SECTION 5

LU2: Diffusion
 Learning Outcomes

LO12: Describe atomic diffusion mechanisms.

LO13: Distinguish between steady-state and nonsteady-state
diffusion.
LO14: Define and apply Fick’s Laws for diffusion.
 Introduction
In many engineering applications, diffusion of one type of
atom in the crystal structure of another, in the solid state, is
required to enhance performance.
Examples are of such applications are : case hardening of
steel through diffusion of carbon (left), doping of silicon
chips with phosphorus or aluminum (middle), and joining of
dissimilar components such as ceramics and metals (right).
 Cont…Types of Diffusion
Interdiffusion/ Impurity Diffusion
The process by which atoms of one metal or compound diffuse into another

Self-diffusion
Diffusion type that occurs in pure metals and atoms exchanging positions are of the
same type.
 Diffusion Mechanisms
Diffusion is a process by which one matter is transported
through another matter.
Examples:
• Movement of smoke particles in air : Very fast process
• Movement of dye in water : Relatively slow process
• Solid state reactions: Very restricted movement due strong atomic
bonds
In solids, thermal atomic vibrations allow some atoms to move.
Atoms move/diffuse in solids by TWO MECHANISMS
1. Vacancy or Substitutional Diffusion Mechanism
2. Interstitial Diffusion Mechanism
Vacancies are necessary as they lower the energy needed to
break the bonds between atoms.
 Vacancy or Substitutional Diffusion
Example: If atom ‘A’
has sufficient energy, DE*,
it moves into the vacancy;
called self diffusion.

Activation Activation Activation

energy of energy to energy to
= +
self form a move to a
diffusion vacancy vacancy

Activation Activation
Melting Temperature Range
Metal Crystal Structure Energy Energy
Point (°C) Studied (°C)
kJ/mol kcal/mol
Zinc 419 HCP 240–418 91.6 21.9
Aluminum 660 FCC 400–610 165 39.5 Activation energies for self
Copper 1083 FCC 700–990 196 46.9 diffusion:
Nickel 1452 FCC 900–1200 293 70.1
α iron 1530 BCC 808–884 240 57.5 as the melting point
Molybdenum
*Silicon
2600
1414
BCC
Diamond Cubic
2155–2540
927–1377
460
483
110
115
increases, activation energy
**Carbon Diamond Diamond Cubic 1800–2100 655 156 also increases
 Interstitial Diffusion Mechanism
Atoms move from one
interstitial site to another.
The diffusing atoms must
be much smaller than the
matrix atom.
The diffusing atoms must not be
larger than available interstitial
sites.
Example:
Carbon (r = 0.077 nm) interstitially diffuses FCC γ iron sites (r =
0.053 nm).
Fick’s 1st Law – Steady State Diffusion
The flux or flow of diffusing atoms is given by

J = Flux or net flow of atoms, atoms/m2.s

dc
J = −D D = Diffusion coefficient, m2/s
dx
dc 1 / dx
dc
= Concentration Gradient, (atoms/m3) (1/m)
dx
For steady state diffusion condition, the net flow of atoms by
atomic diffusion is equal to diffusion D times the diffusion
gradient dc/dx.
Example: Diffusivity of carbon in FCC iron at 500°C is
5 × 10-15 m2/s and at 1000°C is 3 × 10-11 m2/s; higher
temperatures lead to higher diffusivity.
 Steady State Diffusion
In steady state diffusion, there is no change in concentration of
solute atoms at different planes in a system, over a period of
time.
No chemical reaction occurs. Only net flow of atoms.

Net flow of atoms

Per unit area per
unit time = J
 Example 5.1
A plate of iron is exposed to a carburizing (carbon-rich) atmosphere on one side,
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 (5x10-3 and 10-2 m) beneath the carburizing surface are 1.2. and 0.8 kg/m3,
respectively. Assume a diffusion coefficient of 3 x 10-11 m2/s at this temperature.

