Chapter Outline

“Crystals are like people, it is the defects in them which

tend to make them interesting!” - Colin Humphreys.
• Defects in Solids
¾ 0D, Point defects
9 vacancies
9 interstitials
9 impurities, weight and atomic composition
¾ 1D, Dislocations
9 edge
9 screw
¾ 2D, Grain boundaries
9 tilt
9 twist
¾ 3D, Bulk or Volume defects

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 Why are defects important?

Bonding
+
Crystal Structure Properties
+

Defects

Defects have a profound impact on the various properties of

materials:
Production of advanced semiconductor devices require not
only a rather perfect Si crystal as starting material, but also
involve introduction of specific defects in small areas of
the sample.
Defects are responsible for color (& price) of a diamond
crystal.
Forging a metal tool introduces defects … and increases
strength of the tool.

2
 Defects can be introduced/removed during processing

Composition

Bonding Crystal Structure

Thermomechanical
Processing

defects introduction and manipulation

Microstructure

Processing allows one to achieve the required properties

without changes in composition of the material, but just
by manipulating the crystal defects.
Control (and intentional introduction) of defects is in the core
of many types of material processing.

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 Defects in Crystals

A 2D representation of a
perfect single crystal with
regular arrangement of atoms.

But … structures of real

materials can be better
represented by the schematic
drawing to the left.

Schematic drawing of a poly-crystal with defects by

Helmut Föll, University of Kiel, Germany.

Real crystals are never perfect, there are always defects

4
 Types of Defects

Defects may be classified into four categories depending on

their dimension:

¾ 0D, Point defects: atoms missing or in irregular places

in the lattice (lattice vacancies, substitutional and interstitial
impurities, self-interstitials)

¾ 1D, Linear defects: groups of atoms in irregular

positions (e.g. screw and edge dislocations)

¾ 2D, Planar defects: the interfaces between

homogeneous regions of the material (e.g. grain
boundaries, stacking faults, external surfaces)

¾ 3D, Volume defects:

extended defects (pores, cracks)

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 Point Defects: Vacancies

Vacancy = absence of an atom

from its normal location in a
perfect crystal structure

Vacancies are always present in crystals and they are

particularly numerous at high temperatures, when atoms
are frequently and randomly change their positions leaving
behind empty lattice sites (vacancies).

How many vacancies are there?

Statistical thermodynamics predicts that the number of
vacancies, Nv, have very strong dependence on
temperature, T, and can be estimated using the Boltzmann
distribution:
N v = N s exp⎛⎜ − v ⎞
Q
k T ⎟
⎝ B ⎠

where Ns is the number of regular lattice sites, kB is the

Boltzmann constant, Qv is the energy needed to form a
vacant lattice site in a perfect crystal, and T the
temperature in Kelvin (note, not in oC or oF).
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 Equilibrium number of vacancies (continued)

N v = N s exp⎛⎜ − v ⎞
Q
k T ⎟
⎝ B ⎠

¾ Vacancies are required to be present in a crystal at

any temperature!
¾ The concentration of vacancies increases sharply
with temperature.

We can estimate for copper:

• at room temperature - one vacancy pet 1015 lattice sites
• at high temperature, just below the melting point - one
vacancy for every 10,000 atoms.

Note, that the above equation gives the lower end

estimation of the number of vacancies in real materials, a
large numbers of additional (non-equilibrium) vacancies
can be introduced in a growth process or as a result of
further treatment (plastic deformation, quenching from
high temperature to the ambient one, etc.)

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 Example: number of vacancies in Cu at room T

N v = N s exp⎛⎜ − v ⎞
Q
k T ⎟
⎝ B ⎠

The Boltzmann’s constant kB = 1.38 × 10-23 J/atom-K =

8.62 × 10-5 eV/atom-K
The temperature in Kelvin T = 27o C + 273 = 300 K.
kBT = 300 K × 8.62 × 10-5 eV/K = 0.026 eV
The energy for vacancy formation Qv = 0.9 eV/atom
The number of regular lattice sites Ns = NAρ/Acu
NA = 6.023 × 1023 atoms/mol
ρ = 8.4 g/cm3
Acu = 63.5 g/mol

(6.023 ×10 23 atoms )× ⎛⎜ 8.4 g

mol ⎝ 3
⎞⎟
cm ⎠
Ns = = 8 × 10 22 atoms
63.5 g cm 3
mol

atoms ⎛ − 0.9 eV atom ⎞=

N v = 8 ×10 22
exp⎜ ⎟
cm 3
⎝ 0.026 eV atom ⎠

= 7.4×107 vacancies cm3

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 Other point defects: self-interstitials, impurities
Schematic representation
of different point defects:
(1) vacancy;
1
3 (2) self-interstitial;
(3) interstitial impurity;
(4,5) substitutional impurities
4
The arrows show the local
2
stresses introduced by the
point defects.
Due to the local stresses
5 introduced by point defects,
they can feel each other
(interact) and feel external
stresses.
The interactions can give a directionality to otherwise
random jumps of atoms.
Self-interstitials:
Self-interstitials in metals introduce large distortions in the
surrounding lattice ⇒ the energy of self-interstitial
formation is ~ 3 times larger as compared to vacancies (Qi
~ 3×Qv) ⇒ equilibrium concentration of self-interstitials is
very low (less than one self-interstitial per cm3 at room T).
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 Impurities
Impurities - atoms which are different from the host

