SCHA031 2023

Solid state: Structures of solids

LECTURE NO 05 When substances freeze, or separate

as a solid from solution, they tend to
form crystals

01 MAR Crystals have highly regular features

and are said to possess symmetry or be
symmetrical

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1 2

The symmetry, or repetitive pattern, in

crystalline solids is called a lattice Lattice and Unit cells
• The lattice is a three-dimensional, infinite array of points,
the lattice points, each of which is surrounded in an
The particles that make up the lattice are identical way by neighbouring points, and which defines
the basic repeating structure of the crystal.
called lattice points.

The basic repeating unit in a lattice is called

the unit cell.

• Starting from a unit cell, the entire lattice can The line of dots is called
be generated by repeating the unit cell in all the lattice and each
directions lattice point (dot) must
have identical
• The same unit cell can describe many surroundings.
different structures
3 4

• The relationship
between the
The simplest and most symmetrical three-
lattice
dimensional lattice is called a simple cubic
parameters in 3D or primitive cubic lattice
gives rise to the
seven crystal
systems.

•
• Has one host atom at each corner
– edge length (a) = 2r
– where r is the radius of the atom or ion.

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 Only 1/8 of each atom lies in a

particular simple cubic unit cell

• Each simple cubic unit cell contains:

1/8 atom
8 corners   1 atom
corner

• Two additional cubic lattices are

possible: face-centered cubic (fcc) and
body-centered cubic (bcc)

7 8

• Lattice points in a fcc unit • A number of metals and compounds have

cell are found at each of the
eight corners and in the cubic lattices
center of each face. A fcc
unit cell contains 1 atom
from the eight corners plus
6*1/2=3 atoms from each
face for a total of 4 atoms.

• Lattice points in a bcc unit

cell are located at each of
the eight corners and in the
center of the unit cell. A bcc
unit cell contains 2 atoms.
Copper and gold both crystallize in an fcc
structure. The unit cell in gold is larger because
copper atoms are smaller than gold atoms.

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Body-centered Cubic (BCC) Face-centered Cubic (FCC)

• has one atom at each corner and one in has one atom
the center centered in
4r
 edge length a each face,
3 and one at
each corner

a  2 2r

11 11.9 Crystalline solids have an ordered internal structure 12

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A unit cell of NaCl shows how to weight lattice points:

corners have a weight of 1/8, faces a weight of 1/2, and
edges a weight of 1/4. This unit cell contains four sodium
and four chloride ions.

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Density of metal in a unit cell

• Find mass and the volume of a unit cell

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The length of the unit cell edge in the Potassium iodide, KI has a cubic unit

? iron (BCC) structure is 286 pm. What is

the radius of the iron atom? ? cell with a cell edge of 705 pm. The
density of KI is 3.12 g/cm 3. How many
K+ ions and I- ions are contained in the
b 2  2a 2 unit cell?
c 2  a 2  b2
 c 2  3a 2 • Volume unit cell = (7.05 x 10-8 cm)3
i.e. c  3a but for bcc c  4rFe
• Mass of unit cell = Volume x Density
3a  4rFe (mass of 1 K+, & 1 I- ion).
3  286 pm 
 rFe  3a   124 pm
4 4 • Total no. of ions = 4
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Chromium (Mr = 52 g.mol-1) has the

• i.e. 4 K+ and 4 I- ions per unit cell

• There are 4 lattice points in the unit cell
? monoatomic body-centered cubic
structure. Its density is 7.19 g/cm 3, and
the length of the edge of the unit cell is
288.4 pm. Use these data to calculate
• Therefore fcc lattice
a value for the Avogadro’s constant.

