Diffusion

Diffusion
• How does diffusion occur?
• Why is diffusion 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?
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 Important Concepts
 Applications of Diffusion
 Activation Energy for Diffusion
 Mechanisms for Diffusion
 Rate of Diffusion (Fick’s First Law)
 Factors Affecting Diffusion
 Composition Profile (Fick’s Second Law)
 Applications of Diffusion
 Nitriding - Carburization for Surface Hardening
of Steels
 p-n junction - Dopant Diffusion for
Semiconductor Devices
 Manufacturing of Plastic Beverage
Bottles/MylarTM Balloons
 Sputtering, Annealing - Magnetic Materials for
Hard Drives
 Hot dip galvanizing - Coatings and Thin Films
 Thermal Barrier Coatings for Turbine Blades
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• Furnace for heat treating steel using carburization.
• Carburizing is the addition of carbon to the surface of
low-carbon steels at temperatures ranging from 1560°F
to 1740°F.
• Hardening is achieved when a high carbon martensitic
case with good wear and fatigue resistance is
superimposed on a tough, low-carbon steel core.
[Link]
 Case Hardening
• Case hardening or surface
hardening is the process of hardening
the surface of a metal, often a low
carbon steel, by diffusing elements into
the material's surface, forming a thin
layer of a harder alloy.
• Carbon atoms diffuse into the iron
lattice atoms at the surface.
• This is an example of interstitial
diffusion.
• The C atoms make iron (steel) harder.

“Carbide band saw blade can cut

through case hardened materials.” 6
Diffusion means atoms moving and changing places. This
happens in solids and liquids, exactly in the same way that
an unpleasant smell moves from one part of a room to
another even without wind, then dissipates after some
time.

Doping means the introduction of impurities into

the semiconductor crystal to deliberately change its
conductivity due to deficiency or excess of
electrons
 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.
3. Result: Doped light regions: Si atoms
semiconductor
regions.

light regions: Al atoms

silicon

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 Atomic Diffusion in Solids
• Diffusion is a process by which a matter is transported
through another material.
• Examples:
 Movement of smoke particles in air : Very fast.
 Movement of dye in water : Relatively slow.
 Solid state reactions : Very slow because of
bonding.

5-2
 Diffusion how atoms move in solids
Diffusion mechanisms
 Vacancy diffusion
 Interstitial diffusion
 Impurities

 Mathematics of diffusion
 Steady-statediffusion (Fick’s first law)
 Nonsteady-State Diffusion (Fick’s second law)

 Factors that influence diffusion

 Diffusing species
 Host solid
 Temperature
 Microstructure

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 What is diffusion?

Diffusion transport by atomic motion.

Inhomogeneous material can become homogeneous by diffusion.

Temperature should be high enough to overcome energy barrier.
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 Inter-diffusion vs. Self-diffusion
Concentration Gradient  Interdiffusion (or Impurity Diffusion).

(Heat)

Before After

Self-diffusion:
one-component material, atoms are of same type.
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 Diffusion Mechanisms (I)
Vacancy diffusion
Atom migration Vacancy migration

Before After

To jump from lattice site to lattice site, atoms need energy to break bonds with
neighbors, and to cause the necessary lattice distortions during jump.
Therefore, there is an energy barrier.
Energy comes from thermal energy of atomic vibrations (Eav ~ kT)

Atom flow is opposite to vacancy flow direction.

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 Diffusion Mechanisms (II)

Interstitial diffusion
Interstitial atom Interstitial atom
after diffusion
before diffusion

Generally faster than vacancy diffusion because bonding of

interstitials to surrounding atoms is normally weaker and
there are more interstitial sites than vacancy sites to jump to.
Smaller energy barrier
Only small impurity atoms (e.g. C, H, O) fit into
interstitial sites.
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 Flux of diffusing atoms, J.
Number of atoms diffusing through unit area
per unit time [atoms/(m2s)]
or
Mass of atoms diffusing through unit area per
unit time [kg/(m2 s)]
Mass: J = M / (A t)  (1/A) (dM/dt)

J
A

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 Steady-State Diffusion
Diffusion flux does not change with time
Concentration profile:
Concentration (kg/m3) vs. position
Concentration gradient: dC/dx (kg / m4)
dC C CA  CB
 
dx x xA  xB

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 Steady-State Diffusion
Fick’s first law: J proportion to dC/dx

dC
J  D D=diffusion coefficient
dx

Concentration gradient is ‘driving force’

Minus sign means diffusion is ‘downhill’: toward

lower
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concentrations
 Nonsteady-State Diffusion
Concentration changing with time
Fick’s second law
C J
 
t x
 2C
 D
x 2
Find C(x,t)

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Atom needs enough thermal energy to break bonds and
squeeze through its neighbors.