¾ All real solids are impure. Very pure metals 99.9999%

- one impurity per 106 atoms
¾ May be intentional or unintentional
Examples: carbon added in small amounts to iron
makes steel, which is stronger than pure iron. Boron
added to silicon change its electrical properties.
¾ Alloys - deliberate mixtures of metals
Example: sterling silver is 92.5% silver – 7.5% copper
alloy. Stronger than pure silver.

substitutional impurity interstitial impurities

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 Solids with impurities - Solid Solutions
Solid solutions are made of a host (the solvent or
matrix) which dissolves the minor component
(solute). The ability to dissolve is called solubility.

¾ Solvent: in an alloy, the element or compound

present in greater amount
¾ Solute: in an alloy, the element or compound
present in lesser amount
¾ Solid Solution:
9 homogeneous
9 maintain crystal structure
9 contain randomly dispersed impurities
(substitutional or interstitial)
¾ Second Phase: as solute atoms are added, new
compounds / structures are formed, or solute forms
local precipitates (discussed in Chapter 9)

Whether the addition of impurities results in formation of

solid solution or second phase depends the nature of the
impurities, their concentration and temperature, pressure…

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 Substitutional Solid Solutions

Ni

Cu

Factors for high solubility:

¾ Atomic size factor - atoms need to “fit” ⇒ solute
and solvent atomic radii should be within ~ 15%
¾ Crystal structures of solute and solvent should be
the same
¾ Electronegativities of solute and solvent should be
comparable (otherwise new inter-metallic phases
are encouraged)
¾ Generally, in metals, more solute goes into
solution when it has higher valency than solvent

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 Interstitial Solid Solutions

Carbon interstitial
atom in BCC iron

Interstitial solid solution of C in α-Fe. The C atom is small

enough to fit, after introducing some strain into the BCC
lattice.

Factors for high solubility:

¾ For fcc, bcc, hcp structures the voids (or interstices)
between the host atoms are relatively small ⇒ atomic
radius of solute should be significantly less than
solvent
Normally, maximum solute concentration ≤ 10%, e.g. 0.25
wt.% for C in α-Fe (BCC), 2.06 wt.% for C in γ-Fe (FCC).
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 Composition / Concentration
Composition can be expressed in
¾ weight percent, useful when making the solution
¾ atom percent, useful when trying to understand the
material at the atomic level
‰ Weight percent (wt %): weight of a particular element
relative to the total alloy weight. For two-component
system, concentration of element 1 in wt. % is
m1
C 1
wt
= × 100
m1 + m2
m1 and m2 are masses of the two components

‰ Atom percent (at %): number of moles (atoms) of a

particular element relative to the total number of moles
(atoms) in alloy. For two-component system,
concentration of component 1 in at. % is
nm1
C =1
at
× 100
nm1 + nm2

where nm1 = m’1/A1, m’1 is mass in grams of component 1

A1 is atomic mass of component 1

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 Composition Conversions

Weight % to Atomic %:
wt
C 1 A2
C1 = wt
at
× 100
C1 A2 + C2 A1
wt

wt
C 2 A1
C2 = wt
at
× 100
C1 A2 + C2 A1
wt

Atomic % to Weight %:

C1at A1
C1wt = at × 100
C1 A1 + C2 A2
at

C2at A2
C2wt = at × 100
C1 A1 + C2 A2
at

Textbook, pp. 96-99

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 Composition Conversions

From Weight % to mass per unit volume (g/cm3):

C1wt C2wt
C1 = wt C2 = wt
C1 C2wt C1 C2wt
+ +
ρ1 ρ2 ρ1 ρ2
C1 and C2 are concentrations of the first and second
components in g/cm3

Average density & average atomic weight in a binary alloy

100
Average density ρ ave = wt
of a binary alloy C1 C2wt
+
ρ1 ρ2

Average atomic weight C1at A1 + C2at A2

of a binary alloy Aave =
100

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 Dislocations—Linear Defects
Dislocations are linear defects: the interatomic bonds are
significantly distorted only in the immediate vicinity of the
dislocation line. This area is called the dislocation core.
Dislocations also create small elastic deformations of the
lattice at large distances.

Dislocations are very important in mechanical properties of

material (Chapters 6, 7, 8). Introduction/discovery of
dislocations in 1934 by Taylor, Orowan and Polyani
marked the beginning of our understanding of mechanical
properties of materials.

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 Description of Dislocations—Burgers Vector
To describe the size and the direction of the lattice
distortion caused by a dislocation we should introduce so-
called Burgers vector b. To find the Burgers vector, we
should make a circuit from from atom to atom counting the
same number of atomic distances in all directions. If the
circuit encloses a dislocation it will not close. The vector
that closes the loop is the Burgers vector b.

