SOLID STATE DIFFUSION

Solid state diffusion refers to the movement of atoms in solids

which is accompanied by a change of concentration of the
components in certain zones of the solids.

A prerequisite for solid state diffusion is the presence of

imperfections in the crystal structure. Solid state diffusion
can hardly take place without imperfections. Large amount
of activation energy will be required for solid state diffusion
in a perfect crystal.
 Solid state diffusion

 Mass flow process by which species change their position relative to

their neighbours
 Driven by thermal energy and a gradient
 Thermal energy → thermal vibrations → Atomic jumps

Concentration / chemical potential

Gradient Electric

Magnetic

Stress
 Processing Using Diffusion
• Case Hardening:

-- Diffuse carbon atoms

into the host iron atoms
at the surface.
-- Example of interstitial
diffusion is a case
hardened gear.

• Result: The presence of C atoms makes iron (steel) harder.

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.

light regions: Al atoms

silicon
Adapted from Figure 18.27, Callister &
Rethwisch 8e. 4
 Thermally activated processes
Arrhenius equation for thermally activated process:
Q
rate  Ce RT
where:
C is a constant (rate w/o temperature)
Q is activation energy
T is absolute temperature

Some of the thermally activated processes are formation of point

defects, case hardening, manufacturing of microchips, creep rate, solid
state diffusion, electrical conductivity etc
Activation energy for solid state diffusion:
It is the energy barrier that must be overcome by thermal
activation so that an atom from one stable position goes to
another stable position

Process path showing how an atom must overcome an activation

energy, q, to move from one stable position to a similar adjacent
position.
 Estimation of activation energy

Q
rate  Ce RT

where:
C is a constant (rate w/o temperature)
Q is activation energy
T is absolute temperature

Note: this is a “Semi-log” plot

 Diffusion mechanism

• vacancy mechanism

• Interstitial mechanism

• Interchange mechanism
 Vacancy mechanism:

Atomic migration (“Diffusion”) occurs by a mechanism of vacancy migration.

Note that the overall direction of material flow (the atom) is opposite to the
direction of vacancy flow.

So diffusion
is faster at
higher
temperature
since more
vacancies
will exist in
the lattice!
Vacancy Mechanism
 Diffusion Mechanisms
Vacancy Diffusion:

• atoms exchange with vacancies

• applies to substitutional impurities atoms
• rate depends on:
-- number of vacancies
-- activation energy to exchange.

increasing elapsed time

11
 DIFFUSION MECHANISMS
Interstitial Mechanism
 Diffusion Mechanisms
• Interstitial diffusion – smaller atoms can
diffuse between atoms.

Adapted from Fig. 5.3(b), Callister & Rethwisch 8e.

More rapid than vacancy diffusion

13
 Interstitial mechanism
Diffusion by an ‘interstitialcy’ mechanism illustrates the random-walk
nature of atomic migration (which is quicker as temperature increases)

Diffusion of importance to material engineers is observed to

occur by both mechanisms – vacancy migration and random
moving interstitials
Direct Interchange and Ring
 Types of diffusion

• Self diffusion

•Inter diffusion

•Surface diffusion

•Volume diffusion

• Grain boundary diffusion

• Self-diffusion: In an elemental solid, atoms also migrate.

Label some atoms After some time

C
C
A D
A
D
B
B

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:

Diffusion flux (J):

dC
Concentration gradient( ):dx

Diffusivity (D):

Steady state :

Unsteady state:

Fick’s First Law is for steady state diffusion

Fick’s second law is for unsteady diffusion

Steady state and unsteady state diffusion

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

C 1 C1 Fick’s first law of diffusion

dC
C2 JD
C2
dx
x1 x2 D  diffusion coefficient
x
dC C C2  C1
if linear  
dx x x2  x1

24
 Diffusion and Temperature

• Diffusion coefficient increases with increasing T.

æ Qd ö
D = Do expç- 
è RT ø

D = diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]

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(300ºC) = 7.8 x 10-11 m2/s

Qd = 41.5 kJ/mol

What is the diffusion coefficient at 350ºC?

