Chapter 5: Diffusion

MS31007: Materials Science

Instructor:
Prasana Kumar Sahoo
[email protected]
 What should be the properties of the Steel Gear?

Case Hardening: Hardening the surface of a metal by

exposing it to impurities that diffuse into the surface region
and increase surface hardness.

Common example of case hardening is carburization of steel. Diffusion of carbon atoms (interstitial
mechanism) increases concentration of C atoms and makes iron (steel) harder.
 Chapter Outline
Diffusion - how do atoms move through solids?
ƒ Diffusion mechanisms
Vacancy diffusion
Interstitial diffusion
Impurities
ƒ The mathematics of diffusion
Steady-state diffusion (Fick’s first law)
Nonsteady-State Diffusion (Fick’s second law)

❑ Factors that influence diffusion

Diffusing species
Host solid
Temperature
Microstructure

• Why is it an important part of processing?

• How can the rate of diffusion be predicted for some simple cases?
 What is diffusion?
Glass tube filled with water and add a ink drop Diffusion is material transport by atomic motion.
• At time t = 0, add some drops of ink to one
end of the tube.
• Measure the diffusion distance, x, over some
time.

Em

Process path showing how an atom must overcome an

activation energy, Em, to move from one stable position to
a similar adjacent position

• Inhomogeneous materials can become

homogeneous by diffusion.
Why do the random jumps of atoms result in • For an active diffusion to occur, the
a flux of atoms from regions of high temperature should be high enough to
concentration towards the regions of low
overcome energy barriers to atomic The box must overcome an increase in potential energy, ∆E, in
concentration? order to move from one stable position to another
motion.
 Diffusion – Thermally Activated Process
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.
- The energy necessary for motion, Ev, is called the activation energy for vacancy motion.

This energy comes from the thermal energy of

atomic vibrations (Eav ~ kBT)

Schematic representation of the

diffusion of an atom from
Ev its original position into a vacant lattice
site.
Ei
Activation energy Em has to be supplied
to the atom so that it could break inter-
atomic bonds and to move into the new
position.
 Diffusion Mechanisms
Substitutional Diffusion: • applies to substitutional impurities
Vacancy diffusion
• atoms exchange with vacancies
• rate depends on:
--number of vacancies
--activation energy to exchange.

Which is faster?

Requires small impurity atoms

(e.g. C, H, O) to fit into interstices in host.

Interstitial diffusion is generally faster than vacancy

diffusion because bonding of interstitials to the
surrounding atoms is normally weaker and there are
many more interstitial sites than vacancy sites to jump to.
Interstitial diffusion
 Self-diffusion and Inter- diffusion
Self-diffusion is diffusion in one-component Interdiffusion: In an alloy, atoms tend to migrate from
material, when all atoms that exchange positions regions of large concentration.
are of the same type.
Label some atoms Initially After some time

C
A
D
B
After some time

100%

0
Concentration Profiles
 Diffusion in 2D Materials Heterostructures
MoSe2 WSe2 MoSe2 WSe2 P. Sahoo et al. Nature 2018
Monolayer

MoSe2

WSe2

Atomic ball model 0 1

W Atomic Fraction

1 1
per column (x)

0 0
-30 -20 -10 0 10 20 30 -20 -10 0 10 20
Atomic Column Atomic Column
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.
Metal–oxide–semiconductor field-effect transistor (MOSFET)

Simplified process
of fabrication of a
CMOS inverter on
p-type substrate in
semiconductor
microfabrication
 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
 Diffusion Flux : Fick’s First Law
Diffusion is a time-dependent process
• Diffusion flux: the mass number of atom or M diffusing through and perpendicular to a unit
cross-sectional area of solid per unit of time.

