14/08/2024 Ciência dos Materiais I 1

DIFFUSION
Wagner Souza Machado
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Class Objectives

• Describe the diffusion phenomenon and the main

diffusion mechanisms.
• Describe Fick's First Laws (steady state).
• Describe Fick's Second Laws (transient state).
• Define “Diffusion Coefficient” and perform calculations
based on its equation.
• Describe the factors that affect diffusion.
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História
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History
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WHY STUDY Diffusion?

Materials are often heat-treated to
improve or change their properties.

Steel gear has its hardness and resistance

to fatigue failure increased by the diffusion
of excess carbon or nitrogen in the outer
surface layer.
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Introduction
Electric current → charge transport

DIFFUSION → mass transport

electrical potential Concentration

difference difference
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Diffusion Concept

Diffusion and
convection occurs in
liquids and gases

In solids, mass transport Cross-sectional TEM image of

occurs essentially by 10 nm Au deposited on
Poly(trimethylene carbonate) at
diffusion 290°C (Tsub < Tg). Metal atoms
can be seen diffusing into the
polymer
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Diffusion in Solids
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Diffusion Mechanisms

From an atomic perspective, diffusion is

just the stepwise migration of atoms
from lattice site to lattice site.

Two conditions must be met:

• there must be an empty adjacent site
• the atom must have sufficient energy

Two models dominate for metallic diffusion:

• Vacancy Diffusion
• Interstitial Diffusion
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Vacancy Diffusion
Atoms can move from one site to another
if there is sufficient energy to overcome
a local activation energy barrier.

The activation energy for diffusion is the sum of the energy

required to form a vacancy and the energy to move the vacancy.
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Vacancy Diffusion
Resultado de imagem para vacancy diffusion
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Interstitial Diffusion
Interstitial atoms like hydrogen, carbon, etc, must squeeze through
openings between interstitial sites to difuse around in a crystal.

The activation energy for diffusion is the energy required for these
small atoms to squeeze through openings between host lattice atoms.
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Interstitial Diffusion
Interstitial diffusion is generally
faster than vacancy diffusion.
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Diffusion in Solids
The phenomenon of diffusion may be demonstrated
with the use of a diffusion couple.

Heat treatment
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Diffusion in Solids

The process by which atoms of one metal diffuse into

another is termed interdiffusion, or impurity diffusion.
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Diffusion in Solids
Diffusion also occurs for pure metals, but all atoms
exchanging positions are of the same type; this is termed
self-diffusion.
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Diffusion in Solids
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Diffusion Flux
How fast does diffusion occur?
Diffusion is a time-
dependent process. What is the mass transfer rate?

This rate is frequently expressed as a

diffusion flux (J)

𝑴
𝑱=
𝑨𝒕
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FICK’S FIRST LAW

Fick’s law of diffusion

explains the diffusion process
(movement of molecules from
higher concentration to
lower concentration region)
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FICK’S FIRST LAW

According to Fick’s law of diffusion, In one dimension:
“The Flux due to diffusion is
proportional to the concentration
𝒅𝑪
𝑱∝
gradient”. 𝒅𝒙
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FICK’S FIRST LAW

𝒅𝑪 𝒅𝑪
𝑱∝ 𝑱 = −𝑫
𝒅𝒙 𝒅𝒙

The constant of proportionality D is In three dimensions:

called the Diffusion Coefficient
𝑱Ԧ = −𝑫. 𝛁𝑪
The unit of D is m2/s.

• squared velocity of the diffusing particles,

For biological molecules,
• temperature,
D range from 10−11 to
• viscosity of the fluid,
10−10 m2/s.
• size of the particles.
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Steady State Diffusion

When the diffusion process reaches a state wherein
the diffusion flux does not change with time, this is
termed steady-state diffusion.

Ex: Purification of hydrogen gas

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Steady State Diffusion

The concentration C versus position (or
distance) x plot, result a curve that is
termed concentration profile.

The slope at a particular point on

this curve is the concentration
gradient (𝑑𝐶/𝑑𝑥).
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Example – Fick’s First Law

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Nonsteady-State Diffusion
Most practical diffusion situations are nonsteady-state ones.

