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## Diffusion and Ficks law

Prof.P. Ravindran,
Department of Physics, Central University of Tamil

http://folk.uio.no/ravi/PMAT2013

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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## Diffusion, flux, and Ficks law

Diffusion:
(1) motion of one or more particles of a system relative to
other particles (Onsager, 1945)

## (2) It occurs in all materials at all times at temperatures

above the absolute zero

## (3) The existence of a driving force or concentration gradient

is not necessary for diffusion

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## Gas Liquid Solid

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## Mass Transport Of Solutes

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## They all depend on

Diffusion (conduction)

## What is diffusion? The transport of material--atoms

or molecules--by random motion

## What is conduction? The transport of heat or electrons

by random motion.

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Diffusion

## Mass transport by atomic motion

Mechanisms
Gases & Liquids random (Brownian) motion

## Cause (Driving force)

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## 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.

x (mm)

time (s)

## Possible to measure concentration

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Mass Transfer
Mass transfer occurs when a component in a mixture goes from one point to
another.

## Convection is the mass transfer between a boundary surface and a moving

fluid or between relatively immiscible moving fluids.

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Example of Mass Transfer
Mass transfer can occur by either diffusion or by convection.

## Stirring the water with

a spoon creates forced
convection.

## That helps the sugar

molecules to transfer to
the bulk water much
faster.

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## After adding milk and

sugar, why do we stir our
coffee?

Diffusion is slow!

## Agitation (or stirring) can move fluids much larger

distances in the same amount of time, which can
accelerate the diffusion process.
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Example of Mass Transfer

Air Blood
Oxygen

## High oxygen concentration Low oxygen concentration

Low carbon dioxide concentration High carbon dioxide concentration

Carbon dioxide

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Diffusion

## Diffusion (also known as molecular diffusion)

is a net transport of molecules from a region of
higher concentration to a region of lower
concentration by random molecular motion.

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Diffusion
A B Liquids A and B are separated from each other.

Separation removed.

## A goes from high concentration of A to low

A B concentration of A.
B goes from high concentration of B to low
concentration of B.

## Molecules of A and B are uniformly distributed

everywhere in the vessel purely due to the
DIFFUSION.

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## Brownian motion causes the ink particles to move erratically

in all directions. A concentration of ink particles will
disperse.
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Concentrated Region

Molecules in a concentrated
region will disperse into the
rest of the medium. C1
x

The difference in
concentrations is the
C2
C C1 C2

x x

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Diffusion Constant

## Different materials pass

through an area at C1
different rates.
x
Depends on concentrate
A
Depends on medium D

## O2 in water: D = 1.0 x 10-9 m2/s

DNA in water: D = 1.3 x 10-12 m2/s

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## Values for Diffusivity D

Temperature Diffusivity
(C) (cm2/s)
CO2-N20 0 0.096
(gas)
Ar-O2 20 0.2
Ethanol(5%)-Water 25 1.13E-05
(liquid)
Water(13%)-Butanol 30 1.24E-05
H2-Ni 85 1.16E-08
(solid)
Al-Cu 20 1.30E-30

## Greater the diffusivity, greater the flux!

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Diffusion & Transport 18

## Whenever there is an imbalance of a commodity in a medium, nature tends to redistribute it until

a balance or equality is established. This tendency is often referred to as the driving force,
which is the mechanism behind many naturally occurring transport phenomena.

## The commodity simply creeps away during

redistribution, and thus the flow is a diffusion
process. The rate of flow of the commodity is
proportional to the concentration gradient dC/dx,
which is the change in the concentration C per unit
length in the flow direction x, and the area A normal
to flow direction.

kdiff is the diffusion coefficient of the medium, which is a measure of how fast a commodity diffuses
in the medium, and the negative sign is to make the flow in the positive direction a positive
quantity (note that dC/dx is a negative quantity since concentration decreases in the flow
direction).
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The diffusion coefficients and thus diffusion rates of gases depend strongly on
temperature.
The diffusion rates are higher at higher temperatures.
The larger the molecular spacing, the higher the diffusion rate.
Diffusion rate: gases > liquids > solids

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## We can develop an understanding of mass transfer in a short time with little

effort by simply drawing parallels between heat and mass transfer.

