Mse Diffusion 1 Student
Mse Diffusion 1 Student
Mse Diffusion 1 Student
Gradient Electric
Magnetic
Stress
Processing Using Diffusion
• Case Hardening:
3
Processing Using Diffusion
• Doping silicon with phosphorus for n-type semiconductors:
• Process: 0.5 mm
1. Deposit P rich
layers on surface.
magnified image of a computer chip
silicon
2. Heat it.
3. Result: Doped light regions: Si atoms
semiconductor
regions.
Q
rate Ce RT
where:
C is a constant (rate w/o temperature)
Q is activation energy
T is absolute temperature
• vacancy mechanism
• Interstitial mechanism
• Interchange mechanism
Vacancy mechanism:
So diffusion
is faster at
higher
temperature
since more
vacancies
will exist in
the lattice!
Vacancy Mechanism
Diffusion Mechanisms
Vacancy Diffusion:
• Self diffusion
•Inter diffusion
•Surface diffusion
•Volume diffusion
17
Interdiffusion:
In an alloy, atoms tend to migrate from regions of high concentration to
regions of low concentrations.
After some time
Initially
18
The interdiffusion of
materials A and B.
Although any given A
or B atom is equally
likely to “walk” in any
random direction, the
concentration
gradients of the two
materials can result in
a net flow of A atoms
into the B material,
and vice versa.
Interdiffusion of copper and nickel
on the microscopic scale.
Quantifying Diffusion
Important terms:
Diffusivity (D):
Steady state :
Unsteady state:
D f(c)
Steady state
J f(x,t)
D = f(c)
Diffusion
D f(c)
Non-steady state
J = f(x,t)
D = f(c)
Diffusion Flux
It is defined as the mass or number of atoms diffusing through and
perpendicular to a unit cross sectional area of solid per unit time.
moles (or mass) diffusing mol kg
J Flux or
surface area time cm s m2s
2
• Measured empirically
– Make thin film (membrane) of known surface area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
membrane
M=
M l dM mass
J slope
J
At A dt diffused
time
23
Steady-State Diffusion
Rate of diffusion independent of time
dC
Concentration gradient =
dx
dC
C2 JD
C2
dx
x1 x2 D diffusion coefficient
x
dC C C2 C1
if linear
dx x x2 x1
24
Diffusion and Temperature
æ Qd ö
D = Do expç-
è RT ø
25
Temperature dependence of diffusivity
Q
Arrhenius type
kT
D D0 e
Problem-1:
At 300ºC the diffusion coefficient and activation energy for Cu in Si are
D transform data ln D
Temp = T 1/T
Q
1 Q
1
ln
D
2ln
D
0
d
and
ln
D1ln
D
0
d
RT
2 RT
1
D
2 Q
1
d1
ln
D
2
ln
D
1ln
D
1 RT
2T
1
27
Q
d 11
D
2D
1
exp
R T
2 T
1
T1 = 273 + 300 = 573 K
12
1
41
,
500
J/m
1
1
D
(
7
2.
810
x
m/s)
exp
8
.
314
J/m
-
K
62
K
57
K
28
Quantifying Diffusion:
Fick’s First Law:
dc
“Diffusion flux is proprotional to concentration gradient”
J
dx
dC
JD
dx
Flow direction
A
dc
J
dx
dc
J D
dx
1 dn dc
J D
A dt dx
“The rate of change of concentration is equal to the rate of change in the magnitude of diffusion flux in the direction of
diffusion”
c x cx
D
t x x
in the usual case where D is
independent of Concentration
cx 2 cx
D 2
t u
Solution to Fick’s second law (Equation 5.10) for the case of a semi-
infinite solid, constant surface concentration of the diffusing species c s ,
initial bulk concentration c0, and a constant diffusion coefficient, D.
We will consider this model as a Non-Steady State (transient) Diffusion system
Fick’s II law
x
Accumulation J x J x x
J
Accumulation J x J x x
Jx Jx+x x
c J Atoms 1 Atoms
x J x J x x m3 s .m m 2 s J
t x
c J c c
x x D Fick’s first law
t x t x x
c c D f(x) c 2c
D D 2
t x x t x
c 2c
D 2
t x
c →
c →
x→ x→
Area
0 u →
Non-steady State Diffusion
• Copper diffuses into a bar of aluminum.
Surface conc.,
Cs of Cu atoms bar
pre-existing conc., Co of copper atoms
Cs
B.C. at t = 0, C = Co for 0 x
at t > 0, C = CS for x = 0 (constant surface conc.)
C = Co for x =
36
Solution:
C x , t Co x
1 erf
Cs Co 2 Dt
37
Applications based on Fick’s II law Carburization of steel
Surface is often the most important part of the component, which is prone to degradation.
Surface hardening of steel components like gears is done by carburizing or nitriding.
Pack carburizing → solid carbon powder used as C source.
