1/19/2023

Introduction to Nanomaterials

Atomic Bonding Band Structure and

Surfaces

Electronic Structure
Each orbital at discrete energy level is determined
by quantum numbers.

Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n-1)
ml = magnetic 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½

1
 1/19/2023

Electron Energy States

Atomic Interaction

2
 1/19/2023

Major Types of Bonding

• Ionic Bonding
– forms ionic compounds
– transfer of e-
• Covalent Bonding
– forms molecules
– sharing e-
• Metallic Bonding
– Occurs between like atoms of a metal
– Valence e- are mobile
– Positive ions in a sea of electrons
5

Secondary Bonding

Arises from interaction between weak dipoles

asymmetric electron
clouds

+ - + -
secondary
bonding

3
 1/19/2023

Properties From Bonding: Tm

• Bond length, r • Melting Temperature, Tm

Energy
r

• Bond energy, Eo r
o r
Energy
smaller Tm

unstretched length larger Tm

r
o r
Eo = Tm is larger if Eo is larger.
“bond energy”

Properties From Bonding : a

• Coefficient of thermal expansion, a
Th
e
pi
ct
ur
e
length, L o coeff. thermal expansion
ca
n't
be
dis
pl
ay

unheated, T 1
ed
.

DL DL
Lo
= a (T 2 -T 1)
heated, T 2

• a ~ symmetric at ro

Energy

unstretched length
r
o a is larger if Eo is smaller.
r
larger a
Eo
Eo smaller a
8

4
 1/19/2023

Band Structures in Materials

Formation of Energy Bands

Overlapping levels
Outer levels begin to interact
gas
Broadening of energy
levels as atoms approach
Electron energy

The width of the band is

proportional to the
strength of the overlap
(bonding) between
10
atomic orbitals

5
 1/19/2023

Electron Energy Band Structures

Adapted from Fig. 18.2, Callister & Rethwisch 8e.

11

Band Structure Representation

Adapted from Fig. 18.3,

Callister & Rethwisch 8e.

12

6
 1/19/2023

Conduction & Electron Transport

• Metals (Conductors):
-- for metals empty energy states are adjacent to filled states.
-- thermal energy Partially filled band Overlapping bands
excites electrons Energy Energy
into empty higher
energy states.
-- two types of band empty
structures for metals band
- partially filled band partly
- empty band that filled filled
overlaps filled band band band

filled states
filled states
filled filled
band band

13

Energy Band Structures: Insulators &

Semiconductors
• Insulators: • Semiconductors:
-- wide band gap (> 2 eV) -- narrow band gap (< 2 eV)
-- few electrons excited -- more electrons excited
across band gap across band gap
Energy empty Energy empty
conduction conduction
band band
GAP ?
GAP

filled filled
valence valence
band band
filled states
filled states

filled filled
band band
14

7
 1/19/2023

Charge Carriers in Insulators and

Semiconductors
Adapted from Fig. 18.6(b),
Callister & Rethwisch 8e.
Two types of electronic charge
carriers:
Free Electron
– negative charge
– in conduction band

Hole
– positive charge
– vacant electron state in
the valence band

Move at different speeds - drift velocities

15

Effect of Energy Band Structure at Nanoscale

• Number of atoms involved are very small compared to

macroscopic crystalline solid

• Interaction at Different Level – Band structure is affected by

size

• Example: Quantum dots – band gap increases with

decreasing size

• Light emitted at narrower spectrum, high energy and small

wavelength

16

8
 1/19/2023

Effect of Energy Band Structure at Nanoscale

• Emitted wave has high energy and frequency with decreasing

quantum dot size 17

Crystal Structure
&
Surface Structure

18

9
 1/19/2023

Crystal Structure

19

Bravais Lattice

20

10
 1/19/2023

Planar Density: Close Packed Plane

Solution: At T < 912ºC iron has the BCC structure.
2D repeat unit

(100) 4 3
a= R
3

Adapted from Fig. 3.2(c), Callister & Rethwisch 8e. Radius of iron R = 0.1241 nm
atoms
2D repeat unit 1
1 atoms atoms
Planar Density = = = 12.1 = 1.2 x 1019
2
area a2 4 3 nm 2 m2
R
2D repeat unit 3
21

Linear Density: Close Packed Direction

Number of atoms
• Linear Density of Atoms  LD = Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm

# atoms
a
2
LD = = 3.5 nm -1
Adapted from
Fig. 3.1(a), length 2a
Callister & Rethwisch
8e.

22

11
 1/19/2023

FCC Stacking Sequence

• ABCABC... Stacking Sequence
• 2D Projection

B B
C
A
A sites B B B
C C
B sites B B
C sites

A
• FCC Unit Cell B
C

23

Body Centered Cubic Structure (BCC)

APF & Coordination Number

24

12
 1/19/2023

Face Centered Cubic Structure (FCC)

APF & Coordination Number

25

Coordination Number at Surfaces: FCC

If the surface exposes {111} planes the coordination number is: 9

If the surface exposes {100} planes the coordination number is: 8

If the surface exposes {110} planes the coordination number is: 267

13
 1/19/2023

Coordination Number at Surfaces: BCC

If the surface exposes {111} planes the coordination number is: 4

If the surface exposes {100} planes the coordination number is: 4

If the surface exposes {110} planes the coordination number is: 6
27

Surface Energy in Stable Structure

28

14
 1/19/2023

Surface Energy

The sum of all the excess energies of the surface

atoms is the surface energy.

In terms of Gibbs free energy: dG ≡ −SdT +VdP +γdA

Surface tension is the average stored energy

per unit surface area.

 = E (Stored)/A

29

Surface Energy for FCC in {100} Plane

30

15
 1/19/2023

Surface Energy for FCC in {111} Plane

31

Broken Bond Model for Surface Energy

Broken bond parallel to close packed interface – (cos /a )*1/a

Additional broken bonds out of closed packed plane - (sin /a )*1/a

Surface energy per unit area = {(cos  + sin )/a2}*(0.5)

32

16
 1/19/2023

Variation of Surface Energy with ‘’

33

Wulff Construction

For FCC

Gives estimation of equilibrium shape of isolated single

crystal when constructed in 3D
34

17
 1/19/2023

Surface Layers of Nanoparticles

 Important because surface area increases with decrease
in size

Considering 10 nm nanoparticle, 49% of it’s atoms would

be on surface

35

Surface Area in Nanomaterials

 Controlling free energy through minimizing the surface

area by

Homogeneous Means – Shape or configuration change

Heterogeneous Means – Introducing second phase on top of

surface

36

18
 1/19/2023

Surface Reconfiguration – to reduce

energy

Two Ways

 Homogeneous Relaxation and Construction – structural

alteration

Heterogeneous adsorption – second medium on surface

37

Surface Relaxation

Vertical Surface Lateral Surface

Relaxation Relaxation

38

19
 1/19/2023

Surface Reconstruction
 Change in relative position of atoms on surface to
minimize energy

Si (100) surface before and after reconstruction

39

Adsorption
 Surface atoms attract other atoms or molecules to
decrease surface energy

Adsorbates can sit on different sites and are named

accordingly

40

20