Temperature
The driving force for mass transfer is
the concentration difference.
Both heat and mass are transferred
from the more concentrated regions to
the less concentrated ones.
If there is no difference between the
concentrations of a species at different
parts of a medium, there will be no
mass transfer.

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Ficks Law
( , , )
x y z
During diffusion we assume particles move in the
direction of least density. They move down the

## In mathematical terms we will

assume

J Du
Where D is a constant of
proportionality called the Diffusion
Born: 1829
Cassel, Germany
Died: 1879

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Ficks Law

## The rate of diffusion depends on the concentration gradient,

area (A) , and diffusion constant (D).
C1 C2
J DA
t

J measures mol/m3.
There is a diffusion time t for diffusion in one direction over
a distance Dx.
x 2
t
2D
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## In each of these examples, molecules (or heat)

are moving down a gradient!

concentration)
dci
Ficks Law: Ji D
dz

## Ji is called the flux. It has units of amount of material diffused

(l 2 )(t )

l2
D is called the diffusion coefficient. It has units of
t

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Mass is transferred by conduction (called diffusion) and convection only.
Rate of mass Ficks law of
diffusion diffusion
DAB is the diffusion coefficient (or
mass diffusivity) of the species in the
mixture
CA is the concentration of the species
in the mixture

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## 4) Transdermal drug delivery

5) Influenza epidemics

6) Chemical reactions

## 7) Absorption of oxygen into the bloodstream

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Back to a drop of ink in a glass
of water If consider diffusion in the z-
direction only:
How does the concentration profile
change with time?
t=0
(add ink drop all
ink located at z =
t
0)
z
z=0
A measure of the spread due to diffusion is the diffusion length
Ld = (4Dt)0.5, where D is the diffusivity coefficient and t is time.
Note: for small time, spreading is quick, but for long times it
slows down. Thats why you stir your coffee after adding
cream. Diffusion doesnt work fast enough over long distances.
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## Ficks first law

c
dc
J D 0
dx
dc x
J D
dx
D diffusion coefficient
c
dc
J D 0
dx
x
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Continuum description of diffusion

## Divide a box of particles into small cubic bins of size L

j+
j

x-L x x+L

j: flux of particles (number of particles per unit area per unit time)
c: concentration of particles (number of particles per unit volume)

Random walk in 1D; half of particles in each bin move to the left and
half to the right.
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Right, left and total fluxes at x are given by

c( x L / 2) AL
1 1
c( x L / 2) AL
j 2
, j 2
At At
j j j
L
c( x L / 2) c( x L / 2)
2t

## Taylor expanding the concentrations for small L gives

L L dc L dc
j c ( x ) c ( x )
2t 2 dx 2 dx

L2 dc dc
D , Fick' s law
2t dx dx
Generalise to 3D: j D c
Flux direction: particles move from high concentration to low concentration

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Conservation laws:
Total number of particles is conserved.
If there is a net flow of particles inside a bin, j j
c(x,t)
the concentration inside must increase by
the same amount.
x-L/2 x x+L/2
c( x, t t ) c( x, t )AL j ( x L / 2) j ( x L / 2)At
c L dj L dj
L j ( x) j ( x)
t 2 dx 2 dx
dc dj

dt dx
dc
j
Generalise to 3D: dt
(similar to charge conservation)
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Integrate the conservation equation over a closed volume V with N parts

dc
dt dV j dV
V V

d

dt V
c dV j n da (Divergence theorem)
S

dN
(rate of change of N = - total flux out)
dt

We can use the conservation equation to eliminate flux from Ficks eqn.
dc dj d 2c dc d 2c
j D , D 2 D 2 nd
dx dx dt Ficks 2 law
dx dx Diffusion eq.

