UNIT 02-NANO TECHNOLOGY

Session 03
Microstructure and Defects in
Nanocrystalline Materials

Contents
Introduction
3.1 “Crystalline State” and Its Advantages
3.2 Arrangements of Atoms and Ions in Crystalline Solids
3.3 Defects of Crystalline Materials
3.4 Defects in Nanocrystalline Materials
Summary
Learning Outcomes

Introduction
Nanocrystalline materials consists of crystallite sizes in the range
of a few nanometers (5 – 20 nm). Nanocrystalline materials show
decreased elasticity, melting temperature and thermal
conductivity, increased magnetic strength and energy density with
novel optical properties. Defects play a major role in these
nanocrystalline materials. Before going into detailed discussion
about the defects of nanocrystalline materials, let’s first discuss
crystalline materials and their defects in general.

3.1 “Crystalline State” and Its Advantages

The main characteristic feature of the crystalline state is its high
degree of order or regularity in the arrangement of the atoms. The
need for this regularity in the arrangement can be explained using
thermodynamics. From the viewpoint of thermodynamics, the
equilibrium structural state of a system is the minimization of the
free energy. For a solid, the related free energy can be
approximated as internal energy. Thus, the free energy is
minimized by minimizing internal energy with reference to the
lattice energy that is relevant to the interatomic potentials. Since
the interatomic potential usually decreases with decreasing
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separation distance, most materials would adopt a very densely

packed structure at low temperature. Such low-temperature,
densely packed states can be said to be low in internal energy or to
have a high degree of order.

3.2 Arrangements of Atoms and Ions in

Crystalline Solids
The simple way to describe the crystalline structure is to consider
that it consists of a three-dimensional arrangement of lattice points
in space which is known as the face lattice, shown in Figure 3.1,
where a, b, and c represent the unit length of each axis, t1 and t2
represent translation vectors.

Figure 3.1 – A three-dimensional arrangement of lattice points. 1

The unit cell, the repeating unit of space lattice, is defined by three
lattice translation vectors. Thus, the edge of unit cell must be
lattice translation, and the magnitude of “lattice translation
vectors” is called lattice parameter or lattice constant. While one
space lattice can have several different unit cells, conventionally,
unit cells are chosen which have a simple geometry and contain
only a few lattice points.
It was found that there are only 14 different ways to arrange the
lattice points in space satisfying the definition of a space lattice,
i.e., each point has identical surroundings. The 14 different point
lattices are called Bravais lattices and are shown in Figure 3.2.
where, P is primitive cell, I is body-centered cell, F is face-
centered cell, C is side-centered cell.

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Figure 3.2 – The 14 different Bravais lattices and seven crystal

systems. 1

3.3 Defects of Crystalline Materials

Th real crystalline materials are never perfect, they contain
imperfections. These imperfections can be classified into below
groups.

1. Point defects
Point defects can be further classified into 1) vacancies, 2)
Impurities and 3) interstitials. Interstitials could be self-interstitial
or an interstitials impurity (Figure 3.3).

Figure 3.3 – Illustration of the possible point defects in metal

crystal. 1
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a. Schottky defects
These point defects can be stoichiometric or non-stoichiometric.
Schottky defects are examples for stoichiometric defects. Schottky
disorder involves the existence of equal amounts of cation and
anion vacancies (Figure 3.4).

Figure 3.4 – Schottky defect2

b. Frenkel defects
The defect structure involves equal numbers of vacancy and
interstitials of cation. Frenkel defects are formed when a cation on
the normal site is transformed to an interstitial site, no new lattice
sites are created in the process (Figure 3.5). Anti-Frenkel defects
involves equal numbers of vacancy and interstitials of anion.

Figure 3.5 – Frenkel defect2

c. Non-stoichiometric defects
A nonstoichiometric defect indicates the presence of an excess or
deficit of cations or anions. These can be classified into two types:
1) intrinsic and 2) extrinsic non-stoichiometry. Intrinsic non-
stoichiometry is formed by partial oxidation or reduction of a
stoichiometric ionic solid. Extrinsic non-stoichiometry is formed
during the incorporation of foreign ions.

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2. Line defects
Line defects are dislocations of a crystal lattice (Figure 3.6).

Figure 3.6 – Dislocation of a crystal.2

a. Grain boundaries
Grain boundary is an interface between two crystals or grains of
the same phase where there is an orientation different in the atom
arrangement across the interface (Figure 3.7).

Figure 3.7 – Grain boundary.2

3.4 Defects in Nanocrystalline Materials

Crystal lattice imperfections like, point, linear, planer and volume
defects govern the properties of a material. The atomic structure
of nano structured materials is bit different from conventional
crystalline materials. In nanocrystalline materials, a substantial
fraction of atoms lies at the grain boundaries and interfaces.
Therefore, nanomaterials exhibit vastly different properties
compared to bulk materials. The main defect types observed in
nanocrystals are vacancies, grain boundaries, dislocations, twins,
stacking faults and triple junctions.

