ENMT608958

# Lecture 6

Physical Properties of Nanomaterials

2
 OUTLINE

 Introduction
 Melting point and lattice constant
 Mechanical properties
 Optical properties
 Electrical conductivity
 Ferroelectrics and dielectrics
 Superparamagnetism

3
 INTRODUCTION

 The properties of solids are altered with great reductions in

particle size.
 This effect does not come into play by going from macro to
micro dimensions; however, it becomes dominant when the
nanometer size range is reached.
 Some known physical properties of nanomaterials are related to
different origins:
 Large fraction of surface atoms
 Large surface energy
 Spatial confinement
 Reduced imperfection

4
 INTRODUCTION

Few examples:
 Materials reduced to the nanoscale can suddenly show very
different properties compared to what they exhibit on a
macroscale, enabling unique applications:
 Opaque substances become transparent (copper);
 Inert materials become catalysts (platinum);
 Stable materials turn combustible (aluminum);
 Solids turn into liquids at room temperature (gold);
 Insulators become conductors (silicon).

5
 INTRODUCTION

Few examples (cont):

 Nanomaterials may have lower melting point or phase transition
temperature due to a huge fraction of surface atoms.
 Mechanical properties may reach theoretical strength due to
reduced probability defects.
 Optical properties can be different from the bulk due to an
increased band gap, or change in color due to surface plasmon
resonance.

6
 INTRODUCTION

Few examples (cont):

 Electrical conductivity may decrease due to increase in surface
scattering, or may be better due to better ordering in
microstructure.
 Magnetic properties differ from the bulk due to huge surface
energy.
 Increased perfection would have appreciable impact on the
chemical and physical properties.

7
 MELTING POINT & LATTICE CONSTANTS

 Nanoparticles of metals, inert gas, semiconductors, and

molecular crystals are all found to have lower melting
temperatures as compared with their bulk forms when the
particle size decreases below 100 nm.
 The lowering of the melting points in general may be explained
by the fact that the surface energy increases with a decreasing
size.
 The decrease in the phase transition temperature can be
attributed to the changes in the surface energy to volume energy
ratio as a function of particle size.

8
 MELTING POINT & LATTICE CONSTANTS

 The relationship between the melting points of a bulk material,

Tb, and a particle, Tm, is given by:

 2

 2Tb    γs  3 
Tb  Tm     γ s  γ l   
 Hρ s rs    γl  
 
 where rs is the radius of the particle, H is molar latent heat of
fusion, and  and  are surface energy and density, respectively.

9
 MECHANICAL PROPERTIES

 Mechanical properties of materials increase with a decreasing

size (Hall Petch equation)
 It has been found that whisker can have a mechanical strength
approaching to the theoretical as first demonstrated by Herring
and Galt in 1952.
 Calculated strength of perfect crystal exceeds that of real ones by
two or more orders of magnitude.
 Increase of mechanical strength becomes appreciable only when
the diameter of whisker is less than 10 microns.

10
 MECHANICAL PROPERTIES
 Two mechanisms have been proposed to
explained the enhanced strength of
nanowires or nanorods:
1. To ascribe the increase of strength to
the high internal perfection of the
nanowires or whisker, the smaller the
cross-section of a whisker or
nanowires, the less is the probability
of finding in it any imperfection such
as dislocation, micro-twins, and
impurity precipitates.
2. Perfection of the side faces of whisker
or nanowires; the smaller the 11
structures the less surface defects.
 HOW STRONG A PERFECT CRYSTAL?
 Assuming sinusoidal behavior
Q
2πx
   max sin
b Energy (a)
where  is applied shear stress; max is max.
P R
theoretical strength; x is distance atoms are Displacement (x)
moved; and b is distance between 0 b/2 b
equilibrium position.
 For elastic strain:   Gγ (b)

x 3b/4 Displacement (x)

 For a small value of elastic strain: γ  Force
b/4
a
where a is a distance between slip planes.

