EEE 3394

Electronic Materials
Fall 2015
WEEK 2

Kinetic Molecular Theory

KMT of gases
What is it? What do we need
from Newtons 2nd Law
it for?
dp/dt=Force
Links the macroscopic
properties of gases and
solids to the kinetic energy
of atoms/molecules;
Explains the pressure of
Empirical
gases heat capacity of
Result
metals average speed of
N
electrons in
RT
PV
semiconductors etc.
NA
Assumes that
atoms/molecules of gases, See assumptions in text .
liquids, solids are in
..molecules in constant motion ..
constant motion when
collision time negligible
above absolute zero
compared to free motion ..
temperature
collisions are elastic .. no
effect from external forces etc.

Derivation
Consider N molecules inside
a cubic volume of side a
The change in momentum of
a molecule that collides
with one of the walls is
Force exerted by gas on a
wall is equal to the rate of
change in momentum
The total pressure is equal to
the total force per unit area

Due to random motion and

collisions, mean square
velocity in x direction2same
as in y and z directions
average velocity is 1/3 of vx

Nmv
P
3V

p 2mv x

p 2mv x
mv x2
F

t (2a )
a
vx
P

2
2
2
2
mv x2
mv x3
.... mv xN
Total force mv x1
mN v x2

a2
a3
a3

Derivation
Compare

Nmv 2 2 1
PV
N
mv 2
2
3
3

N
RT
PV
NA
where k is Boltzmans
constant
Therefore
the mean square velocity is
proportional to T! adding
heat to a gas raises its
temperature and total
internal energy!
Rise in internal energy per
unit temperature HEAT

1
3 R
3
2
KE mv
T kT
2
2 NA
2

Heat Capacity
... Energy (U) increase per
unit temperature (T)

dU
C
dT

Molar Heat Capacity Cm:

heat capacity of one mole
for a monatomic gas

3
1
2
U NA mv NAkT
2
2
C

dU 3
3
NAk R
dT 2
2

above based on constant volume because all added

energy is considered to contribute to the temperature rise
and not volume expansion (i.e. doing work to increase
volume)

Maxwells Principle of
Equipartition of Energy
Ix=0
... assigns 1/2kT to each
independent way
(degrees of freedom) a
molecule can absorb
energy

vz

vx

x
z
Iz

For example:
3 degrees of freedom
5 degrees of freedom
z

U 3 kT
2

U 5 kT
x v
y
2

(a)

Iy

yaxisoutofpaper

Degrees of Freedom:
Monatomic gas 3 translational
Diatomic gas 5 3 + 2 rotational
Solid 6 3 kinetic energy of vibration +
3 potential energy of spring i.e. bond stretching
therefore Cm=3R

Molecular Velocity and Energy

Distribution
Relative number of molecules
per unit velocity (s/km)

Term average velocity used to this point

2.5
v*
therefore a range of velocity
values exists
vav
i.e. VELOCITY
vrms
2 DISTRIBUTION
298K (25C)
v*

vavlarger values
Velocities from zero1.5
(at collision) to
vrms

1
1000K
(727C)
The Velocity Distribution is described by
the
MaxwellBoltzmann distribution
function
0.5
0

500

1000
Speed(m/s)

m
nv 4 N

2 kT

2
mv

2kT

v 2e

1500

2000

Maxwell-Boltzmann Distribution for

Translational Energies (monatomic gas)

1
2

kT

With nE being the number of molecules per unit

volume per unit energy at an energy E!
last term is know as the BOLTZMANN factor
Atoms have a range of energies BUT a mean
energy of 3/2kT !
And another important GENERAL relationship
the PROBABILITY that a certain molecule in
a given system will have an energy E

nE
Ce
N

E

kT

1
2

E e

Numberof atomsperunit energy, nE

nE

kT

AverageKEat T1.

T1
AverageKEat T2
T2 > T1

EA

Energy, E

Thermally Activated Processes

Arrhenius Behavior
where the rate of change is
proportional to:
E

kT

The Energy EA is characteristic of

the particular process
What are the consequences of high EA
or raising the temperature?

Thermally Activated Processes

A

A*

U = P E (x )
U

A*

U A= U

A*

B
D is p la c e m e n t

Diffusion of an interstitial impurity atom in a crystal from one void

to a neighboring void. The impurity atom at position A must posses
an energy EA to push the host atoms away and move into the
neighboring void at B.
Fig 1.29

O '
A fte r N ju m p s
L
Y
a
q = 90

q = 0

q = 180

q = 270

Fig 1.30

An impurity atom has four site choices for diffusion to a

neighboring interstitial vacancy. After N jumps, the impurity atom
would have been displaced from the original position at O.