• Directional Quantity

• Flux can be measured for:

--vacancies
--host (A) atoms
--impurity (B) atoms
 Concentration Profiles & Flux
• 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:

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

• The minus sign in the equation means that diffusion is down the concentration gradient
 Steady State Diffusion
• Steady State: the concentration profile doesn't change with time.
When concentration C is plotted versus
position (or distance) within the solid x, the
resulting curve is termed the
concentration profile

• Apply Fick's First Law:

the diffusion flux along direction x is
proportional to the concentration gradient

• If Jx)left = Jx)right , then Concentration gradient is the slope at a

particular point on this curve.
dC
J x = −D the slope, dC/dx, must be constant
dx (i.e., slope doesn't vary with
position)!
 dC   dC 
  = 
 dx  left  dx  right The concentration gradient is often called the driving force in diffusion
(but it is not a force in the mechanistic sense).
 Ex: Steady State Diffusion
• Steel plate at 700 C with geometry shown:

• Q: How much carbon transfers

from the rich to the deficient side?
Example: Hydrogen Purification from Compact Palladium Membrane

disc-shaped Pd-based membrane

 Non-Steady-State Diffusion: Fick’s second law
In many real situations the concentration C(x) profile and the
concentration gradient are changing with time.

The changes of the concentration profile can be

described in this case by a differential equation,
Fick’s second law.
• To conserve matter: • Fick's First Law:

if D does not depend on x

• Governing Eqn.:
 Solution to Fick’s second law
If none of the diffusing atoms reaches the bar end during the time over which diffusion takes place

Boundary Condition: a semi-infinite solid in which the surface concentration is held constant

"error function" Suppose that it is desired to achieve some specific

concentration of solute, C1, in an alloy;

Cx represents the concentration at depth x after time t.

 Tabulation of Error Function Values

"error function"

The simplest mathematical solution

which describes situations where a finite, rather than continuous,

surface concentration S (in units of atoms/cm2) is present.

Such finite sources are used in diffusional doping of semiconductors.

 Time evolutions of diffusional profiles
constant surface source finite surface source

(A) Sequence of concentration profiles generated by

diffusion from a constant surface source. (B) Gaussian diffusion profiles from a finite surface source.
Average diffusant concentrations and distances are dotted in.
A complementary error function solution governs the
mass transport. A quadrupling of the diffusion time (t2 = 4t1) results in a doubling
of the diffusional penetration (x2 = 2x1,).
 Ex: Non Steady State Diffusion
Copper diffuses into a bar of aluminum.

• Copper diffuses into a bar of aluminum.

• 10 hours at 600 C 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.

• Answer: Note: values of D are

provided here.
Factors that influence diffusion
 Factors That Influence Diffusion
1. Temperature

• Diffusivity increases with T.

D0 – temperature-independent pre-exponential (m2/s)

Qd – the activation energy for diffusion (J/mol or eV/atom)
R – the gas constant (8.31 J/mol-K or 8.62×10-5 eV/atom-K)
T – absolute temperature (K)

The above equation can be rewritten as

The activation energy Qd and pre-exponential D0, therefore, can be estimated by plotting
lnD versus 1/T or logD versus 1/T. Such plots are called Arrhenius plots.
 Diffusion – Temperature Dependence

Arrhenius plot of the diffusivity

Graph of log D vs. 1/T has slop of –Qd/2.3R, intercept of log Do of carbon in a-iron over a range of
temperatures
 Temperature dependence: Interstitial and vacancy
diffusion mechanisms (I)

Diffusion of interstitials is typically faster as compared to the vacancy diffusion

Arrhenius plot of diffusivity mechanism (self-diffusion or diffusion of substitutional atoms)
data for a number of metallic systems.
 Diffusion: Role of the microstructure

• Self-diffusion coefficients for Ag depend on the diffusion path. Schematic illustration of how a coating of impurity B can penetrate more deeply into
• In general the diffusivity if greater through less restrictive structural grain boundaries and even further along a free surface of polycrystalline A, consistent
with the relative values of diffusion coefficients (Dvolume < Dgrain boundary < Dsurface)
regions – grain boundaries, dislocation cores, external surfaces.
 DIFFUSION IN POLYMERIC MATERIALS
Interest is the diffusive motion of small foreign molecules (e.g., O2, H2O, CO2, CH4) between the molecular chains
rather than in the diffusive motion of chain atoms within the polymer structure
• A polymer’s permeability and absorption characteristics relate to the degree to which foreign substances diffuse
into the material.