Gas carburizing → Methane gas CH4 (g) → 2H2 (g) + C (diffuses into steel).
C(+x, 0) = C1
C(0, t) = CS
Cs
A = CS
B = CS – C1
A 0.2% carbon steel needs to be surface carburized such that the concentration
Problem-2:
of carbon at 0.2mm depth is 1%. The carburizing medium imposes a surface
concentration of carbon of 1.4% and the process is carried out at 900C
(where, Fe is in FCC form).
Data: D0 (C in -Fe) 0.7 104 m 2 / s Q 157 kJ / mole
x
The solution to the Fick’ second law: C ( x, t ) A B erf (1)
2 Dt
The constants A & B are determined from boundary and initial conditions:
C (0, t ) A CS 0.014 , C (, t ) A B C0 0.002 or C ( x, 0) A B C0 0.002
x x
B CS C0 0.012 , C ( x, t ) 0.014 0.012 erf C(x, t) CS (CS-C0) erf
2 Dt 2 Dt
4
2 10-4
C (2 10 m , t1 ) 0.01 0.014 0.012 erf C ( x, t ) C S x
2 Dt = erf
1
C0 CS 2 Dt
1 2 10-4
erf (2)
3 2 Dt
1
C(x,t)
C
s
C(x,t)
medium
Carburizing
Co Component
t
x C(x,t)
The following points are to be noted:
The mechanism of C diffusion is interstitial diffusion
Q
The diffusivity ‘D’ has to be evaluated at 900C using: D D0 exp
RT
1.4 1 2 10-4
From equation (2) erf
3 2 Dt
1.2 1
2 10-4
1.0
t erf 1 (0.3333) 0.309
0.8
2 7.14 1012 t1
%C
2
0.6 1 104
t = t1 = 14580s t1 12 14580 s
0.4 t = 1000s
7.14 10 0.33
t = 7000s
t =0
0.2
x
Solution: C ( x , t ) C x A B erf
2 Dt
Boundary conditions: (1) C(o,t) = cs at x = 0
Cs C x x Cx Co x
erf 1 erf
C s Co 2 Dt Cs Co 2 Dt 42
C(x,t)
C
s
C(x,t)
medium
Carburizing
Co Component
t
x C(x,t)
C( x , t ) Co x
Solution (cont.): 1 erf
Cs Co 2 Dt
t = 49.5 h x = 4 x 10-3 m
Cx = 0.35 wt% Cs = 1.0 wt%
Co = 0.20 wt%
C( x, t ) Co 0.35 0.20 x
1 erf 1 erf ( z )
Cs Co 1.0 0.20 2 Dt
erf(z) = 0.8125
Solution (cont.):
We must now determine from Table 5.1 the value of z for which the
error function is 0.8125. An interpolation is necessary as follows
45
Solution (cont.):
• To solve for the temperature at Qd
which D has the above value, we T
R(lnDo lnD)
use a rearranged form of Equation
(5.9a);
148
,
000
J/m
T
52
12
1
(
8.
314
J/mol
-
K)(ln
2.
3
x10
m/s
ln
2.
6
x10
m/s
46
Problem-4:
R = 8.314 J/mol.K;
2
Do 0.25 10 m
4
s
C(x,t)
Cs
Aluminium Aluminium
sheet Duralumin sheet
(Cu=4%, Al=95%, Mg=0.5%,
Mn=0.5%)
C(x,t)
o t
0.10 mm
0.20 mm 20 mm 0.20 mm
x
C ( x, t ) C x A B erf
2 Dt
C1
o
Problem-5:
Given m2 KJ J
Do 0.7 10 4
Q 157 R 8.314
s mol molK
A = C1
B = C2 – C1
x
C ( x, t ) C x A B erf
2 Dt
C Concentration
x
0.6 C x 0.8 erf
2 Dt 0.8
x 0.6
erf 0.75
2 Dt
Cx
x
0.81
2 Dt
o
Q x
D Do e RT
1.378310 11 m2
s
x 0.81 2 Dt 0.722mm
Applications based on Fick’s II law Doping of semiconductors
p-type semiconductors are manufactured by doping Group XIII element like Boron with
Group XIV element like Si or Ge.
n-type semiconductors are manufactured by doping Group XV element like Phosphorus
with Group XIV element like Si or Ge.
Pure semiconductors like Si or Ge are kept in Boron or Phosphorus rich environment to
manufacture p-type or n-type semiconductors respectively.
Boron or Phosphorus atoms get diffused into Si or Ge.
A = CS
B = CS – Co
C(x,t)
Cs C(x,t)
Co
t
x C(x,t)
Problem-6:
A and B welded together and heated to high temperature (kept constant → T0)
f(t)|x
Cavg If D = f(c)
↑t c(+x,t) c(-x,t)
i.e. asymmetry about y-axis
A B
C1
x →