Crystalline Solid Amorphous Solid

Particles are completely disorganized

Particles are arranged in orderly fashion
 Single Crystals and Polycrystalline Materials
Single crystal: atoms are in a repeating or periodic array over the entire
extent of the material
Polycrystalline material: comprised of many small crystals or grains.
The grains have different crystallographic orientation. There exist atomic
mismatch within the regions where grains meet. These regions are called
grain boundaries.

Grain Boundary
 Polycrystalline Materials

Atomistic model of a nanocrystalline solid by Mo Li,

JHU
15
 Lattices
A lattice is a regular infinite arrangement of points in which every point has
the same environment as any other point. A lattice in 2 dimensions is called
a net and a regular stacking of nets gives us a 3-dimensional lattice.

2-D net Stacks of 2-D nets

produce 3-D lattices.
Lattice
 Lattices and Unit Cell
Since lattices consist of infinitely repeating patterns, one needs only to look at a the smallest
repeat unit to describe the lattice. The smallest repeat unit that will generate the entire lattice
(by translation) is called the Unit Cell. It is defined by three repeat distances (a, b, and c) and
three angles (a, b, g), where a is the angle between b and c, b is the angle between a and c, and g is
the angle between a and b.

Unit cell parameters (a, b, c, a, b, g) are chosen to best represent the highest-possible symmetry of
the crystal and are given right-handed axes (a is along x, b is along y and c is along z) with angles
that are either all ≥ 90º or all ≤ 90º.
Unit Cell: The smallest unit by repeating which entire lattice can be generated.
 Unit Cell
• Rule: Must represent the symmetry elements of the
whole!

If a crystal has symmetry, the unit cell must have at least that much symmetry
Crystal Lattices and Unit Cells

Crystal lattice is the depiction of three dimensional

arrangements of constituent particles (atoms,
molecules, ions) of crystalline solids as points. Or the
geometric arrangement of constituent particles of
crystalline solids as point in space is called crystal
lattice.
 Lattices
The lattice can be considered as a kind of scaffold upon which the
structure of the crystal is built. For a crystal, the lattice is a 3-dimensional
array and the structural motif will be located in a hypothetical box called
the unit cell.
Unit Cell: The smallest portion of a crystal lattice is called Unit Cell.
By repeating in different directions unit cell generates the entire lattice.

Parameters of a unit cell:

•A unit cell is characterized by six parameters. These
parameters are three edges (a, b and c) and angles
between them (α, β and γ).

If a crystal has symmetry, the unit cell

must have at least that much symmetry

Crystal Lattice
Types of Unit Cells:
What are the symmetries of the 7 crystal systems?
 Minimum symmetry of the 7 crystals systems are listed in the table below.
 As an example: cubic crystals have four 3-fold axes (at least), while a trigonal crystal has
only one 3-fold axis (but can have other symmetries). Tetragonal crystals have one 4-fold
axis at least (but cannot have three 4-fold axes).
The characteristic symmetry refers to the minimum symmetry
that needs to be present.

Characteristic symmetry
Cubic Four 3-fold rotation axes We have stated that basis of definition of
(two will generate the other two) crystals is ‘symmetry’ and hence the
Hexagonal One 6-fold rotation axis classification of crystals is also based on
(or roto-inversion axis) symmetry.
Tetragonal (Only) One 4-fold rotation axis The essence of the required symmetry is
(or roto-inversion axis) listed in the table
Trigonal (Only) One 3-fold rotation axis  more symmetries may be part of the
(or roto-inversion axis) point group in an actual crystal.
Orthorhombic (Only) Three  2-fold rotation axes
(or roto-inversion axis) Note that the symmetry being considered is the
point group symmetry. The translational
Monoclinic (Only) One 2-fold rotation axis
components are ‘dropped’ while noting the
(or roto-inversion axis)
symmetry. E.g. 63 screw axis is written as a ‘6’.
Triclinic None (only translational symmetry)

Note: translational symmetry is always present in crystals (i.e. even in triclinic crystal)
 Bravais Lattices
• Assembly of the lattice points in 3-D results in 14 possible
combinations
• Those 14 combinations may have any of the 7 crystal
system (class) symmetries
• These 14 possibilities are the Bravais lattices
Bravais Lattices
14 Bravais Lattices divided into 7 Crystal Systems Refer to slides on Lattice for more on these