Energy needed energy barrier

Called the activation energy Em (like Q)
Ener
gy

Em Vacancy
Atom

Distance

Diagram for Vacancy Diffusion

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Diffusion Thermally Activated Process
 Diffusion – Thermally Activated Process

Room temperature (kBT = 0.026 eV)

Typical activation energy Em (~ 1 eV/atom) (like Qv)

Therefore, a large fluctuation in energy is needed for

a jump.

Probability of a fluctuation or frequency of jump,

Rj R  R exp  
E
 k T
m
 
j 0
B

R0 = attempt frequency proportional to vibration

frequency
20 Swedish chemist Arrhenius
 Calculate Activated Diffusion
1. Probability of finding a vacancy in an adjacent
lattice site :
P  [Link]  
Q
 v k T 
times  B 
2. Probability of thermal fluctuation

R j  R0 exp  
Em
 k BT 
 

The diffusion coefficient = Multiply

D  [Link]    Q 
E
  m k T  exp   V k T 
 B   B 

D  D0 exp  
Qd
 k BT 
 

Arrhenius dependence.
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 Diffusion – Temperature Dependence
dC Diffusion coefficient is the measure of mobility of
J  D
dx diffusing species.
D  D0 exp    D exp   Qd 
Qd
   
 RT  0
 kT 

D0 – temperature-independent (m2/s)
Qd – the activation energy (J/mol or eV/atom)
R – the gas constant (8.31 J/mol-K)
or
kB - Boltzman constant ( 8.6210-5 eV/atom-K)
T – absolute temperature (K)

Q  1  Qd  1 
ln D  ln D0  d   or log D  log D0   
R T  2.3 R  T 

Arrhenius Plots
(lnD) vs. (1/T) or (logD) vs. (1/T)
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 Diffusion – Temperature Dependence (II)

Graph of log D vs. 1/T has slop of –Qd/2.3R,

intercept of ln Do
Qd  1 
log D  log D 0   
2.3R  T 

 log D1  log D 2 
Qd  2.3R  
 1 T1  1 T2 
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 Diffusion – Temperature Dependence (III)

Arrhenius plot:
Diffusivity for metallic systems
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 Diffusion of different species

Smaller atoms diffuse more readily

Diffusion faster in open lattices or in open directions

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 Diffusion: Role of the microstructure (I)

Self-diffusion coefficients for Ag

Depends on diffusion path
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Grain boundaries and surfaces less restrictive
 Diffusion: Role of the microstructure (II)

Plots are from computer simulations

Initial positions are shown by the circles, paths are shown by lines. See
difference between mobility in the bulk and in the grain boundary.
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 Factors that Influence Diffusion
 Temperature - diffusion rate increases very rapidly
with increasing temperature

 Diffusion mechanism - interstitial is usually faster

than vacancy

 Diffusing and host species - Do, Qd is different for

every solute, solvent pair

 Microstructure - diffusion faster in polycrystalline

vs. single crystal materials because of the rapid
diffusion along grain boundaries and dislocation
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cores.
 Diffusion
Diffusion - Mass transport by atomic motion.
Diffusion is a consequence of the constant thermal
motion of atoms, molecules and particles that
results in material moving from areas of high to low
concentration.

Mechanisms
• Brownian motion is the seemingly random
movement of particles suspended in a liquid or gas.
• Solids – vacancy diffusion or interstitial diffusion.
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 Interdiffusion
• Interdiffusion (impurity diffusion): In an alloy, atoms
tend to migrate from regions of high concentration to
regions of low concentration.
After some time

Initially

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

specific atom movement After some time

C
C

A D
A
D
B
B

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 Diffusion Mechanisms
• Atoms in solid materials are in constant motion, rapidly changing
positions.
• For an atom to move, 2 conditions must be met:
1. There must be an empty adjacent site, and
2. The atom must have sufficient (vibrational) energy to break
bonds with its neighboring atoms and then cause lattice
distortion during the displacement.
At a specific temperature, only a small fraction of the atoms is
capable of motion by diffusion. This fraction increases with
rising temperature.
• There are 2 dominant models for metallic diffusion:
1. Vacancy Diffusion
2. Interstitial Diffusion
 Vacancy Diffusion
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurity atoms
• rate depends on:
-- number of vacancies
-- activation energy to exchange.

increasing elapsed time

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 Interstitial Diffusion
• Interstitial diffusion – smaller atoms (H, C, O,
N) can diffuse between atoms.

