Crystalline Structure

Regular and repeating structural units

Unit cell : a simplest and representative structural unit
Lattice parameters : a, b, c, o, |,
Crystalline structure - Perfection
7 Systems and 14 Lattices
THE SEVEN CRYSTAL SYSTEMS
7 Systems and 14 Lattices
THE FOURTEEN CRYSTAL (BRAVAIS) LATTICES
Point lattice : arrays of points
with identical surroundings
in three dimensional space

Point lattice + atom group
= periodic atom array
Crystal Lattice
Crystal Lattice
Body-Centered Cubic (BCC)
Metal Structures
Structure : Body-centered cubic (bcc)
Bravais lattice : bcc
Atoms/unit cell:
Typical metals : -Fe, V, Cr, Mo, and W
2
8
1
8 1 = +
Face-Centered Cubic (FCC)
Metal Structures
Structure : face-centered cubic (fcc)
Bravais lattice : fcc
Atoms/unit cell :
Typical metals : -Fe, Al, Ni, Cu, Ag, Pt and Au
4
8
1
8
2
1
6 = +
Hexagonal Close-Packed (HCP)
Metal Structures
Structure : hexagonal close-packed (hcp)
Bravais lattice : hexagonal
Atoms/unit cell :
Typical metals : Be, Mg, -Ti, Zn and Zr
2
12
1
4
6
1
4 1 = + +
C
B
A
C
B
A
B
A
B
A
B
A
FCC HCP
Metal Structures
CRYSTALLINE FORMS OF IRON THE FCC AND BCC FORMS OF IRON
SHOWN AS CUT-AWAY CUBES
Cubic Close Packed (Austenite)
Body Centered Cubic (Ferrite)
Austenite
Ferrite
Metal Structures
Close-packed Layer of Atoms
BODY CENTERED CUBIC
CUBIC CLOSE PACKED
(Face Centered Cubic)/
HEXAGONAL CLOSE PACKED
Close-packing and the Metallic Elements
Crystal Structure Review
Ceramic Structures
MX type
CsCl structure
NaCl structure
Structure : CsCl-type
Bravais lattice: simple cubic
Ions/unit cell : 1Cs
+
+1Cl
-
Structure : NaCl-type
Bravais lattice: fcc
Ions/unit cell : 4Na
+
+4Cl
-
Typical ceramics
: MgO, CaO, FeO, and NiO
Fluorite (CaF
2
) unit cell
Ceramic Structures
Structure : flourite (CaF
2
) -type
Bravais lattice: fcc
Ions/unit cell : 4Ca
2+
+8F
-
Typical ceramics : UO
2
, ThO
2
, and TeO
2
F
-
ions located at corners of a cube ( at type positions)
4
1
4
1
4
1
Perovskite (CaTiO
3
) unit cell
Ceramic Structures
Structure : perovskite (CaTiO
3
) -type
Bravais lattice: simple cubic
Ions/unit cell : 1Ca
2+
+1Ti
4+
+3O
2-
Typical ceramics : CaTiO
3
, BaTiO
3
Diamond cubic structure (Si, Ge)
0 = z
a z
4
1
=
a z
2
1
=
a z
4
3
=
z
Semiconductor Structures
Diamond cubic structure (Si, Ge)
Semiconductor Structures
Zinc blende structure (ZnS, GaAs, ...)
0 = z a z
4
1
=
a z
2
1
=
a z
4
3
=
z
Semiconductor Structures
Unit cell of the form of
polyhexamethylene adipamide
or nylon 66
Polymeric Structures
Diamond
Graphite
Allotropes/Polymorphs
A material is said to be allotropic or polymorphic if
it occurs in two or more forms that have different
crystal structures, each of which is comprised of the
same atoms ( i.e., polymorphs have the same atomic
structure). Each different crystallographic form
(structure) is an allotrope/polymorph.

Carbon is allotropic:
it can exist as GRAPHITE (hexagonal crystal structure)
or as DIAMOND (cubic crystal structure). Carbon may
also form as a BUCKYBALL. Finally, carbon is
frequently amorphous (no crystal structure) and is then
variously described as Carbon Black, Lamp Black
and Soot.
Buckyball (Fullerene)
Carbon Nanotube
Carbon Nanotube
Notation
for lattice positions
Lattice Positions, Directions, and Planes
Lattice translations
Lattice Positions, Directions, and Planes
Notation for lattice directions
Lattice Positions, Directions, and Planes
Family of directions
Lattice Positions, Directions, and Planes
Notation for lattice planes
( ) 010 ( ) 110 ( ) 111 ( ) 133
a
b
c
h
k
l
i
120
o
) 0001 (
) 0 1 01 ( ) 0 2 11 (
Lattice Positions, Directions, and Planes
Family of planes
) 010 (
) 00 1 (
) 001 (
) 100 (
) 0 1 0 (
) 1 00 (
} 100 {
) 11 1 ( ) 111 ( ) 1 11 ( ) 1 1 1 (
} 111 {
) 1 1 1 ( ) 1 1 1 ( ) 1 1 1 ( ) 1 1 1 (
Lattice Positions, Directions, and Planes
Single Crystalline / Polycrystalline
How to identify unknown crystalline materials?
How to determine crystal structure?
X-ray Diffraction
Transmission electron
diffraction by TEM
X-Ray Diffraction
Shadow of a square array of four small ball
bearings, nearby and very far away.
What is diffraction?
Diffraction : deviation from geometrical optics
Diffraction is the result of radiation being scattered by a regular array
of scattering centers whose spacing is about the same as the
wavelength of the radiation.
X-Ray Diffraction
Electromagnetic radiation spectrum
X-Ray Diffraction
Braggs Law : diffraction condition

For scattering of waves in phase,
path difference of wave = AB + BC
=

: wavelength of X-ray
d : spacing of crystal planes
u : Bragg angle
2u : diffraction angle

u
sin 2
hkl
d n
=
X-Ray Diffraction
Braggs law is a necessary
condition but not sufficient
condition for diffraction.

X-Ray Diffraction
Rules for determining the diffracting {hkl} planes in cubic crystals
Bravais lattice Reflections present Reflections absent
Body-centered cubic (bcc) h+k+l = even number h+k+l = odd number
Face-centered cubic (fcc) h, k, l unmixed (i.e., all
even or all odd)
h, k, l mixed (not all odd
or all even)
h
2
+k
2
+l
2
{hkl}
FCC BCC
1
2 110
3 111
4 200 200
5
6 211
7
8 220 220
9
10 310
Miller indices of the diffracting planes for BCC and FCC lattices
X-Ray Diffraction
Interpreting experimental x-ray diffraction data for metals with
cubic crystal structures
u sin 2
hkl
d =
2
2 2 2 2
2
4
) (
sin
a
l k h + +
=

u
2 2 2
2 2 2
2
2
sin
sin
B B B
A A A
B
A
l k h
l k h
+ +
+ +
=
u
u
Where u
A
and u
B
are two diffracting angles
associated with the principal diffracting
planes {h
A
k
A
l
A
} and {h
B
k
B
l
B
}, respectively.
X-Ray Diffraction
ex) An x-ray diffractometer recorder chart for an element which has either
the BCC or the FCC crystal structure shows diffraction peaks at the
following 2u angles: 40, 58, 86.8, 100.4, and 114.7. The wavelength of
the incoming x-ray used was 0.154 nm.

(a) Determine the cubic structure of the element.
(b) Determine the lattice constant of the element.
(c) Identify the element.
X-Ray Diffraction