dc
Generalise to 3D: D 2c (analogy with the Schroedinger Eq.)
dt
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Once the initial conditions are specified, the diffusion equation can be
solved numerically using a computer.
Special cases:

## 2. Steady-state diffusion: c(x) = c0 for x < 0 and c(x) = cL for x >L

No time dependence, dc 0,
dj
0, j const.
dt dx
dc j
j D , c xb
dx D
j c L c0
c0 b, c L L c0 j D
D L

cL c0
c x c0 for 0 x L
L
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## Diffusion, flux, and Ficks law

Ficks second law: mass balance of fluxes

## Analogy: gain or loss in your bank account per month =

Your salary (\$\$ per month) - what you spend (\$\$ per month)

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## Diffusion, flux, and Ficks law

Ficks second law: mass balance of fluxes

## 1. We need to solve the partial differential diffusion equation. (a)

analytical solution (e.g., Crank, 1975) or (b) numerical methods

## 2. We need to know initial and boundary conditions. This is

straightforward for exercise cases, less so in nature.

## 3. We need to know the diffusion coefficient

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c x

c x
time

x
How can we find out c(x,t) ?

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## N = number of particles in volume V

Flux in 1 dimension:

A
J(x+x)
J (x) J (x+x) J
V
J(x)
x x
x

N
J ( x) A J ( x x) A A[ J ( x x) J ( x)] A J
t
dJ dJ dc d ( N / V ) dJ
A x V
dx dx dt dt dx
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## How can we find out c(x,t) ?

dc dJ

dt dx 2
dc d c
D 2
dc dt dx
J D
dx
Fick' s law We can find out c(x,t) !
Ficks second law

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Ficks Laws

## Combining the continuity equation with the first

law, we obtain Ficks second law:

c c 2
D 2
t x

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## Solutions to Ficks Laws depend on the

boundary conditions.

Assumptions
D is independent of concentration
Semiconductor is a semi-infinite slab with either
Continuous supply of impurities that can move into
wafer
Fixed supply of impurities that can be depleted

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## The simplest solution is at

steady state and there is no
variation of the concentration
c 2
D 2 0
with time
Concentration of diffusing
impurities is linear over
distance
x
This was the solution for the
flow of oxygen from the

c( x ) a bx
surface to the Si/SiO2
interface.

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## For a semi-infinite slab with a constant (infinite) supply

of atoms at the surface

x
c( x, t ) co erfc
2 Dt
The dose is

Q cx, t dx 2c0 Dt
0

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## Complimentary error function (erfc) is defined as

erfc(x) = 1 - erf(x)
The error function is defined as

exp d
z
2
erf ( z ) 2

0
This is a tabulated function. There are several
approximations. It can be found as a built-in
function in MatLab, MathCad, and Mathematica

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## This solution models short diffusions from a gas-phase

or liquid phase source
Typical solutions have the following shape

c0
Impurity concentration, c(x)

c ( x, t )

1 2 3

cB

## Distance from surface, x

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## Solutions To Ficks Second Law

x2
Constant source diffusion has Q
a solution of the form c( x, t ) e 4 Dt
Dt
Here, Q is the dose or the
total number of dopant
atoms diffused into the Si
Q c( x, t )dx
0

Q
The surface concentration is c(0, t )
given by: Dt
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## Limited source diffusion looks like

c01
c ( x, t )
Impurity concentration, c(x)

c02

1 2 3

cB

## Distance from surface, x

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Ficks Second Law: The Diffusion 46

Equation
Consider a small region of space (volume
for 3D, area for 2D)

## Jx(x) molecules flow in and Jx(x+dx)

molecules flow out (per unit area or distance
per unit time).

