I/Ic
Displayed
 Selecting Appropriate 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 Values

• Choose the appropriate structure : Many materials have

polymorphs that have the same chemical ′
formula, but different
structures. These have different 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 𝑠𝑠.
• Match the reference to the specimen as closely as possible.
• Use quality marks and indicators to select the best quality
reference.
Selecting 𝐼𝐼⁄𝐼𝐼𝐶𝐶 − Structure

TiO2 TiO2
Rutile Brookite
I/Ic = 3.54 I/Ic = 3.06

Formulae are the same,

TiO2 pattern, structure and I/Ic
Anatase are distinctly different
I/Ic = 5.04
 Structure
You can select many fields that
From Search Results help you determine the structure
use the Preferences Tab by matching these data to the
experimental data.
to select fields
These include:

Chemical Name, Mineral Name

System and Space Group Number

(SG#)

Pearson, Prototype Structure and

LPF Prototype Structure

Reduced Cell, Author Cell and

Crystal Cell

Strong Line (D1, D2, D3) and

Long Line (L1, L2, L3)
 Match Reference to Experiment

Temperature can
expand or contract
the unit cell – and
change I/Ic.

• All the known factors that can alter a structure: temperature, pressure, anion
or cation substitution, synthesis conditions, vacancies, stress, strain, etc. will
change atom positions, electron density distribution, and therefore alter peak
intensities and the 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 ratio.
• The above factors are changes in the 𝐾𝐾𝑖𝑖𝑖𝑖 factor in the equation for quantitative
analysis.
• Select a reference that most closely matches your experiment!
 Matching References

From the Results Form,

select Preferences,
add Database Comments

Editor comments contain information on specimen preparation, impurities, temperature of data

collection and other factors that can change 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 . They can guide you to the appropriate choice.
 𝐼𝐼⁄𝐼𝐼𝐶𝐶 for Quartz
Space Group P3221
75 Determinations
High Temp
Data plotted from
Series
PDF-4+ Search Form
of I/Ic versus reduced
cell a, editor comments
describe T, P conditions

Ambient Data

Effect of Temp and Pressure

for Quartz I/Ic High Pressure Series
Synthetic Materials
Using Quality Marks and Indicators

The database contains many quality

Indicators. These include:

Indicator High Quality Value

Quality Mark S
Status Primary
SS/FOM Highest Number
R-Factor Lowest Number

Database Comments: This includes

comments from editors and statistical
analyses conducted on the data.

The indicators are defined in the

Help documentation in the database.

Use “Preferences” to display quality marks and indicators.

 Using Quality Marks and Indicators
Poor Quality
Low Quality Marks are designations B and O
Low Quality Status would be a “Deleted” pattern
R-factors >0.10 (i.e., 10%) and SS/FOM’s below 10 are
indications of poor quality

• In general, any data meeting the above criteria should not be used in a quantitative
analysis calculation as the ICDD’s editorial analysis and review would indicate that the
calculation may result in large errors.

• The data are included because there may not be better alternative choices for a
particular material or the entry may contain other types of unique data (i.e., measured
physical properties, novel synthesis, etc.).
 Using Cross References
What if a Search/Match program identified an entry with a poor-quality mark or poor-
quality indicator?

- Check the Cross References

In this example, a Search/Match program identified

entry PDF 04-08-7810, which has an 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 of 3.6 and a
“B” Quality Mark. The editors’ comments mention
that the atomic parameters were derived (not
experimentally determined or calculated) from the
original publication. This results in low precision for
the cell parameters and 𝐼𝐼 ⁄𝐼𝐼𝐶𝐶 values.

Solution: The entry contains cross-references

identified in the “Miscellaneous Tab” of the entry.
The primary (high quality) entry is highlighted and
is an active link in the database. The primary
entry has an I/Ic of 3.61 and is an “S” quality
entry.
 Application
Examples

• Using ICDD’s SIeve and SIeve+ programs, materials are identified,

peak intensities of each phase are calculated and I/Ic values are
displayed – allowing the user to calculate concentrations by the RIR
method.
• Many software distributors have RIR calculation modules, which
can perform multiple, simultaneous calculations for complex
mixtures, use integrated intensities and correct for absorption – all
in a matter of seconds!
 SIeve+
Input experimental
data.

Two phase identification in the

analysis of an unknown.

Ia
=
Ib

Results summary

This results in 96% magnesium aluminum silicate and

4% cerium zirconium oxide and uses peak intensities.
Automated RIR Analysis
Vendor Software – Same Example

Raw Data RIR Calculation

Difference Plot
This software calculated 92% magnesium
aluminum silicate and 7% cerium zirconium
oxide using integrated intensities.
Precise Lattice Parameter by
Nelson – Riley Method
 Precise Lattice Parameter by Nelson – Riley
Method
• To determine the lattice parameter to within 1× 10−5 nm.
• Must know the peak position to within 0.02° 𝑎𝑎𝑎𝑎 2𝜃𝜃 = 160°.
• Systematic errors :
1. Leads to Inaccurate Results
2. Precision without accuracy
• Pseudo-Voigt which lies between Lorentz and Gauss generally works
well.
• High angle peaks required.
 Precise Lattice Parameter by Nelson – Riley
Method
• Debye – Scherrer (DS) Camera is used as we can measure high angle
peaks.
• DS Camera can be used to measure peaks having angles about 175°.
• For a cubic material : 𝑎𝑎 = 𝑑𝑑 ℎ2 + 𝑘𝑘 2 + 𝑙𝑙 2
• 𝑑𝑑 − spacing is given by Bragg’s Law : 𝑛𝑛𝜆𝜆 = 2𝑑𝑑 sin 𝜃𝜃
• Precision in measurement of a or d depends on precision in
derivation of sin 𝜃𝜃 .
 Precise Lattice Parameter by Nelson – Riley
Method
• Differentiation of the Bragg equation with respect to θ provides us
with the same result.
• 𝜆𝜆 = 2𝑑𝑑 sin 𝜃𝜃
• Take partial derivative of the Bragg equation :
• 0 = 2∆𝑑𝑑 sin 𝜃𝜃 + 2𝑑𝑑 cos 𝜃𝜃 ∆𝜃𝜃
∆𝑑𝑑
• = − cot 𝜃𝜃 ∆𝜃𝜃
𝑑𝑑
• For a cubic system:
• 𝑎𝑎 = 𝑑𝑑 ℎ2 + 𝑘𝑘 2 + 𝑙𝑙 2
 Precise Lattice Parameter by Nelson – Riley
Method
• Therefore:
• ∆𝑎𝑎 = ∆𝑑𝑑 ℎ2 + 𝑘𝑘 2 + 𝑙𝑙 2
∆𝑎𝑎 ∆𝑑𝑑
• = = − cot 𝜃𝜃 ∆𝜃𝜃
𝑎𝑎 𝑑𝑑
∆𝑎𝑎 ∆𝑑𝑑
• The term 𝑜𝑜𝑜𝑜 is the fractional error in 𝑎𝑎 (or 𝑑𝑑) caused by a
𝑎𝑎 𝑑𝑑
given error in 𝜃𝜃.
• The fractional error approaches zero as 𝜃𝜃 approaches 90°.
 Precise Lattice Parameter by Nelson – Riley
Method
• The key to high precision in parameter measurements lies in the use
of back reflected beams having 2𝜃𝜃 values as near to 180° as possible.
• It is impossible to reach 180°.
• Values of 𝑎𝑎 will approach the true value as we approach 2𝜃𝜃 = 180°
𝑖𝑖. 𝑒𝑒. , 𝜃𝜃 = 90° .
• We can’t measure 𝑎𝑎 values at 2𝜃𝜃 = 180°.
• We must plot measured values and extrapolate to 2θ = 180° versus
some function of θ.
 Precise Lattice Parameter by Nelson – Riley
Method
• Make sure that the functions of 𝜃𝜃 produce data that can be fit with a
straight line.
• This allows for extrapolation with higher confidence.
• There are different types of extrapolation functions for different types
of systematic error in 𝑎𝑎 (or 𝑑𝑑).
• Naturally there are different types of systematic errors associated
with different x-ray instruments.
 Systematic Errors in Diffractometers
1. Misalignment of the Instrument :
• The center of the diffracted beam must intersect the diffractometer
axis at the 0° position of the detector slit.
2. Use of a Flat Specimen Instead of a Curved One to Correspond to
the Diffractometer Circle :
• Minimized by reducing horizontal divergence of the incident beam.
3. Absorption of the Specimen :
• Select specimen thickness to get reflections with maximum intensity
possible (little absorption).
 Systematic Errors in Diffractometers
4. Displacement of Specimen from the diffractometer axis must be
minimized :
• This is generally the largest source for error in d.
∆𝑑𝑑 𝐷𝐷𝑐𝑐𝑐𝑐𝑐𝑐 2 𝜃𝜃
• = − , 𝑅𝑅 = 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷
𝑑𝑑 𝑅𝑅 sin 𝜃𝜃
• D = Specimen displacement parallel to the reflecting plane normal
5. Vertical Divergence of the Incident Beam :
• This error is minimized by reducing the vertical width of the receiving
slit.
 Which Extrapolation Functions to Use
• For error types (2) and (3) :
∆𝑑𝑑
∝ 𝑐𝑐𝑐𝑐𝑐𝑐 2 𝜃𝜃 → ∴ 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸 ∝ 𝑐𝑐𝑐𝑐𝑐𝑐 2 𝜃𝜃
𝑑𝑑
• For error type (4) :
∆𝑑𝑑 𝑐𝑐𝑐𝑐𝑐𝑐 2 𝜃𝜃 𝑐𝑐𝑐𝑐𝑐𝑐 2 𝜃𝜃
∝ → ∴ 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸 ∝
𝑑𝑑 sin 𝜃𝜃 sin 𝜃𝜃
• For error of type (5) :
∆𝑑𝑑 𝑐𝑐𝑐𝑐𝑐𝑐 2 𝜃𝜃 𝑐𝑐𝑐𝑐𝑐𝑐 2 𝜃𝜃 𝑐𝑐𝑐𝑐𝑐𝑐 2 𝜃𝜃 𝑐𝑐𝑐𝑐𝑐𝑐 2 𝜃𝜃
∝ + → ∴ 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸 ∝ +
𝑑𝑑 sin 𝜃𝜃 𝜃𝜃 sin 𝜃𝜃 𝜃𝜃
 General Information
∆𝑑𝑑
• At low 2𝜃𝜃, sin 𝜃𝜃 → 0, which causes → ∞.
𝑑𝑑
• Bad idea to use low 2𝜃𝜃.
• What can we use?
• USE HIGH ANGLE LINES.
• If we want to know 𝑎𝑎0 to ±0.0001 𝐴𝐴,̇ we need to know 2𝜃𝜃 to 2𝜃𝜃 to
± 0.02° at 2𝜃𝜃 = 160°.
 How are Precise Lattice Parameters
Measured?
• Carefully align the diffractometer.
• Make sure the specimen is flat and on axis.
• Use small slits (fixed in most instruments).
• Extrapolate peak positions to high 2θ using a method/function that
minimizes the influence of systematic errors.
• Determine peak positions by maximum intensity or by proper curve
fitting.
Precise Lattice Parameter by
Cohen’s Method
 Order Disorder Transformation
• In most substitutional solid solutions, the two kinds of atoms A and B
are arranged more or less at random on the atomic sites of the lattice.
• There are some solutions which have this random structure only at
elevated temperatures.
• When these solutions are cooled below a certain critical temperature
𝑇𝑇𝐶𝐶 , the A atoms arrange themselves in an orderly, periodic manner on
one set of atomic sites, and the B atoms do likewise on another set.
• The solution is then said to be ordered or to possess a superlattice.
• When this periodic arrangement of A and B atoms persists over very
large distances in the crystal, it is known as long – range order.
 Order Disorder Transformation
• If the ordered solution is heated above 𝑇𝑇𝐶𝐶 , the atomic arrangement
becomes more or less random again and the solution is said to be
disordered.
• The change in atom arrangement which occurs on ordering produces
changes in a large number of physical and chemical properties, and
the existence of ordering may be inferred from some of these
changes.
• However, the only conclusive evidence for a disorder – order
transformation is a particular kind of change in the XRD pattern of the
substance.
 Order Disorder Transformation
• Example : AuCu3 − 𝑇𝑇𝐶𝐶 = 390℃.
• The gold and copper atoms of AuCu3 , above a critical temperature of
about 390°C, are arranged more or less at random on the atomic sites
of a face-centered cubic lattice, as illustrated in Fig. 13-1(a).
• If the disorder is complete, the probability that a particular site is
occupied by a gold atom is simply 1/4, the atomic fraction of gold in
the alloy, and the probability that it is occupied by a copper atom is
3/4, the atomic fraction of copper.
• These probabilities are the same for every site and, considering the
structure as a whole, we can regard each site as being occupied by a
statistically "average" gold – copper atom.
 Order Disorder Transformation
• Below the critical temperature, the gold atoms in a perfectly ordered
alloy occupy only the corner positions of the unit cube and the
copper atoms the face-centered positions, as illustrated in Fig. 13 –
1(b).
• Both structures are cubic and have practically the same lattice
parameters.
 Order Disorder Transformation
Disordered Structure:
• 𝑓𝑓𝐴𝐴𝐴𝐴𝐴𝐴 = 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑜𝑜𝑜𝑜 𝐴𝐴𝐴𝐴 𝑓𝑓𝐴𝐴𝐴𝐴 + 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑜𝑜𝑜𝑜 𝐶𝐶𝐶𝐶 𝑓𝑓𝐶𝐶𝐶𝐶
𝑓𝑓𝐴𝐴𝐴𝐴 +3𝑓𝑓𝐶𝐶𝐶𝐶
• 𝑓𝑓𝐴𝐴𝐴𝐴𝐴𝐴 =
4
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝐴𝐴𝐴𝐴𝐴𝐴 1 + 𝑒𝑒 𝜋𝜋𝜋𝜋 ℎ+𝑘𝑘
+ 𝑒𝑒 𝜋𝜋𝜋𝜋 ℎ+𝑙𝑙
+ 𝑒𝑒 𝜋𝜋𝜋𝜋 𝑘𝑘+𝑙𝑙

• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 4𝑓𝑓𝐴𝐴𝐴𝐴𝐴𝐴 = 𝑓𝑓𝐴𝐴𝐴𝐴 + 3𝑓𝑓𝐶𝐶𝐶𝐶 − 𝑖𝑖𝑖𝑖 ℎ𝑘𝑘𝑘𝑘 = 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢.

• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 0 − 𝑖𝑖𝑖𝑖 ℎ𝑘𝑘𝑘𝑘 = 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚.
 Order Disorder Transformation
Ordered Structure:
11 1 1 11
• Au = (000), Cu = 0 , 0 , 0
22 2 2 22
𝜋𝜋𝜋𝜋 ℎ+𝑘𝑘 𝜋𝜋𝜋𝜋 ℎ+𝑙𝑙
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝐴𝐴𝐴𝐴 + 𝑓𝑓𝐶𝐶𝐶𝐶 𝑒𝑒 + 𝑒𝑒 + 𝑒𝑒 𝜋𝜋𝜋𝜋 𝑘𝑘+𝑙𝑙
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝐴𝐴𝐴𝐴 + 3𝑓𝑓𝐶𝐶𝐶𝐶 − 𝑖𝑖𝑖𝑖 ℎ𝑘𝑘𝑘𝑘 = 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢.
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝐴𝐴𝐴𝐴 − 𝑓𝑓𝐶𝐶𝐶𝐶 − 𝑖𝑖𝑖𝑖 ℎ𝑘𝑘𝑘𝑘 = 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚.
• The ordered alloy thus produces diffraction lines for all values of hkl,
and its diffraction pattern therefore resembles that of a simple cubic
substance.
 Order Disorder Transformation
• In other words, there has been a change of Bravais lattice on
ordering; the Bravais lattice of the disordered alloy is face-centered
cubic and that of the ordered alloy simple cubic.
• The diffraction lines from planes of unmixed indices are called
fundamental lines, since they occur at the same positions and with
the same intensities in the patterns of both ordered and disordered
alloys.
• The extra lines which appear in the pattern of an ordered alloy, arising
from planes of mixed indices, are called superlattice lines, and their
presence is direct evidence that ordering has taken place.
 Order Disorder Transformation
• The ordered structure therefore produces a weak 100 reflection.
𝐼𝐼𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝐼𝐼𝑠𝑠 𝑓𝑓𝐴𝐴𝐴𝐴 −𝑓𝑓𝐶𝐶𝐶𝐶 2 79−29 2
• = = = = 0.09
𝐼𝐼𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙 𝐼𝐼𝑓𝑓 𝑓𝑓𝐴𝐴𝐴𝐴 +3𝑓𝑓𝐶𝐶𝐶𝐶 2 79+3×29 2
• 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 − Ordered = Tetragonal, and Disordered = BCC.
• Au – Cu systems have sluggish diffusion i.e. the structure is preserved.
𝛽𝛽 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵 𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇
• The Alloy is stable at RT over a composition range of 46 to 50 atomic
percent Zn, and so can be represented by the formula 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶.
• At higher temperatures its structure is BCC, with Cu and Zn atoms
distributed at normal.
• Below 460℃, ordering occurs, the cell corners are occupied by Cu
atoms and the Zn toms occupies the Zn atoms.
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝐶𝐶𝐶𝐶 + 𝑓𝑓𝑍𝑍𝑍𝑍 , 𝑖𝑖𝑖𝑖 ℎ + 𝑘𝑘 + 𝑙𝑙 = 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒.
• 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = 𝑓𝑓𝐶𝐶𝐶𝐶 − 𝑓𝑓𝑍𝑍𝑍𝑍 , 𝑖𝑖𝑖𝑖 ℎ + 𝑘𝑘 + 𝑙𝑙 = 𝑜𝑜𝑜𝑜𝑜𝑜.
𝛽𝛽 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵 𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇
• In other words, there are fundamental lines, those for which (ℎ +
𝑘𝑘 + 𝑙𝑙) is even, which are unchanged in intensity whether the alloy is
ordered or not. And there are superlattice lines, those for which (h + k
+ I) is odd, which are present only in the pattern of an alloy exhibiting
some degree of order, and then with an intensity which depends on
the degree of order present.
• In 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶, on the other hand, ordering is so rapid that disorder existing
at an elevated temperature cannot be retained at room temperature,
no matter how rapid the quench. Therefore, any specimen of 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 at
room temperature can be presumed to be almost completely
ordered.
𝛽𝛽 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵 𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇
• Atomic Weight of Cu = 29.
• Atomic Weight of Zn = 30.
𝐼𝐼𝑠𝑠 𝑓𝑓𝐶𝐶𝐶𝐶 −𝑓𝑓𝑍𝑍𝑍𝑍 2 29−30 2
• = = ≈ 0.0003
𝐼𝐼𝑓𝑓 𝑓𝑓𝐶𝐶𝐶𝐶 +𝑓𝑓𝑍𝑍𝑍𝑍 2 29+30 2
• This ratio is so low that the superlattice lines of ordered 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 can be
detected by x-ray diffraction only under very special circumstances.
(The powder pattern of this alloy, ordered or disordered, ordinarily
appears to be that of a body-centered cubic substance.)
𝛽𝛽 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵 𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇
• Thus the superlattice lines are not easily distinguished from the
background and therefore the XRD Pattern of Ordered Beta Brass not
easily distinguished from that of Disordered Beta Brass.
• So XRD cannot be used to detect ordering in Beta Brass.
• So Anomalous Dispersion Correction is required.
• In 𝛽𝛽 Brass the diffusion is extremely fast.
• We use Zn target to observe order disorder transformation.
• We can also use synchrotron diffraction.
Determination of Phase Diagram
 General Principles
• The key to the interpretation of the powder patterns of alloys is the
fact that each phase produces its own pattern independently of the
presence or absence of any other phase.
• Thus a single-phase alloy produces a single pattern while the pattern
of a two-phase alloy consists of two superimposed patterns, one due
to each phase.
• Assume, for example, that two metals A and B are completely soluble
in the solid state, as illustrated by the phase diagram of Fig. 12-1.
 General Principles
• The solid phase 𝛼𝛼, called a continuous solid solution, is of the
substitutional type; it varies in composition, but not in crystal
structure, from pure A to pure B, which must necessarily have the
same structure.
• The lattice parameter of 𝛼𝛼 also varies continuously from that of pure
A to that of pure B.
• Since all alloys in a system of this kind consist of the same single
phase, their powder patterns appear quite similar, the only effect of a
change in composition being to shift the diffraction-line positions in
accordance with the change in lattice parameter.
 General Principles
• More commonly, the two metals A and B are only partially soluble in
the solid state.
• The first additions of B to A go into solid solution in the A lattice,
which may expand or contract as a result, depending on the relative
sizes of the A and B atoms and the type of solid solution formed
(substitutional or interstitial).
• Ultimately the solubility limit of B in A is reached, and further
additions of B cause the precipitation of a second phase.
• This second phase may be a B-rich solid solution with the same
structure as B, as in the alloy system illustrated by Fig. 12-2(a).
 General Principles
• Here the solid solutions 𝛼𝛼 and 𝛽𝛽 are called primary solid solutions or
terminal solid solutions.
• Or the second phase which appears may have no connection with the
B-rich solid solution, as in the system shown in Fig. 12-2(b).
• Here the effect of supersaturating 𝛼𝛼 with metal B is to precipitate the
phase designated 𝛾𝛾.
• This phase is called an intermediate solid solution or intermediate
phase.
• It usually has a crystal structure entirely different from that of either
𝛼𝛼 or 𝛽𝛽, and it is separated from each of these terminal solid solutions,
on the phase diagram, by at least one two-phase region.
 General Principles
• Phase diagrams much more complex than those just mentioned are
often encountered in practice, but they are always reducible to a
combination of fairly simple types.
• When an unknown phase diagram is being investigated, it is best to
make a preliminary survey of the whole system by preparing a series
of alloys at definite composition intervals, say 5 or 10 atomic percent,
from pure A to pure B.
• The powder pattern of each alloy and each pure metal is then
prepared.
 General Principles
• These patterns may appear quite complex but, no matter what the
complexities, the patterns may be unraveled and the proper
sequence of phases across the diagram may be established, if proper
attention is paid to the following principles:
1. Equilibrium. Each alloy must be at equilibrium at the temperature
where the phase relations are being studied.
2. Phase sequence. A horizontal (constant temperature) line drawn
across the diagram must pass through single-phase and two-phase
regions alternately.
 General Principles
3. Single-phase regions. In a single-phase region, a change in
composition generally produces a change in lattice parameter and
therefore a shift in the positions of the diffraction lines of that
phase.
4. Two-phase regions. In a two-phase region, a change in composition
of the alloy produces a change in the relative amounts of the two
phases but no change in their compositions.
• These compositions are fixed at the intersections of a horizontal "tie
line" with the boundaries of the two-phase field.
 General Principles
• Thus, in the system illustrated in Fig. 12-2(a), the tie line drawn at
temperature 𝑇𝑇1 shows that the compositions of 𝛼𝛼 and 𝛽𝛽 at
equilibrium at this temperature are 𝑥𝑥 and 𝑦𝑦 respectively.
• The powder pattern of a two-phase alloy brought to equilibrium at
temperature 𝑇𝑇1 will therefore consist of the superimposed patterns of
𝛼𝛼 of composition 𝑥𝑥 and 𝛽𝛽 of composition 𝑦𝑦.
• The patterns of a series of alloys in the 𝑥𝑥𝑥𝑥 range will all contain the
same diffraction lines at the same positions, but the intensity of the
lines of the 𝛼𝛼 phase relative to the intensity of the lines of the 𝛽𝛽
phase will decrease in a regular manner as the concentration of B in
the alloy changes from 𝑥𝑥 to 𝑦𝑦, since this change in total composition
decreases the amount of 𝛼𝛼 relative to the amount of 𝛽𝛽.
 General Principles
• These principles are illustrated with reference to the hypothetical
alloy system shown in Fig. 12-3.
• This system contains two substitutional terminal solid solutions 𝛼𝛼 and
𝛽𝛽, both assumed to be face-centered cubic, and an intermediate
phase 𝛾𝛾, which is body-centered cubic.
• The solubility of either A or B in 𝛾𝛾 is assumed to be negligibly small:
the lattice parameter of 𝛾𝛾 is therefore constant in all alloys in which
this phase appears.
• On the other hand, the parameters of 𝛼𝛼 and 𝛽𝛽 vary with composition
in the manner shown by the lower part of Fig. 12-3
 General Principles
• Since the B atom is assumed to be larger than the A atom, the
addition of B expands the A lattice, and the parameter of 𝛼𝛼 increases
from 𝑎𝑎1 for pure A to 𝑎𝑎3 for a solution of composition 𝑥𝑥, which
represents the limit of solubility of B in A at room temperature.
• In two-phase (𝛼𝛼 + 𝛾𝛾) alloys containing more than 𝑥𝑥 percent B, the
parameter of 𝛼𝛼 remains constant at its saturated value 𝑎𝑎3 .
• Similarly, the addition of A to B causes the parameter of 𝛽𝛽 to
decrease from 𝑎𝑎2 to 𝑎𝑎4 at the solubility limit, and then remain
constant in the two-phase (𝛾𝛾 + 𝛽𝛽) field.
 General Principles
• Calculated powder patterns are shown in Fig. 12-4 for the eight alloys
designated by number in the phase diagram of Fig. 12-3.
• It is assumed that the alloys have been brought to equilibrium at
room temperature by slow cooling.
• Examination of these patterns reveals the following:
1. Pattern of pure A (FCC)
2. Pattern of 𝛼𝛼 almost saturated with B. The expansion of the lattice
causes the lines to shift to smaller angles 2𝜃𝜃.
 General Principles
3. Superimposed patterns of 𝛼𝛼 and 𝛾𝛾. The 𝛼𝛼 phase is now saturated
and has its maximum parameter 𝑎𝑎3 .
4. Same as pattern 3, except for a change in the relative intensities of
the two patterns which is not indicated on the drawing.
5. Pattern of pure 𝛾𝛾 (body-centered cubic).
6. Superimposed patterns of 𝛾𝛾 and of saturated 𝛽𝛽 with a parameter of
𝑎𝑎4 .
7. Pattern of pure 𝛽𝛽 with a parameter somewhat greater than 𝑎𝑎4 .
8. Pattern of pure B (face-centered cubic).
 General Principles
• When an unknown phase diagram is being determined, the
investigator must, of course, work in the reverse direction and deduce
the sequence of phases across the diagram from the observed
powder patterns.
• This is done by visual comparison of patterns prepared from alloys
ranging in composition from pure A to pure B, and the previous
example illustrates the nature of the changes which can be expected
from one pattern to another.
 General Principles
• Corresponding lines in different patterns are identified by placing the
films side by side as in Fig. 12-4 and noting which lines are common
to the two patterns.
• This may be difficult in some alloy systems where the phases involved
have complex diffraction patterns, or where it is suspected that lines
due to 𝐾𝐾𝛽𝛽 radiation may be present in some patterns and not in
others.
• It is important to remember that a diffraction pattern of a given phase
is characterized not only by line positions but also by line intensities.
 General Principles
• This means that the presence of phase X in a mixture of phases
cannot be proved merely by coincidence of the lines of phase X with a
set of lines in the pattern of the mixture; the lines in the pattern of
the mixture which coincide with the lines of phase X must also have
the same relative intensities as the lines of phase X.
• The addition of one or more phases to a particular phase weakens the
diffraction lines of that phase, simply by dilution, but it cannot change
the intensities of those lines relative to one another.
• Finally, it should be noted that the crystal structure of a phase need
not be known for the presence of that phase to be detected in a
mixture: it is enough to know the positions and intensities of the
diffraction lines of that phase.
 General Principles
• Phase diagram determination by x-ray methods usually begins with a
determination of the room-temperature equilibria.
• The first step is to prepare a series of alloys by melting and casting, or
by melting and solidification in the melting crucible.
• The resulting ingots are homogenized at a temperature just below the
solidus to remove segregation, and very slowly cooled to room
temperature.
• Powder specimens are then prepared by grinding or filing, depending
on whether the alloy is brittle or not.
 General Principles
• If the alloy is brittle enough to be ground into powder, the resulting
powder is usually sufficiently stress-free to give sharp diffraction lines.
• Filed powders, however, must be re-annealed to remove the stresses
produced by plastic deformation during filing before they are ready
for x-ray examination.
• Only relatively low temperatures are needed to relieve stresses, but
the filings should again be slowly cooled, after the stress-relief
anneal, to ensure equilibrium at room temperature.
 General Principles
• Screening is usually necessary to obtain fine enough particles for x-ray
examination, and when two-phase alloys are being screened, the
precautions should be observed.
• After the room-temperature equilibria are known, a determination of
the phases present at high temperatures can be undertaken.
• Powder specimens are sealed in small evacuated silica tubes, heated
to the desired temperature long enough for equilibrium to be
attained, and rapidly quenched.
• Diffraction patterns of the quenched powders are then made at room
temperature.
 General Principles
• This method works very well in many alloy systems, in that the
quenched powder retains the structure it had at the elevated
temperature.
• In some alloys, however, phases stable at high temperature will
decompose on cooling to room temperature, no matter how rapid the
quench, and such phases can be studied only by means of a high-
temperature camera or diffractometer.
• The latter instrument is of particular value in work of this kind
because it allows continuous observation of a diffraction line.
 General Principles
• For example, the temperature below which a high-temperature phase
is unstable, such as a eutectoid temperature, can be determined by
setting the diffractometer counter to receive a prominent diffracted
beam of the high-temperature phase, and then measuring the
intensity of this beam as a function of temperature as the specimen is
slowly cooled.
• The temperature at which the intensity falls to that of the general
background is the temperature required, and any hysteresis in the
transformation can be detected by a similar measurement on heating.
Determination of Solvus Line
 Determination of Solvus Line
• Solvus line is part of phase diagram.
• Limited solid solubility.
• On this line solid solubility varies with temperature.
• Solid solubility/concentration of solute decreases as temperature
decreases.
• Demarcation between single phase and 2 – phase region.
• Two methods used:
1. Disappearing Phase Method
2. Parametric Method
 Disappearing Phase Method
• One method of locating such curves is based on the "lever law." This
law, with reference to Fig. 12.7 for example, states that the relative
proportions of 𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝛽𝛽 in an alloy of composition 𝑧𝑧 in equilibrium at
temperature 𝑇𝑇1 is given by the relative lengths of the lines 𝑧𝑧𝑧𝑧 and 𝑧𝑧𝑧𝑧,
or that
• 𝑊𝑊𝛼𝛼 𝑧𝑧 − 𝑥𝑥 = 𝑊𝑊𝛽𝛽 (𝑦𝑦 − 𝑧𝑧)
• 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤, 𝑊𝑊𝛼𝛼 and 𝑊𝑊𝛽𝛽 denote the relative weights of 𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝛽𝛽 if x, y, and
z are expressed in weight percent.
 Disappearing Phase Method
• The weight fraction of 𝛽𝛽 in the alloy varies linearly with composition
from 0 at point x to 1 at point y.
• The intensity of any diffraction line from the 𝛽𝛽 phase also varies from
zero at x to a maximum at y, but the variation with weight percent B is
not generally linear.
• Nevertheless, this variation may be used to locate the point x. A
series of alloys in the two-phase region is brought to equilibrium at
temperature T1 and quenched.
 Disappearing Phase Method
• From diffraction patterns made at room temperature, the ratio of the
intensity 𝐼𝐼𝛽𝛽 of a prominent line of the 𝛽𝛽 phase to the intensity 𝐼𝐼𝛼𝛼 of a
prominent line of the 𝛼𝛼 phase is plotted as a function of weight
percent B.
𝐼𝐼𝛽𝛽
• The composition at which the ratio extrapolates to zero is taken as
𝐼𝐼𝛼𝛼
the point x. (Use of the ratio 𝐼𝐼𝛽𝛽 ⁄𝐼𝐼𝛼𝛼 rather than 𝐼𝐼𝛽𝛽 alone eliminates the
effect of any change which may occur in the intensity of the incident
beam from one diffraction pattern to another.
 Disappearing Phase Method
• However, this ratio also varies nonlinearly with weight percent B.
Other points on the solvus curve are located by similar experiments
on alloys quenched from other temperatures. This method is known,
for obvious reasons, as the disappearing-phase method.
• Since the curve of 𝐼𝐼𝛽𝛽 ⁄𝐼𝐼𝛼𝛼 vs. weight percent B is not linear, high
accuracy in the extrapolation depends on having several experimental
points close to the phase boundary which is being determined.
• The accuracy of the disappearing-phase method is therefore
governed by the sensitivity of the x-ray method in detecting small
amounts of a second phase in a mixture, and this sensitivity varies
widely from one alloy system to another.
 Disappearing Phase Method
• The intensity of a diffraction line depends on, among other things, the
atomic scattering factor f, which in turn is almost directly proportional
to the atomic number Z.
• Therefore, if A and B have nearly the same atomic number, the
𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝛽𝛽 phases will consist of atoms having almost the same
scattering powers, and the intensities of the 𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝛽𝛽 diffraction
patterns will also be roughly equal when the two phases are present
in equal amounts.
• Under favorable circumstances such as these, an x-ray pattern can
reveal the presence of less than 1 percent of a second phase.
 Disappearing Phase Method
• On the other hand, if the atomic number of B is considerably less
than that of A, the intensity of the 𝛽𝛽 pattern may be so much lower
than that of the 𝛼𝛼 pattern that a relatively large amount of 𝛽𝛽 in a two-
phase mixture will go completely undetected.
• This amount may exceed 50 percent in extreme cases, where the
atomic numbers of A and B differ by some 70 or 80 units.
• Under such circumstances, the disappearing-phase x-ray method is
practically worthless.
 Disappearing Phase Method
• On the whole, the microscope is superior to x-rays when the
disappearing-phase method is used, in as much as the sensitivity of
the microscope in detecting the presence of a second phase is
generally very high and independent of the atomic numbers of the
elements involved.
• However, this sensitivity does depend on the particle size of the
second phase, and if this is very small, as it often is at low
temperatures, the second phase may not be detectable under the
microscope.
 Disappearing Phase Method
• Hence the method of microscopic examination is not particularly
accurate for the determination of solvus curves at low temperatures.
• Whichever technique is used to detect the second phase, the
accuracy of the disappearing-phase method increases as the width of
the two-phase region decreases.
• If the 𝛼𝛼 + 𝛽𝛽 region is only a few percent wide, then the relative
amounts of 𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝛽𝛽 will vary rapidly with slight changes in the total
composition of the alloy, and this rapid variation of 𝑊𝑊𝛼𝛼 ⁄𝑊𝑊𝛽𝛽 will
enable the phase boundary to be fixed quite precisely.
 Disappearing Phase Method
• This is true, for the x-ray method, even if the atomic numbers of A
and B are widely different, because, if the (𝛼𝛼 + 𝛽𝛽) region is narrow,
the compositions of 𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝛽𝛽 do not differ very much and neither do
their x-ray scattering powers.
 Parametric Method
• Based on variation of lattice parameter with composition.
• Change in lattice parameter of 𝛼𝛼 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 up to maximum
solubility.
• Lattice parameter remains constant beyond maximum solubility.
 Parametric Method
• Steps:
Series of Alloys 1 to 7

Brought to Equilibrium at T1

Quenched at Room Temperature

Lattice parameter of 𝛼𝛼 is measured for each alloy and plotted against composition

