EMT282

PRINCIPLES OF ENGINEERING MATERIAL

Lecture 3: Crystal Structure

Dr. Rozana Aina Maulat Osman

Microelectronic Engineering
Block 9: Room 00-01-0A
04-9885532
 Materials and Packing
Materials – Atoms/ions arrangement

• Crystalline material - Material whose atoms and

ions arranged in a pattern (long-range order)

• amorphous or noncrystalline - Material whose

atoms and ions that are not arranged in a long
range, periodic, and repeated manner (short-
range order )
 Materials and Packing
Crystalline materials...
• atoms pack in periodic
• eg: -metals
-many ceramics
-some polymers

Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline
-glass
3
 Materials and Packing
crystalline SiO2

crystalline

noncrystalline SiO2
Semi-crystalline

amorphous

Adapted from Fig. 3.18(b),

Callister 6e.
 Crystal Systems and Bravais Lattice
• Only seven different types of unit cells are necessary to create all
point lattices.
 Cubic
 Tetragonal
 Rhombohedra
 Orthorhombic
 Hexagonal
 Monoclinic
 Triclinic

• According to Bravais (1811-1863) fourteen standard unit cells can

describe all possible lattice networks.

• The four basic types of unit cells are:

 Simple
 Body Centered
 Face Centered
 Base Centered

3-3
 Types of Unit Cells
• Cubic Unit Cell
 a=b=c
 α = β = γ = 900

Simple Body Centered

Face centered

• Tetragonal
 a =b ≠ c
 α = β = γ = 900

Simple Body Centered

3-4 After W.G. Moffatt, G.W. Pearsall, & J. Wulff, “The Structure and Properties of Materials,” vol. I: “Structure,” Wiley, 1964, p.47.)
 Types of Unit Cells (Cont..)
• Orthorhombic
 a≠ b≠ c
 α = β = γ = 900

Simple Base Centered

Body Centered
Face Centered
• Rhombohedral
 a =b = c
 α = β = γ ≠ 900

Simple
3-5 After W.G. Moffatt, G.W. Pearsall, & J. Wulff, “The Structure and Properties of Materials,” vol. I: “Structure,” Wiley, 1964, p.47.)
 Types of Unit Cells (Cont..)

• Hexagonal
 a≠ b≠ c Simple
 α = β = γ = 900

• Monoclinic
 a≠ b≠ c Base
 α = β = γ = 900 Centered
Simple

• Triclinic
 a≠ b≠ c
 α = β = γ = 900
Simple

3-6 After W.G. Moffatt, G.W. Pearsall, & J. Wulff, “The Structure and Properties of Materials,” vol. I: “Structure,” Wiley, 1964, p.47.)
 Principal Metallic Crystal Structures
• 90% of the metals crystallize into three densely packed
crystal structures: Body Centered Cubic (BCC), Face Centered
Cubic (FCC) or Hexagonal Close Packed (HCP) crystal
structure.
• HCP is denser version of simple hexagonal crystal structure.
• Most metals crystallize in these dense-packed structures
because energy is released (more stable) as the atoms come
closer together and bond more tightly with each other.

BCC Structure FCC Structure HCP Structure

3-7
• Example:
The cube side of the unit cell of body-centered cubic iron at
room temperature is equal to 0.287X10-9m or 0.287(nm)2.
Therefore, if unit cells of pure iron are lined up side by side in
1mm, how many unit cells we have in 1mm?

31unit cell
110  9
 3.48  10 6
unit cells
0.287 10
 Body Centered Cubic (BCC) Crystal
Structure
• Represented as one atom at each corner of cube and one at
the center of cube.
• Each atom has 8 nearest neighbors.
• Therefore, coordination number is 8.
• Examples :- movie
 Chromium (a=0.289 nm)
 Iron (a=0.287 nm)
 Sodium (a=0.429 nm)

Figure 3.4 a&b

3-8
 BCC Crystal Structure (Cont..)

