MSE:5073/6073

Nanostructured Materials:
Science & Technology

Tue,Thu: 10:45 AM-12:05 PM

Lecture #5-6
Nanostructured Materials: Science and
Technology

Ashutosh Tiwari
Department Of Materials Science & Engineering
University of Utah, USA

Venue: I.I.T. Roorkee

 What holds atoms together

Fig. Total potential energy of a pair of atoms as a function of separation distance, x.

At large separation distances, attractive forces pull the atoms toward one another,
toward the equilibrium separation distance. At small separations, repulsive forces
dominate.
 Bonds

Ionic Bond Covalent Bond Metallic Bond van der Waals

Table 4.1 Main Type of Bonding

Bonding Among Atoms and molecules Within Solids

Ionic Oppositely charged atoms are Crystal structure is formed by an array of atoms
attracted to one another to make held together by opposing charges. Example:
molecules. Example: Na+ and Cl- Magnesium oxide, a crystal formed by O2- and
make the NaCl molecule Mg2+ molecules

Covalent Two atoms share electrons; their Crystal structure is formed by an array of atoms
atomic orbitals overlap to make a sharing electron orbitals. Example: Diamond,
molecular orbital. Example: Two made from C atoms each sharing electrons with
hydrogen atoms make the H2 four other C atoms
molecule
Van der Two atoms are attracted to one Atoms already organized as a solid are still
Waals another by weak electrostatic subject to weak interaction forces with other
(three forces. Example: Polar H2O atoms. Example: Covalently bonded layers of
types) molecules clings to one another, carbon in graphite stack-like paper with weak van
endowing water with unique der Waal forces; layers can slide, making
characteristics graphite soft
Metallic The same as “Within Solids” Metal atoms are held together by a “sea” of “gas”
of electrons; these electrons can move freely
among the atoms, making metals conductive.
Example: Coper atoms in a telephone wire
Note: These bonding mechanism are those that enable atoms to form molecules as well as solids.
Much about the way matter behaves can be explained by the way in which the atoms are held
together.
 IONIC BOND
bond formed between
two ions by the
transfer of electrons
 Ionic Bond
• Between atoms of metals and
nonmetals with very different
electronegativity
• Bond formed by transfer of electrons
• Produce charged ions all states.
Conductors and have high melting
point.
• Examples; NaCl, CaCl2, K2O
 Formation of Ions from Metals
• Ionic compounds result when metals react with
nonmetals
• Metals lose electrons to match the number of
valence electrons of their nearest noble gas
• Positive ions form when the number of
electrons are less than the number of protons
Group 1 metals  ion 1+
Group 2 metals  ion 2+
• Group 3 metals  ion 3+
 Formation of Sodium Ion
Sodium atom Sodium ion
Na  – e  Na +

2-8-1 2-8 ( = Ne)

11 p+ 11 p+
11 e- 10 e-
0 1+
 Formation of Magnesium Ion
Magnesium atom Magnesium ion

Mg  – 2e  Mg2+

2-8-2 2-8 (=Ne)

12 p+ 12 p+
12 e- 10 e-
0 2+
 Fluoride Ion
unpaired electron octet
  1-
:F + e : F:
 

2-7 2-8 (= Ne)

9 p+ 9 p+
9 e- 10 e-
0 1-
ionic charge
Ionic Bonds: One Big Greedy Thief Dog!
How much energy and how big a force hold the NaCl molecule together?

First, we need to know the separation distance, x. We know Na has an atomic

radius of 186 pm. However, when the Na atom loses an electron, it shrinks. Na+
has a radius of 97 pm. The opposite is true of Cl, which upon acquiring an extra
electron grows in radius from 99 to 181 pm. The sum of these two ionic radii is
0.278 nm. The dielectric constant of air is 1. The binding energy is therefore ?
How much energy and how big a force hold the NaCl molecule together?

