Lecture 3: Diffusion in Solids

Department: EEE/BME
Faculty/School: National Higher Polytechnic Institute
Code: EEEE3109
Course Title: Material Science for Electrical and Electronic Engineering
Semester: First
Credit value: 02
Time: 13:30 -15:00
Day: Friday
Office/Hours:
Instructors: Prof Geh/ Engr. Taah

Learning Objectives;
▪ Name and describe the two atomic mechanisms of diffusion.
▪ Distinguish between steady-state and non-steady-state diffusion.
▪ Write Fick’s first and second laws in equation form, and define all parameters.
▪ Note the kind of diffusion for which each of these equations is normally applied.
▪ Calculate the diffusion coefficient for some material at a specified temperature, given the appropriate
diffusion constants.
▪ Note one difference in diffusion mechanisms for metals and ionic solids.

3.1 Introduction
Many reactions and processes that are important in the treatment of materials rely on the transfer of mass
either within a specific solid (ordinarily on a microscopic level) or from a liquid, a gas, or another solid
phase. This is accomplished by diffusion.
Diffusion refers to the movement of atoms in solids. Diffusion is relative flow of one material into
another. Mass flow process by which species change their position relative to their neighbors. Diffusion
of a species occurs from a region of high concentration to low concentration (usually). More accurately,
diffusion occurs down the chemical potential (µ) gradient. Diffusion is driven by thermal energy and a
‘gradient’ (usually in chemical potential). In this course we will essentially restrict ourselves to
concentration gradients. Usually, concentration gradients imply chemical potential gradients; but there are
exceptions to this rule. Hence, sometimes diffusion occurs ‘uphill’ in concentration gradients, but downhill
in chemical potential gradients. Thermal energy leads to thermal vibrations of atoms, leading to atomic
jumps. In the absence of a gradient, atoms will still randomly ‘jump about’, without any net flow of matter.
There are hundreds of applications and technologies that depend on either enhancing or limiting diffusion.
The following are just a few examples.

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3.2 Mechanisms for Diffusion
The disorder vacancies create (increased entropy) helps minimize the free energy and, therefore, enhances
the thermodynamic stability of a crystalline material.
Crystalline materials also contain other types of
defects. In materials containing vacancies, atoms move
or ‘‘jump’’ from one lattice position to another. This
process, known asself-diffusion, can be detected by
using radioactive tracers. As an example, suppose we
were to introduce a radioactive isotope of gold (Au198)
onto the surface of normal gold197(Au). After a period
of time, the radioactive atoms would move into the
normal gold. Eventually, the radioactive atoms would
be uniformly distributed throughout the entire regular
gold sample. Although self-diffusion occurs
continually in all materials, its effect on the material’s
behavior is generally not significant.
Diffusion of unlike atoms in materials also occurs
(Figure 5-4). Consider a nickel sheet bonded to a
copper sheet. At high temperatures, nickel atoms
gradually diffuse into the copper and copper atoms
migrate into the nickel. Again, the nickel and copper
atoms eventually are uniformly distributed. There are
two important mechanisms by which atoms or ions can
diffuse.
Figure 3.1 The process of diffusion of copper atoms into nickel

3.2.1 Vacancy Diffusion

In self-diffusion and diffusion involving substitutional atoms, an atom leaves its lattice site to fill a nearby
vacancy (thus creating a new vacancy at the original lattice site).
This mechanism involves the interchange of an atom from a normal lattice position to an adjacent vacant
lattice site or vacancy, as represented schematically in Figure 3.2a. As diffusion continues, we have
countercurrent flows of atoms and vacancies, called vacancy diffusion. The number of vacancies, which
increases as the temperature increases, helps determine the extent of both self-diffusion and diffusion of
substitutional atoms.; significant concentrations of vacancies may exist in metals at elevated temperature.
Since diffusing atoms and vacancies exchange positions, the diffusion of atoms in one direction corresponds
to the motion of vacancies in the opposite direction. Both self-diffusion and interdiffusion occur by this
mechanism; for the latter, the impurity atoms must substitute for host atoms.