NA 
NM r

2  52 g.mol 1 
V
 288.4  1012 m 
106 cm3 3
7.19 g.cm3  3
1m
 6.05  1023 atoms / mol
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PRACTICE: Silver has a structure CONCLUDING REMARKS

? based on a cubic lattice. The edge of

the unit cell is found to have a length of
408 pm by X-ray diffraction. The density
• Not all solids are crystalline

of silver is 10.6 g/cm3. How many atoms  Glass is a general term used to refer to a
of silver are there in the unit cell? What noncrystalline or amorphous solid
type of cubic lattice is the structure of • Amorphous solids lack the long-range repetitive
internal structure found in crystals
silver based on?
• For this reason they are sometimes called
100 cm supercooled liquids, a term suggesting the kind
a  408 x 10 12 m x structural disorder found in liquids
1m
 Crystalline structure can be determined using the
technique of X-ray diffraction
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X-ray diffraction : The Basics

• X-rays interact with electrons in matter.
• X-rays are scattered by the electron clouds
LECTURE NO 06 of atoms.
X-rays interact with electrons in matter and a
beam of X-rays impinging on a sample will be
scattered in various directions by the atomic
electrons. If the scattering centres are separated
by distances comparable to the wavelength of the
06 MAR X-rays then interference between the X-rays
scattered from particular electron centres can
occur. For an ordered array of scattering centres
this can give rise to interference maxima and
18 | 23 minima.

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X-rays
 X-rays emitted from
atoms are in phase in
some directions and
out of phase in others.

The layers of atoms in a crystalline solid are separated by

This gives rise to a
the distance d . The X - rays of wavelength  enter and
diffraction pattern that
can be used to emerge at an angle  relative to the layers of atoms.
determine the structure According to the Bragg equation emerging X - rays that
of the crystalline solid have intensity are related by n  2d sin  , where n is
that contains the atoms. an integer.

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The Interplanar Spacing, d(hkl) Calculate the interplanar spacing, d

• Can be found for each set of planes provided we know
the unit cell parameters.
e.g. for a CUBIC unit cell:
? /separations of (a) the {123} planes and (b)
the {246} planes of an orthorhombic unit cell
with a = 0.82 nm, b = 0.94 nm, and c = 0.75
nm.
d(100) = a
d(010) = b (= a)
d(030) = ( 13 )a 1 12 22 32
d(110) = ( )a 1     17.5
2

For unit cells with  =  =  = 90º d 2 0.82 0.94 0.75

d  0.24 nm
1 h2 k 2 l 2
  
d 2 a 2 b2 c 2

Which for a CUBIC unit cell simplifies to

1 h2  k 2  l 2

d2 a2
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The investigation of structure

I ∞ (Wave amplitude)2

The regions of
constructive
interference show up
as regions of
enhanced intensity
The separation of the {220} planes is half that of the {110}
planes.

Generally: (the separation of the planes {nh, nk, nl} is n times

smaller than the separation of the {hkl} planes.

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The Bragg’s (William and his son, Bragg’s Law

Laurence)
They have taken a
Used a single crystal lattice plane as a semi-
and a monochromatic transparent mirror.
beam of X-rays and
rotated a crystal until
a reflection was And model a crystal as
detected. a stacks of reflecting
lattice planes of
separation, d.

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Derivation of Bragg’s law

When the net path-length difference (AB +
BC) is not an integer no. of wavelength, the
Consider the reflection of two parallel rays waves interfere destructively.
of the same wavelength, by two adjacent
planes of a lattice.
Constructive inter: AB + BC = nλ …2

One ray strike point D on the upper plane

and other at point B. Therefore: nλ = 2dsinθ Bragg’s law

The net path-length difference of the two

rays is
AB + BC = 2dsinθ ……….1

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Take nth-order reflection as arising from A reflection from the (111) planes of a cubic
the {nh, nk, nl} planes. n =1 (first-order)
? crystal was observed at a glancing angle of
11.2o when Cu Kα X-rays of wavelength 154
pm were used. What is the length of the side
Note: Bragg’s law is used in the of the unit cell?
determination of the spacing, d between The crystal is cubic, the separation, d is related
the layers in the lattice. to the length of the side of the unit cell, a, by
sinθ = (h2 +k2 + l2)½(λ/2a).
  
a  h2  k 2  l 2   
 2 sin  
 154 pm 
 3  
 2 sin 11.2 
 687 pm 7 | 36

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The Debye and Sherrer method X-ray powder photographs

Used monochromatic radiation and
powdered sample.