First, we need to know the separation distance, x. We know Na has an atomic

radius of 186 pm. However, when the Na atom loses an electron, it shrinks. Na+
has a radius of 97 pm. The opposite is true of Cl, which upon acquiring an extra
electron grows in radius from 99 to 181 pm. The sum of these two ionic radii is
0.278 nm. The dielectric constant of air is 1. The binding energy is therefore

(1)(−1) (1.602 × 10−19 𝐶)2

𝐸= −9 −12 2 −1 −2
= −8.3 × 10−19 𝐽
4𝜋(0.278 × 10 𝑚)(8.854 × 10 𝐶 𝑁 𝑚 )(1)

This energy is attractive. The binding force is

(1)(−1) (1.602 × 10−19 𝐶)2 −9 𝑁
𝐹= = −3 × 10
4𝜋(0.278 × 10−9 𝑚)2 (8.854 × 10−12 𝐶 2 𝑁 −1 𝑚−2 )(1)
 COVALENT BOND
bond formed by the
sharing of electrons
Fig. 4.3 A covalent bond between hydrogen atoms. The probability of finding an
electron in the H2 molecule is highest in the region between the two nuclei.
 Covalent Bond
• Between nonmetallic elements of similar
electronegativity.
• Formed by sharing electron pairs
• Stable non-ionizing particles, they are
not conductors at any state
• Examples; O2, CO2, C2H6, H2O, SiC
Bonds in all the
polyatomic
ions and
diatomics are
all covalent
bonds
 NONPOLAR
COVALENT BONDS
when electrons are shared
equally

H2 or Cl2
POLAR COVALENT
BONDS

when electrons are shared but

shared unequally

H2O
Polar Covalent Bonds: Unevenly
matched, but willing to share.
METALLIC BOND
bond found in
metals; holds metal
atoms together
very strongly
 Metallic Bond
• Formed between atoms of metallic
elements
• Electron cloud around atoms
• Good conductors at all states, lustrous,
very high melting points
• Examples; Na, Fe, Al, Au, Co
Metallic Bonds: Mellow dogs with plenty
of bones to go around.
Metallic Bond, A Sea of
Electrons
 van der Walls Force
These forces are short-range in nature and lead to weak
bonds among atoms and molecules. Although weaker than
covalent, metallic and ionic forces, van der Walls forces
have a significant impact on the physical properties and
behavior of all matter, and are especially relevant at the
nanoscale.

dipole-dipole force
dipole-induced-dipole force
dispersion force
4.2.4.2 Repulsive Forces

There is one final component of the van der Waals interaction between
molecules; this component is repulsive. Repulsion dominates the interaction of
molecules as soon as they are too close together– when their electronic orbital
begin to overlap. These repulsive forces are quantum mechanical in nature and
referred to by many names – exchange repulsion, hard core repulsion (Fig.
shows below), steric repulsion, and , in the case of ions, born repulsion.
 12 6
2𝑟𝑣𝑑𝑤 2𝑟𝑣𝑑𝑤
𝐸 𝑥 =𝜀 −2
𝑥 𝑥 (4.3)

In this equation, ε is known as the well depth and 𝑟𝑣𝑑𝑤 as the van der Waal radius (or
hard sphere radius). We can see both the attractive van der Waals interaction (which
varies with the inverse-sixth power of the separation distance) and the repulsive
interaction(which tends to vary by roughly the inverse-12th power of the distance).
The parameters ε and 𝑟𝑣𝑑𝑤 vary by atom. This relation is shown graphically in Fig.
4.6. At large separation distances (not shown), the interaction forces fall of as the 7th
(instead of the 6th) power of the distance.
(2𝑟𝑣𝑑𝑤 )12 (2𝑟𝑣𝑑𝑤 )6
𝐹 𝑥 = 12𝜀 −
𝑥 13 𝑥7 (4.4)

The van der Waals forces enable creatures such as geckos and spiders to cling to
walls and ceilings. Such creatures have nanoscale hair on their feet. The size and
abundance of their hair mean that a great deal of surface area of their bodies can
make contact with a surface. The van der Waals forces from so many molecular
interactions between the wall and the hair hold the creature to the wall with orders of
magnitude more force that of gravity’s relentless downward pull.
Fig. 4.6 The van der Waals interaction. The graph shows the van der Waals forces
between two molecule separated by a distance x. The attractive forces dominate at
larger separation distances, but the repulsive forces dominate at closer range
(separation distances of about twice the molecular radius, rm, if both molecules are
the same). The combination of these repulsive and attractive forces (shown as
dotted lines) governs the van der Waals force interaction (thick blue line).
 𝐻𝑅
𝐸(𝑥)𝑠𝑝ℎ𝑒𝑟𝑒−𝑠𝑢𝑟𝑓𝑎𝑐𝑒 =− (4.4)
6𝑥