A Symmetry based concept ‘Translation’ based concept

Crystal System Shape of UC Bravais Lattices

P I F C
1 Cubic Cube   
2 Tetragonal Square Prism (general height)  
3 Orthorhombic Rectangular Prism (general height)    
4 Hexagonal 120 Rhombic Prism 
5 Trigonal Parallelepiped (Equilateral, Equiangular) 
6 Monoclinic Parallogramic Prism  
7 Triclinic Parallelepiped (general) 

P Primitive
Why are some of the entries missing? I Body Centred
 Why is there no C-centred cubic lattice?
 Why is the F-centred tetragonal lattice missing? F Face Centred
 ….? C A/B/C- Centred
08/08/2019
Mystery of Missing Entries
 Mystery of the missing entries in the Bravais List! What we choose
P I F C
1 Cubic Cube    

UC-1

But then Cubic crystals need not have any 4-fold axes!!
Hence Cannot be called Cubic (cubic lattices do need to have!)

Hence even though this lattice remains as it is  it is called Simple Tetragonal lattice
(which is smaller in size)
 Note that this simple tetragonal
cell has a specific c/a ratio of (2)
(while in general simple tetragonal
cells can have any c/a ratio).
 Actually UC-1 (above) is a C-
centred tetragonal cell!
Symmetry is the
issue here
Mystery of the missing entries in the Bravais List! What we choose
P I F C
2 Tetragonal Square Prism (general height)   

Smaller sized Body Centred Cell is chosen

FCT = BCT
Face Centred Tetragonal = Body Centred Tetragonal

Size is the issue here

Mystery of the missing entries in the Bravais List! What we choose
P I F C
2 Tetragonal Square Prism (general height)   

Smaller sized Simple Cell is chosen

CCT = ST
C Centred Tetragonal = Simple Tetragonal
Mystery of the missing entries in the Bravais List!
P I F C
4 Hexagonal 120 Rhombic Prism  

Body Centred Orthorhombic

Putting a lattice point at body centre

destroys the 6-fold axis
 Continued…
In fact not even the 3-fold
survives and the lattice type is
Body Centred Orthorhombic

Note: there is no remnant 3-fold either (if there were one then
A B C, but there is no lattice point at C (at z = ½)).

Not all lattice points are shown

BCO unit cell

 Mystery of the missing entries in the Bravais List! P I F C
4 Hexagonal 120 Rhombic Prism  

Simple Orthorhombic
Putting a lattice point at
body centre
destroys the 6-fold axis

In fact not even the 3-fold

survives and the lattice type is
Simple Orthorhombic

Note: there is no remnant 3-fold either (if there were one then
A B, but there is no lattice point at C (at z = 0)).
Lattice Planes and Miller Indices
Where does crystallographer see the Miller indices?

• Common crystal faces are parallel

to lattice planes

• Each diffraction spot can be

regarded as a X-ray beam reflected
from a lattice plane, and therefore
has a unique Miller index.

203.199.213.48/834/1/Structuresofsolids.ppt
Lattice Planes and Miller Indices
 Lattice Planes and Miller indices

 A Miller index is a series of coprime integers that are inversely

proportional to the intercepts of the crystal face or crystallographic
planes with the edges of the unit cell.

 It describes the orientation of a plane in the 3-D lattice with respect

to the axes.

The general form of the Miller index is (h, k, l) where h, k, and l are
integers related to the unit cell along the a, b, c crystal axes.
Miller Indices
Rules for determining Miller Indices:

1. Determine the intercepts of the

face along the crystallographic axes,
in terms of unit cell dimensions.

2. Take the reciprocals

3. Clear fractions

4. Reduce to lowest terms

An example of the (111) plane (h=1,

k=1, l=1) is shown on the right.
 Another example:

In this case the plane intercepts the a axis

at one unit length and also the c axis at
one unit length. The plane however, never
intersects the b axis. In other words, it can
be said that the intercept to the b axis is
infinity. The intercepts are then
designated as 1,infinity,1. The reciprocals
are then 1/2, 1/infinity, 1/1. Knowing
1/infinity = 0 then the indices become
(101).