Repeat at other temperatures

 Parametric Method
• Two Branches:
1. Inclined – Lattice Parameter increases as wt.% B increases.
2. Horizontal – Lattice Parameter remains constant as wt.% B
increases.
• Variables:
1. Lattice Parameter
2. Wt.% B
3. Temperature
Stereographic Projection
 The Stereographic Projection
• Stereographic Projection is a 2D map of all the angular relationships
in 3D.
• Crystal drawings made in perspective or in the form of plan and
elevation, while they have their uses, are not suitable for displaying
the angular relationship between lattice planes and directions.
• But frequently we are more interested in these angular relationships
than in any other aspect of the crystal, and we then need a kind of
drawing on which the angles between planes can be accurately
measured and which will permit graphical solution of problems
involving such angles.
• The stereographic projection fills this need.
 The Stereographic Projection
• The orientation of any plane in a crystal can be just as well
represented by the inclination of the normal to that plane relative to
some reference plane as by the inclination of the plane itself.
• All the planes in a crystal can thus be represented by a set of plane
normals radiating from some one point within the crystal.
• If a reference sphere is now described about this point, the plane
normals will intersect the surface of the sphere in a set of points
called poles.
• This procedure is illustrated in Fig. 2.25, which is restricted to the
{100} planes of a cubic crystal.
 The Stereographic Projection
• The pole of a plane represents, by its position on the sphere, the
orientation of that plane.
• A plane may also be represented by the trace the extended plane
makes in the surface of the sphere, as illustrated in Fig. 2-26, where
the trace ABCDA represents the plane whose pole is 𝑃𝑃1 .
• This trace is a great circle, i.e., a circle of maximum diameter, if the
plane passes through the center of the sphere. A plane not passing
through the center will intersect the sphere in a small circle.
• On a ruled globe, for example, the longitude lines (meridians) are
great circles, while the latitude lines, except the equator, are small
circles.
 The Stereographic Projection
• The angle 𝛼𝛼 between two planes is evidently equal to the angle
between their great circles or to the angle between their normals
(Fig. 2.26).
• But this angle, in degrees, can also be measured on the surface of the
sphere along the great circle KLMNK connecting the poles 𝑃𝑃1 and 𝑃𝑃2
of the two planes, if this circle has been divided into 360 equal parts.
• The measurement of an angle has thus been transferred from the
planes themselves to the surface of the reference sphere.
• In crystallography, we prefer the equiangular stereographic projection
since it preserves angular relationships faithfully although distorting
areas.
 Wulff Net
• The device most useful in solving problems involving the
stereographic projection is the Wulff net shown in Fig. 2.29.
• It is the projection of a sphere ruled with parallels of latitude and
longitude on a plan parallel to the north-south axis of the sphere.
• The latitude lines on a Wulff net are small circles extending from side
to side and the longitude lines (meridians) are great circles
connecting the north and south poles of the net.
• These nets are available in various sizes, one of 18-cm diameter giving
an accuracy of about one degree, which is satisfactory for most
problems; to obtain greater precision, either a larger net or
mathematical calculation must be used.
 Wulff Net
• Wulff nets are used by making the stereographic projections on
tracing paper and with the basic circle of the same diameter as that of
the Wulf net; the projection is then superimposed on the Wulff net,
with the centers a ways coinciding.
 Finding Angle between Planes
• To return to our problem of the measurement of the angle between
two crystal planes, we saw in Fig. 2.26 that this angle could be
measured on the surface of the sphere along the great circle
connecting the poles of the two planes.
• This measurement can also be carried out on the stereographic
projection if, and only if, the projected poles lie on a great circle.
• In Fig. 2.30, for example, the angle between he planes A and B, or C
and D can be measured directly, simply by counting the number of
degrees separating them along the great circle on which they lie.
 Finding Angle between Planes
• Note that the angle C – D equals the angle E – F, there being the same
difference in latitude between C and D as between E and F.
• If the two poles do not lie on a great circle, then the projection is
rotated relative t the Wulff net until they do lie on a great circle,
where the desired angle measurement can then be made.
• Figure 2.31(a) is a projection of the two poles 𝑃𝑃1 and 𝑃𝑃2 shown in
perspective in Fig. 2.26, and the angle between them is found by the
rotation illustrated in Fig. 2.31 (b).
• This rotation of the projection is equivale t to rotation of the poles on
latitude circles of a sphere whose north-south axis is perpendicular to
the projection plane.
 Trace of a Pole
• As shown in Fig. 2.26, a plane may be represented by its trace in the
reference sphere.
• This trace becomes a great circle in the stereographic projection.
Since every point on this great circle is 90° from the pole of the plane,
the great circle may be fi und by rotating the projection until the pole
falls on the equator of the underlying Wulff net and tracing that
meridian which cuts the equator 90° from the pole, as illustrated in
Fig. 2.32.
 Trace of a Pole
• If this is done for two poles, as in Fig. 2.33, the angle between the
corresponding planes may also be found from the angle of
intersection of the two great circles corresponding to these poles; it is
in this sense that the stereographic projection is said to be angle-true.
• This method of angle measurement is not as accurate, however, as
that shown in Fig. 2.31 (b).
• We often wish to rotate poles around various axes. We have already
seen that rotation a out an axis normal to the projection is
accomplished simply by rotation of the projection around the center
of the Wulff net.
 Trace of a Pole
• Rotation about an axis lying in the plane of the projection is
performed by, first, rotating the axis about the center of the Wulff net
until it coincides with the north-south axis if it does not already do so,
and, second, moving the poles involved along their respective latitude
circles the required number of degrees.
• Suppose it is required to rotate the poles 𝐴𝐴1 and 𝐵𝐵1 shown in Fig.2.34
by 60° about the NS axis, the direction of motion being from W to E
on the projection.
 Trace of a Pole
• Then 𝐴𝐴1 moves to 𝐴𝐴2 along its latitude circle as shown.
• 𝐵𝐵1 , however, can rotate only 40° before finding itself at the edge of
the projection; we must then imagine it to move 20° in from the edge
to the point 𝐵𝐵2 on the other side of the projection, staying always on
its own latitude circle.
• The final position of this pole on the positive side of the projection is
at 𝐵𝐵2 diametrically opposite 𝐵𝐵1′ .
 Miller Indices of a Pole
• 𝑎𝑎, 𝑏𝑏, 𝑎𝑎𝑎𝑎𝑎𝑎 𝑐𝑐 are three coordinate axes.
• ℎ: 𝑘𝑘: 𝑙𝑙 = (𝑝𝑝𝑝𝑝: 𝑞𝑞𝑞𝑞: 𝑟𝑟𝑟𝑟)
𝑑𝑑
• 𝑝𝑝 = cos 𝜌𝜌 = ⁄
𝑎𝑎 ℎ
𝑑𝑑
• 𝑞𝑞 = cos 𝜎𝜎 =
𝑏𝑏/𝑘𝑘
𝑑𝑑
• 𝑟𝑟 = cos 𝜏𝜏 =
𝑐𝑐/𝑙𝑙
 What is a Pole Figure and What are the
Methods to Measure it
• Pole figure is a stereogram with its axis defined by a reference frame
(external) with particular ℎ𝑘𝑘𝑘𝑘 plotted onto it from all the crystallites
present in a polycrystalline sample.
• It can be measured by using X-Ray and Neutron Diffraction.
• Qualitative idea about Crystallite Orientation can also be obtained
from Polarized Light Optical Microscopy (POLM).
• In quantitative description of crystallographic texture, typically, 3
angles (Eulers angles) are required.
 What is a Pole Figure and What are the
Methods to Measure it
• Pole figure do not measure all 3 angles. The orientation distribution
function needs to be calculated from the measured pole figures.
• Pole figures have low resolution. It provides variation in diffracted
intensity with respect to the sample reference frame.
• Map of crystal planes in sample reference frame.
• Using stereographic projections, diffracted intensities as iso –
intensities lines.
Cube Component = 100 < 001 >
 Cube Texture (100)[001] : Cube – On – Face
• Observed on recrystallization of FCC metals.
• The 001 poles are parallel to the three directions (RD, TD, ND).
 Cube Texture (100)[001] : Cube – On – Face
• To measure {100} pole figure, we isolate these particular planes by X-
Ray Diffraction.
• 𝑛𝑛𝜆𝜆 = 2𝑑𝑑 sin 𝜃𝜃
• 𝜆𝜆 = 𝑑𝑑 sin 𝜃𝜃
• To see {100} planes fix 𝑑𝑑100 , so that sin 𝜃𝜃100 is fixed. Therefore, 𝜃𝜃 is
fixed.
• So when 𝜃𝜃 is fixed, we fix the source and detector.
• Similarly we fix 𝜃𝜃110 𝑎𝑎𝑎𝑎𝑎𝑎 𝜃𝜃111 to get {110} and {111} pole figures
respectively.
 How Do We Measure Pole Figures
• Crystal structure is known, so 𝑎𝑎 is fixed.
1 ℎ2 +𝑘𝑘 2 +𝑙𝑙 2
• =
𝑑𝑑 2 𝑎𝑎2
• 𝑛𝑛𝜆𝜆 = 2𝑑𝑑 sin 𝜃𝜃
• Calculate 𝜃𝜃ℎ𝑘𝑘𝑘𝑘 to measure {hkl} pole figure.
• Fix the arrangement i.e. source and detector.
• Bulk sample is used.
• Sample has RD, ND and TD.
• RD is perpendicular to the beam direction.
 How Do We Measure Pole Figures
• The sample is rotated about its axis (ND) by 360°, then it is tilted by
5° and then rotated again by 360° along ND and then tilted again by
5° and the steps are repeated again.
• The sample is tilted from 0° 𝑡𝑡𝑡𝑡 90° in steps of 5°.
• Pole figure is a map of tilt and rotation.
• While rotating whenever we have maximum number of crystallites
oriented to give diffraction from the particular {hkl} plane, we get
high intensity and at other places we have low intensities.
• When the sample is random we get equal intensities everywhere.
• When the sample is textured then we get clusters having high
intensities.
 Quantitative Phase Analysis of a Powdered
Mixture (Direct Comparison Method)
• Direct Comparison Method does not require any external standard
unlike the RIR (Reference Intensity Ratio) Method.
• It applies for two phases.
• Example :
1. Retained Austenite (RA) in Steels
2. Al – Si Alloys (Si is not miscible in Al)
• Here powdered or randomly oriented material is required.
• Randomly Oriented Material – RA in steel – martensite structure is
randomly oriented structure at room temperature.
 Quantitative Phase Analysis of a Powdered
Mixture (Direct Comparison Method)
• 𝐼𝐼 ∝ 𝐹𝐹 2 . 𝑝𝑝. 𝐿𝐿𝐿𝐿𝐿𝐿. 𝑇𝑇𝑇𝑇. 𝐴𝐴𝐴𝐴
𝐼𝐼0 𝐴𝐴𝜆𝜆3 𝜇𝜇0 2 𝑒𝑒 4 1 2 1+𝑐𝑐𝑐𝑐𝑐𝑐 2 2𝜃𝜃 𝑒𝑒 −2𝑀𝑀
• 𝐼𝐼ℎ𝑘𝑘𝑘𝑘 = 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 . 𝑝𝑝.
32𝜋𝜋𝜋𝜋 4𝜋𝜋 𝑚𝑚2 𝑉𝑉 2 𝑠𝑠𝑠𝑠𝑠𝑠2 𝜃𝜃 cos 𝜃𝜃 2𝜇𝜇
• 𝐼𝐼ℎ𝑘𝑘𝑘𝑘 = 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼
• 𝐼𝐼0 = 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝑜𝑜𝑜𝑜 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵
• 𝜆𝜆 = 𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊
• 𝑟𝑟 = 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝑜𝑜𝑜𝑜 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
• 𝜇𝜇0 = 4𝜋𝜋 × 10−7
• 𝐴𝐴 = 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑜𝑜𝑜𝑜 𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵
 Quantitative Phase Analysis of a Powdered
Mixture (Direct Comparison Method)
• 𝑒𝑒 = 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑜𝑜𝑜𝑜 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒
• 𝑚𝑚 = 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒
• 𝑉𝑉 = 𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉 𝑜𝑜𝑜𝑜 𝑈𝑈𝑈𝑈𝑈𝑈𝑈𝑈 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
• We calculate volume of unit cell from diffraction peak values, do not
take the theoretical values.
• Calculate precise lattice parameter by Nelson – Reilly Method or
Cohen’s Method.
𝐼𝐼0 𝐴𝐴𝐴𝐴 𝜇𝜇0 2 𝑒𝑒 4
• In the above equation, let 𝐾𝐾2 =
32𝜋𝜋𝜋𝜋 4𝜋𝜋 𝑚𝑚2
 Quantitative Phase Analysis of a Powdered
Mixture (Direct Comparison Method)
1 2 1+𝑐𝑐𝑐𝑐𝑐𝑐 2 2𝜃𝜃
• 𝑅𝑅 = 2 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 . 𝑝𝑝. 𝑒𝑒 −2𝑀𝑀
𝑉𝑉 𝑠𝑠𝑠𝑠𝑠𝑠2 𝜃𝜃 cos 𝜃𝜃
𝐾𝐾2 𝑅𝑅
• 𝐼𝐼 =
2𝜇𝜇
• 𝜇𝜇 = 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
• 𝜇𝜇𝑚𝑚𝑚𝑚𝑚𝑚 = 𝜇𝜇1 𝜌𝜌1 + 𝜇𝜇2 𝜌𝜌2
• 𝐿𝐿𝐿𝐿𝐿𝐿 𝑢𝑢𝑢𝑢 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑡𝑡𝑡𝑡𝑡𝑡 𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝛽𝛽
𝐾𝐾2 .𝑅𝑅𝛼𝛼 .𝐶𝐶𝛼𝛼
• 𝐼𝐼𝛼𝛼 =
2𝜇𝜇𝑚𝑚𝑚𝑚𝑚𝑚
𝐾𝐾2 .𝑅𝑅𝛽𝛽 .𝐶𝐶𝛽𝛽
• 𝐼𝐼𝛽𝛽 =
2𝜇𝜇𝑚𝑚𝑚𝑚𝑚𝑚
 Quantitative Phase Analysis of a Powdered
Mixture (Direct Comparison Method)
𝐼𝐼𝛼𝛼 𝑅𝑅𝛼𝛼 𝐶𝐶𝛼𝛼
• = .
𝐼𝐼𝛽𝛽 𝑅𝑅𝛽𝛽 𝐶𝐶𝛽𝛽
• 𝐶𝐶𝛼𝛼 + 𝐶𝐶𝛽𝛽 = 1
• 𝐶𝐶 = 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
• Calculate 𝐶𝐶𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝐶𝐶𝛽𝛽 for various peaks and take the mean of them to
get 𝐶𝐶𝛼𝛼 𝑎𝑎𝑎𝑎𝑎𝑎 𝐶𝐶𝛽𝛽 .
• In Direct Comparison Method we need to calculate R for all peaks and
all phases.
• Only possible for 2 or 3 phases.
 Quantitative Phase Analysis of a Powdered
Mixture (Direct Comparison Method)
• One of the most used methods to determine RA in Steel.
• Overlapping peaks are not to be considered.
Reciprocal Space
 Reciprocal Lattice
• Properties are reciprocal to the crystal lattice.
• Real Space − Basis Vectors = 𝑎𝑎⃗1 , 𝑎𝑎⃗ 2 , 𝑎𝑎⃗ 3 .
∗ 1
• 𝑏𝑏 1 = 𝑎𝑎⃗2 × 𝑎𝑎⃗3
𝑉𝑉
1
• 𝑏𝑏 ∗ 2 = 𝑎𝑎⃗ 3 × 𝑎𝑎⃗1
𝑉𝑉
1
• 𝑏𝑏 ∗ 3 = 𝑎𝑎⃗1 × 𝑎𝑎⃗2
𝑉𝑉
• 𝑏𝑏𝑖𝑖∗ 𝑐𝑐𝑐𝑐𝑐𝑐 𝑏𝑏𝑏𝑏 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 𝑎𝑎𝑎𝑎 𝑎𝑎⃗𝑖𝑖∗ .
1 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂 1 1
• 𝑏𝑏3∗ = 𝑏𝑏3∗ = 𝑎𝑎⃗1 × 𝑎𝑎⃗ 2 = = =
𝑉𝑉 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂 .𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻 𝑜𝑜𝑜𝑜 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑂𝑂𝑂𝑂 𝑑𝑑001
 Reciprocal Lattice
• 𝑏𝑏3∗ 𝑖𝑖𝑖𝑖 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑡𝑡𝑡𝑡 𝑎𝑎⃗1 𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎⃗2 .
• The reciprocal lattice is created by interplanar spacing.
1
• 𝑏𝑏1∗ =
𝑑𝑑100
1
• 𝑏𝑏2∗ =
𝑑𝑑010
• A reciprocal vector is perpendicular to the corresponding real lattice
plane.
∗
• 𝑔𝑔⃗ℎ𝑘𝑘𝑘𝑘 = ℎ𝑏𝑏1∗ + 𝑘𝑘𝑏𝑏2∗ + 𝑙𝑙𝑏𝑏3∗ .
 Reciprocal Lattice
• The length of a reciprocal lattice vector is the reciprocal of the spacing
of the corresponding real lattice plane.
∗ ∗ 1
• 𝑔𝑔ℎ𝑘𝑘𝑘𝑘 = 𝑔𝑔⃗ℎ𝑘𝑘𝑘𝑘 = .
𝑑𝑑ℎ𝑘𝑘𝑘𝑘
• Planes in the crystal become lattice points in the reciprocal lattice.
• Alternate construction of the real lattice.
• Reciprocal lattice point represents the orientation and spacing of a set
of planes.
 (01) 02 12 22