N
J x x J x x dx dy
t
N
c J x x J x x dx
sincec N / dxdy
t dx
J
J x x J x x dx x definition of the derivative
x
c 2 c c
D 2 sinceJ x D
t x x

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dc d 2c
Flux in 1 dimension: D 2
dt dx

dc d 2c d 2c
Flux in 2 dimensions: D 2 2
dt dx dy

## If there is a chemical reaction:

dc d 2
c d 2
c
F
number of particles produced
F D 2 2
volumetime dt dx dy

dp d p d p
2 2
For biological populations: F ( p) D 2 2
dt dx dy
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## Diffusion is the redistribution of atoms

from regions of high concentration of
mobile species to regions of low
concentration. It occurs at all temperatures,
but the diffusivity has an exponential
dependence on T.
Predeposition: doping often proceeds by
an initial predep step to introduce the
"Predep" Drive-in required dose of dopant into the substrate.
controlled dose constant dose
Silicon Drive-In: a subsequent drive-in anneal
then redistributes the dopant giving the
required xJ and surface concentration.

## Ion Implantation and Annealing Solid/Gas Phase Diffusion

Advantages Room temperature mask No damage created by doping
Precise dose control Batch fabrication
1011 - 1016 atoms cm-2 doses
Accurate depth control

## Problems Implant damage enhances Usually limited to solid solubility

diffusion
Dislocations caused by damage Low surface concentration hard
may cause junction leakage to achieve without a long drive-
in
Implant channeling may affect Low dose predeps very difficult
profile

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## Dopants are soluble in bulk silicon

up to a maximum value before they
precipitate into another phase.

## Dopants may have an electrical

solubility that is different than the
solid solubility defined above.
One example - As4V - electrically
inactive complex.

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Types of diffusion

## Interstitial diffusion - C in Fe, H in Ti, etc.

Vacancy diffusion
Self diffusion, tracer diffusion - healing of defects, time-
dependent mechanical phenomena
Chemical diffusion - diffusion of one element through
another, solid state chemical reactions

Bulk diffusion
Diffusion in grain boundaries, lattice defects
Surface diffusion

## Diffusion is a statistical phenomenon, driven by the

random motion of atoms.
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## Diffusion is a thermally activated

process, resulting in an exponential
temperature dependence:

D = D0 exp(-Q/kT)

## It can also depend on orientation relative

to the crystal axes.

## Interstitials diffuse much faster than

substitutional impurities and matrix atoms.

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Phenomenological description

## Ficks law: jD c jD in cm2/s; c in particles/cm3

c
Continuity: jD 0
t
c
Combined: Dc
t
c To be solved for c(x,t) or c(r,t)
If D = const. D 2c
t

Typical 1/2
solution depends on x/(Dt) .
One can define a diffusion front that travels as x2 ~ 6Dt
If defined that way, about 99% of the diffusing element is still
behind the diffusion front.

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Rough correlations

## D0 for self diffusion in metals ~ 1 cm2/s (0.1 to 10)

HD / Tm ~ 1.5*10-3 eV/K

HD / Lm ~ 15

## These relationships are useful if no measured data are

available. Typically estimates of diffusion are quite
rough, there is a huge variation, high accuracy is not
needed. Also, defects and impurities influence diffusion
very much, it is difficult to control it.

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Examples
Temperature is uniformly T = 912C, the alpha-gamma transition of iron.
Diffusion time t = 1 h =3600 s, distance x2 = 6Dt

## Self diffusion in alpha Fe: D0 = 2.0 cm2/s, HD = 2.5 eV

D = 2.0 exp(-2.5/8.6*10-5*11850) = 4.4*10-11 cm2/s, x ~ 10 m
Self diffusion in gamma Fe: D0 = 0.4 cm2/s, HD = 2.8 eV
D = 4.6*10-13 cm2/s, x ~ 1 m
60Co in alpha Fe: D = 0.2 cm2/s, H = 2.4 eV
0 D
D = 1.2*10-11 cm2/s, x ~ 5 m
C in alpha Fe: D0 = 0.004 cm2/s, HD = 0.83 eV
D = 1.2*10-6 cm2/s, x ~ 1.6 mm
C in gamma Fe: D0 = 0.67 cm2/s, HD = 1.6 eV
D = 1.0*10-7 cm2/s, x ~ 0.5 mm