203.199.213.48/834/1/Structuresofsolids.ppt
 Crystalline Planes
?
?

Direction Vectors
001 Plane
110 Planes
111 Planes
09/08/2019
Miller Indices for Negative Intercept
 Equivalent Planes

c
b
a

Cubic: a = b = c ; a = b = g = 90

(100)  (010)  (001) : collective

representation {100}

61
Equivalent Planes in Tetragonal System
16/08/2019
 Equivalent Planes

c
b
a

Cubic: a = b = c ;  =  =  = 90

(100)  (010)  (001) : collective

representation {100}

59
Equivalent Planes in Tetragonal System

1200
1200
1200
Miller Indices of Hexagonal System
Problem:
In hexagonal system symmetry related planes and directions
DO NOT have Miller Indices which are permutations.
Crystallographic Direction and Miller Indices
Crystallographic Directions
Crystallographic Directions
Directions
Crystallographic Convention
Remember
22/08/2019
Diffraction
 Diffraction

Width of the slit ~ Wavelength of light

nλ=d*sinθ
 Mechanism of X-ray Generation

Wavelength (nm)
 Basis of X-ray Diffraction by Crystal
 The electrons oscillate under the influence of the incoming X-Rays and become secondary sources
of EM radiation.
 The secondary radiation is in all directions.
 The waves emitted by the electrons have the same frequency as the incoming X-rays  coherent.
 The emission can undergo constructive or destructive interference.

Secondary
Incoming X-rays emission

Oscillating charge re-radiates  In phase with

the incoming x-rays

Schematics

Sets nucleus into oscillation

Sets Electron cloud into oscillation
Small effect  neglected
Braggs Contribution
BRAGG’s EQUATION
Warning: we are using ray diagrams in spite of
being in the realm of ‘physical optics’ Let us consider scattering across planes

Click here to visualize

constructive and
destructive interference

See Note Ӂ later

 A portion of the crystal is shown for clarity- actually, for destructive interference to occur
many planes are required (and the interaction volume of x-rays is large as compared to that shown in the schematic).
 The scattering planes have a spacing ‘d’.
 Ray-2 travels an extra path as compared to Ray-1 (= ABC). The path difference between
Ray-1 and Ray-2 = ABC = (d Sin + d Sin) = (2d.Sin).
 For constructive interference, this path difference should be an integral multiple of :
n = 2d Sin  the Bragg’s equation. (More about this sooner).
 The path difference between Ray-1 and Ray-3 is = 2(2d.Sin) = 2n = 2n. This implies that if Ray-1
and Ray-2 constructively interfere Ray-1 and Ray-3 will also constructively interfere. (And so forth).
 Bragg Law
• See Figure. The length DE is the same as EF, so the total
distance traveled by the bottom wave is expressed by:
• Constructive interference of the radiation from
successive planes occurs when the path difference is an
integral number of wavelengths. Note that line CE = d =
distance between the 2 layers
l
EF  d sin  d sin 
DE Giving:
DE  EF  2d sin  n  2d sin 
This is called the
Bragg Law
 Bragg Law
• Consider crystals as made up of parallel planes of atoms.
Incident waves are reflected specularly from parallel
planes of atoms in the crystal, with each plane reflecting
only a very small fraction of the radiation, like a lightly
silvered mirror.
• In mirrorlike reflection, the angle of incidence is equal to
the angle of reflection.
Incident Angle  θ
Reflected angle  θ
X-ray
Wavelength  λ
Total Diffracted
Angle  2θ
 Bragg Law (Bragg Equation)
2d sin   n
d = Spacing of the Planes, n = Order of Diffraction.
• Because sin θ ≤ 1,
Bragg reflection can only occur for
wavelengths satisfying: n  2d
• This is why visible light can’t be used. No diffraction
occurs when this condition is not satisfied.
• The diffracted beams (reflections) from any set
of lattice planes can only occur at particular
angles predicted by Bragg’s Law.
23/08/2019
 Bragg Law
• See Figure. The length DE is the same as EF, so the total
distance traveled by the bottom wave is expressed by:
• Constructive interference of the radiation from
successive planes occurs when the path difference is an
integral number of wavelengths. Note that line CE = d =
distance between the 2 layers
l
EF  d sin  d sin 
DE Giving:
DE  EF  2d sin  n  2d sin 
This is called the
Bragg Law
Wavelength of not changing
Powder X-ray Diffraction (PXRD)
 Sample holder

