DIFFUSION IN SOLIDS

• How does diffusion occur?

• Why is it an important part of processing?

• How can the rate of diffusion be predicted for some simple

cases?
• How does diffusion depend on structure and
temperature?

ESO205: Nature & Properties of Materials Instructor: Dr. Anish Upadhyaya

 DIFFUSION: THE PHENOMENA (1)
• Interdiffusion: In an alloy, atoms tend to migrate from regions
of
Initially large concentration. After some time

Cu Ni
100% 100%

0 0
Concentration Profiles Concentration Profiles
Interdiffusion
 DIFFUSION: THE PHENOMENA (2)

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

Label some atoms After some time

C
C
A D
A
D
B
B
 DIFFUSION MECHANISMS
Substitutional Diffusion:
• applies to substitutional impurities
• atoms exchange with vacancies
• rate depends on:
--number of vacancies
--activation energy to exchange.

increasing elapsed time

Mechanisms of Diffusion
 DIFFUSION SIMULATION
• Simulation of interdiffusion across an interface:

• Rate of substitutional diffusion depends on:

--vacancy concentration
--frequency of jumping.
 INTERSTITIAL SIMULATION
• Applies to interstitial impurities.
• More rapid than vacancy diffusion.
• Simulation:
--shows the jumping of a
smaller atom (gray) from
one interstitial site to
another in a BCC
structure. The
interstitial sites
considered here are
at midpoints along the
unit cell edges.
 PROCESSING USING DIFFUSION (1)
• Case Hardening:
--Diffuse carbon atoms
into the host iron atoms
at the surface.
--Example of interstitial
diffusion is a case
hardened gear.

• Result: The "Case" is

--hard to deform: C atoms
"lock" planes from shearing.
--hard to crack: C atoms put
the surface in compression.
 PROCESSING USING DIFFUSION (2)
• Doping Silicon with P for n-type semiconductors:
• Process:
0.5mm
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
 MODELING DIFFUSION: FLUX
• Flux:
1 dM  kg  atoms 
J    or  
A dt 2
m s  2
 m s 
• Directional Quantity x-direction
y J
y

Jx Unit area A
Jz x through
z which
• Flux can be measured for: atoms
--vacancies move.
--host (A) atoms
--impurity (B) atoms
 CONCENTRATION PROFILES & FLUX
• Concentration Profile, C(x): [kg/m3]
Cu flux Ni flux

Concentration Concentration
of Cu [kg/m 3 ] of Ni [kg/m 3 ]

Position, x
• Fick's First Law:
flux in x-dir. Diffusion coefficient [m 2 /s]
[kg/m 2 -s] dC
Jx   D concentration
dx gradient [kg/m 4 ]
• The steeper the concentration profile,
the greater the flux!
 STEADY STATE DIFFUSION
• Steady State: the concentration profile doesn't
change with time.
Steady State:
J x(left) J x(right) J x(left) = Jx(right)
x
Concentration, C, in the box doesn’t change w/time.
dC
• Apply Fick's First Law: J x  D
dx
dC  dC 
• If Jx)left = Jx)right , then     
dx left dx right

• Result: the slope, dC/dx, must be constant

(i.e., slope doesn't vary with position)!
 EX: STEADY STATE DIFFUSION
• Steel plate at /m
3
kg
700C with =1
.2
/m
3
C1 kg
geometry =0
.8
shown: Carbon C2 Steady State =
rich straight line!
gas Carbon
deficient
gas
D=3x10 -11 m 2 /s
0 x1 x2

10
5m
• Q: How much

m
m

m
carbon transfers
from the rich to C2  C1   9 kg
J  D 2.4  10
the deficient side? x2  x 1 m 2s
 NON STEADY STATE DIFFUSION
dx
• Concentration profile,
C(x), changes J(left) J(right)
w/ time.
Concentration,
C, in the box
• To conserve matter: • Fick's First Law:
J (right)  J (left)  dC dC
 J  D or
dx dt dx
dJ  dC dJ  d2 C (if D does
 D not vary
dx dt dx dx 2 with x)
equate
• Governing Eqn.:
dC d 2C
=D
dt dx 2
 EX: NON STEADY STATE DIFFUSION
• Copper diffuses into a bar of aluminum.
Surface conc.,
C s of Cu atoms bar
pre-existing conc., C o of copper atoms
C( x,t)
Cs

t3
t2
t1
to
Co
position, x
• General solution: C(x, t)  C o   x 
1  erf  
2 Dt 
Cs  Co
"error function"
 PROCESSING QUESTION
• Copper diffuses into a bar of aluminum.
• 10 hours at 600C gives desired C(x).
• How many hours would it take to get the same C(x)
if we processed at 500C?
Key point 1: C(x,t500C) = C(x,t600C).
Key point 2: Both cases have the same Co and Cs.
• Result: Dt should be held constant.
C (x ,t)  Co  x 
= 1  erf  
 2Dt 
(Dt) 500ºC =(Dt) 600ºC
C C
s o
5.3 x10 -13 m 2 /s 10hrs
(Dt) 600
• Answer: t 500   110 hr
D 500
4.8x10 -14 m 2 /s
Grube Solution to Fick’s Second Law

Cm  C  x 
 erf  
Cm  C1  2 Dt 
(C  C2 )
Cm  1
2
Van Ostrand - Dewey Solution to Fick’s Second Law

C2  C  x 
 erf  
C2  C1  2 Dt 
 DIFFUSION DEMO
• Glass tube filled with water.
• At time t = 0, add some drops of ink to one end
of the tube.
• Measure the diffusion distance, x, over some time.
• Compare the results with theory.

to x (mm)
t1
t2
t3
time (s)
xo x1 x2 x3
 DIFFUSION DEMO: ANALYSIS
• The experiment: we recorded combinations of
t and x that kept C constant.
to
t1
t2
t3
xo x1 x2 x3
 
C(x i , t i )  Co x
 1 erf 

i 
 = (constant here)
Cs  Co 
2 Dt i 

• Diffusion depth given by:

x i  Dt i
 DATA FROM DIFFUSION DEMO
( )
4 B
BBBB
3.5 BB
BBB

B B
3 B
B
2.5
2 Linear regression fit to data:
1.5 ln[ x(mm )]  0.58 ln[ t(min)]  2.2
1 R2  0.999
0.5
0
0 0.5 1 1.5 2 2.5 3
ln[t(min)]

• Experimental result: x ~ t0.58

• Theory predicts x ~ t0.50
• Reasonable agreement!
 DIFFUSION AND TEMPERATURE
• Diffusivity increases with T.
pre-exponential [m 2 /s] (see Table 5.2, Callister 6e )
activation energy
 Q  [J/mol],[eV/mol]
diffusivity D  Do exp  d  (see Table 5.2, Callister 6e )
 RT 
gas constant [8.31J/mol-K]
• Experimental Data:
1500
1000

600

300
T(C)
10 -8 D has exp. dependence on T
C
in

D (m 2 /s) Ci Recall: Vacancy does also!

-

n
Fe

-Fe D interstitial >> D substitutional

10 -14 C in -Fe Cu in Cu
Zn

C in -Fe Al in Al
Fe

in Cun 

Al

Fe in -Fe
Cu in -Fe
F

in
in
ei e

Fe in -Fe
Al
 -F

Zn in Cu
10 -20
Cu

0.5 1.0 1.5 2.0 1000K/T

 SUMMARY: STRUCTURE & DIFFUSION
Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• lower melting T materials • higher melting T materials

• materials w/secondary • materials w/covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• cations • anions

• lower density materials • higher density materials