• Each unit cell has eight 1/8

atom at corners and 1
full atom at the center.
• Therefore each unit cell has
(8x1/8 ) + 1 = 2 atoms

• Atoms contact each

other at cube diagonal
Figure 3.5
Therefore, lattice 4R
constant a =
3
3-9
• Iron at 20C is BCC with atoms of atomic radius 0.124nm.
Calculate the lattice constant, a, for the cube edge of the iron
unit cell.

Solutions:
From Fig. 3.5, it is seen that the atoms in the BCC unit cell touch
across the cube diagonals. Thus, if a is the length of the cube
edge, then

3a  4 R, where R is the radius of the iron atom.

Therefore
4 R 4(0.124nm)
a   0.2864nm
3 3
 Atomic Packing Factor of BCC Structure
If the atoms in the BCC unit cell are considered to be spherical,
Volume of atoms in unit cell
Atomic Packing Factor =
(APF) Volume of unit cell

 4R 3 
Vatoms = 2. = 8.373R3
 
 3 
3
 4R 
V unit cell = a3 =   = 12.32 R3
 
 3 

8.723 R3
Therefore APF = 12.32 R3 = 0.68

3-10
 Face Centered Cubic (FCC) Crystal
Structure
• FCC structure is represented as one atom each at the corner
of cube and at the center of each cube face.
• Coordination number for FCC structure is 12
• Atomic Packing Factor is 0.74
• Examples :- movie , NaCl , Zn blende
 Aluminum (a = 0.405)
 Gold (a = 0.408)

Figure 3.6 a&b

3-11
 FCC Crystal Structure (Cont..)

• Each unit cell has eight 1/8

atom at corners and six ½
atoms at the center of six
faces.
• Therefore each unit cell has
(8 x 1/8)+ (6 x ½) = 4 atoms

Movie
• Atoms contact each other
across cubic face diagonal
Therefore, lattice 4R
constant , a = Figure 3.7
2
3-12
 Atomic Packing Factor of FCC Structure

Volume of atoms in unit cell

Atomic Packing Factor =
(APF) Volume of unit cell

 4R 3 
Vatoms = 4. = 16.746R3
 3 

3
V unit cell = a3 =  4R 
  = 22.617 R3
 2

8.723 R3
Therefore APF = 12.32 R3 = 0.74

FCC is crystal structure is more close-packed than BCC crystal structure

3-10
 Hexagonal Close-Packed Structure
• The HCP structure is represented as an atom at each of 12
corners of a hexagonal prism, 2 atoms at top and bottom
face and 3 atoms in between top and bottom face.
• Atoms attain higher APF by attaining HCP structure than
simple hexagonal structure.
• The coordination number is 12, APF = 0.74.

Figure 3.8 a&b

3-13 After F.M. Miller, “Chemistry: Structure and Dynamics,” McGraw-Hill, 1984, p.296
 HCP Crystal Structure (Cont..)
• Each atom has six 1/6 atoms at each of top and bottom
layer, two half atoms at top and bottom layer and 3 full
atoms at the middle layer.
• Therefore each HCP unit cell has
(2 x 6 x 1/6) + (2 x ½) + 3 = 6 atoms
• Examples:-
 Zinc (a = 0.2665 nm, c/a = 1.85)
 Cobalt (a = 0.2507 nm, c.a = 1.62)

• Ideal c/a ratio is 1.633.

Figure 3.8 c
3-14 After F.M. Miller, “Chemistry: Structure and Dynamics,” McGraw-Hill, 1984, p.296
 HCP Crystal Structure (Cont..)

Referring to (c) the atoms at locations “1” contribute 1/6 of an atom, whereas the atoms
At locations marked “2” contribute 1/12 of an atom.

Thus, the atoms at the eight corner of the unit cell contribute one atom
(4(1/6)+4(1/12)=1).

There is one atom at the center inside the unit cell, therefore, total number of atoms in a
unit cell is 2 (1 at corners and 1 ant center).
 Atom Positions in Cubic Unit Cells
• Cartesian coordinate system is use to locate atoms.
• In a cubic unit cell
 y axis is the direction to the right.
 x axis is the direction coming out of the paper.
 z axis is the direction towards top.
 Negative directions are to the opposite of positive directions.