X-ray tube

Detector

Slit boxes

The view of Bruker D8 Advance diffractometer with stationary X-ray

source and synchronized rotations of both the detector arm and
sample holder
Video of Powdered XRD machine
Applications of PXRD
Crystalline Nature of Samples
Peak Intensity is related to multiplicity or equivalent planes
29.08.2019
PXRD
PXRD
Single Crystal X-ray Diffraction
 Four Circle Diffractometer

For single crystals

 LNT

X-ray CCD - Detector

Crystal

Goniometer

X-ray source, goniometer + crystal, N2-cooling and CCD Detector

One of the several hundreds of CCD images with diffraction spots
Starting with an indexed reciprocal lattice, an incident X-ray beam must
pass through the origin (000) point, corresponding to the direct undiffracted
beam of X-rays.
To be able to collect as many different reflections as possible, it is thus
necessary to be able to rotate the reciprocal lattice to a great extent…
Summary of Crystal Structure Determination
 05/09/2019

Taught without slides. However, I am providing glimpses of todays discussion

in the following few slides.

Go through the book of A. R. West (page no. 153-155)

 Intensities
X-rays scattered by electrons - electrons are in atoms

Scattering power f of atom at  = 0° is

no. electrons (atomic no.) x scattering power of one e—
The scattering factor is equal to the number of electrons around the
atom at θ= 0,the drops off as θ increases.
 Scattering of X-rays by an atom

• Distances between the electrons in an atom are short.

• Path difference XY is less than one wavelength (>λ/2 but less than λ).

• Only partial destructive interference occurs.

• The net effect of such interference is to cause a gradual decrease in

scattered intensity with increasing angle, 2θ.
• X-rays interact with the electrons in the crystal,
therefore a crystal with more electrons with more
strongly scatter X-rays.

• The effectiveness of scattering X-rays is called the

scattering factor (or form factor) with the symbol f.

• The scattering factor depends on the number of

electrons around the atom, the Bragg angle θ, and the
wavelength (λ) of the X-rays.

• The scattering power decreases as the Bragg angle

increases.
 06/09/2019

Structure factor calculation of different cubic systems were done in board

hkl Miller Indices

xj , yj , zj  atomic coordinate of jth atom.

11/09/2019
Cl at 000 and Cs at ½ ½ ½

Cl Cs

Cl Cs

fCl + fCs
fCl - fCs
NaCl
(200, 220, 222, 420, 422 etc.)

(111, 311, 331, 333 etc.)

(110, 221 etc.)

2
Table Systematic absences due to lattice type
Lattice type Rule for reflection to be observed

Primitive, P None
Body centred, I hkl; h + k + l = 2n
Face centred, F hkl; h, k, l either all odd or all even
Side centred, e.g. C hkl; h + k = 2n
Rhombohedral, R hkl; −h + k + l = 3n or (h − k + l = 3n)
KCl

NaCl
Solving Single Crystal Structures
A set of structure factors, Fcalc, are determined for comparison with
the Fobs magnitudes.

with good quality crystals, one might expect to see R below 0.05
Direct-method aided protein crystal
structure
19/09/2019
X-rays with λ= 154.2 pm produce reflections from the 111 and 200 planes of FCC Cu of
density 8.935 g / cm3. At what angles will these reflections appear? Which will give
maximum intensity? 21.71 degree, 25.28 degree

X-ray of λ=0.1537 nm from a Cu target are diffracted from the (111) plane of an FCC metal.
The Bragg angle is 19.2 degree. Calculate the Avogadro number if the density of the crystal
is 2698 kg/m3 and the atomic weight is 26.98.