Diffusion properties of polymers are often characterized in terms of a permeability coefficient (denoted by PM),
where for the case of steady-state diffusion through a polymer membrane, Fick’s first law is modified as

J is the diffusion flux of gas through the membrane [(cm3STP)/(cm2∙s)],

PM is the permeability coefficient, Δx is the membrane thickness,
ΔP is the difference in pressure of the gas across the membrane

Permeability Coefficient P at 25°C for Oxygen, Nitrogen, Carbon

M

For small molecules in nonglossy polymers the Dioxide, and Water Vapor in a Variety of Polymers
permeability coefficient can be approximated as the
product of the diffusion coefficient (D) and solubility of
the diffusing species in the polymer (S)

P = DS
M

When the diffusing molecular species is in the

gas phase, solubility is equal to S= C/P
C is the concentration of the diffusing species in the
polymer, and P is the partial pressure (in units of Pa)
 Diffusion in Fuel Cells

Prototype fuel-cell-powered Toyota sport utility vehicle evaluated at the

University of California, Davis.

By stacking enough cells in series, sufficient

power to run automobiles and other large-scale
systems is possible.

• As hydrogen flows into the fuel cell on the anode side, the hydrogen gas is separated into hydrogen ions (protons) and electrons at the surface of a
platinum catalyst.
• The hydrogen ions diffuse across the membrane and combine with oxygen and electrons at the surface of another platinum catalyst on the cathode
side (producing water, the only emission from a hydrogen fuel cell!).
• The electrons cannot pass through the nonconductive membrane and, instead, produce a current from the anode to the cathode via an external
circuit that provides about enough power for a single lightbulb
 Processing Using Diffusion: Doping Silicon with P
• 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.

Schematic concentration profile of P

silicon diffusing from a continuous source
into silicon doped with boron.
 Oxidation of Silicon
Key steps in the processing of integrated circuits involves
the controlled oxidation of silicon to form a high-quality
SiO2 thin film

During steady-state oxide growth J2 = J3

Considering only transport and

reaction in the solid, steps 2 Mass flux
J3 is also proportional to the rate at which
and 3 can be modeled by
oxide grows
The rate of chemical reaction at the Co and Ci –
interface is proportional to both the oxygen oxygen concentrations at the oxide growth rate
concentration Ci and the rate constant Ks, gas and Si02 interface
so that the amount of oxide formed per unit Xo is the Si02 thickness at any
time No is the number of oxidant molecules
time and area is flux J3 incorporated into a unit volume of oxide film
Rate constant Ks
 Oxidation of Silicon
Experimental determinations of SiO2 kinetics in O2
and H2O ambients, plotted in dimensionless
coordinates.
Reaction rate limited

Diffusion limited

Limiting cases of reaction rate and diffusion-

controlled oxidation are indicated,
Where A = 2D/Ks and B = 2C0D/N0.
 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

 Nonsteady-State Diffusion: Fick’s second law

C: depends both on time

and distance

Fick’s second law relates the rate of change of composition with time to the curvature of the concentration profile:

Concentration increases with time in those parts of the system where concentration profile has a positive curvature. And
decreases where curvature is negative.

The phenomenological description based on the Fick’s laws is valid for any atomic mechanism of diffusion.
Understanding of the atomic mechanisms is important, however, for predicting the dependence of the atomic
mobility (and, therefore, diffusion coefficient) on the type of interatomic bonding, temperature, and
microstructure.