PHYS2141: PHYSICS OF NANOMATERIALS

(Elective)

• Text Books: 1.Nano: The Essentials – Understanding Nano Science and

Nano Technology by T . Pradeep.
2. B S Murthy, P Shankar, Baldev Raj, B B Rath and James Murday-
Textbook of Nano science and Nanotechnology, University Press-IIM.
➢ P.P. Charles, J.O. Frank Introduction to Nanotechnology, Wiley InterScience, 2003.
➢ K.KChattopadhyay,A.N.Banerjee, Introduction to Nanoscience and Nanotechnology,
PHI, 2011.

Dr. B.Rajesh Kumar, Dept of Physics, GSS 1

 Defects in Nanocrystalline materials

How can we classify defects in materials?

❑ Defects can be classified based on some of the following methods:

➢ Dimensionality
➢ Based on association with Symmetry and Symmetry Breaking
➢ Based on their origin
➢ Based on their position
➢ Based on the fact that if the defect is with respect to a geometrical entity or a
physical property

Dr. B.Rajesh Kumar, Dept of Physics, GSS 2

 Microstructure in Nanocrystalline materials
The microstrucural features of importance in nanomaterials include:
•Grain size, distribution and morphology
•The nature of grain boundaries and interphase interfaces
•Nature of intragrain defects
•Composition profiles across grains and interfaces
•Residual impurities from processing
Classification scheme for nanostructured materials based on microstructure

Dr. B.Rajesh Kumar, Dept of Physics, GSS 3

Classification Based on Dimensionality
❑ Truly speaking any defect exists in 3D. However, the ‘effective dimension’ may be lower.
E.g. the strain field of a dislocation is in 3D, but it is a ‘line-like’ defect. Similarly, a
vacancy is point-like.
❑ In special circumstances the dimension of defect may be lowered (e.g. in a 2D crystal a
dislocation is point or a crack may be planar (2D)).

CLASSIFICATION OF DEFECTS BASED ON DIMENSIONALITY

0D 1D 2D 3D
(Point defects) (Line defects) (Surface / Interface) (Volume defects)

Vacancy Dislocation Surface Twins

Impurity Disclination Interphase boundary Precipitate

Frenkel defect Grain boundary Faulted region

Dispiration
Schottky defect Twin boundary Voids/Cracks

Stacking faults Thermal vibration

Anti-phase
Dr. B.Rajesh Kumar, Dept of Physics,boundaries
GSS 4
Vacancy

❑ Missing atom from an atomic site

❑ Atoms around the vacancy displaced
❑ Tensile stress field produced in the vicinity

Tensile Stress
Fields ?
Dr. B.Rajesh Kumar, Dept of Physics, GSS 5
Vacancy

❑ Missing atom from an atomic site is called a vacancy.

❑ Atoms around the vacancy displaced from their equilibrium positions.
❑ This gives rise to a stress field in the vicinity of the vacancy.
❑ Based on their origin vacancies can be:
➢ Random/Statistical (thermal vacancies, which are required by thermodynamic
equilibrium) or
➢ Structural (due to off-stoichiometry in a compound).
❑ Based on their position vacancies can be random or ordered. (Ordered defects become
part of the crystal structure and are ‘no longer defects’ in the usual sense).
❑ Vacancies play an important role in diffusion of substitutional atoms and in many
other processes/effects in materials science, including climb of edge dislocations,
some forms of creep and increased resistivity.
❑ Non-equilibrium concentration of vacancies can be generated by:
➢ quenching from a higher temperature
➢ bombardment with high energy particles
➢ plastic deformation.
➢ off-stoichiometry in ordered compounds. Etc.

Neighbouring atoms are

displaced from their
equilibrium position in a
Dr. B.Rajeshperfect
Kumar,crystal
Dept of Physics, GSS 6
 Relative
size
Interstitial
Compressive
Impurity Stress
Fields
Substitutional

Compressive stress
fields

❑ SUBSTITUTIONAL IMPURITY Tensile Stress

• Foreign atom replacing the parent atom in the crystal Fields
• E.g. Cu sitting in the lattice site of FCC-Ni
❑ INTERSTITIAL IMPURITY
• Foreign atom sitting in the void of a crystal
• E.g. C sitting in the octahedral void
Dr. B.Rajesh Kumar, Dept ofin HTGSSFCC-Fe
Physics, 7
❑ In some (rare) situations the same element can occupy both a lattice position and an
interstitial position ► e.g. B in steel.
❑ By using ion irradiation or some other ‘strong forces’ an substitutional atoms may be
forced to occupy an interstitial position.
❑ The diffusion mechanism of these two types of point defects (interstitial vs substitutional)
is different. This is because for the diffusion of substitutional atom the neighbouring site
has to be vacant; while in the case of interstitial diffusion the neighbouring site is usually
vacant (as the solubility of interstitial atoms is small).