(11) 01 11
21
(10)
(21)

10 20
00

Real Lattice The reciprocal lattice has a natural origin! Reciprocal Lattice

a2
*
 b2
a1 *
b1
The reciprocal lattice

Note that vectors in reciprocal space are

perpendicular to planes in real space (as
constructed!)
But do not measure distances from the figure!
 Reciprocal Crystal
• Reciprocal Lattice is the reciprocal of a primitive lattice and is purely
geometrical. It does not deal with intensities of the points.
• For non – primitive cells (lattices with additional points) and for
crystals decorated with motifs (Crystal = Lattice + Motif) the
reciprocal lattice points have to be weighted in with the
corresponding scattering power 𝐹𝐹ℎ𝑘𝑘𝑘𝑘 2 .
• Some of the reciprocal lattice points go missing (or may be scaled up
or down in intensity).
• Making of Reciprocal Crystal (Reciprocal Lattice decorated with a
motif of scattering power).
 Reciprocal Crystal
• The Ewald Sphere construction further can select those points which
are actually observed in a diffraction experiment.
• In a crystal based on a particular lattice the intensities of a particular
reflection are modified. They may even go missing.
• Position of the diffracted spots = Lattice.
• Intensities of the diffraction spots = Motif.
• Diffraction Pattern :
1. Position of the diffraction spots = Reciprocal Lattice.
2. Intensities of the diffraction spots = Motif of Intensities.
 Reciprocal Crystal
• Crystal = Lattice + Motif.
• There are two ways of constructing the Reciprocal Crystal :
1. Construct the lattice and decorate each lattice point with
appropriate intensities.
2. Use the concept as that for the real crystal.
Examples of 3D Reciprocal
Lattices weighted with Scattering
2
Power 𝐹𝐹ℎ𝑘𝑘𝑘𝑘
Read these slides in parallel → Read the slides on Structure Factor Calculations

SC Examples of 3D Reciprocal Lattices weighed in with scattering power (|F|2)

Selection rule: All (hkl) allowed

In ‘simple’ cubic crystals there are No missing reflections
Reciprocal Crystal = SC
+  SC lattice with Intensities as the motif at each ‘reciprocal’ lattice point.
Single sphere  The unit cell for the reciprocal lattice and the reciprocal crystal are the
motif same in this case.

Lattice = SC

1/a
a SC crystal
=
1/a
a
a 1/a

Weighing factor for each point “motif”

Figures NOT to Scale F2 = f 2
FCC Reciprocal Crystal = BCC
BCC lattice with Intensities as the motif
 Selection rule FCC: h, k, l unmixed (all odd or all
even).
 Allowed reflections: 111, 200, 220...
 Forbidden reflections: 100, 110, 112...
 BCC lattice with Intensities (16f2) as the motif at each
‘reciprocal’ lattice point.
a  The unit cell for the reciprocal lattice and the reciprocal
crystal are NOT the same in this case.
 The basis vectors for the UC of the reciprocal lattice:
(b1)*, (b2)*, (b3)*.
 The basis vectors for the UC of the reciprocal crystal:
(c1)*, (c2)*, (c3)*.
Important note:
 The 100, 110, 112, etc. points in the reciprocal lattice exist (as the
corresponding real lattice planes exist), however the intensity
decorating these points is zero.
100 missing
reflection (F = 0)

Weighing factor for each 110 missing reflection

point “motif” (F = 0)

F 2 = 16 f 2
Figures NOT to Scale
 Selection rule BCC: (h+k+l) even allowed Reciprocal Crystal = FCC
BCC In BCC 100, 111, 210, etc. go missing
FCC lattice with Intensities as the motif

100 missing
reflection (F = 0)

2/a
Weighing factor for
each point “motif”

F2 = 4 f 2

Figures NOT to Scale

 Diagrams not to scale

Positional Order In a strict sense this is not a crystal !!

High T disordered

BCC

Probabilistic occupation of each BCC lattice site:

50% by Cu, 50% by Zn
G = H − TS 470ºC

Sublattice-1 (SL-1)

Sublattice-2 (SL-2)

Low T ordered SC

SL-1 occupied by Cu and SL-2 occupied by Zn. Origin of SL-2 at (½, ½, ½)

Example of superlattice spots in a TEM diffraction pattern

The spots are

~periodically arranged

[112]
[111] [011]
Superlattice spots

SAD patterns from a BCC phase (a = 10.7 Å) in as-cast Mg4Zn94Y2 alloy showing important zones
Ewald Sphere
 The Ewald Sphere
• The reciprocal lattice points are the values of momentum transfer for
which the Bragg’s equation is satisfied.
• For diffraction to occur the scattering vector must be equal to a
reciprocal lattice vector.
• Geometrically, if the origin of reciprocal space is placed at the tip of 𝑘𝑘𝑖𝑖
then diffraction will occur only for those reciprocal lattice points lie
on the surface of the Ewald Sphere.
 Bragg’s Law Revisited
• 𝑛𝑛𝜆𝜆 = 2𝑑𝑑ℎ𝑘𝑘𝑘𝑘 sin 𝜃𝜃ℎ𝑘𝑘𝑘𝑘
𝜆𝜆⁄2 1⁄𝑑𝑑ℎ𝑘𝑘𝑘𝑘
• sin 𝜃𝜃ℎ𝑘𝑘𝑘𝑘 = =
𝑑𝑑ℎ𝑘𝑘𝑘𝑘 2⁄𝜆𝜆
• Draw a circle with the diameter 2⁄𝜆𝜆.
• Construct a triangle with the diameter as the hypotenuse and 1⁄𝑑𝑑ℎ𝑘𝑘𝑘𝑘
as a side (any triangle inscribed in a circle with the diameter as the
hypotenuse is a right – angle triangle) : 𝐴𝐴𝐴𝐴𝐴𝐴.
• The angle opposite the 1⁄𝑑𝑑 side is 𝜃𝜃ℎ𝑘𝑘𝑘𝑘 (from the rewritten Bragg’s
Equation).
 * * 1
g hkl = g hkl =
d hkl
 The Ewald Sphere Construction
• The Ewald Sphere construction generates the diffraction pattern.
𝜆𝜆⁄2 1⁄𝑑𝑑ℎ𝑘𝑘𝑘𝑘
• sin 𝜃𝜃ℎ𝑘𝑘𝑘𝑘 = = .
𝑑𝑑ℎ𝑘𝑘𝑘𝑘 2⁄𝜆𝜆
1
• Crystal related information is present in the reciprocal crystal − .
𝑑𝑑ℎ𝑘𝑘𝑘𝑘
2
• Radiation related information is present in the Ewald Sphere − .
𝜆𝜆
 Ewald Sphere
• The Ewald Sphere touches the
Reciprocal Space
reciprocal lattice (for point 41).
• Bragg’s Equation is satisfied for 41.
• ∆𝐾𝐾 = 𝐾𝐾 = 𝑔𝑔⃗ = Diffraction Vector.
• Diameter of Sphere is very large as
the wavelength is very low.
2θ
KD • So sphere is nearly flat, and we see
Ki diffraction from many points.
02

01
∆K (41)

00 10 20
Ewald Sphere → X – Rays
 Ewald Sphere → X – Rays
• The 111 reflection is observed at a smaller angle θ111 as compared to
the 222 reflection
• λ(Cu Kα) = 1.54 Å, 1/λ = 0.65 Å−1 (2/λ = 1.3 Å−1), aAl = 4.05 Å, d111 =
2.34 Å, 1/d111 = 0.43 Å−1 .
 The Powder Method
• In the powder method we use monochromatic radiation (λ is fixed),
but θ is variable (the sample consists of crystallites in various
orientations).
• A cone of ‘diffraction beams’ are produced from each set of planes
(e.g. (111), (120) etc.)
• A diffractometer is typically used in modern XRD studies, which
moves in an arc and can intersect these cones and give rise to peaks
in a ‘powder diffraction pattern’.
 The Powder Method
• Let us consider two planes (say with indices {111})− the green plane
and the blue plane. These are residing in two different crystals and
are perfectly oriented at Bragg angle for diffraction.
• These two set of planes result in the blue and green diffracted beams.
• Similar planes (again from the {111} family as an illustration) from
other crystallites in the specimen can be obtained by using the axis of
rotation (red font). This forms a cone of diffracted beams.
• Similar planes (again from the {111} family as an illustration) from
other crystallites in the specimen can be obtained by using the axis of
rotation (red font). This forms a cone of diffracted beams.
 The Powder Method
• In a powder sample, due to ‘all’ orientations of the crystallites the
point ‘P’ ‘expands’ a circle with center at ‘O’.
• The intersection of the Ewald sphere with the ‘crystal sphere’ is a
circle and this gives rise to the cone of intensity.
• Circle of intersection of the ‘Ewald sphere’ with the crystallites sphere
• In a power sample the point P can lie on a sphere centered around O
due all possible orientations of the crystals.
1
• The distance PO = .
𝑑𝑑ℎ𝑘𝑘𝑘𝑘
Cone of diffracted rays
 Circular Section through the spheres
made by the hkl reflections