Thermally Activated Processes

DIFFUSION ??
EA for P diffusion in Si is 3.69 eV
D is the diffusion coefficient
and
DO is a constant (10.5 cm2/s)
Rms distance in t seconds is
WATCH out for the units
Start using eV for energy
And K for Temperature
kT at room temp. is 0.0258 eV
D(RT)=1.08x10-61cm2/s
in 5 minutes
L(RT)=8.04x10-26 m
L(200C)=1.74x10-14 m
L(800C)=0.00171 m
L(1100C)=0.134 m

D DO e

EA

kT

L 2Dt

Equilibrium Concentration of
Vacancies
also a thermally activated process

E v
nv N exp
kT
nv = vacancy concentration
N = number of atoms per unit volume
Ev = vacancy formation energy

Phase and Phase

Diagram
Phase: a HOMOGENEOUS portion of a chemical system that has same
structure, composition and properties everywhere.
Phase Diagram: A Temp vs Phase diagram in which various phases of a
system are identified by lines and regions.

Liquidus
Solidus
Isotherm or Tie
line
Melting Point

100% Cu

100% Ni

Phase Diagrams T vs. Composition

Isomorphous ??
same morphology
everywhere
For pure Cu (or Ni) T
remains constant as
liquid solidifies (or
solid melts)
Not for alloy; i.e.
temperature does
not remain constant
as liquid solidifies (or
solid melts)
Initial crystal
formation
nucleation

Phase Diagram
Liquid

LIQUID

SO
LID
US

L0
1300
L0:
all liquid
L1:
S(36%Ni)
nucleation begins
L1
S1
1200
what is the composition of the L(20%Ni)
solid?
L2
X
S2
go to S1
L
3
(28%Ni)
S3
what is the composition of the S
SOLID
(13%
N
i)
L
(-PHASE)
liquid?
1100
go to L1
S4
X:
S(20%Ni)
both solid and liquid
what are the compositions of the
1000
solid and liquid?
0
20
40
60
go to S2 and L2
wt.%Ni
PureCu C0
what fraction is solid and what
fraction is liquid?
C CO 0.28 0.20
Use Lever Rule
WL S

53.3%
C

C
0.28

0.13
S3:
S
L
opposite of L1; i.e. nearly all
solid!
C CL 0.20 0.13
What is the composition of the
WS O

46.7%
CS CL 0.28 0.13
solid and liquid?
go to S3 and L3

TEMPERATURE(C)

L(20%Ni)

LIQ
UI
DU
S

What Happens @

Phase Diagrams Binary

Eutectic
Solvus Curve:
defines the
solubility limit
boundary

400
L

L IQ U ID

M
N

300

+ L

Eutectic
Point/Temperature:
Composition of alloy
that results in the
lowest melting point
temperature
TWO solid phases
(different
compositions and
Structures):
Pb-rich and Sn rich

200

S O L ID U S
C
18 3 C
1 9 .2 %

L+
S O L ID U S D

6 1 .9 %

Q '

9 7 .5 %

100

SO L ID U S

R'

R ''

0
0
P ure P b

20

40
60
80
C o m p o s it io n in w t .% S n

100
P u re S n

The equilibrium phase diagram of the Pb-Sn alloy. The microstructures

on the left show the observations at various points during the cooling of
a 90%Pb-10%Sn from the melt along the dashed line (the overall alloy
composition remains constant at 10 %Sn)

Pb-Sn Binary Eutectic:

10% Sn
Point Q
M:
N:
O:
P:
R:
L:
Both
What
Nearly
All
First
solid
solid
nuclei
Lisand
all
the
a;
a
solid
and
appears
a;
of
phase

;
a;
begin
Composition
content
nucleation
to form
of the
ofbegins;
a?
alloy? (L
i.e.+ a);
liquid

composition:
10%
Sn
small
what
Composition
fraction
amount
of
is
ofa-phase
and
fraction
is L?
What
Composition:
Whatis
are
the
the
composition
10%
compositions?
Sn 4 0what
of
the
last
drops
of
0
What
is the
liquid?
L
L
composition of
A
What
USE
3%
Sn
LEVER
isthe
98%
RULE
Sn
the -phase?
L IQ U ID
M
300
N
composition
C
ofL
O
a=0.07
Go across to the
B
the
How
-phase?
much
is
?

+
L
C
solidus
line and
L=0.15
L+

E
SO L ID U S
200
S O L ID U S
S O L ID U S D
C

read
it!

0.07
P
And
how
much
is
a?
18 3C
9 7 .5 %
1 9 .2 %
6 1 .9 %
CO=0.10

Q '
Q
Go
to the
Whatacross
is the

100

composition
of and
solvus
USE
LEVER
line
RULE

the L-phase?
read it!
R ''
R' R

CO Ca 0.10 0.07
W

the
37.5%
Go
across
to
L
C

C
0.98

0.10
0.07 92.6%
a O 0.15
W CL Cline

liquidus
and
C C 0.98 0.03
read it! 0.015

W
0S

Pure Pb

CO CL 0.20 0.13
40
46.7%
60
80
100
CS 20 CL C o 0.28

0.13
P
u
re S n
m p o s it io n in w t .% S n

Lever Rule
Lever Rule: a tool to determine
% wt of each phase of a binary
equilibrium phase diagram.

End of Chapter 01
Excluded Book Sections
1.3.6
1.4.2
1.6
1.8.3
1.9.4, 1.9.5
1.10
1.11
1.13
Suggested Example Problems
1.2, 1.7, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17