12
 HOW STRONG A PERFECT CRYSTAL?

d 2π 2πx
 Differentiation of sinusoidal equation wrt. distance:   max cos
dx b b
 d  2π
    max
 dx  x 0 b
d  d  dγ  x dγ 1
Note:     and for small elastic strain: γ and 
dx  dγ  dx  a dx a
d
 While from   Gγ we get that G
dγ

 Thus 2π G or G because a = b for most crystal

 max   max 
b a 2π

13
 MECHANICAL PROPERTIES

 Yield strength and hardness of polycrystalline materials are

known to be dependent on the grain size on the
micrometer scale, following the Hall-Petch relationship:
k
 ys  0 
d
where 0 is the lattice frictional stress, k is a material
constant, and d is the average grain size.

14
 MECHANICAL PROPERTIES

 However, Hall-Petch relation does not work well

for nano grain size because it predicts unrealistic
strengths; in this case, key consideration is grain
400
diameter versus grain boundary area on which 350
nCu
Nanocrystalline copper
dislocations pile up, and the yield strength is 300

True stress (MPa)

given by Li’s equation: 250

 ys   0  Gb 
200
150 Cu
Microcrystalline copper
100

 where 0 is the frictional stress; α is a constant, in 50

the order of 0.4; G is shear modulus; b is Burgers 0

0 2 4 6 8 10 12 14
vector; and ρ is the dislocation density. True strain (%)

15
 OPTICAL PROPERTIES

 The reduction of material’s dimension has pronounce effects on

the optical properties.
 The size dependence can be generally classified into two groups:
 Related to surface plasmon resonance.
 Due to the quantum size effects.

16
 SURFACE PLASMON RESONANCE
 Surface plasmon is the coherent excitation of all the free electrons
within the conduction band, leading to an in-phase oscillation.

 When the size of a metal nanocrystal is smaller than the

wavelength of incident radiation, a surface plasmon resonance
(SPR) is generated.
17
 SURFACE PLASMON RESONANCE

 The electric field of an incoming light induces a polarization of

the free electrons relative to the cationic lattice.
 The net charge difference at the nanoparticle boundaries (the
surface), which in turn acts as a restoring force.
 In this manner, a dipolar oscillation of electrons is created with
a certain frequency.
 Thus, the surface plasmon resonance is a dipolar excitation of
the entire particle between the negatively charge free electrons
and its positively charge lattice.

18
 QUANTUM SIZE EFFECTS
 When the size of a nanocrystal is
smaller than the de Broglie
wavelength (p = h), electrons
and holes are spatially confined
and electric dipoles are formed,
and “discrete electronic energy
level” would be formed.

 Similar to “a particle in a box”,

the energy separation between
(a) nanocrystals, (b) nanowires, (c) thin films,
adjacent levels increases with and (d) enlarge band gap between valence and
decreasing dimensions. conduction band.

19
 SOME TERMINOLOGIES

 Nanocrystals are specifically denoted to single crystal

nanoparticles.
 Quantum dots are used to described small particles that exhibit
quantum size effects.
 Quantum wires are referred to as quantum wires when
exhibiting quantum effects.

20
 ELECTRICAL CONDUCTIVITY
 Can be grouped into:
 Surface scattering
 Change of electronic structure
 Quantum transport
 Effect of microstructures
 Increasing in perfection such as reduced impurity, structural
defects and dislocations, would affect the electrical conductivity
of nanostructures and nanomaterials.

21
 SURFACE SCATTERING

 Electrical conduction in metals or Ohmic conduction can be

described by various electron scattering, and the total resistivity,
T, of a metal is a combination of the contribution of individual
and independent scattering, known as Matthiesen’s rule:
T =Th + D
where Th is the thermal resistivity, and D is the defect
resistivity.