The 440 reflection is not observed

(as the Ewald sphere does not intersect
the reciprocal lattice point sphere)

Ewald sphere construction for Al

Allowed reflections are those for
h, k and l unmixed
 The 331 reflection is not observed

Ewald sphere construction for Cu

Allowed reflections are those for
h, k and l unmixed
 The Powder Method
• Diffraction conditions occur when the tip of the scattering vector 𝑔𝑔∗
falls on a point of the reciprocal space.
• The condition is fulfilled by all points on the Ewald Sphere of a radius
1⁄𝜆𝜆 , tangent to the origin and to the 2⁄𝜆𝜆 sphere.
• In a powder diffraction measurement, the Ewald Sphere can be
thought as rotating inside the 2⁄𝜆𝜆 sphere.
• In a powder (polycrystalline material) measurements, several points
can be in diffraction condition simultaneously i.e., for the same 2𝜃𝜃.
 The Powder Method
• This property is expressed by the concept of multiplicity of a
diffraction peak, i.e., the number of equivalent planes.
𝑆𝑆
• 𝐾𝐾𝑖𝑖 =
𝜆𝜆
𝑆𝑆0
• 𝐾𝐾𝑑𝑑 =
𝜆𝜆
𝑆𝑆⃗ − 𝑆𝑆⃗0 ∗
• ∆𝐾𝐾 = = 𝑔𝑔ℎ𝑘𝑘𝑘𝑘 = General Condition for Diffraction.
𝜆𝜆
General Condition for Electron
Diffraction and Laue Conditions
 General Condition for Electron Diffraction
• 𝑂𝑂 = 𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜.
• 𝐴𝐴 = 𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑎𝑎 𝑝𝑝𝑝𝑝1 , 𝑞𝑞𝑞𝑞2 , 𝑟𝑟𝑟𝑟3 .
• ∴ 𝑂𝑂𝑂𝑂 = 𝑝𝑝𝑝𝑝1 + 𝑞𝑞𝑞𝑞2 + 𝑟𝑟𝑟𝑟3
• 𝜆𝜆 = 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤.
• 𝑆𝑆0 = 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣.
• 𝑆𝑆 = 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣.
• Phase Difference Calculations
• 𝛿𝛿 = 𝑢𝑢𝑢𝑢 + 𝐴𝐴𝐴𝐴 = 𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷.
 General Condition for Electron Diffraction
• 𝛿𝛿 = 𝑢𝑢𝑢𝑢 + 𝐴𝐴𝐴𝐴 = 𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 = 𝑂𝑂𝑂𝑂 + 𝑂𝑂𝑂𝑂
• 𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 = 𝑆𝑆0 . 𝑂𝑂𝑂𝑂 + −𝑆𝑆 . 𝑂𝑂𝑂𝑂 = −𝑂𝑂𝑂𝑂 𝑆𝑆 − 𝑆𝑆0 .
2𝜋𝜋𝜋𝜋 𝑆𝑆−𝑆𝑆0
• 𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 = 𝜙𝜙 = = −2𝜋𝜋 . 𝑂𝑂𝑂𝑂
𝜆𝜆 𝜆𝜆
𝑆𝑆−𝑆𝑆0
• 𝐿𝐿𝐿𝐿𝐿𝐿 = ℎ𝑏𝑏1 + 𝑘𝑘𝑘𝑘2 + 𝑙𝑙𝑙𝑙3
𝜆𝜆
• ℎ, 𝑘𝑘, 𝑙𝑙 are continuously variable in space (integer/non – integer both).
• 𝜙𝜙 = −2𝜋𝜋 ℎ𝑏𝑏1 + 𝑘𝑘𝑘𝑘2 + 𝑙𝑙𝑙𝑙3 . 𝑝𝑝𝑝𝑝1 + 𝑞𝑞𝑞𝑞2 + 𝑟𝑟𝑟𝑟3
• 𝜙𝜙 = −2𝜋𝜋(ℎ𝑝𝑝 + 𝑘𝑘𝑘𝑘 + 𝑙𝑙𝑙𝑙)
 General Condition for Electron Diffraction
• 𝜙𝜙 should be integral multiple of 2𝜋𝜋 for constructive interference. That
is possible only if ℎ , 𝑘𝑘 , 𝑙𝑙 are integers.
𝑆𝑆−𝑆𝑆0 ∗
• = ℎ𝑏𝑏1 + 𝑘𝑘𝑘𝑘2 + 𝑙𝑙𝑙𝑙3 = 𝐻𝐻 = 𝑔𝑔ℎ𝑘𝑘𝑘𝑘 = 𝐻𝐻∗
𝜆𝜆
• So the general condition for diffraction is,
𝑆𝑆 − 𝑆𝑆0 ∗ 1
= ℎ𝑏𝑏1 + 𝑘𝑘𝑘𝑘2 + 𝑙𝑙𝑙𝑙3 = 𝑔𝑔ℎ𝑘𝑘𝑘𝑘 =
𝜆𝜆 𝑑𝑑ℎ𝑘𝑘𝑘𝑘
 Laue Conditions
𝑆𝑆−𝑆𝑆0
• = 𝐻𝐻 = ℎ𝑏𝑏1 + 𝑘𝑘𝑘𝑘2 + 𝑙𝑙𝑙𝑙3
𝜆𝜆
𝑆𝑆−𝑆𝑆0
• 𝑎𝑎1 . = 𝑎𝑎1 . ℎ𝑏𝑏1 + 𝑘𝑘𝑘𝑘2 + 𝑙𝑙𝑙𝑙3 = ℎ
𝜆𝜆
• 𝑆𝑆𝑆𝑆 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑎𝑎𝑎𝑎𝑎𝑎,
𝑎𝑎1 . 𝑆𝑆 − 𝑆𝑆0 = ℎ𝜆𝜆
𝑎𝑎2 . 𝑆𝑆 − 𝑆𝑆0 = 𝑘𝑘𝜆𝜆
𝑎𝑎3 . 𝑆𝑆 − 𝑆𝑆0 = 𝑙𝑙𝜆𝜆
• By geometry, 𝑆𝑆 − 𝑆𝑆0 = 2 sin 𝜃𝜃
𝑆𝑆−𝑆𝑆0 2 sin 𝜃𝜃 1
• = = 𝐻𝐻ℎ𝑘𝑘𝑘𝑘 = → 2𝑑𝑑 sin 𝜃𝜃 = 𝜆𝜆 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝑔𝑔′ 𝑠𝑠 𝐿𝐿𝐿𝐿𝐿𝐿 .
𝜆𝜆 𝜆𝜆 𝑑𝑑ℎ𝑘𝑘𝑘𝑘
Transmission Electron
Microscopy
Wavelength of the Electron Beam in the TEM
• Wavelength of the electron beam in the TEM after application of the
relativistic correction is,
1⁄
1.5 2
• 𝜆𝜆 = (𝑖𝑖𝑖𝑖 𝑛𝑛𝑛𝑛)
𝑉𝑉+10−6 𝑉𝑉 2
• 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤, 𝑉𝑉 = 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣.
• Wavelength of the electron beam in the TEM without relativistic
correction is,
1
1.5 ⁄2
• 𝜆𝜆 = (𝑖𝑖𝑖𝑖 𝑛𝑛𝑛𝑛)
𝑉𝑉
 Electron – Matter Interaction
• We need to make the sample electron transparent, i.e. the thickness
of sample should be 10 to 50 nm.
• Only Focused Ion Beam (FIB) Milling can make perfect samples for
TEM.
• Auger Electrons, Back Scattered Electrons, Secondary Electrons, Light
Photons, Coherent Elastic, Incoherent Elastic and Inelastic
Interactions occur.
• BSE Imaging, SE Imaging , EDS, Diffraction, Fores Scatter Imaging,
STEM can take place.
• AES cannot take in TEM.
 Electron – Matter Interaction
• Conduction also takes.
• Primary Beam = 1 𝑡𝑡𝑡𝑡 300 𝑘𝑘𝑘𝑘𝑘𝑘.
• Detector is very costly (1 detector = 50 lakh).
• Electron Energy Loss Spectroscopy (EELS).
• Central portion of sample is used for imaging which is micron in size.
• Therefore multiple samples are required.
• Sample preparation is difficult.
• Cathodoluminescence is used for identification of minerals.
 Electron – Matter Interaction
• Inelastically scattered electrons give the most faithful reconstruction
of the sample.
• Incoherent Elastically Scattered Electrons – STEM (High Z and Low Z).
• There are two types of elastic scattering :
1. Incoherent Scattering = This is the case when the specimen has an
amorphous structure. The deflected electron waves have no phase
relation to the specimen.
2. Coherent Scattering = This is the case when the specimen has a
crystalline structure. There is now a phase relation between the
specimen and the rays are deflected under defined angles
(Diffraction Mode).
 Bragg Equation
• 𝑛𝑛𝜆𝜆 = 2𝑑𝑑 sin 𝜃𝜃
• For 100 𝑘𝑘𝑘𝑘𝑘𝑘 electrons, the wavelength is 0.0037 𝑛𝑛𝑛𝑛.
• 𝑑𝑑 = 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠, 𝑖𝑖𝑖𝑖 𝑖𝑖𝑖𝑖 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 0.1 𝑡𝑡𝑡𝑡 0.4 𝑛𝑛𝑛𝑛.
• 𝜃𝜃 = 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴, 𝑖𝑖𝑖𝑖 𝑡𝑡𝑡𝑡𝑡 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝑜𝑜𝑜𝑜 0.5° 𝑡𝑡𝑡𝑡 2.0°.
• For higher values of voltage, angles are smaller.
• The entire diffraction pattern is spanned within a 2°/5° cone around
the incident beam.
Table : 𝑑𝑑 spacing and Bragg’s angles for diffraction by 100 𝑘𝑘𝑘𝑘𝑘𝑘 electrons in 𝐴𝐴𝐴𝐴 sample; 𝑎𝑎𝐴𝐴𝐴𝐴 = 0.405 𝑛𝑛𝑛𝑛

𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷 (𝒉𝒉𝒉𝒉𝒉𝒉) 𝒅𝒅 (𝒏𝒏𝒏𝒏) sin 𝜃𝜃 𝜽𝜽 °