• Atom positions are

located using unit
distances along the
axes.

Figure 3.10 b
3-15
 Directions in Cubic Unit Cells
• In cubic crystals, Direction Indices are vector components of
directions resolved along each axes, resolved to smallest
integers.
• Direction indices are position coordinates of unit cell where
the direction vector emerges from cell surface, converted to
integers.
• The Direction Indices are enclosed by square brackets with no
separating commas.

Figure 3.11
3-16
Two important things to remember for
direction indices……
• Note that all parallel direction vectors have
the same direction indices.
• Directions are said to be crystallographical
equivalent if the atom spacing along each
direction is the same.
Example:
[100],[010],[001],[010],[001],[100]=<100>
Equivalent directions are called indices of family
or form.
Example:
Draw the following direction vectors in cubic
unit cells.
a)[100] and [110]
b) [112]
c)[110]
d) [321]
Solutions:
 Miller Indices for Crystallographic Planes
• Miller Indices are used to refer to specific lattice planes of
atoms.
• They are reciprocals of the fractional intercepts (with
fractions cleared) that the plane makes with the
crystallographic x,y and z axes of three nonparallel edges of
the cubic unit cell.
z Miller Indices =(111)

x
3-19
 Miller Indices - Procedure
Choose a plane that does not pass
through origin

Determine the x,y and z intercepts

of the plane

Find the reciprocals of the intercepts

Fractions? Clear fractions by

multiplying by an integer
Place a ‘bar’ over the to determine smallest set
Negative indices of whole numbers

Enclose in parenthesis (hkl)where h,k,l

are miller indices of cubic crystal plane
forx,y and z axes. Eg: (111)

3-20
Let try together...

Plane for (111)

 More....

Plane for (010)

 Miller Indices - Examples
z
• Intercepts of the plane at
x,y & z axes are 1, ∞ and ∞
(100) • Taking reciprocals we get
y (1,0,0).
x • Miller indices are (100).
x *******************
• Intercepts are 1/3, 2/3 & 1.
• taking reciprocals we get
(3, 3/2, 1).
• Multiplying by 2 to clear
fractions, we get (6,3,2).
• Miller indices are (632).
Figure 3.14
3-21
Miller Indices - Examples
 Miller Indices - Examples
• Plot the plane (101)
Taking reciprocals of the indices
we get (1 ∞ 1).
The intercepts of the plane are
x=1, y= ∞ (parallel to y) and z=1.
Figure EP3.7 a
******************************
• Plot the plane (2 2 1)
Taking reciprocals of the indices
we get (1/2 1/2 1).
The intercepts of the plane are
x=1/2, y= 1/2 and z=1.

Figure EP3.7 c

3-22
 Remember….
• All equal spaced parallel planes are indicated
by the same Miller indices.
• If sets of equivalent lattice planes are related
by the symmetry of the crystal system, they
are called planes of a family or form.
• Example: Miller indices (100), (010), (001) are
designated as a family by notation {100}.
 Comparison of FCC and HCP crystals
• Both FCC and HCP are close packed and have
APF 0.74.
• FCC crystal is close packed in (111) plane while
HCP is close packed in (0001) plane.

Figure 3.19 a&b

3-28 After W.G. Moffatt, G.W. Pearsall, & J. Wulff, “The Structure and Properties of Materials,” vol. I: “Structure,” Wiley, 1964, p.51.)
 Structural Difference between HCP and FCC
Plane A
Consider a layer ‘a’ void
of atoms (Plane ‘A’) ‘b’ void

Another layer (plane ‘B’) Plane A

of atoms is placed in ‘a’ Plane B
Void of plane ‘A’ ‘a’ void
‘b’ void

Third layer of Atoms placed Third layer of Atoms placed

in ‘b’ Voids of plane ‘B’. (Identical in ‘a’ voids of plane ‘B’. Resulting
to plane ‘A’.) HCP crystal. In 3rd Plane C. FCC crystal.