Dr. B.Rajesh Kumar, Dept of Physics, GSS 8

 Dislocations
• Dislocations are very important imperfections in real
materials.
• Dislocations are line imperfections in otherwise perfect
lattices.
• Dislocations are formed during solidification or when the
material is deformed.
• Dislocations strongly affect the mechanical, electronic and
photonic properties of materials.
• There are two basic types of dislocations – edge and screw
dislocations.

Dr. B.Rajesh Kumar, Dept of Physics, GSS 9

 Edge dislocation
➢ Edge dislocation is considered positive when compressive
stresses present above the dislocation line, and is represented
by ┴.
➢ If the stress state is opposite i.e. compressive stresses exist
below the dislocation line, it is considered as negative edge
dislocation, and represented by ┬.
A schematic view of edge dislocations are shown in figure

Dr. B.Rajesh Kumar, Dept of Physics, GSS 10

 Screw dislocations:

The perfect crystal in a) is cut and sheared one atom spacing in

b) and c). The line along which the shearing occurs is a screw
dislocation. A Burgers vector b is required to close a loop of
equal atom spacings around the screw dislocation.

Dr. B.Rajesh Kumar, Dept of Physics, GSS 11

 a) b) c)

The perfect crystal in a) is cut and an extra plane of atoms is

inserted in b). The bottom edge of the extra plane is an edge
dislocation in c). A Burgers vector b is required to close a loop of
equal atom spacings around the edge dislocation.
Dr. B.Rajesh Kumar, Dept of Physics, GSS 12
 Stacking Fault
❑ Stacking faults are typically described for close packed structures.
❑ An error in the sequence of stacking atomic planes (close packed planes) leads to a
Stacking fault.
❑ This can be ‘thought of as’ inclusion or removal of a plane.
❑ A stacking fault is defined by a shift vector.
❑ In a stacking fault the nearest neighbours are undistorted by the next nearest neighbours
are different than in the perfect crystal.
❑ In CCP crystals when the perfect dislocation splits into partials, the included region in the
slip plane is stacking fault (i.e. the stacking fault is bounded by two partials).
❑ Stacking faults can be right across the crystal or can be limited to a certain region (as in the
figures in the next slide). In the case of limited faults, they are bounded by dislocations.

FCC stacking …ABC ABC ABC ABC…

FCC stacking
with a stacking fault
…ABC AB AB ABC…

Thin region of HCP type of stacking

Dr. B.Rajesh Kumar, Dept of Physics, GSS 13
 Perfect region

Faulted region

Intrinsic

Stacking faults
Two breaks introduced into
the stacking sequence
Extrinsic

Dr. B.Rajesh Kumar, Dept of Physics, GSS 14

 FCC stacking
…ABC ABC ABC ABC…
of close packed planes

FCC stacking
with a stacking fault
…ABC AB AB ABC…

Thin region of HCP type of stacking

❑ In the above example the nearest neighbour configuration is the same but the
configuration of the next-nearest neighbours is different than that in FCC

❑ The energy per unit area of the stacking fault is the stacking fault energy (SFE)
❑ Stacking fault energy ~ 0.01 – 0.05 J/m2
❑ Stacking fault in HCP can lead to thin region of FCC kind of stacking
Dr. B.Rajesh Kumar, Dept of Physics, GSS 15
 Grain boundaries
➢Crystalline solids are, usually, made of number of grains separated by grain
boundaries.
➢ Grain boundaries are several atoms distances wide, and there is mismatch of
orientation of grains on either side of the boundary as shown in Figure. When this
misalignment is slight, on the order of few degrees (< 10˚), it is called low angle grain
boundary.
➢These boundaries can be described in terms of aligned dislocation arrays. If the low
grain boundary is formed by edge dislocations, it is called tilt boundary, and twist
boundary if formed of screw dislocations.
➢Both tilt and twist boundaries are planar surface imperfections in contrast to high
angle grain boundaries. For high angle grain boundaries, degree of disorientation is
of large range (> 15˚). Grain boundaries are chemically more reactive because of
grain boundary energy.
➢In spite of disordered orientation of atoms at grain boundaries, polycrystalline
solids are still very strong as cohesive forces present within and across the boundary.

Dr. B.Rajesh Kumar, Dept of Physics, GSS 16

 Twin boundaries
➢Twin boundaries occur in pairs such that the orientation change
introduced by one boundary is restored by the other (shown in Figure).
➢The region between the pair of boundaries is called the twinned region.
Twins which forms during the process of recrystallization are called
annealing twins, whereas deformation twins form during plastic
deformation.
➢Twinning occurs on a definite crystallographic plane and in a specific
direction, both of which depend on the crystal structure.
➢Annealing twins are typically found in metals that have FCC crystal
structure (and low stacking fault energy), while mechanical/deformation
twins are observed in BCC and HCP metals.
➢Annealing twins are usually broader and with straighter sides than
mechanical twins

Dr. B.Rajesh Kumar, Dept of Physics, GSS 17

VOIDS (Or Pores)

Voids (or pores) are caused by gases that are trapped during solidification or by
vacancy condensation in the solid state. They are almost always undesirable
defects. Their principal effect is to decrease mechanical strength and promote
fracture at small loads.