Solution pg134

Fick’s 1st Law

𝑑𝑐 𝑐1−𝑐2
𝐽 = −𝐷 𝑑𝑥 = −𝐷 𝑥1−𝑥2
Fick’s 2nd Law: Non-steady State Diffusion
In non-steady diffusion, the concentration of solute atoms at any
point in metal changes with time.
Ficks 2nd law: Rate of compositional change is equal to diffusivity
times the rate of change of concentration gradient.

dCx d  dcx 
Change of concentration of
solute atoms with change in
= D 
time in different planes

dt dx  dx 
 Fick’s Second Law – Solution
Cs − C x  x 
= erf 
Cs − C0  2 Dt  Gaussian error function
𝑥
𝑧= 2 𝐷𝑡
𝐶𝑥 − 𝐶0 𝑥
= 1 − 𝑒𝑟𝑓
𝐶𝑠 − 𝐶0 2 𝐷𝑡

Cs = Surface concentration of
diffusing element (atoms/m3)

C0 = Initial uniform concentration

of element in the solid (atoms/m3)

Cx = Concentration of element at
a distance x from surface (atoms/m3)
Initial condition: For t = 0, C = C0 at 0 ≤ x ≤ ∞
x = distance from the surface (m)
Boundary conditions: For t > 0, C = Cs (the
D = diffusivity (m2/s) constant surface concentration) at x = 0 For t
> 0, C = C0 at x = ∞
t = time (s)
 Example 5.2
For some applications, it is necessary to harden the surface of a steel (or
iron–carbon alloy) above that of its interior. One way this may be
accomplished is by increasing the surface concentration of carbon in a
process termed carburizing; the steel piece is exposed, at an elevated
temperature, to an atmosphere rich in a hydrocarbon gas, such as methane
(CH4). Consider one such alloy that initially has a uniform carbon
concentration of 0.25 wt% and is to be treated at 950°C (1750°F). If the
concentration of carbon at the surface is suddenly brought to and
maintained at 1.20 wt%, how long will it take to achieve a carbon content of
0.80 wt% at a position 0.5 mm below the surface? The diffusion coefficient
for carbon in iron at this temperature is 1.6 × 10−11 m2 /s; assume that the
steel piece is semi-infinite.

Solution pg137
𝐶𝑥 − 𝐶0 𝑥
= 1 − 𝑒𝑟𝑓
𝐶𝑠 − 𝐶0 2 𝐷𝑡
 Example 5.3
The diffusion coefficient for copper in aluminum at 500°C and 600°C are 4.8x10-14 and
5.3x10-13 m2/s, respectively. Determine the appropriate time at 500°C that will produce
the same diffusion result (in terms of concentration of Cu at some specific point in Al) as
a 10-hour heat treatment at 600°C.

Solution pg138

𝑥02 𝑥02
=
𝐷1 𝑡1 𝐷2 𝑡2
 Factors That Influence Diffusion
Diffusivity, D, depends upon
o Diffusing Species
• Type of diffusion mechanism: interstitial or substitutional
• Type of crystal structure of the solvent lattice and size of the interstitial site size ( FCC
is larger than BCC)
• Type of crystal imperfection: more open structures (grain boundaries) increase
diffusion
• The concentration of diffusing species: higher concentrations of diffusing solute
atoms will affect diffusivity
o Temperature: as the temperature increases, diffusivity increases
Diffusivity (m2/s) Diffusivity (m2/s)
Solute Solvent (Host Structure)
500°C (930°F) 1000°C (1830°F)

Carbon FCC iron (5×10-15)* 3 × 10−11

Diffusivity of
Carbon BCC iron 10−12 (2 × 10−9)
selected solute
Iron FCC iron (2 × 10−23) 2 × 10−16 species in
Iron BCC iron 10−20 (3 × 10−14) selected solvents
Nickel FCC iron 10−23 2 × 10−16

Manganese FCC iron (3 × 10−24) 10−16

 Cont… Temperature
Temperature has a profound influence on the coefficients and diffusion rates.