Plane A Plane A
Plane B Plane B
Plane A Plane C

Figure 3.20
3-29
 Volume Density
• Volume density of metal = v Mass/Unit cell
= m/v = Volume/Unit cell

• Example:- Copper (FCC) has atomic mass of 63.54 g/mol and

atomic radius of 0.1278 nm.
4R 4  0.1278nm = 0.361 nm
a= =
2 2
Volume of unit cell = V= a3 = (0.361nm)3 = 4.7 x 10-29 m3
FCC unit cell has 4 atoms.
(4atoms)(63.54 g / mol)  106 Mg 
Mass of unit cell = m =   = 4.22 x 10 -28 Mg
6.02 1023 atoms / mol  g 

v 
m

4.22  10 28 Mg
 8.98
Mg
 8.98
g

V 4.7  10 29 m 3 m3 cm 3
3-30
 Planar Atomic Density
Equivalent number of atoms whose
Planar atomic density=  =
centers are intersected by selected area
• p
Selected area

• Example:- In Iron (BCC, a=0.287), The (110) plane intersects

center of 5 atoms (Four ¼ and 1 full atom).
 Equivalent number of atoms = (4 x ¼ ) + 1 = 2 atoms
Area of 110 plane = 2a  a  2a 2


2
=
2 0.287
p 2

17.2atoms 1.72  1013

 
nm 2 mm 2
Figure 3.22 a&b

3-31
 Linear Atomic Density
Number of atomic diameters
intersected by selected length

• Linear atomic density =  l

=
of line in direction of interest
Selected length of line

• Example:- For a FCC copper crystal (a=0.361), the [110]

direction intersects 2 half diameters and 1 full diameter.
 Therefore, it intersects ½ + ½ + 1 = 2 atomic diameters.
 Face diagonal fcc = √2a

Length of line = 2  0.361nm

 l

2atoms

3.92atoms

3.92  106 atoms

2  0.361nm nm mm

Figure 3.23
3-32
 Polymorphism or Allotropy
• Metals exist in more than one crystalline form. This is caller
polymorphism or allotropy.
• Temperature and pressure leads to change in crystalline
forms.
• Example:- Iron exists in both BCC and FCC form
Liquid
depending on the temperature. Iron

-2730C 9120C 13940C 15390C

α Iron γ Iron δ Iron

BCC FCC BCC

3-33
 Crystal Structure Analysis
• Information about crystal structure are obtained using X-
Rays.
• The X-rays used are about the same wavelength (0.05-0.25
nm) as distance between crystal lattice planes.

35 KV

(Eg:
Molybdenum)

Figure 3.25

3-34 After B.D. Cullity, “Elements of X-Ray Diffraction, “ 2d ed., Addison-Wesley, 1978, p.23.
 X-Ray Spectrum of Molybdenum
• X-Ray spectrum of Molybdenum is
obtained when Molybdenum is
used as target metal.
• Kα and Kβ are characteristic of
an element.
• For Molybdenum Kα occurs at
wave length of about 0.07nm.
• Electrons of n=1 shell of target
metal are knocked out by
bombarding electrons.
• Electrons of higher level drop
down by releasing energy to
replace lost electrons
Figure 3.26

3-35
 X-Ray Diffraction
• Crystal planes of target metal act as mirrors reflecting X-ray
beam.
• If rays leaving a set of planes
are out of phase (as in case of
arbitrary angle of incidence)
no reinforced beam is
produced.
Figure 3.28

• If rays leaving are in phase,

reinforced beams are
produced.