When the sample is powder, at least some

of the crystallites will be orientated so as
to give rise to diffraction.

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What is a powder pattern?

Is produced when X-rays are diffracted from a
sample consisting of a very large number of
randomly oriented crystalline particles.

Bragg’s law determines the position of a reflected

beam.

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X-ray Powder Pattern A modern Diffractometer

• The X-ray beam enter through the hole

on the left and leaves through the hole
on the right.

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Indexing the Reflections Reflections

If the value of h, k, and l for the planes The reflections are predicted by substituting the value of h, k,
responsible for that reflection are known, the and l:
dimensions of the unit cell can be deduced.
Some types of unit cell give characteristic and (hkl) (100) (110) (111) (200) (210) (211) (220) (300)
H2 + k2 +l2 1 2 3 4 5 6 8 9
easily recognizable patterns of lines.
PRIMITIVE CUBIC LATTICE
e.g. In cubic lattice of unit cell dimension, a and
spacing, d given. The angle at which the (hkl) dhkl – spacing is also important.
planes give reflections is

Sinθ = (h2 +k2 + l2)½(λ/2a)

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Primitive cubic lattice FCC lattice

• Has four lattice points per unit cell
In a cubic crystal a = b = c. The POSITIONS:
perpendicular distance, d between Four Na+: 000, ½ ½ 0; ½ 0 ½;0 ½ ½
adjacent planes in a cubic crystal is Four Cl-: ½ 00;0 ½ 0;00 ½; ½ ½ ½

 The diffraction patterns of NaCl and any other FC

dhkl = a/(h2 + k2 + l2)½ crystal (regardless of the crystal system) show an
absence of all reflections for which the indices hkl
are not all even or all odd.

 Observed reflections: 111, 200, 220, 311, 222,

400, 521, 420, etc.,

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BCC lattice Systematic absences

Two positions per unit cell.
i.e. xyz, ½ + x, ½ + y, ½ + z.

Hence two lattice points at 000 and ½ ½ ½

that have identical environments.
An examination of the diffraction data for
BC crystals shows that hkl reflections for
which the sum h + k + l is odd are not
observed.

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Atomic scattering factor, fj The variation of scattering factor of atoms

and ions with atomic number and angle.
• Remember that 2θ is the deviation of the
diffracted beam from the direct X-ray beam.
At very small values of θ, the atomic scattering
factor of a neutral atom is equal to its atomic
number since all the electrons scatter in phase.
• But at larger values of θ, the intensity of scattered
radiation is less because there is interference
between radiation scattered from various parts of
the electron cloud of the atom.

The intensity of reflection depend on the extent to

which the amplitudes of the different atoms are in
phase with one another.

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Scattering Factors of NaCl & KCl

Both crystal have an FCC structure.

The Na+ ions and Cl- ions have different

numbers of electrons and hence have
different scattering factors.
Two sets of reflection may be out of phase.
The K+ ions and Cl- ions have same
numbers of electrons and hence have
similar scattering factors. Therefore the
diffraction pattern in this case is that of a
primitive cubic lattice.

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X-ray Powder Pattern

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SEM of NiO nanoparticles

XRD of NiO-MWCNTs
o
NiO@300 C

(200)
(111)
Diffraction Intensity (arb.unit)

(220)
o
NiO@300 C-MWCNTs

MWCNTs

NiO
NiO
NiO

0 10 20 30 40 50 60 70
2 Theta (deg.)

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Intensity of peaks
I(hkl) α l F(hkl) l2
Depends on : Crystallinity e.g. is it amorphous or is it
 atom (scatttering factor of each atom type) crystalline. If it is crystalline we get very
 Symmetry (systematic absences) sharp peaks. For amorphous materials, we
e.g. for α-Fe, BCC, (100) absent.
get very broad peaks which usually are of
However, for CsCl, Primitive cubic (100) (110) (111),
low intensity.

 Scattering angle, as scatttering angle increases intensity We can influence the intensity of the peak
decreases.
by using high intensity radiation e.g.
 Amount of sample (to get resonable diffraction pattern, we
need to fill sample holder (1 – 2 g). Synchrotron

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