Temperature dependence of diffusion coefficient is:

𝑄𝑑
𝐷 = 𝐷0𝑒𝑥𝑝 −
𝑅𝑇
Where,

D0 = a temperature-independent preexponential (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)

𝑄𝑑 1
𝑙𝑛𝐷 = 𝑙𝑛𝐷0 − −
𝑅 𝑇

or

𝑄𝑑 1
𝑙𝑜𝑔𝐷 = 𝑙𝑜𝑔𝐷0 − −
2.3𝑅 𝑇

Because D0,Qd and R are all constants; the logarithm equations take form of a straight-line
equation: y=b+mx
 Example 5.4
Using the data in Table 5.2, compute the diffusion coefficient for magnesium in aluminum
at 550°C.

Solution pg141
𝑄𝑑
𝐷 = 𝐷0𝑒𝑥𝑝 −
𝑅𝑇
 Example 5.5
Figure 5.7 shows a plot of the logarithm (to the base 10) of the diffusion coefficient
versus reciprocal of absolute temperature for the diffusion of copper in gold.
Determine values for the activation energy and the preexponential.

Solution pg141

From Equation 5.9b the slope of the line segment in Figure 5.7 is equal to −Qd/2.3R,
and the intercept at 1/T = 0 gives the value of log D0. Thus, the activation energy may
be determined as

𝑙𝑜𝑔𝐷1 − 𝑙𝑜𝑔𝐷2
𝑄𝑑 = −2.3𝑅 𝑠𝑙𝑜𝑝𝑒 = −2.3𝑅
1 1
−
𝑇1 𝑇2

𝑄𝑑 1
𝑙𝑜𝑔𝐷 = 𝑙𝑜𝑔𝐷0 − −
2.3𝑅 𝑇
 Design Example 5.1
The wear resistance of a steel gear is to be improved by hardening its surface.
This is to be accomplished by increasing the carbon content within an outer
surface layer as a result of carbon diffusion into the steel; the carbon is to be
supplied from an external carbon-rich gaseous atmosphere at an elevated and
constant temperature. The initial carbon content of the steel is 0.20 wt%,
whereas the surface concentration is to be maintained at 1.00 wt%. For this
treatment to be effective, a carbon content of 0.60 wt% must be established
at a position 0.75 mm below the surface. Specify an appropriate heat
treatment in terms of temperature and time for temperatures between 900
and 1050°C. Use data in Table 5.2 for the diffusion of carbon in 𝛾-iron

Solution
𝐶𝑥 − 𝐶0 𝑥
= 1 − 𝑒𝑟𝑓
𝐶𝑠 − 𝐶0 2 𝐷𝑡

𝑄𝑑
𝐷 = 𝐷0𝑒𝑥𝑝 −
𝑅𝑇
 Industrial Applications of Diffusion – Case
Hardening
Sliding and articulating parts required hard surfaces to avoid
wear.
The surfaces of articulating parts are hardened by gas
carburization.
Steel parts are placed at elevated temperature (927°C) in an
atmosphere of hydrocarbon gas (CH4).
Carbon diffuses into iron surface and fills interstitial space to
make it harder.

Figure shows surface

hardened gear tooth:
the black dots are
indentation marks due
to hardness tests
Carburizing

Carbon Gradients
In Carburized metals
Table : Tabulation of Error Function Values Table 5.2: Diffusion Data
Diffusion in Semiconducting Materials
o One technology that applies solid-state diffusion is the fabrication of
semiconductor integrated circuits (ICs).
o Each integrated circuit chip is a thin square wafer having dimensions on the order
of 6 mm × 6 mm × 0.4 mm; furthermore, millions of interconnected electronic
devices and circuits are embedded in one of the chip faces.
o Single-crystal silicon is the base material for most ICs.
o Precise concentrations of impurities are diffused into these silicon-based
materials to optimize the functionality of IC devices.

o Two heat treatments are used: Pre-deposition step and Drive-in diffusion

o Predeposition step:
• Impurities are deposited in the silicon under constant partial pressure
• Thus, Cs of impurities remain constant over time, and is a function of
position and time according to;
𝐶𝑥 − 𝐶0 𝑥
= 1 − 𝑒𝑟𝑓
𝐶𝑠 − 𝐶0 2 𝐷𝑡
Are normally carried out within temp. range of 900 – 1000°C for <1 hour.
 Cont…
o Drive-in diffusion Step
• Used to transport (drive-in) impurities farther into the silicon in order to provide
a more suitable concentration distribution without increasing the overall
impurity content.
• Carried out at higher temperatures, up to 1200°C.

