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Ch05 Diffusion
Ch05 Diffusion
DIFFUSION IN SOLIDS
ISSUES TO ADDRESS...
• How does diffusion occur?
Chapter 5- 1
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
Chapter 5- 2
DIFFUSION: THE PHENOMENA (1)
• Interdiffusion: In an alloy, atoms tend to migrate
from regions of large concentration.
Initially After some time
Adapted from
Figs. 5.1 and
5.2, Callister
6e.
Cu Ni
100% 100%
0 0
Concentration Profiles Concentration Profiles
Chapter 5- 3
DIFFUSION: THE PHENOMENA (2)
• Self-diffusion: In an elemental solid, atoms
also migrate.
Chapter 5- 4
DIFFUSION MECHANISMS
Substitutional Diffusion:
• applies to substitutional impurities
• atoms exchange with vacancies
• rate depends on:
--number of vacancies
--activation energy to exchange.
Chapter 5- 5
DIFFUSION SIMULATION
• Simulation of
interdiffusion
across an interface:
• Rate of substitutional
diffusion depends on:
--vacancy concentration
--frequency of jumping.
Chapter 5- 6
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 (Courtesy P.M. Anderson)
Chapter 5- 8
PROCESSING USING DIFFUSION (2)
• Doping Silicon with P for n-type semiconductors:
• Process:
0.5mm
1. Deposit P rich
layers on surface.
3. Result: Doped
light regions: Si atoms
semiconductor
regions.
Jx Unit area A
Jz x through
z which
• Flux can be measured for: atoms
--vacancies move.
--host (A) atoms
--impurity (B) atoms
Chapter 5- 10
CONCENTRATION PROFILES & FLUX
• Concentration Profile, C(x): [kg/m3]
Cu flux Ni flux
Position, x
• Fick's First Law:
Diffusion coefficient [m 2 /s]
flux in x-dir.
[kg/m 2 -s] dC
Jx D concentration
dx gradient [kg/m 4 ]
• The steeper the concentration profile,
the greater the flux!
Chapter 5- 11
STEADY STATE DIFFUSION
• Steady State: the concentration profile doesn't
change with time.
Steady State:
J x(left) J x(right) J x(left) = J x(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
10
• Q: How much 5m
m
m
m
carbon transfers
from the rich to C2 C 1 9 kg
J D 2 .4 10
the deficient side? x2 x 1 m 2s
Chapter 5- 13
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 2
dt dx Chapter 5- 14
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 Adapted from
t2 Fig. 5.5,
t1 Callister 6e.
C o to
position, x
• General solution: C(x, t ) C o x
1 erf
2 Dt
Cs Co
"error function"
Values calibrated in Table 5.1, Callister 6e.
Chapter 5- 15
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 s Co
C(x i, t i ) C o x
1 erf i = (constant here)
Cs Co 2 Dt
i
Chapter 5- 17
DATA FROM DIFFUSION DEMO
ln[x(mm)]
4
BB
BBBB
3.5 BB
B B
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)]
600
300
T(C)
10 -8 C in D has exp. dependence on T
- Recall: Vacancy does also!
2
D (m /s) Fe Ci
n
-Fe Dinterstitial >> 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
Cu
10 -20
0.5 1.0 1.5 2.0 1000K/T
Adapted from Fig. 5.7, Callister 6e. (Date for Fig. 5.7 taken from E.A.
Brandes and G.B. Brook (Ed.) Smithells Metals Reference Book, 7th ed., Chapter 5- 19
Butterworth-Heinemann, Oxford, 1992.)
SUMMARY:
STRUCTURE & DIFFUSION
Diffusion FASTER for... Diffusion SLOWER for...
• cations • anions