The diffusion flux and the

concentration gradient at
some local position in a solid
vary with time.
𝝏𝑪 𝝏𝑱
=−
The component that is in 𝝏𝒕 𝝏𝒙
diffusion tends to accumulate
or be depleted.
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Fick’s Second Law

The partial differential equation known as Fick’s second law, is used.

𝜕𝐶 𝜕 𝜕 𝜕𝐶
=− 𝐽 =− −𝐷
𝜕𝑡 𝜕𝑥 𝜕𝑥 𝜕𝑥
𝜕𝐶 𝜕 𝜕𝐶
= 𝐷
𝜕𝑡 𝜕𝑥 𝜕𝑥

If the diffusion coefficient is

independent of composition In three dimensions:

𝝏𝑪 𝝏𝟐 𝑪 𝝏𝑪
=𝑫 𝟐 = 𝑫. 𝛁 𝟐 𝑪
𝝏𝒕 𝝏𝒙 𝝏𝒕
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Fick’s Second Law

One practically important solution is for a semi-infinite
solid in which the surface concentration is held constant.

Frequently, the source of the diffusing species is a gas phase,

the partial pressure of which is maintained at a constant value.
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Fick’s Second Law

1. Before diffusion, any of the diffusing solute atoms in the

solid are uniformly distributed with concentration of C0.

2. The value of x at the surface is zero and increases with

distance into the solid.

3. The time is taken to be zero the instant before the

diffusion process begins.
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Fick’s Second Law

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Fick’s Second Law

Cx represents the concentration
at depth x after time t.

The expression 𝒆𝒓𝒇 𝒙Τ𝟐 𝑫𝒕 is

the Gaussian error function.
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Fick’s Second Law

Values of the Gaussian error function are given in mathematical tables.
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Fick’s Second Law

If the parameters C0, Cs, and D are known, Cx
may be determined at any time and position.
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Fick’s Second Law

Suppose that it is desired to achieve some 𝑪𝟏 − 𝑪𝟎

specific concentration of solute, C1, in an = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
alloy, the left-hand side of Equation is 𝑪𝒔 − 𝑪𝟎

The right-hand side of Equation 𝒙

= 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
is also a constant, 𝟐 𝑫𝒕

Some diffusion computations are facilitated

based on this relationship
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We must now determine from

Table 5.1 the value of z for which
the error function is 0.421

𝒆𝒓𝒇 𝒛 = 𝟎, 𝟒𝟐𝟏
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An interpolation is necessary,
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𝒙
𝒆𝒓𝒇 𝒛 = 𝒆𝒓𝒇 = 𝟎, 𝟒𝟐𝟏 → 𝒛 = 𝟎. 𝟑𝟗𝟐
𝟐 𝑫𝒕

𝒙
𝒛= = 𝟎. 𝟑𝟗𝟐
𝟐 𝑫𝒕
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Factors that Influence Diffusion

Diffusing Species

High energy is
required to squeeze
atoms past each other
during diffusion.

In general, more energy is required for a substitutional

atom than for an interstitial atom.
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Factors that Influence Diffusion

Diffusing Species

For example, at 500oC, α-Fe self-diffusion has D = 3.0 × 10-21 m2/s

and carbon interdiffusion in α-Fe, has D = 1.4 × 10-12 m2/s.
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Factors that Influence Diffusion

Temperature

The temperature dependence

of the diffusion coefficients is:

The activation energy may be thought of as that energy required

to produce the diffusive motion of one mole of atoms
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Factors that Influence Diffusion

D transform ln D
data

Temp = T 1/T

æ Q ö Qd
D = D0 exp ç - d ÷ take natural log lnD = lnD0 -
è RT ø of both sides RT
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Because D0, Qd, and R

are all constants,
equations takes on the
form of an equation of a
straight line:

𝑄𝑑 1
log 𝐷 = log 𝐷0 −
2.3𝑅 𝑇

Having slope of Qd/2.3R

and intercept equal to
log D0. Linear relationships exist
for all cases shown.
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𝑪𝟏 − 𝑪𝟎 𝒙
= 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝑪𝒔 − 𝑪𝟎 𝟐 𝑫𝒕
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Concept Check
Rank the magnitudes of the diffusion coefficients
from greatest to least for the following systems