D transform data ln D

Temp = T 1/T

Q
1 Q
1
ln
D

2ln
D
0
d


and
ln
D1ln
D

0
d



RT

2 RT

1
D
2 Q
 1
d1

ln
D
2
ln
D

1ln
 
 

D
1 RT
2T
1
27
 Q 
d 11

D
2D
1 
exp
  

R T
2 T

1
T1 = 273 + 300 = 573 K

T2 = 273 + 350 = 623 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



D2 = 15.7 x 10-11 m2/s

28
 Quantifying Diffusion:
Fick’s First Law:
dc
“Diffusion flux is proprotional to concentration gradient”
J
dx
dC
JD
dx

moles (or mass) diffusing mol kg

J  Flux   or
surface area time  cm2s m2s
 Fick’s I law
Diffusion coefficient/ diffusivity
No. of atoms dn dc
crossing area A   DA Cross-sectional area
per unit time dt dx Concentration gradient

Matter transport is down the concentration gradient

Flow direction
A

 As a first approximation assume D  f(t)

J  atoms / area / time  concentration gradient

dc
J
dx
dc
J  D
dx
1 dn dc
J  D
A dt dx

dn dc Fick’s first law

  DA
dt dx
 Quantifying Diffusion
Fick’s Second Law:

“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

RHS is the curvature of the c vs x curve

c →
c →

x→ x→

LHS is the change is concentration with time

+ve curvature  c ↑ as t ↑ ve curvature  c ↓ as t ↑

 2

 c  c  x 
 D 2 c( x, t )  A  B erf  
 t  x  2 Dt 
Solution to 2o de with 2 constants
determined from Boundary Conditions and Initial Condition
 Erf () = 1
  Erf (-) = -1
2
Erf     exp u 2

du  Erf (0) = 0
 0  Erf (-x) = -Erf (x)
Exp( u2) →

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 

C(x,t) = Conc. at point x at CS

time t
erf (z) = error function
2 z
y 2 C(x,t)

  0
e dy
Co
erf(z) values are given in the
Table

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 900C
(where, Fe is in FCC form).
Data: D0 (C in  -Fe)  0.7 104 m 2 / s Q  157 kJ / mole

Given: T = 900° C, C0 = C(x, 0) = C(, t) = 0.2 % C,

Cf = C(0.2 mm, t1) = 1% C (at x = 0.2 mm), Cs = C(0, t) = 1.4% C

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 900C using: D  D0 exp  
 RT 

 Q  4  157 103  12 m

2
D  D0 exp    (0.7 10 )exp    7.14 10
 RT   8.314 1173  s

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 1012  t1 
%C 

2
0.6 1  104 
t = t1 = 14580s t1  12    14580 s
0.4 t = 1000s
7.14 10   0.33
t = 7000s
t =0
0.2

0.2 0.4 0.6 0.8 1.0 1.2 1.4

x (in mm from surface) 
 Non-steady State Diffusion
Problem-3:
An FCC iron-carbon alloy initially containing 0.20 wt% C is carburized
at an elevated temperature and in an atmosphere that gives a surface
carbon concentration constant at 1.0 wt%. If after 49.5 h the
concentration of carbon is 0.35 wt% at a position 4.0 mm below the
surface, determine the temperature at which the treatment was
carried out.

 x 
Solution: C ( x , t )  C x  A  B  erf  
 2 Dt 
Boundary conditions: (1) C(o,t) = cs at x = 0

(2) C(x,0) = c o for 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

z  0.90 0.8125  0.7970

z erf(z) 
0.95  0.90 0.8209  0.7970
0.90 0.7970
z 0.8125 z = 0.93
0.95 0.8209

Now solve for D x x2

z D
2 Dt 4z2t
2( 32
x 410
xm) 1
h 
12
1

D
 
2
.
610
x
m/s
2
4
z
t(
4
)
(0
.2 3600
93
)(
49
.
5 s
h)


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

from Table 5.2, for diffusion of C in FCC Fe

Do = 2.3 x 10-5 m2/s Qd = 148,000 J/mol

T = 1300 K = 1027ºC

46
Problem-4:

A 20 mm duralumin plate is covered on both sides by 0.2 mm thick pure

a aluminium sheets. For retaining the corrosion resistance property, the
copper concentration at a depth of 0.1 mm from the outer surface
should not exceed 0.4 %. How long can the material be kept at 823 K
without damaging the corrosion resistance property.