## Notice the very large differences.

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## Vacancy diffusion in a solid and

dislocation climb due to capturing vacancies

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## Surface and interface diffusion

More open, diffusion can take place faster. In fact, dislocations provide
routes for fast diffusion also. Diffusion in grain boundaries makes
predicting the behavior of polycrystals difficult.
Activation energy is lowest for surface diffusion, larger for grain
boundary diffusion, and the highest for bulk diffusion. Therefore, bulk
diffusion dominates at high temperature (larger number of possible
sites) but grain boundary and surface diffusion takes over at lower
temperature.
Technological importance: Thin film deposition, weakening of grain
boundaries by impurities, shape changes of particles, etc.
Diffusion can be accelerated by introducing grain boundaries and other
lattice defects. This is an important benefit from MA (mechanical
alloying).

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Interdiffusion
Interdiffusion: in alloys, atoms tend to migrate from regions
of large concentration.
Initially After some time

100%

0
Concentration Profiles

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Self diffusion

C
A
D
B

## This can be observed on metal surface under UHV conditions

with scanning tunneling microscopy

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Vacancy diffusion or interstitial diffusion
applies to substitutional impurities
atoms exchange with vacancies
Concentration of Vacancies
rate depends on
at temp T
(1) number of vacancies
(2) activation energy to exchange. E
ni
ci e KBT

Vacancy

## The two processes have

an activation energy
(eV/atom).
Interstitial

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Substitution-diffusion
Vacancy Diffusion:
applies to substitutional impurities
atoms exchange with vacancies
rate depends on (1) number of vacancies;
(2) activation energy to exchange.

## increasing elapsed time

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Interstitial diffusion

## More rapid than vacancy Concentration gradient

diffusion

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## 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 "Case" is

-hard to deform: C atoms
"lock" planes from shearing.
-hard to crack: C atoms put
the surface in compression.

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Processing using Diffusion
Doping Silicon with P for n-type semiconductors:
Process:
1. Deposit P rich
layers on surface.

silicon

2. Heat it.
3. Result: Doped
semiconductor
regions.

silicon

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Flux:

1 d
Qm
A dt

## Flux can be measured for:

- vacancies
- host (A) atoms
- impurity (B) atoms
A = Area of flow
Empirically determined:
Make thin membrane of known surface area
Measure how fast atoms or molecules diffuse
through the membrane

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Concentration Profile, C(x): [kg/m3]

Cu flux Ni flux

Concentration Concentration
of Cu [kg/m3] of Ni [kg/m3]

Position, x
Fick's First Law:

dC
Qm,x D
dx D = m2/s

D=diffusion coefficient

## The steeper the concentration profile, the greater the flux!

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Steady State: concentration profile not changing with time.

## Qm,r Qm,l Qm,r = Qm,l

C(x)

dC
Apply Fick's First Law: Qm,x D
dx

## since Qm,l = Qm,r then dC dC

dx left dx right

The slope, dC/dx, must be constant (i.e., doesn't vary with position)

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dC
Qm,x D
Rate of diffusion independent of time dx

C1 C1

dC C C2 C1
C2 if linear
C2 dx x x2 x1

x1 x2
x

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Example: C Diffusion in steel plate
Steel plate at 7000C with
geometry shown:

700 C
Knowns:
C1= 1.2 kg/m3 at 5mm
(5 x 103 m) below surface.

## C2 = 0.8 kg/m3 at 10mm

(1 x 102 m) below surface.

## D = 3 x10-11 m2/s at 700 C.

In steady-state, how much carbon transfers from the rich to the deficient
side?

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Example: Chemical Protection Clothing
Methylene chloride is a common ingredient of paint removers. Besides
being an irritant, it also may be absorbed through skin. When using,
protective gloves should be worn.