N in Fe at 900oC> N in Fe at 700oC> Cr in Fe at 900oC> Cr in Fe at 700oC

~10-10 m2/s > 10-11 m2/s > 10-15 m2/s > 10-18 m2/s >
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Concept Check
Consider the self-diffusion of two hypothetical metals A and B. On a
schematic graph of ln D versus 1/T, plot (and label) lines for both metals,
given that D0(A) > D0(B) and Qd(A) > Qd(B).
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𝑄𝑑 1
log 𝐷 = log 𝐷0 −
2.3𝑅 𝑇

Slope give us -
Qd/2.3R

and intercept at
1000/T = 0 give us
logD0.
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𝑄𝑑 1
log 𝐷 = log 𝐷0 −
2.3𝑅 𝑇
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0,60 − 0,20
= 0,5
1 − 0,20
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0,5 − 0,4755 𝑧 − 0,45

=
0,5205 − 0,4755 0,50 − 0,45

𝑥
𝑧 = 0,4747 =
2 𝐷𝑡
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Diffusion in Semiconducting Materials

Fabrication of semiconductor Each IC chip is a thin square wafer
integrated circuits (ICs). with millions of interconnected
electronic devices and circuits.
Resultado de imagem para integrated circuits

Resultado de imagem para integrated circuits electron microscopy

Single-crystal silicon is the

base material for most ICs.
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Diffusion in Semiconducting Materials

Very precise concentrations of an impurity (or impurities) must be
incorporated into minute spatial regions in a very intricate and detailed
pattern on the silicon chip

Atomic diffusion.

SEM of an IC chip
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Diffusion in Semiconducting Materials

SEM images of an IC chip

A silicon dot map, showing

regions where silicon atoms
are concentrated

An aluminum dot map.

Metallic aluminum is an
electrical conductor and, as
such, wires the circuit elements
together.
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Diffusion in Semiconducting Materials

Two heat treatments are used in silicon
atomic diffusion process.

Predeposition step:
impurity atoms are diffused
into the silicon (doping).

Temperature range of 900oC and

1000oC and for times typically
less than 1 h.
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Diffusion in Semiconducting Materials

Drive-in diffusion step, is used to transport impurity
atoms farther into the silicon.

Provide a more suitable concentration distribution without

increasing the overall impurity content

This treatment is carried out at a

higher temperature than the
predeposition one (up to about
1200oC).
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Diffusion in Semiconducting Materials

If the impurity atoms introduced during the predeposition treatment
are confined to a very thin layer at the surface of the silicon.

The solution to Fick’s second

𝜕𝐶 𝜕2 𝐶
law ( = ) for drive-in
𝐷 2
𝜕𝑡 𝜕𝑥
diffusion takes the form

Q0 represents the total amount of

impurities that were introduced during the
predeposition treatment
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Diffusion in Semiconducting Materials

It can be shown that,

where Cs is the surface concentration,

Dp is the diffusion coefficient, and tp is
the pretreatment time.

Another important diffusion

parameter is junction depth, xj.

Dd and td represent, the diffusion

coefficient and time for the drive-in
treatment.
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Aluminum for Integrated Circuit Interconnects

Deposition of very thin and narrow
conducting circuit paths
The material to be used for
(interconnects).
interconnects must have a high
electrical conductivity.

Discounting material cost, Ag

should be the metal of choice.
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Aluminum for Integrated Circuit Interconnects

After interconnects deposition, it is still necessary to subject the IC chip to
other heat treatments, which may run as high as 500oC

It is necessary to select an
interconnect metal that has a small
value of D in silicon.

Aluminum is indeed used for

interconnects in some integrated
circuits; its extremely low diffusion
coefficient makes it the material of
choice for this application.
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Aluminum for Integrated Circuit Interconnects

An aluminum– copper–silicon alloy (94.5 wt% Al-4 wt% Cu-1.5wt% Si)
is sometimes also used for interconnects; it is more corrosion
resistant than pure aluminum.

More recently, copper

interconnects have also been
used. However, it is first necessary
to deposit a very thin layer of
tantalum or tantalum nitride
beneath the copper, which acts as a
barrier to deter diffusion of copper
into the silicon.
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Other Diffusion Paths

Atomic diffusion may also occur along dislocations, grain

boundaries, and external surfaces.

In special cases, e. g. the diffusion in nanomaterials, the

contribution can be significant because the total boundary
area is very large.
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Referências