111 0.2338 0.00791 0.453

200 0.2025 0.009136 0.523

220 0.1432 0.01292 0.740

311 0.1221 0.01515 0.868

 Ewald Sphere
1
• Radius of Ewald Sphere is .
𝜆𝜆
• The Radius of Ewald Sphere for electrons of 100 𝑘𝑘𝑘𝑘𝑘𝑘 is approximately
270 𝑛𝑛𝑛𝑛−1 .
• Magnitude of Reciprocal Lattice Vector is of the order of
2.5 𝑡𝑡𝑡𝑡 10 𝑛𝑛𝑛𝑛−1 .
• As pointed out earlier, Bragg Angles are small.
• Consequently Ewald Sphere can be approximated to a plane.
 Information from Diffraction Patterns
Single Phase Material
• Electron Beam Direction – By Indexing the Single Crystal Spot Pattern
𝐵𝐵 .
• Operating Reflection 𝑔𝑔⃗ (Reflection used for Imaging).
• 𝑠𝑠,
⃗ deviation from ideal Bragg Diffraction Condition.
• Types of Diffraction Patterns in Conventional TEM are,
1. Spot Diffraction Patterns.
2. Ring Pattens.
3. Kikuchi Lines.
 Basic Relationship in Electron Diffraction
• 𝐿𝐿 = distance between specimen stage and screen.
• 𝜆𝜆 = 𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊.
• 𝐿𝐿𝜆𝜆 = 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶.
• Camera Constant is constant for a particular operating condition.
• From the figure,
𝑅𝑅 𝜆𝜆
• = tan 2𝜃𝜃 = 2𝜃𝜃 = sin 2𝜃𝜃 = 2 sin 𝜃𝜃 = .
𝐿𝐿 𝑑𝑑
• 𝑅𝑅𝑅𝑅 = 𝐿𝐿𝜆𝜆 = 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐.
1
• So, 𝑅𝑅 ∝ .
𝑑𝑑ℎ𝑘𝑘𝑘𝑘
 Basic Relationship in Electron Diffraction
• Zone Axis Direction is same as Beam Direction.
• All planes parallel to the zone axis diffract.
• Ewald Sphere will cut the Reciprocal Lattice.
• If the beam axis is parallel to (111) then the spot diffraction pattern
has hexagonal symmetry/hexagonal pattern.
 Electron Diffraction
• Electron diffraction can be understood by invoking the concept of
reciprocal lattice and the Ewald Sphere.
• The Reciprocal Lattice is related to the Direct Lattice of the Crystal by
a Reciprocal Relationship.
• 𝐻𝐻ℎ𝑘𝑘𝑘𝑘 = ℎ𝑏𝑏1 + 𝑘𝑘𝑘𝑘2 + 𝑙𝑙𝑙𝑙3 .
1
• 𝐻𝐻ℎ𝑘𝑘𝑘𝑘 = .
𝑑𝑑ℎ𝑘𝑘𝑘𝑘
• The Ewald Sphere is a Sphere having a Radius equal to the Reciprocal
of the Wavelength 1⁄𝜆𝜆 .
 Amorphous Materials
• Diffused Ring Pattern.
• Reflecting the Short – Range Ordered Structure.
• Often seen at Contamination Layer or on Carbon Support Film.
 Selected Area Electron Diffraction from
Crystals of Various Sizes
• When the entire beam is within one grain – single crystal – reciprocal
crystal with discrete points – Ewald Sphere has a large radius. So,
Ewald Sphere is able to see all points – Spot Pattern. (Fig a).
• When beam probes five to six grains – spot diffraction patterns of all
grains will be super imposed on each other – discrete points – grainy
ring. Nanocrystalline Sample with Small Beam Size. (Fig b).
• When many grains – for one particular 𝑑𝑑ℎ𝑘𝑘𝑘𝑘 all possible orientations
will come – Ring Pattern Formed – Nanocrystalline Sample with Large
Beam Size. (Fig c).
 Various Types of Electron Diffraction
• TEM can operate in two modes,
1. Parallel Beam Mode.
2. Convergent Beam Mode.
• Parallel Beam Diffraction Mode is used for imaging, SAED, and Ring
Pattern.
• For Advanced Characterization, Convergent Beam Diffraction Method
is used.
• Using Convergent Beam Mode we can observe the Laue Zones, this
mode is used to identify all the 32 Point Groups.
 Various Types of Electron Diffraction
• Microdiffraction – if source is extremely good, then we can make the
beam extremely fine.
• In SAED the inaccuracy is very high. If we tilt the sample holder which
contains the sample by 3° 𝑡𝑡𝑡𝑡 5° , then also the same spot diffraction
pattern is found i.e. spot diffraction is not sensitive to tilt. So it is
always used as approximation.
 Spot Pattern
• Single Crystal within the illumination area.
• The regular arrangement of spots.
• Spot brightness relates to the structure factor.
• Spot position relates to the 𝑑𝑑 spacing.
• We only need to solve for two unknown (spots), then by simple
vectorial addition we can index the rest of the unknows i.e. spots of
the diffraction pattern.
FCC Spot Diffraction Pattern
BCC Spot Diffraction Pattern
 Electron Diffraction
• Diffraction Pattern is located at the back focal plane of the objective
lens.
• This is true for both Optical Microscope (OM) and Transmission
Electron Microscope (TEM).
• For any lens, if we place an object at a distance 𝑓𝑓 from the lens, then
the diffraction pattern of that object is obtained a distance 𝑓𝑓 from the
lens on the opposite side of the object, i.e., the diffraction pattern is
obtained at the back focal plane of the objective lens.
• Image of the object is formed at the image plane.
 Electron Diffraction
• If we project the image plane, then we get the image of the specimen
on the screen. Similarly is we project the back focal plane of the
objective lens then we obtain the diffraction pattern of the specimen
on the screen using the intermediate lenses and the projector lens.
• That is we can obtain both the image and diffraction pattern from the
same spot of the specimen. This is done by changing the aperture of
the objective lens.
• The Objective Lens has two apertures,
1. Objective Aperture (for imaging).
2. Selected Area Diffraction Aperture (for diffraction).
 Electron Diffraction
• Back focal plane – Coherent Elastic Scattering.
• Image Plane – Elastic Scattering.
• Calibration is required.
• Calibration is done by nanocrystalline Ni/Au Sample.
• Ni is preferred as it is very easy to prepare nanoparticles of Ni.
 Diffraction with Parallel Illumination and
Conical Illumination
• Parallel beams are focused at the back focal plane.
• Parallel illumination results in sharp spots at the plane.
• These sharp spots provide us the information about the type of
material that we are probing using TEM.
• Conical illumination results in discs at the plane.
• These discs can be magnified in order to get information about Laue
Zones, both High Order Laue Zones (HOLZ) and Low Angle Laue Zones
(LOLZ), and Point Groups.
Diffraction Mode and Image Mode
 Indexing Ring Patterns – Determination of
Camera Constant
1. Measure the Radii 𝑅𝑅 of various rings.
2. If the Crystal Structure of the Material is known, 𝑅𝑅 can be related to
the values of ℎ2 + 𝑘𝑘 2 + 𝑙𝑙 2 of the allowed Reflections.
3. Plot 𝑅𝑅 as a function of ℎ2 + 𝑘𝑘 2 + 𝑙𝑙 2 ; slope of the Linear Plot is
equal to 𝐿𝐿𝜆𝜆⁄𝑎𝑎 .
4. Any Error in assigning ℎ, 𝑘𝑘, 𝑙𝑙 values for the Rings will be shown up as
significant deviation from the linear plot.
 Indexing Ring Patterns – Determination of
Camera Constant
𝑎𝑎 𝐿𝐿𝐿𝐿
• 𝑅𝑅𝑅𝑅 = 𝐿𝐿𝜆𝜆 → 𝑅𝑅 = 𝐿𝐿𝜆𝜆 → 𝑅𝑅 = ℎ2 + 𝑘𝑘 2 + 𝑙𝑙 2
ℎ2 +𝑘𝑘 2 +𝑙𝑙 2 𝑎𝑎
• Find Camera Constant for that Accelerating Voltage and Operating
Conditions.
• This is done by using Nanocrystalline Ni or Nanocrystalline Au Sample.
• If we don’t carry out the Calibration we cannot find out the Camera
Constant. So we don’t have Material Property.
• So we cannot compare the Diffraction Pattern of an Unknown
Material with our Database to find out its Lattice Parameter.
 Indexing Ring Patterns – Determination of
Camera Constant
• We will know what type of material it is BCC, FCC, SC, HCP, etc. –
qualitatively we will know. But we cannot compare it quantitatively.
• Diffraction Patterns are scaled with Camera Constant.
 Plasmons
• Plasmons are collective oscillations of free electrons that occur when
the electron beam passes through the free electron gas.
• Plasmon Energy is Quantized.
• Plasmon Energy also changes with Electron Density which depends on
the Local Composition of the Sample.
• Plasmons may be used for Microanalysis through Energy Loss Imaging
to help to focus image.
• The mean free path for plasmon excitation is about 100 𝑛𝑛𝑛𝑛. This can
be used for measuring sample thickness.
 Plasmons
• Plasmon Scattering.
• There are some advanced techniques based on which we can
determine sample thickness using this.
 Phonons
• Bonds vibrate when struck by high energy electrons creating lattice
oscillations – essentially equivalent to heating the sample.
• Phonons are responsible for the thermal diffuse scattering observed
around electron diffracting pattern spots. Sample cooling reduces this
effect.
• The mean free path for phonon excitation is 350 𝑛𝑛𝑛𝑛 for 𝐴𝐴𝐴𝐴 and only a
few 𝑛𝑛𝑛𝑛 for 𝐴𝐴𝐴𝐴.
• This is depended on the Atomic Number of the Sample.
• So lighter elements are difficult to image using TEM as there will be a
lot of phonon scattering which will heat the sample and would create
point defects.
 Scattering Events
1. Single Scattering :
• Each electron scatters only once on average while traversing the
sample.
• Good for TEM analytical work.
• For this the sample should be electron transparent i.e. its thickness
should be in between 50 − 100 𝑛𝑛𝑛𝑛.
• Use FIB Milling to make the sample electron transparent.
 Scattering Events
2. Plural Scattering :
• Each electron scatters more than once but less than 20 times.
• Used for Conventional Work.
3. Multiple Scattering :
• Each electron scatters more than 20 times as it traverses the sample.
• Sample is too thick for any reasonable analytical work, difficult to
predict what will happen to electron.
 Beam Damage
• There are two types of electron beam damage.
• Radiolysis : Inelastic Scattering (mainly heating of the sample) breaks
the chemical binds of certain materials. For example, 𝑆𝑆𝑆𝑆𝑆𝑆2 is easily
damaged through radiolysis in a 300 𝑘𝑘𝑘𝑘 𝑇𝑇𝑇𝑇𝑇𝑇. Polymers and Ceramics
are also easily subjected to radiolysis.
• Good thermal contact between the sample and the stage can reduce
electron beam heating of the sample. Higher operation voltages
minimize heat transfer.
• Knock on damage : Direct displacement of atoms from the crystal
lattice creating point defects. It is directly related to the beam energy.
 Outline
• Electron Sources (Electron Guns) :
1. Thermionic : 𝐿𝐿𝐿𝐿𝐿𝐿6 𝑜𝑜𝑜𝑜 𝑊𝑊 − 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹.
2. Field Emission Gun (FEG) : Cold or Schottky.
• Lenses :
1. Focusing.
2. Aberration.
3. Probe Size.
 Outline
• Detectors :
1. Electron Detectors.
2. X – Ray Detectors.
3. Energy Loss Spectrometer.
• Imaging :
1. Diffraction.
2. Bright Field (BF) Imaging.
3. Dark Field (DF) Imaging.
4. Phase Contrast Imaging.
5. Scanning Transmission Electron Microscope (STEM).
6. Holography Mode.
 Electron Sources
𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺 𝑩𝑩𝑩𝑩𝑩𝑩𝑩𝑩𝑩𝑩𝑩𝑩𝑩𝑩𝑩𝑩𝑩𝑩𝑩𝑩 𝜷𝜷 𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺 𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺 𝝁𝝁𝝁𝝁 𝑬𝑬𝑬𝑬𝑬𝑬𝑬𝑬𝑬𝑬𝑬𝑬 𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺 ∆𝑬𝑬 𝑳𝑳𝑳𝑳𝑳𝑳𝑳𝑳𝑳𝑳𝑳𝑳𝑳𝑳𝑳𝑳 (𝒉𝒉𝒉𝒉)
𝑨𝑨/ 𝒎𝒎𝟐𝟐 ⁄𝒓𝒓𝒓𝒓𝒓𝒓 𝒆𝒆𝒆𝒆
𝑊𝑊 109 10 1−3 40 − 100
𝐿𝐿𝐿𝐿𝐿𝐿6 5 × 105 5 1−2 500 − 1000
𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝐹𝐹𝐹𝐹𝐹𝐹 1013 0.005 0.3 > 1000
𝐻𝐻𝐻𝐻𝐻𝐻 𝐹𝐹𝐹𝐹𝐹𝐹 1013 0.015 1.0 1000
 Calculating the Beam Diameter (or called
Probe Size in Convergent Beam)
• The beam diameter is defined as the Full Width Half Maximum
(FWHM) of the Gaussian Distribution.
• The actual beam diameter results from :
a) The diameter of the original beam leaving the electron gun i.e. the
ideal gaussian probe diameter, 𝑑𝑑𝐺𝐺 .
b) Broadened by the effect of spherical and chromatic aberrations in
the lenses, 𝑑𝑑𝑆𝑆 𝑎𝑎𝑎𝑎𝑎𝑎 𝑑𝑑𝐶𝐶 .
c) Diffraction at the aperture, 𝑑𝑑𝐷𝐷 .
• Final Probe Diameter = 𝑑𝑑𝐺𝐺 + 𝑑𝑑𝑆𝑆 + 𝑑𝑑𝐶𝐶 + 𝑑𝑑𝐷𝐷 .
• This will give us the intensity and spread of the beam.
 Calculating the Beam Diameter (or called
Probe Size in Convergent Beam)
• All effects depend on the current density, 𝑗𝑗𝐶𝐶 , convergence angle,
𝛼𝛼𝑝𝑝 , brightness, 𝛽𝛽, spherical/chromatic aberration coefficient, 𝐶𝐶𝑆𝑆 /𝐶𝐶𝐶𝐶 ,
and wavelength, 𝜆𝜆.
• The intensity of a well aligned beam is a Gaussian Distribution.
 Lens System in TEM
• Camera Constant = 𝐿𝐿𝜆𝜆
• 𝐿𝐿 = 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑎𝑎𝑎𝑎𝑎𝑎 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠.
• Calibration required.
• 8 to 12 lenses in TEM so focusing is difficult.
• Intermediate lenses are used for magnification.
• The column is very narrow, so the maximum diameter of sample is 3
mm.