If butyl rubber gloves (0.04 cm thick) are used, what is the diffusive flux of
methylene chloride through the glove?
glove
paint C1
2
tb
6D

C2 skin
remover x1 x2

Data:
D in butyl rubber: D = 110 x10-8 cm2/s
surface concentrations: C1 = 0.44 g/cm3 C2 = 0.02 g/cm3
Diffusion distance: x2 x1 = 0.04 cm
C2 - C1 g
Jx = -D = 1.16 x 10-5
x 2 - x1 cm2 s

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Example: Diffusion of radioactive atoms
0
Surface of Ni plate
63 at 1000 C contains
63 and 50% Ni (non-radioactive).
4 microns below surface Ni /Ni = 48:52
Lattice constant of Ni at 1000 C is 0.360 nm. -9 2
Experiment shows that self-diffusion of Ni is 1.6 x 10 cm /sec

63
What is the flux of Ni atoms through a plane 2 m below surface?

## (4Ni / cell )(0.5Ni 63 / Ni ) (4Ni / cell )(0.48Ni 63 / Ni )

C1 C2
(0.36x 109 m )3 / cell (0.36x 109m )3 / cell
42.87x 1027 Ni 63 / m 3 41.15x 1027 Ni 63 / m 3

## 13 2 (41.15 42.87)x 1027 Ni 63 / m 3

(1.6x 10 m /sec)
6 (4 0)x 10 m
0.69x 1020 Ni 63 / m 2 s

How many Ni
63
atoms/second through cell? J (0.36nm )2 9 Ni 63 / s

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Concentration profile,
C(x), changes w/ time.

## To conserve matter: Fick's First Law:

Governing Eqn.:

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Non-Steady-State Diffusion: another look
Concentration profile,
C(x), changes w/ time.

## Rate of accumulation C(x)

C C J x J x
dx J x J xdx dx J x (J x dx) dx
t t x x

## Using Ficks Law: C J x C Ficks

D
t x x x 2nd Law

2
c c c
If D is constant: Fick's Second "Law" D D

2
t x x

x

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Non-Steady-State Diffusion: C = c(x,t)
concentration of diffusing species is a function of both time and position
2
c
Fick's Second "Law" c D

2
t

x

## Copper diffuses into a bar of aluminum.

Cs
B.C. at t = 0, C = Co for 0 x
at t > 0, C = CS for x = 0 (fixed surface conc.)
C = Co for x =

## Adapted from Fig. 6.5,

Callister & Rethwisch 3e.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Cu diffuses into a bar of Al. CS

C(x,t)
2
c c
Fick's Second "Law": D

2 Co
t

x

Solution:

## "error function Values calibrated in Table 6.1

2 z
erf (z)

0
e y 2
dy
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FCC iron-carbon alloy initially containing 0.20 wt% C is carburized at an elevated
temperature and in an atmosphere that gives a surface C content 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, what temperature was treatment done?
Solution
C( x, t ) Co 0.35 0.20 x
1 erf 1 erf ( z ) erf(z) = 0.8125
Cs Co 1.0 0.20 2 Dt

Using Table 6.1 find z where erf(z) = 0.8125. Use interpolation. z erf(z)
0.90 0.7970
z 0.90 0.8125 0.7970 z 0.8125
So, z = 0.93
0.95 0.90 0.8209 0.7970 0.95 0.8209
x x2
Now solve for D z D
2 Dt 4z 2t
x2 (4 x 103 m)2 1h 11
D 2 2.6 x 10 m2
/s
4z t (4)(0.93) (49.5 h) 3600 s
2

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Solution (cont.):
To solve for the temperature at which D Qd
has the above value, we use a T
rearranged form of Equation (6.9a); R(ln Do ln D)
D=D0 exp(-Qd/RT)

## Do = 2.3 x 10-5 m2/s Qd = 148,000 J/mol D 2.6 x 1011 m2 /s

148,000 J/mol
T
(8.314 J/mol-K)(ln 2.3x105 m2 /s ln 2.6x1011 m2 /s)

T = 1300 K = 1027C

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
Example: Processing 77

## Copper diffuses into a bar of aluminum.

10 hours processed at 600 C gives desired C(x).
How many hours needed to get the same C(x) at 500 C?

