Imperfections: Good or Bad?

• Structural imperfections (defects)

• Compositional imperfections (impurities)

1
 Structural Imperfections
• A perfect crystal has the lowest internal
energy E
• Above absolute zero at constant volume, the
system responds by minimizing the free
energy F = E - TS, where T is the absolute
temperature and S entropy

2
Structural Imperfections
Equilibrium
defect
concentration
E

F = E – TS

Defect
concentration

–TS
3
 Compositional Imperfections
• Impurities always present in materials
• Without impurities, semiconductor devices
and advanced engineering materials not
possible
• Si devices cannot function without low-
level impurities
• Silver not useable as utensils without
addition of copper
4
 Solid Solutions
• Consider addition of Ni into Cu (both FCC)
• Ni atoms occupy Cu sites
• Substitutional solid solution
• Rules of miscibility
– Atomic size
– Crystal structure
– Electronegativity
– (Valence)
5
 Ni/Cu
• Atomic size: 0.125 nm vs 0.128 nm
• Crystal structure: both FCC
• Electronegativity: 1.91 vs 1.90
• Valence: both +2

Fully miscible

6
 Zn/Cu
• Atomic size: 0.139 nm vs 0.128 nm
• Crystal structure: HCP vs FCC
• Electronegativity: 1.65 vs 1.90
• Valence: both +2

Cu can only dissolve 38 at. % Zn

7
 Solid Solutions
• Consider addition of Ni into Cu (both FCC)
• Ni atoms occupy Cu sites
• Substitutional solid solution
• Rules of miscibility
– Atomic size Minimize elastic strain
– Crystal structure Minimize elastic strain
– Electronegativity Minimize chemical reactivity
– (Valence) and possibly elastic strain

8
 Two Types of Solid Solutions
• Substitutional - impurity or solute atoms
occupying regular lattice sites, e.g., Ni in
Cu
• Interstitial - impurity or solute atoms
occupying “holes” between lattice sites,
e.g., C in Fe
– Applicable for small atoms, e.g., C
– Low solubility

9
 Intrinsic Point Defects
• Interstitials
• Vacancies, produced by
– thermal excitation
⎛ Q ⎞
vacancy N = N exp⎜
⎜− v⎟⎟
(missing v kT
⎝ ⎠
atom)
– energetic particle
bombardment, e.g., neutron
irradiation in a nuclear
interstitial
€ reactor
site

0D defects 10
Frenkel and Schottky Defects
Frenkel
defect

Schottky
defects

Result: lower density Result: no density change

11
 Point Defects in Ionic Crystals
Consider the following 3 situations:
1. Generation of a cation (+ve) vacancy in
stoichiometric NaCl
2. Loss of oxygen from TiO2
3. Introduction of oxygen in NaCl

12
 Line Defects
• Edge Dislocations
• Screw Dislocations

1D defects 13
 Edge Dislocation
Inserting an extra half-plane of atoms into the crystal

Region of
compression
b

Region of
tension

14
 Edge Dislocation
• Formed by having an extra half-plane of
atoms
• One part under compression, one part under
tension
• Scavenger of impurity atoms (Cottrell
atmosphere)
• Important in controlling plastic deformation

15
Motion of Dislocation under
Shear Stress

16
Screw Dislocation

17
 Grain Boundaries
• Transition regions between grains
• More open structure
• Segregation of impurity atoms
• Obstacles against dislocation motion,
transport of electrons and lattice vibrations
(charge and heat)

2D defects 18
 Precipitates
• Addition of C to Fe forms Fe3C
• Addition of Cu to Al forms various CuAl
intermetallic compounds
• These form precipitates that are harder than
the matrix, improving mechanical
properties

3D defects 19
 Atomic Diffusion
• Without defects such as vacancies or
interstitials, atomic diffusion would have
been very slow, and useful engineering
materials could not have been produced
• Diffusion as a musical chair process,
facilitated by atoms jumping into adjacent
vacancies or interstitial sites.