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1. Dislocations
Dislocations are, in general, stable in conventional
microcrystalline materials, though not thermodynamically
stable defects. However, when the magnitude of the critical
distance becomes comparable with that of the grain size, as
in nanomaterials, the stability of dislocations is altered
significantly. Hence, with decreasing grain size of
nanograined materials, dislocation stability is reduced, due
to the large grain boundary area.
2. Twins and stacking faults
Although thermodynamically metastable, planar defects are
often observed, even after annealing, in many faceted
nanomaterials, including nanorods and nanowires. These
planar defects include twins and stacking faults. For
example, many bulk metals have the face-centred cubic
structure, but nanocrystals and nanorods of the same
material often exhibit various structural modifications such
as single or multiple symmetric twinning, as well as five-
fold cyclic twinning, resulting in decahedral and truncated
decahedral nanostructures below critical siges.
• Multiply twined nanoparticles
Multiply twinned particles (MTP) with a pseudo five-fold
symmetry are observed frequently in nanocrystalline particles and
thin films of cubic face-centred metals, diamond-type
semiconductors (C, Si, Ge) and alloys. MTP are formed by
sequential cyclic five-fold twinning, with each twin sharing a
common twin plane boundary with the adjacent twin. It is known,
for example, that twinning in FCC occurs along the {111} plane.
The angle between two {111} planes is 70.53 degrees. Thus,
repeated twinning five times will still not result in 360 degrees but
will result in an annular gap of about 7.35 degrees. Thus, the
fivefold symmetry formed from an FCC structure should have a
distortion due to the geometrical arrangements along the five-fold
axis (Figure 3.8).

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Figure 3.8 - Schematic of five-fold twinned cubic lattice showing

the annular mismatch created by repetitive twinning.2
3. Voids
Voids in nanocrystallites may be situated at either triple
junctions or as large porosities due to insufficient
compaction and sintering of nanocrystallites synthesized
from the powder route. It is suggested that triple junction
voids arise because of relaxation of nanocrystalline grain
boundaries.
4. Grain boundaries
A schematic representation of a hard-sphere model of an
equiaxed nanocrystalline metal was shown in Figure 3.9.
Two types of atoms can be distinguished: crystal atoms with
nearest-neighbour configurations corresponding to the
lattice (black circles) and boundary atoms with a variety of
interatomic spacings (white circles). Nanocrystalline
materials typically contain a high number of interfaces with
random orientation relationships, and consequently, a
substantial fraction of atoms lies in the interfaces.

Figure 3.9 – The hypothetical structure of a nanomaterial. 2

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5. Triple junctions and disclinations

It has been suggested that the triple junctions can be
described based on the disclination defect model.
Disclinations (Figure 3.10) are line defects. For example,
consider a solid rubber ball. If you cut a slit in it of width
only as thick as a blade and then try to forcefully bring
together the ends of the cut portion, the resultant defect is a
dislocation. Instead, if you cut a wedge in the ball and now
try to bring the cut ends together, the resultant defect is a
disclination. Unlike dislocations, the elastic stress fields of
disclinations diverge with distance. The triple junctions may
be considered to form a network of disclinations. These
triple junctions are linear defects that play a significant role
in the mechanical, thermodynamic and kinetic properties of
polycrystals. This role may be particularly important in
nanocrystalline materials, where the grain boundaries are
short and contain a small number of structural units.

Figure 3.10 – Schematic showing a disclination. 2

Summary

Nanocrystalline materials, characterized by small crystallite sizes

in the range of a few nanometers, exhibit distinct properties such
as reduced elasticity, melting temperature, and thermal
conductivity, along with enhanced magnetic strength, energy
density, and unique optical properties. Defects play a significant
role in these materials, but before exploring their specific defects,
it is essential to understand crystalline materials and their
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imperfections. The crystalline state, known for its high degree of

order, minimizes internal energy through a regular arrangement of
atoms. Point defects, including vacancies, impurities, and
interstitials, as well as line defects like grain boundaries,
contribute to imperfections in crystalline materials. In
nanocrystalline materials, additional defects such as vacancies,
grain boundaries, dislocations, twins, stacking faults, and triple
junctions play a crucial role, impacting their properties and
behavior.

Learning Outcomes
After completion of this session, students should be able to,
1. Understand the unique properties and advantages of
nanocrystalline materials.
2. Identify and classify defects in crystalline materials.
3. Analyze and interpret defects specific to nanocrystalline
materials.

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