Dr. B.Rajesh Kumar, Dept of Physics, GSS 18

Electrical properties
 The Van-der-Pauw method is used to determine the
electrical transport properties of materials (bulk and
thin films) like the electrical conductivity, the
resistivity, the hall constant, the charge carrier
concentration and the charge carrier mobility.

Sample configuration for the Hall

coefficient measurement using Van der
Pauw measurement technology, with an
applied magnetic field perpendicular to
the sample surface.
Magnetic Moment (M): The magnetic moment of a magnet is a quantity that determines the

force that the magnet can exert on electric currents and the torque that a magnetic field will

exert on it.

Isotropic: Properties of a material are identical in all directions.

anisotropic: Properties of a material depend on the direction

It will respond to an applied magnetic field in the same way, regardless of which

direction the field is applied. This is known as magnetic isotropy.

In contrast, magnetically anisotropic materials will be easier or harder to magnetize

depending on which way the object is rotated.

Magnetic properties

Magnetization curves and magnetic

susceptibility as a function of temperature.
VSM (Vibrational Sample Magnetometer}
The technique provides information about
the following mechanical properties:
1. Hardness
2. Elastic properties
3. Time-dependent deformation
Thermal properties: Thermal Conductivity in Nanomaterials:-
Thermal conductivity refers to the ability of a given material to conduct/transfer heat. It is
generally denoted by the symbol 'k' but can also be denoted by 'λ' and 'κ'.

➢ In general, increasing the number of grain boundaries will enhance

phonon scattering at the disordered boundaries, resulting in lower
thermal conductivity.
➢ Thus, nanocrystalline materials would be expected to have lower
thermal conductivity compared to conventional materials.
➢ However, as the grain sizes assume nanodimensions, their size
becomes comparable to the mean free paths of phonons that transport
thermal energy.
➢ Thus, nanomaterials can show widely different properties compared
to coarse-grained materials, due to the photon confinement and
quantization effects of photon transport.
➢ It has been observed that in addition to the grain size, the shape also
has an influence on the Dr.thermal
B.Rajesh Kumar, Dept of Physics, GSS
properties of nanomaterials. 37
For example, one dimensional nanowires may offer ultralow thermal conductivities.
In nanowires, quantum confinement of phonons in 1D can result in additional
polarization modes compared to that observed in bulk solids.
The strong phonon–phonon interactions and enhanced scattering at grain boundaries
result in a significant reduction in thermal conductivity of nanostructures.
Silicon nanowires are known to exhibit thermal conductivity at least about two orders of
magnitude smaller than that of bulk silicon.

Dr. B.Rajesh Kumar, Dept of Physics, GSS 38

The use of a nanofluid to enhance thermal transport is another promising application of
the thermal properties of nanomaterials.
Nanofluids represent the class of liquids that have a stable colloidal dispersion of
nanoparticles distributed uniformly in the medium.
It has been observed that dispersion of a wide variety of nanoparticles of oxides,
nitrides, metals, metal carbides and nanofibres, such as single- and multi-walled carbon
nanotubes, can significantly enhance the thermal conductivity of the fluid.

Dr. B.Rajesh Kumar, Dept of Physics, GSS 39

Melting Point Property:- Melting-point depression is the phenomenon of reduction
of the melting point of a material with reduction of its size.

➢ This phenomenon is very prominent in nanoscale materials, which melt at

temperatures lower than bulk materials.

➢ The melting temperature of a bulk material is not dependent on its size.

➢ However as the dimensions of a material decrease towards the atomic scale, the
melting temperature scales with the material dimensions.

➢ The decrease in melting temperature can be on the order of tens to hundreds of

degrees for metals with nanometer dimensions.

➢ Melting-point depression is most evident in nanowires, nanotubes and

nanoparticles, which all melt at lower temperatures than bulk amounts of the
same material.
Dr. B.Rajesh Kumar, Dept of Physics, GSS 40
Changes in melting point occur because nanoscale materials have a much larger surface-to-
volume ratio than bulk materials, drastically altering their thermodynamic and thermal
properties.
The melting temperature of a nanoparticle decreases sharply as the particle reaches critical
diameter, usually < 50 nm for common engineering metals.
Figure (1) shows the shape of a typical melting curve for a metal nanoparticle as a function
of its diameter.

Dr. B.Rajesh Kumar, Dept of Physics, GSS 41

Dr. B.Rajesh Kumar, Dept of Physics, GSS 42
Dr. B.Rajesh Kumar, Dept of Physics, GSS 43