20
 Atomic Diffusion
• Jumping out of vacancies or interstitials
requires the breaking of bonds
• Correlation between activation energy for
diffusion and bond energy, e.g.,
– Al: activation energy for diffusion = 165
kJ/mole; melting point = 660 C
– Mo: activation energy for diffusion = 460
kJ/mole; melting point = 2600 C
21
 Fick’s Laws
dC J = # diffusing atoms crossing
1st Law J = −D
dx unit area per unit time

C = atom concentration
2
∂C ∂C
2nd Law =D 2 x = position, t = time
€ ∂t ∂x

where D is the diffusion constant or

diffusivity
€ ⎛ Q ⎞ Q = activation energy for
D = Do exp⎜− ⎟ diffusion, T = temperature
⎝ kBT ⎠
22
 Activation Energy for Diffusion
• Correlates with bond strength
• Depends on the openness of the diffusion
path compared with atomic size, e.g.
– C in BCC iron (900K): D = 1.710-10 m2/s
– C in FCC iron (900K): D = 5.9 10-12 m2/s
• Grain boundaries more open --> smaller D
• Surface diffusion fastest
23
 Activation Energy for Diffusion
Diffusion aided by other factors
• Electrical currents - electromigration
• Additional vacancies e.g., neutron irradiation
• Stress gradient Minimize strain energy

24
 Diffusion Profile for a 1D
Concentration Step
1.2
Cs
1 Cx − Co ⎛ x ⎞
= 1− erf ⎜ ⎟
Cs − Co ⎝ 2 Dt ⎠
0.8

0.6

0.4
€
t=0 t=1 t=4
0.2
concentration C(x)
Co
0
-0.5 0.5 1.5 2.5 3.5
position (x)

25
 Error Function
z
2
erf (z ) =
π
∫ exp(−y 2 )dy
0

1.2
1
€ 0.8
0.6
erf(z)
0.4
0.2
0
0 0.5 1 1.5 2 2.5
z 26
 Diffusion Distance

xRMS = 2Dt
1. Heat diffusion follows the same equation as Fick’s
second law
2. Average heat diffusion distance = (2kt)1/2, where k is
known as thermal diffusivity

27
 Heat Diffusion Distance

x RMS = 2kt
• For xRMS = 1 cm, k ~ 1 cm2/sec (estimated for pure Cu)
• Solving, t = 0.45 sec.
• Estimate actual time to temperature ~ 3t = 1.35 sec.

€ Actual experimental value?

28
 Example: Case Hardening
• Diffuse carbon into steel surface to increase
surface hardness (hard case)
• Gas carburizing or plasma carburizing using a
carbon-containing gas
• Typical carbon concentration in the % range
• Surface concentration Cs controlled by gas
pressure

29
Example: Impurity Diffusion into
Silicon
• Diffuse impurity atoms into silicon to change
electrical properties
• Concentration in the ppm range
• Impurity atoms usually introduced in the form of
hydrides, e.g. use PH3 to introduce P
• Surface concentration controlled by pressure of
dopant gas molecules

30
 Diffusion in Biological Systems
• Diffusion of small molecules such as oxygen,
carbon dioxide, water and ethanol through cell
membranes - passive diffusion (based on
concentration gradient)
• Major component of cell membrane is the
phospholipid double layer
• Molecules dissolve in the phospholipid double
layer and diffuse across the cell membrane, e.g.,
osmosis
31
 Facilitated Diffusion
• Certain biochemical processes require
diffusion of species not soluble in the
phospholipid double layer, or opposite to
concentration gradient
• Diffusion of ions, charged molecules (e.g.,
amino acids), or large polar molecules (e.g.,
sugar molecules) across cell membrane -
facilitated diffusion
32
 Facilitated Diffusion
Phospholipid
double layer Transported Carrier
molecule protein

(a) (b)

(c) (d)

33
 Facilitated Diffusion
Transported ions

Phospholipid Ion channel with Ion channel

double layer gate closed with gate open

(a) (b)
34
 Ion Channels
• Important for transmission of nerve
impulses
• Fast diffusion - 1000 ions/sec
• For membrane thickness of 10 nm, this
corresponds to a diffusivity of 510-11
m2/sec at 37 C
• As a comparison, diffusion of C in steel is
about 10-10 m2/sec at ~1000 C
35
 What have we learned from
Chapter 2
• Impurity atoms go into substitutional or
interstitial sites (solid solutions)
• Four rules of solubility or miscibility
• Defects (0D, 1D, 2D and 3D)
• Diffusion as a musical chair process
– Related to bond strength
– Fick’s laws
– Application in steels, semiconductor and
biological systems 36