A XRD experiment was performed with CuK radiation, using a diffractometer on a FCC
Crystal (hetero-atom) with lattice parameter= 3.61 A. What are the Miller indices of the
planes with lowest and highest Bragg angles? 111, 420
XRD pattern for gold nanocrystals exhibiting fcc lattice (real space) is given below. Peak-
1 is at the lowest possible 2 value for this crystal. Assign the (hkl) values for all the three
peaks.
Peak-1

Peak-2

Peak-3
Derive the structure factors for the unit cell of MoSi2. Hence prove that there will be
no reflection from 100 plane, however, 110 plane will give strong reflection in X-ray
diffraction experiment.
 MoSi2

4.
(1/2, 1/2, 2/3+1/6)

(0,0,1/3) (½,½, ½)
2.
(1,0,1/3) 3.
1. (1/2, 1/2, 1/6)

(0,0,0)
 Reciprocal Lattice

Reciprocal lattice vector 𝑯𝒉𝒌𝒍 = 𝒉𝒃𝟏 + 𝒌𝒃𝟐 + 𝒍𝒃𝟑

 1

bi aj = 0 ( i≠ j)
= 1 (i=j)

𝑯𝒉𝒌𝒍 = 𝒉𝒃𝟏 + 𝒌𝒃𝟐 + 𝒍𝒃𝟑 Direction of 𝑯𝒉𝒌𝒍 is perpendicular to

hkl plane.
𝟏
𝑯𝒉𝒌𝒍 =
𝒅𝒉𝒌𝒍
 Cubic Lattice:

In reciprocal lattice

11 1
1/a
Ref: Kittel’s Introduction to Solid State Physics, page- 8-10
Ref: Kittel’s Introduction to Solid State Physics, page- 8-10
Ref: Kittel’s Introduction to Solid State Physics, page- 10-40
 Ewald Construction

 The reciprocal crystal is a map of the crystal in

reciprocal space, but it does not tell us which
spots/reflections would be observed in an actual
experiment.

 The aim of the Ewald is to determine which lattice

points (in reciprocal space) will results in a diffracted
signal for a given wavelength.
Reflection from 101 plane will be present, as it will obey the Bragg’s condition

Reflection from 201 plane will be absent, as it will not obey the Bragg’s condition
 The Ewald Sphere

When a reciprocal lattice point intersects the Ewald sphere, a

reflection will occur and can be observed at the 2q angle of the inscribed
triangle. To be able to collect as many different reflections as possible, it is
thus necessary to be able to rotate the reciprocal lattice to a great
extent…
 The Ewald Sphere
Our need to rotate the crystal in numerous ways to bring all of the
families of planes into reflection (i.e. to make RL point intersect with the
Ewald sphere) explains the design of the goniometer portion of the
diffractometer. The 4-circles of the goniometer allows the crystal to be rotated
in virtually any direction while remaining in the X-ray beam. The labels for
each of the goniometer axes (f, c, w, and q) are indicated on the diagram
below. Note that there are different designs (such as the Kappa geometry)
that accomplish the same task.
Video Related to Ewald Sphere and Diffraction
https://www.youtube.com/watch?v=H3NeiImTJOA
In Laue diffraction, the range of wavelengths available affords a spherical torus (with
minimum and maximum radii of 1/λmax and 1/λmin, respectively) wherein the diffraction
condition is met. Consequently, a number of reflections lie in the wavelength band (shaded in
grey) and so, in Laue diffraction, many reflections satisfy the Bragg condition simultaneously.
𝑭𝒉𝒌𝒍 = 𝒇𝒊 𝒆𝒙𝒑−(𝑹.𝑯𝒉𝒌𝒍
𝒊

𝑯𝒉𝒌𝒍 = 𝒉𝒃𝟏 + 𝒌𝒃𝟐 + 𝒍𝒃𝟑 (reciprocal)

𝑭𝒉𝒌𝒍
10/10/2019
Description of crystal Structure
-Close packing
Crystal Structure and Close Packing
Let us examine the difference between Closed-cubic Packing
and Hexagonal-Cubic Packing:

203.199.213.48/834/1/Structuresofsolids.ppt
8
Q: If the HCP crystal has only a 3-fold axis why does it come under the ‘Hexagonal class*’ of crystals?
Let us examine the difference between Closed-cubic Packing
and Hexagonal-Cubic Packing:

203.199.213.48/834/1/Structuresofsolids.ppt
15
Why CCP is also called FCC?
Why CCP is also called FCC?
 BCC packing

Some metals do not adopt a close-packed structure but have a slightly less efficient
packing method: this is the body-centred cubic structure.