• Carried out under oxidizing atmosphere so as to form an oxide layer (SiO2)on

the surface.
• Diffusion rates are relatively slow through this SiO2.
 Cont…
If we assume that the impurity atoms introduced during predeposition treatment are
confined to a very thin layer at the surface of the silicon, the solution to Fick’s second law
for drive-in diffusion takes the form;

𝑄0 𝑥2
𝐶(𝑥, 𝑡) = 𝑒𝑥𝑝 −
𝜋𝐷𝑡 4𝐷𝑡

Q0 is the total amount of impurities in the solid that were introduced during
predeposition treatment (in number of impurity per unit area);
𝐷𝑝 𝑡𝑝
𝑄0 = 2𝐶𝑠
𝜋
where Cs is the surface concentration for the predeposition step, which was held
constant, Dp is the diffusion coefficient, and tp is the predeposition treatment time

Junction depth (xi): represents the depth at which the diffusing impurity concentration is
equal to the background concentration of that impurity in the silicon (CB).

Dd and td represent, respectively, the diffusion 𝑄0

𝑥𝑖 = 4𝐷𝑑 𝑡𝑑 𝑙𝑛
coefficient and time for the drive-in treatment. 𝐶𝐵 𝜋𝐷𝑑 𝑡𝑑
 Example 5.6
Boron atoms are to be diffused into a silicon wafer using both predeposition and drive-
in heat treatments; the background concentration of B in this silicon material is known
to be 1 × 1020 atoms/m3 . The predeposition treatment is to be conducted at 900°C for
30 min; the surface concentration of B is to be maintained at a constant level of 3 ×
1026 atoms/m3 . Drive-in diffusion will be carried out at 1100°C for a period of 2 h. For
the diffusion coefficient of B in Si, values of Qd and D0 are 3.87 eV/atom and 2.4 ×
10−3 m2 /s, respectively.
(a) Calculate the value of Q0.
(b) Determine the value of xj for the drive-in diffusion treatment.
(c) Also for the drive-in treatment, compute the concentration of B atoms at a position
1 μm below the surface of the silicon wafer.

Solution pg145
(a) The value of Q0 is calculated using Equation 5.12. However, before this is possible,
it is first necessary to determine the value of D for the predeposition treatment [Dp
at T = Tp = 900°C (1173 K)] using Equation 5.8. (Note: For the gas constant R in
Equation 5.8, we use Boltzmann’s constant k, which has a value of 8.62 × 10−5
eV/atom∙K). Thus; 𝑄𝑑
𝐷 = 𝐷0𝑒𝑥𝑝 − K (Boltzmann’s constant) =
𝑘𝑇𝑝 8.62x10-5 eV/atom.K

𝐷𝑝 𝑡𝑝
𝑄0 = 2𝐶𝑠
𝜋
 Cont…
(b) Computation of the junction depth requires that we use Equation 5.13. However,
before this is possible, it is necessary to calculate D at the temperature of the drive-in
treatment [Dd at 1100°C (1373 K)]. Thus;
𝑄𝑑
𝐷𝑑 = 𝐷0𝑒𝑥𝑝 −
𝑘𝑇𝑝

𝑄0
𝑥𝑖 = 4𝐷𝑑 𝑡𝑑 𝑙𝑛
𝐶𝐵 𝜋𝐷𝑑 𝑡𝑑

(c) At x = 1 μm for the drive-in treatment, we compute the concentration of B atoms

using Equation 5.11 and values for Q0 and Dd determined previously as follows:

𝑄0 𝑥2
𝐶(𝑥, 𝑡) = 𝑒𝑥𝑝 −
𝜋𝐷𝑑𝑡 4𝐷𝑑𝑡