• Very strong magnetic field is present in the column so magnetic
samples are not used.
 Lens System in TEM
• If we are imaging a magnetic sample, then we need to use special
sample holder so that sample does not float.
• Alignment is very necessary in TEM.
• Vibrations is very large problem in case of TEM.
• So we need a vibration proof room.
• Diameter of sample used in TEM is 3mm.
 Condenser Lenses
• The condenser lenses is operated in three modes :
1. Focused.
2. Underfocused.
3. Overfocused.
 C2 is Focused
• The focus of the lens is on the
• The illumination area is at a minimum. The beam is probe (micro or
nano probe).
• The beam is at its least coherent and most convergent.
• The intensity of illumination on the viewing screen is the greatest.
• Image contrast will be reduced.
• For routine TEM work, never operate in such beam condition.
• For thick poor – transmission sample, focusing C2 will compensate for
poor transmission.
 C2 is Focused
• The convergent beam mode, focusing C2, is used for CBED
(Convergent Beam Electron Diffraction) and STEM (Scanning TEM).
• Since convergence destroys the coherency and image contrast, the
beam has to be scanned to form an image i.e. STEM image.
 C2 is Underfocused
• The beam is focused below the specimen.
• The illumination area increases.
• The beam is parallel and coherent.
• The parallel illumination is essential to get the sharpest diffraction
patterns and the best image contrast.
• The small aperture reduces the electron current falling on the sample,
and decreases the angle of beam convergence, and therefore
increases the coherence of the beam.
 C2 is Underfocused
• The parallel beam mode, underfocusing C2, is used in SAD (Selected
Area Diffraction), and CTEM (Conventional Transmission Electron
Microscopy) modes.
• A higher magnification means strengthening C2, so the beam
illuminates less of the specimen (it is not really parallel, just not very
convergent).
• To underfocus C2, just simply increase the illumination area on the
specimen.
 C2 is Overfocused
• Beam focused above the specimen.
• The beam convergence decreases, and the electrons come from the
cross – over only.
• Lot of noise.
• The cross – over image is above the image plane.
• Overfocusing C2 can check the beam astigmatism.
 Condenser Aperture
• The condenser aperture controls
the fraction of the beam which is
allowed to hit the specimen.
• It therefore helps to control the
intensity of illumination, and in
the SEM, the depth of field.
 Objective Lens and Specimen Stage
• Heart of TEM.
• The objective lens forms an inverted initial image, which is
subsequently magnified.
• In the back focal plane of the objective lens a diffraction pattern is
formed. The objective aperture can be inserted here.
• The objective lens would not usually provide a magnification of more
than 50 × and a TEM is routinely used to view regions of the
specimen which are only a 𝑚𝑚𝑚𝑚 or so across.
 TEM Operation Mode Setting and Beam
Condition
• TEM Operation Modes :
1. Parallel Beam :-
a. Bright Field Imaging Mode.
b. Dark Field Imaging Mode.
c. HRTEM.
d. SAD
2. Convergent Beam :-
a. STEM Mode.
b. CBED Mode.
3. Holography Mode
 TEM Operation Mode Setting and Beam
Condition
• Image Mode : By inserting the aperture or tilting the beam, different
types of images can be formed.
• The most common conditions are :
a) No Aperture – the diffraction pattern is centered on the optical axis.
b) Aperture is centered on the optical axis.
c) Aperture displaced, selecting a diffracted beam.
d) Beam is tilted so that the diffracted beam is on the optical axis.
 TEM Operation Mode Setting and Beam
Condition
• Central Beam allowed to pass = BF Mode.
• Diffracted Beam allowed to pass = DF Mode.
• When we make the aperture very big – many diffraction spots pass
through along with the central one – Phase Contrast Mode (HRTEM).
 Bright Field Mode
• In the bright field (BF) mode of the TEM, an aperture is placed in the
back focal plane (BFP) of the objective lens which allows only the
direct beam to pass.
• In this case, the image results from a weakening of the direct beam by
its interaction with the sample.
• Therefore, mass – thickness and diffraction contrast contribute to
image formation : thick areas, areas in which heavy atoms are
enriched, and crystalline areas appear with dark contrast.
 Bright Field Mode
• It should be mentioned that the interpretation of images is often
impeded by the simultaneous occurrence of the contrast forming
phenomena.
• Areas having heavier elements will diffract the beam to larger angles.
These areas appear darker in the image.
• Areas having lighter elements will diffract the beam to smaller angles.
These areas appear brighter in the image.
• So a contrast is created. A similar effect is observed when the sample
thickness is variable. This is called mass – thickness contrast.
 Bright Field Mode
• If the sample is polycrystalline and the beam is flushing four grains.
The atomic arrangement in these four grains is different. A parallel
coherent beam of electrons is incident on the specimen. The beam
encounters four different types of planes depending on the
orientation of these four grains. The beam is scattered at different
angles by different grains. The degree of scattering of the incident
beam depends on the alignment of the grains with respect to the
incident beam. This is termed as diffraction contrast.
 Bright Field Mode
• In the image we will see four different gray shades depending upon
how strongly or weakly the beam is scattered because of diffraction.
• Mass thickness contrast and diffraction contrast both occur
simultaneously.
 Dark Field Mode
• In the dark field (DF) mode images, the direct beam is blocked by the
aperture while one or more diffracted beams are allowed to pass the
objective aperture.
• Since diffracted beams have strongly interacted with the specimen,
very useful information is present in DF images, for example, about
planar defects, stacking faults or particle size.
 Off Axis DF Image Mode
• Aperture is displaced, a specific off – axis diffracted beam is selected
to form an image.
• Also called “dirty DF image”.
• The off – axis beam suffers aberration and astigmatism and the DF
image is hard to focus.
• The resolution cannot be enhanced.
• Dirty DF imaging mode.
 High Resolution TEM (HRTEM)
• Many beam and two beam conditions.
• To obtain lattice images, a larger objective aperture has to be
selected that allows many beams including the direct beam to pass.
• The image is formed by the interference of the direct beam with the
diffracted beams.
• If the point resolution of the microscope is sufficiently high and a
suitable sample oriented along a zone axis, then HRTEM images are
obtained.
• In many cases, the atomic structure of a specimen can directly be
investigated by HRTEM.
 High Resolution TEM (HRTEM)
• The incident parallel electron beam, ideally a plane wave, interacts
elastically, while passing through the specimen, and the resulting
modulations of its phase and amplitude are present in the electron
wave leaving the specimen.
• The wave here, the object exit wave 𝑜𝑜(𝑟𝑟) thus contains the
information about the object structure.
• Unfortunately, the objective lens is not ideal but has aberrations
(astigmatism, spherical 𝐶𝐶𝑆𝑆 and chromatic 𝐶𝐶𝐶𝐶 aberration) that reduce
image quality.
• The intensity distribution of the exit wave function is described by the
contrast transfer function (CTF).
 STEM Image
• Nano probe is used.
• A BF detector is placed in conjugate plane to the BFP to intercept the
direct beam while a concentric annular dark field (ADF) detector
intercepts the diffracted electrons.
• The signal from either detector are amplified and modulate the STEM
CRT.
• The specimen (Au islands on a C film) gives complementary ADF and
BF images as can be seen by clicking the button opposite.
• Z – contrast image, good for biological samples, particles but not very
good for crystalline samples.
• If we stop the beam from scanning, a CBED pattern is obtained.
 Sample Preparation
• SAMPLE NEEDS TO BE CONDUCTIVE.
• Sample Preparation should not damage the features of the sample.
• Specimen Preparation is an important aspect of the Transmission
Electron Microscopy (TEM) and SEM.
• Methods depend on both the type of material and the information to
obtain.
• Various methods are used to thin the sample to Electron Transparent
Thickness 50 − 100 𝑛𝑛𝑛𝑛 .
 Sample Preparation
• Some of these methods are :
1. Ion Mill Polishing.
2. Electro Polishing.
3. Wedge Polishing.
4. Ultramicrotomy.
5. Focus Ion Beam (FIB) Polishing.
6. Twin Jet Polishing – Cheapest Method.
• Plan – View Specimens : Bulky Sample or Self – Supported Sample.
 Sample Preparation
• Metallic Materials :
1. Cutting a thin slice of sample from bulk material using diamond saw
(very low speed – 250 rpm) with about 0.5 − 1 𝑚𝑚𝑚𝑚.
2. Mechanically grinding the sample to 100 − 150 𝜇𝜇𝜇𝜇 thick using
grinder.
3. Punching the sample into a disc with 3.0 𝑚𝑚𝑚𝑚 diameter using the
disc puncher.
4. Electro Polishing to get a sample with electron transparent
thickness.
 Sample Preparation
• Powder Specimen or Nanomaterials : Grid – Supported Samples :
1. Grind the material.
2. Dissolve the powder into a solution, and mix them, avoiding any
chemical reaction.
3. Homogenize them using ultrasonic cleaner.
4. Splash 1 drop of solution onto a copper grid with carbon supporting
film.
5. Wait until the specimen is dry before observing in TEM.
 Sample Preparation
• Ceramic or Chemical – Sensitive Materials :
1. Cutting a thin slice of sample from bulk material using diamond or wire
saw with a thickness of about 0.5 − 1 𝑚𝑚𝑚𝑚.
2. Mechanically grinding the sample to 100 − 150 𝜇𝜇𝜇𝜇 thick using the
grinder.
3. Cutting the sample into a disc with 3.0 𝑚𝑚𝑚𝑚 diameter using the
ultrasonic cutter.
4. Dimpling the sample to a dimple in center with thickness about < 10 𝜇𝜇𝜇𝜇
using a dimpler.
5. Polishing the sample to an electron transparent 100 − 150 𝑛𝑛𝑛𝑛 using
ion mill polisher.
 Sample Preparation
• Polymers and Bio samples :
1. Mount the sample using resin.
2. Slice sample to 50 − 100 𝑛𝑛𝑛𝑛 thick using ultramicrotome.
3. Stain the sample to increase contrast.
4. See the instrument instruction detail procedure.
 Focused Ion Beam
• Produce cross – section TEM specimens of individual devices (site –
specific).
• Can provide ion beams with lateral resolution less than 10 𝑛𝑛𝑛𝑛.
• Provide a large area of uniform thickness; possible to detect the
localized internal stress around features.
• Good for materials that are not suitable for mechanical grinding and
polishing.
• Less preferential milling is observed, ending the preparation of cross –
section specimens from samples composed of different materials.
• The best way for sample preparation.
 Comparison of TEM with other Atomic
Resolution Microscopes
• The 𝐹𝐹𝐹𝐹𝐹𝐹 𝑎𝑎𝑎𝑎𝑎𝑎 𝑆𝑆𝑆𝑆𝑆𝑆 give information from the surface. The TEM gives
information from inside the material.
• Electron diffraction in the in the TEM allows study of structure of
phases.
• TEM images are more difficult to interpret because information from
three dimensions is projected on to two dimensions.
 Major Factors Affecting TEM Image Contrast
• Major factors affecting TEM image contrast are :
1. Thickness – Scattering.
2. Atomic Number – Scattering.
3. Orientation – Scattering.
4. Defects – Scattering and Diffraction.
 Contrast Mechanisms in TEM
1. Amplitude Contrast.
2. Mass Thickness Contrast.
3. Diffraction Contrast.
4. Phase Contrast.
 Limitations of Conventional TEM while
studying Nanocrystalline Solids
• Aspects not revealed by conventional TEM are,
1. Structure of Nanograin Boundary.
2. Structure of Crystallographic Defects, like Dislocations, Twins,
Stacking Faults.
3. Anti – Phase Domain Boundaries.
4. Presence of a Second Phase at the Nanograin Boundary.