Activation for diffusion = 121 KJ/mole;

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 

Boundary conditions: (1) C(x,0) = 4 % at t = 0 and x < 0

(2) C(x,0) = 0 % at t = 0 and x > 0

 x 
So, A = B = 2 % and erf    0.8
 2 Dt 
Q

D  Do  e RT
 5.2235 10 13 m2 x= 0.10 mm
s
x
Now, from error function table,  0.9
2 Dt

t = time required =5908 sec = 98.5 min

Applications based on Fick’s II law Decarburization of steel
 Carbon atoms diffuse into the surrounding environment from the surface of the component
 Decarburization should be prevented because surface property degrades

Concentration profile Boundary conditions: (1) C(x,0) = C 2 at t = 0 and x < 0

within the component
due to decarburization (2) C(0,t) = C1 at t > 0 and x = 0
for t > 0
C  Concentration
 A = C1
C2  B = C2 – C1
Decarburizing
Steel atmosphere
component

C1

o
Problem-5:

A steel component with carbon content 0.8 % has been decarburized at

950 ˚C for duration of 4 hrs in an atmosphere equivalent to 0 % carbon
at the surface of the component. Determine the minimum depth of
machining to be done so that the carbon content at the surface after
machining is not below 0.6 %.

Given m2 KJ J
Do  0.7 10 4
Q  157 R  8.314
s mol molK

Solution: Here, C2  0.8 C1  0 C ( x, t )  C x  0.6

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 RT
 1.378310 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.

Boundary conditions: (1) C(o,t) = cs at x = 0  C(+x, 0) = Co

(2) C(x,0) = c o for x > 0  C(0, t) = CS

 A = CS
 B = CS – Co
 C(x,t)

Cs C(x,t)

Co
t
x C(x,t)
Problem-6:

In order to manufacture p-type semiconductor boron is doped in pure

silicon. The doping process is carried out using a B2O3 vapour phase at
partial pressure equal to 1.5 Pa. This atmosphere is equivalent to a
surface concentration of 31026 boron atoms per cubic meter. Calculate
the time required to get a boron content of 1023 at a depth of 2 µm.
17 m 2
Given, diffusivity of boron in silicon at doping temperature = 4 10 s
Cs  C x  x 
Solution:  erf  
C s  Co  2 Dt 
Cs  31026 C1  0 C ( x, t )  C x  1023
 x  x
erf    0.99967  2.55
 2 Dt  2 Dt

Putting the values of D and x, we get t = 64.08 min.

 Applications based on Fick’s II law Determination of Diffusivity

‘D’ can be determined experimentally using a diffusion couple.

Steps:
1. The diffusion couple is kept in an atmosphere with high temperature
so that diffusion can take place.
2. It is kept for a fixed time period
3. The diffusion couple is taken out and thin slices of the couple
perpendicular to the diffusion direction are machined out in a
precision lathe.
4. Chemical analysis is carried out to estimate the value of C
(concentration) as a function of x i.e. C = f(x)
5. D is calculated from the available data.
 Applications based on Fick’s II law Determination of Diffusivity

A and B welded together and heated to high temperature (kept constant → T0)

t2 > t1 | c(x,t1) t1 > 0 | c(x,t1) t = 0 | c(x,0)

f(x)|t
C2 Non-steady
Flux state
Concentration →

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 →

 C(+x, 0) = C1  A = (C1 + C2)/2

 C(x, 0) = C2  B = (C2 – C1)/2