22
 SURFACE SCATTERING

 Electron collision with vibrating atoms (phonons) displaced

their equilibrium lattice positions are the source of the thermal
or phonon contribution.
 Impurity atoms, defects such as vacancies and grain boundaries,
disrupt the periodic electrical potential of the lattice and
effectively cause electron scattering.
 Defect resistivity can be further divided into:
 impurity resistivity,
 lattice defect resistivity, and
 grain boundary resistivity.
23
 SURFACE SCATTERING
 Reduction in material dimension would have two different effects on
electrical resistivity:
 An increase in crystal perfection or reduction of defects, which
would result in a reduction in defect scattering, and thus a
reduction in resistivity; however the defect scattering makes a
minor contribution to the total electrical resistivity of metals at
room temperature and thus has very small influence.
 To create an additional contribution to the total resistivity due to
surface scattering, which plays a very important role in determining
the total electrical resistivity of nanosized materials. In nanowires
and thin films, the surface scattering of electrons results in
reduction of electrical conductivity.

24
 CHANGE IN ELECTRONIC STRUCTURE

 A reduction in dimension below critical size, i.e. de Broglie

wavelength, results in a change of electronic structure, leading to
widening and discrete band gap.
 Such a change may also result in a reduced electrical conductivity.
 Some metal nanowires may undergo a transition to become
semiconducting as their diameters are reduced below certain
values, and semiconductor nanowires may become insulator.

25
 QUANTUM TRANSPORT

 Ballistic conduction: occurs when the length of conductor is

smaller than the electron mean-free path; in this case no energy
dissipation and no elastic scattering which may reduce the
electrical conductance.
 Coulomb blockade (charging): occurs when the contact
resistance is larger than the resistance of nanostructures, and
when the total capacitance of the object is so small that adding a
single electron requires significant charging energy.

26
 EFFECT OF MICROSTRUCTURE

 When the size is reduced to a nanomater scale, electrical

conductivity may change due to the formation of ordered
microstructure  polymer fibers demonstrate an enhanced
electrical conductivity.
 The enhancement may be explained by the ordered arrangement
of the polymer chains.
 Within nanometer fibris, polymer are aligned parallel to the axis
of the fibrils, results in increased contribution of intermolecular
conduction.

27
 FERROELECTRICS AND DIELECTRICS

 Ferroelectric materials are polar compound crystals with reversible

spontaneous polarization. Ferroelectric are also pyroelectric and
piezoelectric.
 In a polycrystalline ferroelectric, the ferroelectric properties may
disappear when the particles are smaller than a certain size.
 Such a relation can be understood considering the phase transition
temperature reduce with the particle size.
 A reduction in particle size results in a high temperature crystal
structure stable at low temperatures, and thus the Curie temperature
decreases with a reduced particle size.

28
 SUPERPARAMAGNETISM

 Ferromagnetic particles become unstable when the particle size

reduces below a certain size, since the surface energy provides a
sufficient energy for domains to spontaneously switch
polarization direction.
 As a result, magnetic turn to paramagnetic; however, nanometer
sized ferromagnetic turned to paramagnetic behaves differently
from conventional paramagnetic and is referred to as
superparamagnetics.

29
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license.
The effect of the core
material on the flux density.
The magnetic moment
opposes the field in
diamagnetic materials.
Progressively stronger
moments are present in
paramagnetic,
ferrimagnetic, and
ferromagnetic materials for
the same applied field.
 SUPERPARAMAGNETISM
 Superparamagnetism will include at
least two requirements:
 Magnetization curve show no
hysteresis since that is not a thermal
equilibrium property.
 Magnetization curve for an isotropic
sample must be temperature
dependent to the extent that curves Typical magnetization
taken at different temperature must curves of 2.2 nm iron
particles suspended in
be approximately superimpose when mercury at various
plotted again H/T after correction temperature (a), and
the approximate H/T
for the temperature dependence of superposition
the spontaneous magnetization. observed for their 77K
and 200K data (b).

31