In this equation, H is the so-called Hamaker constant. In the case of solids

separated by air, H≈ 10-19 J.
a. Determine the equation for the attractive force with respect to x.
b. Now determine the force of gravity pulling the sphere down, away from the
surface, as a function of R. Assume that the particle is made of silicon, with a
density of 2330 kg/m3.
c. How large can the sphere be before gravity pulls it away from the surface if they
are separated by 10 nm of air? By 1 nm?
 Crystal Structures

Solids
Crystalline Amorphous
(Long range ordering) (No long range ordering)

A crystal structures is formed by associating with a lattice a regular arrangement

of atoms or molecules (Basis)

Lattice + Basis =
Crystal Structure
In three dimensions there are three lattice constants a, b, and c and three angles:
α between b and c; β between a and c; and γ between a and b.

There are 14 Bravais lattices, ranging from the lowest symmetry triclinic type in
which all three lattice constants and all three angles differ from each other, to the
highest symmetry cubic case in which all the lattice constants are equal and all the
angles are 900.
Ag, Al, Au, Co, Cu, Pb, Pt, Rh,… FCC

Rare gases Ne, Ar, Kr, Xe,… FCC

Mg, Nd, Os, Re, Ru,Y, Zn,… HCP

Alkali Metals Na, K, Rb, Cs… BCC

Some materials like Cr, Li and Sr crystallizes in all of above three crystal
types, depending on the temperature

Po SC
SC BCC FCC
Packing Fraction Calculation SC

Lattice Parameter=a
Radius of atom=r
Simple Cubic: one atom per unit cell

2r=a

Volume occupied by atom Voccupied=4r3/3= 4a3/24

Volume of the cell Vcell=a3

Packing Fraction= Voccupied/Vcell= 4/24=0.5233

Packing Fraction Calculation BCC

Lattice Parameter=a
Radius of atom=r
BCC: two atom per unit cell

4r=a3

Volume occupied by atom Voccupied=2x4r3/3= 2x4x33a3/3x43

Volume of the cell Vcell=a3

Packing Fraction= Voccupied/Vcell= 83 /64= 3 /8=0.6798

Packing Fraction Calculation FCC
Packing Fraction Calculation FCC

4r=a2

Volume occupied by atom Voccupied=4x4r3/3= 4x4x22a3/3x43

Volume of the cell Vcell=a3

Packing Fraction= Voccupied/Vcell= 0.74

FCC and HCP are the closest packed lattices

 74% Packing

What is happening to the remaining space?

In two dimensions the most efficient way to pack identical circles (or spheres) is the
equilateral triangle arrangement corresponding to the hexagonal Bravais lattice.

A
A second hexagonal layer of spheres can be placed on the top of the first to form
the most efficient packing of two layers. Now the third can be placed such that
atoms come just above the atoms in first layer or in the other possible position (C).

A B

HCP ABAB…..
FCC ABCABC….
In the three-dimensional case of close-packed spheres there are spaces or sites
between the spheres where smaller atoms can reside. The point marked by ‘O’ is
called an octahedral site. This is equidistant from the three spheres below it and
three spheres above it. The point marked by ‘T’ is called an tetrahedral site. This is
equidistant from four nearest spheres, one below and three above.

O
T
 Radius of the Tetrahedral hole

R: radius of atoms
r: radius of the tetrahedral hole

Face diagonal=2R
Cube edge=2R sin(450)=√2R
Body diagonal= √3 Cube edge= √6 R
(R+r)=Body diagonal/2
R+r= √6R/2=1.2247 R
r=0.2247 R
Radius of the Octahedral hole
 Radius of the Octahedral hole

Edge of the square=2R

Diagonal=√2x2R= 2√2R
r+R=diagonal/2= √2R
r=(√2-1)R=0.414R
Zinc Blend Structure

GaAs 2 FCC lattices displaced by the

ZnS ¼, ¼, ¼ along the body diagonal

Diamond Structure

Ge
Si
13 atoms nanopartice

If another layer of 42-atoms is layed down around the 13-atom nanoparticle, we get
55-atom nanoparticle with the same dekatessarhedron shape.

N=1, 13,55, 147, 309,..

N=1/3[10n3-15n2+11n-3]
Magic Numbers
Structural Magic numbers derived using minimum volume,maximum
density approach

These magic numbers do not take into account of the electronic structure of
The constituent atoms in the nanoparticle.

Nanoparticles with 1415 atoms and more follow magic numbers very well.