## 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
Cs Co 2 Dt

Note
D(T) are T dependent!
Values of D are provided.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
78

conc.).
EACT

D Do exp
R T

## D = diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]

## T = absolute temperature [K]

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Experimental Data:

1000
1500

600

300
T(C)
10-8

D (m2/s)
Dinterstitial >> Dsubstitutional
C in -Fe Cu in Cu
10-14 C in -Fe Al in Al
Fe in -Fe
Fe in -Fe
Zn in Cu

10-20
0.5 1.0 1.5 1000K/T

## Callister & Rethwisch 3e.

from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals Reference Book, 7th ed.,
Butterworth-Heinemann, Oxford, 1992.)

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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## Example: Comparing Diffuse in Fe

Is C in fcc Fe diffusing faster than C in bcc Fe?

1000
1500

600

300
T(C)
fcc-Fe: D0=2.3x105 (m2/s) 10-8
EACT=1.53 eV/atom
T = 900 C D=5.9x1012(m2/s) D (m2/s)

## bcc-Fe: D0=6.2x107(m2/s) 10-14

EACT=0.83 eV/atom
T = 900 C D=1.7x1010(m2/s)

10-20
0.5 1.0 1.5 1000 K/T

FCC Fe has both higher activation energy EACT and D0 (holes larger in FCC).
BCC and FCC phase exist over limited range of T (at varying %C).
Hence, at same T, BCC diffuses faster due to lower EACT.
Cannot always have the phase that you want at the %C and T you want!
which is why this is all important.
P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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## Diffusion is usually asymmetric, the boundary between

regions is shifting, often difficult to define.

## Very importantly, solid state reactions always take place

at interfaces via diffusion. The products form
intermediate layers that often act as diffusion barriers.
Decreasing the particle size - e.g. by ball milling -
accelerates the reactions.

## Diffusion relates to volume changes, formation of voids,

etc.

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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## Zn diffuses faster than Cu in this

system. As a result, the Cu - brass
interface shifts, the Mo wires
marking the interface drift toward
each other.

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## Di*= tracer diffusion coefficient

w = frequency of a jump to an adjacent site
l = distance of the jump
f = related to symmetry, coordination number

## e.g., diffusion of 56Fe in homogenous olivine (Mg, Fe)2SiO4)

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Diffusion coefficient: multicomponent

## Multicomponent formulation (Lasaga,

1979) for ideal system, elements with the
same charge and exchanging in the same
site

## e.g., diffusion of FeMg olivine

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Diffusion coefficient

## Perform experiments at controlled conditions to

determine D* or DFeMg

## Q = activation energy (at 105 Pa), V =activation

volume, P = pressure in Pascals, R is the gas constant,
and Do = pre-exponential factor.
P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Diffusion coefficient

## New experimental and analytical techniques allow to determine

D at the conditions (P, T, fO2, ai) relevant for the magmatic
processes without need to extrapolation

## Dohmen and Chakraborty (2007)

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Continuum Concept

## The number of blue circles moving left is larger than the

number of blue circles moving right.
We think of concentration as being a point value, but it is
averaged over space.
P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Diffusion Coefficient

Probability of a jump is

Pj Pv Pm e E f kT
e Em kT

## Diffusion coefficient is proportional to

jump probability
E D kT
D D0e
P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Diffusion Coefficient
Typical diffusion coefficients in silicon

## Element Do (cm2/s) ED (eV)

B 10.5 3.69
Al 8.00 3.47
Ga 3.60 3.51
In 16.5 3.90
P 10.5 3.69
As 0.32 3.56
Sb 5.60 3.95
P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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## Diffusion Of Impurities In Silicon