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Figure 3.2 Diffusion mechanisms in materials: (a) vacancy or substitutional atom diffusion and (b)
interstitial diffusion

3.2.2 Interstitial diffusion

The second type of diffusion involves atoms that migrate from an interstitial position to a neighboring one
that is empty. This mechanism is found for interdiffusion of impurities such as hydrogen, carbon, nitrogen,
and oxygen, which have atoms that are small enough to fit into the interstitial positions. Host or
substitutional impurity atoms rarely form interstitials and do not normally diffuse via this mechanism.
When a small interstitial atom or ion is present in the crystal structure, the atom or ion moves from one
interstitial site to another. No vacancies are required for this mechanism. Partly because there are many
more interstitial sites than vacancies, interstitial diffusion occurs more easily than vacancy diffusion. Also,
interstitial atoms that are relatively smaller can diffuse faster.

In most metal alloys, interstitial diffusion occurs much more rapidly than diffusion by the vacancy mode,
since the interstitial atoms are smaller and thus more mobile. Furthermore, there are more empty interstitial
positions than vacancies; hence, the probability of interstitial atomic movement is greater than for vacancy
diffusion.

3.3 Factors Affecting Diffusion

3.3.1 Diffusing Species
The magnitude of the diffusion coefficient D is indicative of the rate at which atoms diffuse. Coefficients,
both self- and interdiffusion. The diffusing species as well as the host material 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, the D value being greater for the carbon interdiffusion (3.0 × 1021 vs. 2.4
× 1012 m 2/s). This comparison also provides a contrast between rates of diffusion via vacancy and
interstitial modes as diffused previously. Self-diffusion occurs by a vacancy mechanism, whereas carbon
diffusion in iron is interstitial.

3.3.2 Temperature
Temperature has a most profound influence on the coefficients and diffusion rates. For example, for the
self-diffusion of Fe in α-Fe, the diffusion coefficient increases approximately six orders of magnitude (from
3.0 × 1021 /s) in rising temperature from 500 to 900◦C (Table 6.2). The temperature dependence of the
diffusion coefficients is to 1.8 × 1015 2 m
𝑄𝑑
𝐷 = 𝐷0 𝑒𝑥𝑝 (− )
𝑅𝑇

where D0 a temperature-independent preexponential (m = /s)

Qd = activation energy the activation energy for diffusion (J/mol or eV/atom)
R = the gas constant, 8.31 J/mol-K or 8.62 × 105 eV/atom-K
T = absolute temperature (K

3.4 Ficks First Law of Diffusion (Steady State Diffusion)

Diffusion is a time-dependent process that is, in a macroscopic sense, the quantity of an element that is
transported with in another is a function of time. Often it is necessary to know how fast diffusion occurs,
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or the rate of mass transfer. This rate is frequently expressed as a diffusion flux (J), defined as the mass (or,
equivalently, the diffusion flux number of atoms) M diffusing through and perpendicular to a unit cross-
sectional area of solid per unit of time. In mathematical form, this may be represented as
𝑀
𝐽=
𝐴𝑡
where A denotes the area across which diffusion is occurring and t is the elapsed diffusion time. In
differential form, this expression becomes
𝑀 𝑑𝑀
𝐽=
𝐴𝑡 𝑑𝑡

The units for J are kilograms or atoms per meter squared per second (kg/m 2 -s or atoms/m 2-s). If the
diffusion flux does not change with time, a steady-state condition exists. One common example of steady-
state diffusion is the diffusion of atoms of a gas through a plate of metal for which the concentrations (or
pressures) of the diffusing species on both surfaces of the plate are held constant.
This is represented in Figure 3.3a. When concentration C is plotted versus position (or distance) within the
solid x, the resulting curve is termed the concentration profile; the slope at a particular point on this curve
is the concentration gradient

Figure 3.3 (a) steady state diffusion across a thin Plate, (b) a linear concentration profile for diffusion
situation in (a)
The rate at which atoms, ions, particles or other species diffuse in a material can be measured by the flux
(J). Here we are mainly concerned with diffusion of ions or atoms. The flux is defined as the number of
atoms passing through a plane of unit area per unit time. Fick’s first law explains the net flux of atoms:

𝑑𝐶
𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑔𝑟𝑎𝑑𝑖𝑒𝑛𝑡 =
𝑑𝑥
Assuming the concentration profile is linear
Δ𝐶 𝐶𝐴 − 𝐶
𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑔𝑟𝑎𝑑𝑖𝑒𝑛𝑡 = =
Δ𝑥 𝑥𝐴 − 𝑥𝐵
Hence the flux is proportional to the concentration gradient through the expression;

𝒅𝑪
𝑱 = −𝑫
𝒅𝒙
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The constant of proportionality D is called the diffusion coefficient, which is expressed in square meters
per second. The negative sign in this expression indicates that the direction of diffusion is down the
concentration gradient, from a high to a low concentration. This equation is called Fick’s first law.
Sometimes the term driving force is used to explain what compels a reaction to driving force occur. For
diffusion reactions, several such forces are possible; but when diffusion is according to Equation 6.3, the
concentration gradient is the driving force. One practical example of steady-state diffusion is found in the
purification of hydrogen gas. One side of a thin sheet of palladium metal is exposed to the impure gas
composed of hydrogen and other gaseous species such as nitrogen, oxygen, and water vapor. The hydrogen
selectively diffuses through the sheet to the opposite side, which is maintained at a constant and lower
hydrogen pressure.
Examples
1. A plate of iron is exposed to a carburizing (carbon-rich) atmosphere on one side and a decarburizing
(carbon-deficient) atmosphere on the other side at 700◦C (1300◦F). If a condition of steady state is
achieved, calculate the diffusion flux of carbon through the plate if the concentrations of carbon at
positions of 5 and 10 mm (5 × 10 -3 and 10 -2m) beneath the carburizing surface are 1.2 and 3 0.8 kg/m2
respectively. Assume a diffusion coefficient of 3 × 10 -11 m2 /s at this temperature.
2. One way to manufacture transistors, which amplify electrical signals, is to diffuse impurity atoms into
a semiconductor material such as silicon (Si). Suppose a silicon wafer 0.1 cm thick, which originally
contains one phosphorus atom for every 10 million Si atoms, is treated so that there are 400 phosphorous
(P) atoms for every 10 million Si atoms at the surface as shown on the Figure below. Calculate the
concentration gradient (a) in atomic percent/cm and (b) in atoms/(cm 3 .cm). The lattice parameter of
silicon is 5.4307 A˚ .

Silicon wafer showing variation of concentration of P atoms

3.5 FICKS II Law Non-Steady state diffusion

Figure 3.4: concentration profiles for non-steady state diffusion taken at three different times t1,

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Fick’s Second Law is an extension of the first law to non-steady state flow. Here, at any given instant, the
flux is not the same at different cross-sectional planes along the diffusion direction x. Also, at the same
cross-section, the flux is not the same at different times. Consequently, the concentration-distance profile
changes with time. Non steady state flow is frequently met with in practical applications of the diffusion
laws.
Consider an elemental slab of thickness ∆𝑥 along the diffusion distance x. Let the slab cross-section be
perpendicular to x and its area be unity. The volume of the slab is then ∆𝑥. Under non steady state
conditions, the flux into the slab Jx is not equal to the flux out of the slab, 𝐽𝑥+∆𝑥 . The rate of accumulation
(or depletion) of the diffusing atoms within this elemental volume is
𝜕𝑐
( ) ∆𝑥
𝜕𝑡
It can be expressed as the difference of fluxes in and out of the slab:

𝜕𝑐 𝜕𝐽
( ) ∆𝑥 = 𝐽𝑥 − 𝐽𝑥+∆𝑥 = 𝐽𝑥 − {𝐽𝑥 + ( ) ∆𝑥}
𝜕𝑡 𝜕𝑥

𝜕𝑐 𝜕𝐽
=−
𝜕𝑡 𝜕𝑥
Recall from Fick’s First law, substituting J,
𝜕𝑐 𝜕 𝜕𝑐
= − (−𝐷 )
𝜕𝑥 𝜕𝑥 𝜕𝑥
If we assume that the diffusion coefficient D is not a function of location x and the concentration (c) of
diffusing species, we can write a simplified version of Fick’s second law as follows
𝜕𝑐 𝜕 2𝑐
= (𝐷 2 2 )
𝜕𝑥 𝜕 𝑥
The solution to this equation depends on the boundary conditions for a particular situation. One solution is
𝑐𝑠 − 𝑐𝑥 𝑥
= 𝑒𝑟𝑓 ( )
𝑐𝑠 − 𝑐0 2√𝐷𝑡
where cs is a constant concentration of the diffusing atoms at the surface of the material, c0 is the initial
uniform concentration of the diffusing atoms in the material, and cx is the concentration of the diffusing
atom at location x below the surface after time. In these equations we have assumed a one-dimensional
model (i.e., we assume that atoms or other diffusing species are moving only in the direction x).

3.6 Applications of Diffusion Based on 2nd law;

a. Experimental Determination of D
The diffusion coefficient D can be determined experimentally using a diffusion
couple. A diffusion couple, consists of two long bars welded. face to face, the concentration of the diffusing
species is one, c2, being higher than that in the other, c1. Diffusion takes place across the common face. In
Figure 3.5, the concentration is shown along the y-axis; the origin of the diffusion direction x is at the
common interface.
b. Carburization of Steel
Surface hardening of steel objects such as gears is frequently done by carburizing or nitriding. The process
consists of diffusing carbon (or nitrogen) into the surface layers of the steel object. In pack carburizing, the
object is packed in solid carbon powder. In gas carburizing, an atmosphere of methane gas that is rich in
carbon surrounds the object to be carburized. Here, the following reaction takes place at the steel surface:
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c. Decarburization of Steel
The opposite of carburization is decarburization. Here, the carbon is lost from the surface layers of the steel,
due to an oxidizing atmosphere that reacts with carbon to produce CO or CO2. The fatigue resistance of steels
is lowered due to decarburization and, therefore, it should be avoided by using a protective atmosphere during
the heat treatment of the steel. When the heat treatment is carried out in a non-protective atmosphere (e.g.,
air), the extent of decarburization can be estimated from the diffusion equation and post-machining operations
can be undertaken to remove the decarburized layer.
d. Doping of Semiconductors
Semiconductor devices are doped with small controlled quantities of impurities for obtaining the desired
electrical characteristics. The dopant atoms may be diffused into the pure semiconductor crystal from a
gaseous atmosphere. The depth of penetration and the amount of dopant in the crystal can be estimated
following the same procedure as given for the carburization problem.

3.7 THE KIRKENDELL EFFECT

In a binary solution of A and B, the rates at which A and B diffuse are not necessarily equal. Usually, the lower
melting component diffuses much faster than the other. This leads to certain interesting effects as first observed
by Kirkendall.
Diffusion in Solids Inert markers (thin rods of a high melting point substance which is insoluble in the diffusion
matrix) are placed at the weld joint of the couple, prior to the diffusion anneal. These markers are found to
shift during the anneal in the same direction as the slower moving species. The extent of this shift is found to
be proportional to the square root of the diffusion time. This kind of movement indicates that the net mass
flow due to the difference in diffusivities is being compensated by a bulk flow of matter in the opposite
direction within the diffusion zone. That is, lattice planes are created on one side of the diffusion zone, while
they are destroyed on the other side, and the resulting bulk flow carries the markers along. Notice that the bulk
flow occurs relative to the ends of the diffusion couple. It is quite a different phenomenon from the diffusion
process itself. In many cases, porosity is observed on the lower-melting component side, indicating that the
bulk flow does not fully compensate for the difference in diffusivities of the two species. The following
analogy of gaseous interdiffusion aids in the understanding of the Kirkendall effect. Let hydrogen and argon
at the same pressure be kept in two chambers interconnected through a tube. A frictionless piston in the tube
separates the gases. On opening an orifice in the piston, the gases inter diffuse. The lighter hydrogen will
diffuse faster, resulting in a pressure difference that will tend to shift the piston in the same direction as the
slower diffusing argon is moving.