3/3/2011

CHAPTER 6:
DIFFUSION IN SOLIDS

Diffusion ‐ Mass transport by atomic motion.
Movement of a atom from an area of high 
concentration of that an area of lower concentration

Gases & Liquids – random motion
Solids – vacancy diffusion or interstitial diffusion

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• Interdiffusion: In an alloy, atoms tend to migrate

from regions of high conc. to regions of low conc.

Initially After some time

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

migrate.

Label some atoms After some time

C
C
A D
A
D
B
B

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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

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Diffusion Simulation
• Simulation of
interdiffusion
across an interface:

• Rate of substitutional
diffusion depends on:
--vacancy concentration
--frequency of jumping.

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• Interstitial diffusion – smaller atoms can 
diffuse between atoms.

More rapid than vacancy diffusion

Processing Using Diffusion
• Case Hardening:
--Diffuse carbon atoms
into the host iron atoms
att the
th surface.
f
--Example of interstitial
diffusion is a case
hardened gear.

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

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Processing Using Diffusion
• Doping silicon with phosphorus for n-type semiconductors:
• Process: 0.5 mm

1 Deposit P rich
1.
layers on surface.
magnified image of a computer chip
silicon

2. Heat it.
3. Result: Doped
p light regions: Si atoms
semiconductor
regions.

light regions: Al atoms

silicon

Diffusion
• How do we quantify the amount or rate of diffusion?

moles (or mass) diffusing mol kg

J ≡ Flux ≡ = or
(surface
f area )(time
ti ) 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=
mass J ∝ slope
diffused
time

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MODELING DIFFUSION:  FLUX

x-direction
• Flux:

Unit area A
through
1 dM ⎡ kg
g⎤ ⎡ atoms⎤
J= ⇒⎢ ⎥ or ⎢ 2 ⎥ which
A dt ⎣m2s ⎦ ⎣ m s ⎦ atoms
move.

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STEADY STATE DIFFUSION
• Steady State: the concentration profile doesn't
change with time.

Jx(left) Jx(right)

x
Concentration, C, in the box doesn
doesn’tt change w/time.

Steady State:
Jx(left) = Jx(right)

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Steady‐State Diffusion
Rate of diffusion independent of time
dC
Flux proportional to concentration gradient =
dx

C1 C1 Fick’s first law of diffusion

dC
C2 C2 J = −D
dx
x1 x2 D ≡ diffusion coefficient
x

dC ΔC C2 − C1
if linear ≅ =
dx Δx x2 − x1
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• Fick's First Law:

flux in x-dir. Diffusion coefficient [m2/s]

[kg/m2-s] dC
Jx = − D concentration
dx gradient [kg/m4]

• Th
The steeper
t the
th concentration
t ti profile,
fil
the greater the flux!

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Diffusion and Temperature
• Diffusion coefficient increases with increasing T.

⎛ Qd ⎞
D = Do exp⎜− RT ⎟
⎝ ⎠

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]

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Diffusion and Temperature
D has exponential dependence on T
1500

1000

600

300

T(°C)
( )
6

10-8

D (m2/s) Dinterstitial >> Dsubstitutional

C in α-Fe Al in Al
10-14 C in γ-Fe Fe in α-Fe
Fe in γ-Fe

10-20
0.5 1.0 1.5 1000 K/T

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Other Diffusion paths

• Diffusion may also occur through Grain Boundaries,

External Surface.
Surface

ƒ This called Short Circuit diffusion

6.7 A sheet of steel 2.5 mm thick has nitrogen atmospheres on both

sides at 900 C and is permitted to achieve a steady-state diffusion
condition. The diffusion coefficient for nitrogen in steel at this
temperature is 1.2 x 10-10 m2/s, and the diffusion flux is found to be 1.0
10-7 kg/m2-s. Also, it is known that the concentration of nitrogen in the
steel at the high-pressure surface is 2 kg/m3. How far into the sheet
from this high
high-pressure
pressure side will the concentration be 0.5 0 5 kg/m3?
Assume a linear concentration profile.

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