Arrhenius plots of diffusion in silicon
o
Temperature ( C) o
Temperature ( C)
-9 1400 1300 1200 1100 1000
10 -4 1200 1100 1000 900 800 700
10

-10
10
-5
10

-11
10
Diffusion coefficient, D (cm /sec)

## Diffusion coefficient, D (cm /sec)

Li
-6
2

10

2
Fe

Cu

-12
10

-7
10
Al
Au

-13 Ga
10
In

-8
B,P 10
Sb 0.6 0.7 0.8 0.9 1.0 1.1
As -1
-14 Temperature, 1000/T (K )
10

## 0.6 0.65 0.7 0.75 0.8 0.85

-1
Temperature, 1000/T (K )

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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## The intrinsic carrier concentration in Si is about 7 x

1018/cm3 at 1000 oC
If NA and ND are <ni, the material will behave as if
it were intrinsic; there are many practical
situations where this is a good assumption

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
93

## Dopants cluster into fast diffusers (P, B, In) and

slow diffusers (As, Sb)
As we develop shallow junction devices, slow
diffusers are becoming very important
B is the only p-type dopant that has a high
solubility; therefore, it is very hard to make
shallow p-type junctions with this fast diffuser

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Successive Diffusions

## To create devices, successive diffusions of n-

and p-type dopants
Impurities will move as succeeding dopant or
oxidation steps are performed
The effective Dt product is
( Dt ) eff D1 (t1 t 2 ) D1t1 D1t 2
No difference between diffusion in one step or in
several steps at the same temperature
If diffusions are done at different temperatures
( Dt ) eff D1t1 D2t2
P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Successive Diffusions
The effective Dt product is given by

Dt eff Di ti
i
Di and ti are the diffusion coefficient and time for ith step
Assuming that the diffusion constant is only a
function of temperature.
The same type of diffusion is conducted (constant or
limited source)

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Interstitial diffusion

## C diffusion in bcc Iron (steel)

Li diffusion in transition metal oxide host
O diffusion on Pt-(111) surface

## In all examples, diffusion occurs on a rigid lattice

which is externally imposed by a host or substrate

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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## Example of interstitial diffusion

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
98
Intercalation Oxide as Cathode in
Rechargeable Lithium Battery

LixCoO2

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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## Individual hops: Transition state theory

E B

E B
* exp
kT

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Lithium

Cobalt

Oxygen

## Single vacancy hop Divacancy hop

mechanism Mechanism

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Lithium

Cobalt

Oxygen
Single vacancy hop Divacancy hop

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Irreversible thermodynamics:
interstitial diffusion of one
component

J L
d
DL
dC
J DC
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Notation

## M = number of lattice sites

N = number of diffusing atoms
vs = volume per lattice site
x = N/M
C=x/vs

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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## Interstitial diffusion: one component

Kubo-Green relations
(linear response statistical mechanics)

D L

Thermodynamic factor
C
N 2
Kinetic coefficient L
1 R t
(2d)tMvsk T i
i1

## R. Gomer, Rep. Prog. Phys. 53, 917 (1990)/

A. Van der Ven, G. Ceder,
Handbook of Materials Modeling, chapt. 1.17, Ed.
S. Yip, Springer (2005).
P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
~ 105

D DJ
Diffusion coefficient Thermodynamic
at 300 K factor

A. Van der Ven, G. Ceder, M. Asta, P.D. Tepesch, Phys Rev. B 64 (2001) 064112

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Interstitial diffusion
(two components)

## C & N diffusion in bcc Iron (steel)

Li & Na diffusion in transition metal oxide
host
O & S diffusion on Pt-(111) surface
In all examples, diffusion occurs on a rigid lattice
which is externally imposed by a host or substrate

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law
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Diffusion in an alloy: substitutional diffusion

## Not interstitial diffusion

Instead, diffusing atoms form the lattice
Dilute concentration of vacancies

P.Ravindran, PHY085 Properties of Materials, 2014 February: Diffusion and Ficks law