The coordination number has dropped from twelve to eight and the packing efficiency is
now 68%, compared with 74% for close-packing.
Occurrence of Packing type in Metals
Packing efficiency and Packing Density
 Atomic Packing Factor (APF)

• APF for a simple cubic structure = 0.52

Adapted from Fig. 3.19,

Callister 6e. 6
 Body Centered Cubic (BCC)
structure
• Close packed directions are cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

• Coordination # = 8

Adapted from Fig. 3.2,

Callister 6e.

(Courtesy P.M. Anderson) 7

 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68

Unit cell contains:

1 + 8 x 1/8
= 2 atoms/unit cell
R
Adapted from a
Fig. 3.2,
Callister 6e.

8
 Face Centered Cubic (FCC)
structure
• Close packed directions are face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

• Coordination # = 12

Adapted from Fig. 3.1(a),

Callister 6e.

(Courtesy P.M. Anderson)

9
 Atomic Packing Factor: FCC
• APF for a body-centered cubic structure = 0.74

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 6e.

10
 (as a = 2R)

For hexagonal system it can be proved that

 Home Assignment

1. Prove that c/a ratio 1.63 for hexagonal pack system

2. If the HCP crystal has only a 3-fold axis why does it come under
the ‘Hexagonal class*’ of crystals?
Octahedral and Tetrahedral Voids
Tetrahedral and Octahedral Holes/Sites/Voids
Octahedral Holes

N spheres, N Octahedral holes

N spheres, 2N tetrahedral holes
Tetrahedral and Octahedral Holes
Structures of some important
Ionic and Covalent Compounds
 NaCl or Rock Salt

Figure. Ionic compounds with anions that are much larger than cations, such as NaCl,
usually form an FCC structure. They can be described by FCC unit cells with cations in
the octahedral holes.
 CsCl

Figure. Ionic compounds with similar-sized cations and anions, such as CsCl, usually
form a simple cubic structure. They can be described by unit cells with either cations
at the corners or anions at the corners.
17/10/2019
 Wurtzite crystal structure

hcp array of sulfide ions with alternate tetrahedral holes occupied by Zn ions. Each atom is
tetrahedrally coordinated
 Perovskite (ABX3)

First, it can be described as a ccp array of A and X atoms

with the B atoms occupying the octahedral holes (compare
with the unit cell of NaCl if you want to check this).
Crystal structure of CH3NH3PbX3 perovskites (X=I, Br and/or Cl). The
methylammonium cation (CH3NH3+) is surrounded by PbX6 octahedra
Diamond and SiC (carborundum)
Graphite Crystal Structure
 Crystal Structures of Fullerene (C60)

Crystal structure may be regarded as a face centred cubic configuration of C60 spheres.
Lattice Energy
 Lattice Energy

The Lattice energy of a crystal is defined as the net potential

energy for the arrangement of charges that forms the
structure.

−787 kJ mol−1
Theoretical Evaluation of Lattice Energy
 NaCl

Na+
The total energy of the crystal, U, is given by summing equations (3.18) and (3.13)
and differentiating with respect to r to find the maximum U value and equilibrium
interatomic distance, re; i.e.
 Refined Equation

(a)

(b)

(c)
Hence the Born repulsive term contributes 10–15% to the value
of U; the zero point vibrational and van der Waals terms
contribute about 1% each and, being of opposite sign, tend to
cancel each other. For most purposes, therefore, we use the
simplified equation.

The magnitude of U depends on six parameters A, N, e,  , Z, and

re, four of which are constant for a particular structure. This leaves
just two, the charge on the ions, Z+Z−, and the internuclear
separation, re. Of these two, charge is the most important since
the product (Z+Z−) is capable of much larger variation than re