3-36 After A.G. Guy and J.J. Hren, “Elements of Physical Metallurgy,” 3d ed., Addison-Wesley, 1974, p.201.)
 X-Ray Diffraction (Cont..)
• For rays reflected from different planes to be in phase, the
extra distance traveled by a ray should be a integral multiple
of wave length λ .

nλ = MP + PN (n = 1,2…)

n is order of diffraction

If dhkl is interplanar distance,

Then MP = PN = dhkl.Sinθ

Therefore, nλ = 2 dhkl.Sinθ
Figure 3.28

3-37 After A.G. Guy and J.J. Hren, “Elements of Physical Metallurgy,” 3d ed., Addison-Wesley, 1974, p.201.)
A sample of BCC iron was place in an xray diffractometer
using x-rays with wavelength, =0.1541nm. Diffraction from
the {110} planes was obtained at 2=44.704 . Calculate a
value for the lattice constant of BCC iron. (assume first order
diffraction, n=1). 2  44.704
  22.35
  2d hkl sin 
 0.1541
d110  
2 sin  2sin 22.35
0.1541
  0.2026nm
20.3803
a  d hkl h 2  k 2  l 2
a (Fe)  d110 12  12  0 2
 (0.2026nm) (1.414)
 0.287nm
 Interpreting Diffraction Data
a
• We know that d hkl

h2  k 2  l 2
Since
  2dSin

Substituting for d, 2aSin


h2  k 2  l 2

Therefore 2 h 2  k 2  l 2
Sin 2 
4a 2
Note that the wavelength λ and lattice constant a are the same
For both incoming and outgoing radiation.

3-38
 Interpreting Diffraction Data (Cont..)
• For planes ‘A’ and ‘B’ we get two equations
2 ( h A 2  k A 2  l A 2 )
Sin 2 A  (For plane ‘A’)
4a 2

2 ( h B 2  k B 2  l B 2 )
Sin 2 B  (For plane ‘B’)
4a 2

Dividing each other, we get

Sin 2 A (hA  k A  l A )
2 2 2


Sin 2 B (hB  k B  l B )
2 2 2

3-39
 X-Ray Diffraction Analysis
• Powdered specimen is used for X-ray diffraction analysis as the
random orientation facilitates different angle of incidence.
• Radiation counter detects angle and intensity of diffracted
beam.

Figure 3.30
3-40 After A.G. Guy “Essentials of Materials Science,” McGraw-Hill, 1976.
 Diffraction Condition for Cubic Cells
• For BCC structure, diffraction occurs only on planes whose
miller indices when added together total to an even number.
I.e. (h+k+l) = even Reflections present
(h+k+l) = odd Reflections absent
Principal diffracting planes are{110}, {200}, {211}, etc.
• For FCC structure, diffraction occurs only on planes whose
miller indices are either all even or all odd.
I.e. (h,k,l) all even Reflections present
(h,k,l) all odd Reflections present
(h,k,l) not all even or all odd Reflections absent.
Principal diffracting planes are {111}, {200}, {220}, etc.
3-41
 Interpreting Experimental Data
• For BCC crystals, the first two sets of diffracting planes are
{110} and {200} planes. 2
Sin  A (12  12  0 2 )
  0.5
Therefore Sin 2 B ( 2 2  0 2  0 2 )

• For FCC crystals the first two sets of diffracting planes are
{111} and {200} planes
Sin 2 A (12  12  12 )
  0.75
Therefore
Sin 2 B ( 2 2  0 2  0 2 )

3-42
 Crystal Structure of Unknown Metal
Unknown
metal

Crystallographic
Analysis

Sin 2 A Sin 2 A
 0.75  0 .5
Sin  B
2
Sin 2 B

FCC BCC
Crystal Crystal
Structure Structure

3-43
 Amorphous Materials
• Random spatial positions of atoms
• Polymers: Secondary bonds do not allow formation
of parallel and tightly packed chains during
solidification. E.g. polyvinylchloride
 Polymers can be semicrystalline. E.g. polyethylene
• Glass is a ceramic made up of SiO4 4- tetrahedron
subunits – limited mobility.
• Rapid cooling of metals (10 8 K/s) can give rise to
amorphous structure (metallic glass).
• Metallic glass has superior metallic properties.
a) long-range order in crystalline silica
b) Silica glass without long-range order
c) Amorphous structure in polymers.