More rapid than vacancy diffusion due to more

mobile small atoms and more empty interstitial sites.
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 Diffusion
• How do we quantify the rate of diffusion?

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 1 dM mass J  slope
J  diffused
At A dt
time

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 Steady-state diffusion across a thin plate
Rate of diffusion is independent of time; the diffusion flux does not change with
time.

The concentration profile shows the concentration (C) vs the position within
the solid (x); the slope at a particular point is the concentration gradient.
 Steady-State Diffusion

Flux proportional to concentration gradient =

dC
dx

C 1 C1 Fick’s first law of diffusion

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

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 Example 1: Chemical Protective Clothing (CPC)

• Methylene chloride is a common ingredient of paint

removers. Besides being an irritant, it also may be absorbed
through skin. When using this paint remover, protective
gloves are worn.
• If butyl rubber gloves (0.04 cm thick) are used, what is the
diffusive flux of methylene chloride through a glove?
• Data:
– diffusion coefficient for butyl rubber:
D = 110x10-8 cm2/s
– surface concentrations: C1 = 0.44 g/cm3
C2 = 0.02 g/cm3

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 Example 1 (cont).
• Solution – assuming linear conc. gradient
glove
C1 dC C2  C1
tb 
2 J -D  D
paint
6D dx x2  x1
skin
remover
C2 Data: D = 110 x 10-8 cm2/s
x1 x2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm

-8 (0.02 g/cm3  0.44 g/cm3 )

2 -5 g
J   (110 x 10 cm /s)  1.16 x 10
(0.04 cm) cm2s

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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]

Activation energy - energy required to produce the movement of 1 mole of atoms by

diffusion.

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 Factors that influence diffusion

• The diffusing species, host material and temperature influence

the diffusion coefficient.
• For example, there is a significant difference in magnitude
between self-diffusion and carbon interdiffusion in α iron at
500 °C.
 Example 2: At 300ºC the diffusion coefficient and activation energy
for Cu in Si are:

D(300ºC) = 7.8 x 10-11 m2/s

Qd = 41,500 J/mol
What is the diffusion coefficient at 350ºC?

Q
transform data  d 
D ln D D  Doexp
 RT ÷


Temp = T 1/T
Qd  1  Qd  1 
ln D300  ln D0    and ln D350  ln D0   
R  T300  R  T350 
D350 Qd  1 1 
 ln D350  ln D300  ln    
D300 R  T 350 T 300 
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 Example 2 (cont.)
 Qd  1 1 
D2  D1 exp    
 R  T2 T1 

T1 = 273 + 300 = 573 K

T2 = 273 + 350 = 623 K

11 2   41,500 J/mol  1 1 

D2  (7.8 x 10 m /s) exp    
 8.314 J/mol - K  623 K 573 K 

D2 = 15.7 x 10-11 m2/s

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 Nonsteady State Diffusion
• The concentration of diffusing species is a
function of both time and position C = C(x,t).
More likely scenario than steady state.
• In this case, Fick’s Second Law is used.

C C 2

Fick’s Second Law D 2

t x

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 Processing – Ex 6.3
• Copper diffuses into a bar of aluminum.
Surface concentration
Cs of Cu atoms bar
pre-existing concentration Co of copper atoms
• 10 hours at 600˚C gives C(x).
• How many hours would it take to get the same C(x) if processed at 500˚C?
C( x, t )  Co  x 
 1  erf 
Cs  Co  2 Dt 

115.5 hrs
• Answer:
 Non-steady State Diffusion
• Example 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. C( x, t )  Co  x 
 1  erf 
Cs  Co  2 Dt 

• Solution: use Eqn. 6.5 48

Example 3 Solution (1):
C( x ,t )  Co  x 
 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

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Example 3 Solution (2):
We must now determine from Table 6.1 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 4z 2t

 x2  (4 x 103 m)2 1h

D   2    2
 2.6 x 10 11
m 2
/s
 4 z t  (4)(0.93) (49.5 h) 3600 s
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 Q
 d 
Example 4 Solution (3): D  Doexp
 RT ÷

• To solve for the temperature at
Qd
which D has the calculated value, T
we use a rearranged form of R(ln D  ln Do )
Equation (6.9a);
from Table 6.2, for diffusion of C in FCC Fe

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

 148,000 J/mol
T
(8.314 J/mol - K)(ln 2.6x1011 m2 /s  ln 2.3x105 m2 /s)

T = 1300 K = 1027°C

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