Dislocations shown above have Burgers vector directed

perpendicular to the dislocation line. These dislocations
are called edge dislocations.

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 Edge and screw dislocations
Dislocations shown in previous slide are edge dislocations.
They have Burgers vector directed perpendicular to the
dislocation line.
There is a second basic type of dislocation, called screw
dislocation. The screw dislocation is parallel to the
direction in which the crystal is being displaced (Burgers
vector is parallel to the dislocation line).

Find the Burgers vector of a screw dislocation.

How a screw dislocation got its name?

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 Mixed/partial dislocations (not tested)

The exact structure of dislocations in real crystals is

usually more complicated than the ones shown in this
pages. Edge and screw dislocations are just extreme forms
of the possible dislocation structures. Most dislocations
have mixed edge/screw character.

To add to the complexity to real defect structures,

dislocation are often split in "partial“ dislocations that have
their cores spread out over a larger area.

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 Where do dislocations come from ?
The number of dislocations in a material is expressed as the
dislocation density - the total dislocation length per unit
volume or the number of dislocations intersecting a unit
area. Dislocation densities can vary from 105 cm-2 in
carefully solidified metal crystals to 1012 cm-2 in heavily
deformed metals.

Most crystalline materials, especially metals, have

dislocations in their as-formed state, mainly as a result of
stresses (mechanical, thermal...) associated with the
forming process.

The number of dislocations

increases dramatically
during plastic deformation
(Ch.7). Dislocations spawn
from existing dislocations,
grain boundaries & surfaces
This picture is a snapshot from
simulation of plastic deformation
in a fcc single crystal (Cu) of
linear dimension 15 micrometers.

http://zig.onera.fr/DisGallery/3D.html

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 Experimental and computational images of
dislocation structures

Dislocations in Ni (the dark lines and loops), transmission

electron microscopy image, Manchester Materials Science Center.

Atomistic simulation of work-hardening in a FCC solid,

IBM-LLNL collaboration.
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 Planar (interfacial) defects
External Surfaces
Surface atoms have have unsatisfied atomic bonds, and
higher energies than the bulk atoms ⇒ Surface energy, γ
(J/m2)
• Minimization of surface areas reduces the energy of the
system (e.g. liquid drop)
• Solid surfaces can “reconstruct” to satisfy atomic bonds
at surfaces.

Grain Boundaries
Polycrystalline material comprised of many small crystals
or grains. The grains have different crystallographic
orientation. There exist atomic mismatch within the
regions where grains meet. These regions are called grain
boundaries.

Grain Boundary
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Surfaces and interfaces have structure that is different from
the bulk and can be reactive → impurities tend to segregate
there.
Since energy is associated with interfaces, grains tend to
grow in size at the expense of smaller grains to minimize
energy. This occurs by diffusion (Chapter 5), which is
accelerated at high temperatures.

High and low angle grain boundaries

Depending on misalignments of atomic planes
between adjacent grains we can distinguish between
the low and high angle grain boundaries

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 Low angle grain boundaries

Small angle grain boundaries can be described as arrays of

dislocations. This is a transmission electron microscope
image of a small angle tilt boundary in Si. The red lines
mark the edge dislocations, the angle between the blue
lines corresponds to the tilt angle.
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Interaction between dislocations and grain boundaries
Motion of dislocations can be impeded by grain boundaries
– increase of the force needed to move then
(strengthening the material).

Grain boundary present a barrier to dislocation motion: slip

plane discontinues or change orientation.
Small angle grain boundaries are not very effective in
blocking dislocations.
High-angle grain boundaries block slip and increase
strength of the material. A stress concentration at end of a
slip plane may trigger new dislocations in an adjacent
grain.
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 Tilt and twist grain boundaries
If the rotation axis that corresponds to the angle of
misorientation between the adjacent grains is parallel to the
boundary plane, the grain boundary is called tilt boundary
(consider joint of two wedges).

A small-angle tilt grain boundary

can be represented as an array of
aligned edge dislocations.

If the misorientation occurs around

an axis that is perpendicular to the
boundary plane, the grain boundary
is called twist grain boundary

Small angle twist boundary an be represented by an array

of screw dislocations (consider joint of two halves of a
cube and twist an angle around the cross section normal)

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 Twin Boundaries (not tested)

Low-energy twin boundaries with mirrored atomic

positions across boundary may be produced by
deformation of materials. This gives rise to shape
memory metals, which can recover their original shape if
heated to a high temperature. Shape-memory alloys are
twinned and when deformed they untwin. At high
temperature the alloy returns back to the original twin
configuration and restore the original shape.

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 Bulk or volume defects

¾ Pores
¾ Cracks
¾ Foreign inclusions

Presence of volume defects can greatly affect

electrical, mechanical, thermal, and optical
properties of the material

A cluster of microcracks in a
melanin granule irradiated by a
short laser pulse.
Computer simulation by Zhigilei and
Garrison.

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Atomistic simulation of crack propagation

V. Bulatov et al., Nature 391, #6668, 669 (1998)

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