Crystallography and

Structure

Overview:

Crystal Structure matter assumes a

periodic shape
Non-Crystalline

or Amorphous structures no
long range periodic shapes
FCC, BCC and HCP common for metals
Xtal Systems not structures but potentials

Point, Direction and Planer IDing in Xtals

X-Ray Diffraction and Xtal Structure

SOME DEFINITIONS
Lattice: 3D array of regularly
spaced points
Crystalline material: atoms
situated in a repeating 3D
periodic array over large atomic
distances
Amorphous material: material
with no such order
Hard sphere representation:
atoms denoted by hard, touching
spheres
Reduced sphere representation
Unit cell: basic building block unit
(such as a flooring tile) that
repeats in space to create the
crystal structure; it is usually a
parallelepiped or prizm

CRYSTAL STRUCTURES
Crystal Structure

Means: PERIODIC ARRANGEMENT OF ATOMS/IONS

OVER LARGE ATOMIC DISTANCES
Leads to structure displaying
LONG-RANGE ORDER that is
Measurable and Quantifiable

All metals, many ceramics, some

polymers exhibit this High Bond
Energy More Closely Packed Structure

Materials Lacking Long range order

Amorphous Materials

These less densely

packed lower bond
energy structures
can be found in Metal
are observed in
Ceramic GLASS and
many plastics

Crystal Systems Some

Definitional information
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
7 crystal systems of varying
symmetry are known
These systems are built by
changing the lattice
parameters:
a, b, and c are the edge
lengths
, , and are interaxial
angles
Fig. 3.4, Callister 7e.

Simple Cubic Structure (SC)

Rare due to low packing density (only Po Polonium -has this structure)

Close-packed directions are cube edges.

Coordination No. = 6
(# nearest neighbors)
for each atom as seen
(Courtesy P.M. Anderson)

Atomic Packing Factor (APF)

Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
APF for a simple cubic structure = 0.52
atoms
unit cell

a
R=0.5a
close-packed directions
contains (8 x 1/8) =
1 atom/unit cell
Adapted from Fig. 3.23,
Callister 7e.

APF =

volume
atom
4
(0.5a) 3
1
3
a3

volume
unit cell

Here: a = Rat*2
Where Rat is the handbook
atomic radius

Body Centered Cubic Structure (BCC)

Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

ex: Cr, W, Fe (), Tantalum, Molybdenum

Adapted from Fig. 3.2,

Callister 7e.

2 atoms/unit cell: (1 center) + (8 corners x 1/8)

(Courtesy P.M. Anderson)

Atomic Packing Factor: BCC

3a

a
2a

Close-packed directions:
length = 4R = 3 a

atoms
volume
4
( 3a/4) 3
2
unit cell
atom
3
APF =
volume
Adapted from
3
a
Fig. 3.2(a), Callister 7e.
unit cell
APF for a body-centered cubic structure = 0.68

Face Centered Cubic Structure (FCC)

Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

Coordination # = 12

Adapted from Fig. 3.1, Callister 7e.

4 atoms/unit cell: (6 face x ) + (8 corners x 1/8)

(Courtesy P.M. Anderson)

Atomic Packing Factor: FCC

APF for a face-centered cubic structure = 0.74
The maximum achievable APF!
2a

a
Adapted from
Fig. 3.1(a),
Callister 7e.

Close-packed directions:
length = 4R = 2 a
(a = 22*R)

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
atoms
volume
4
( 2a/4) 3
4
unit cell
atom
3
APF =
volume
a3
unit cell

COMPARISON OF CRYSTAL
STRUCTURES
Crystal structure coordination #

packing factor

close packed directions

Simple Cubic (SC)

0.52

cube edges

Body Centered Cubic (BCC) 8

0.68

body diagonal

Face Centered Cubic (FCC) 12

0.74

face diagonal

Hexagonal Close Pack (HCP)

12

0.74

hexagonal side

From Hydrogen to Silicon

# of Electrons
1
2
3
Z Name 1s 2s 2p 3s 3p 3d

Notation
1

1H

1s

2 He

1s 2

3 Li

1s 2 2s 1

4 Be

1s 2 2s 2

5B

1s 2 2s 2 2p1

6C

1s 2 2s 2 2p2

7N

1s 2 2s 2 2p3

8O

1s 2 2s 2 2p4

9F

1s 2 2s 2 2p5

10 Ne

1s 2 2s 2 2p6

11 Na

1s 2 2s 2 2p6 3s 1

12 Mg

1s 2 2s 2 2p6 3s 2

13 Al

1s 2 2s 2 2p6 3s 2 3p1

14 Si

1s 2 2s 2 2p6 3s 2 3p2

15 P

1s 2 2s 2 2p6 3s 2 3p3

16 S

1s 2 2s 2 2p6 3s 2 3p4

17 Cl

1s 2 2s 2 2p6 3s 2 3p5

18 Ar

1s 2 2s 2 2p6 3s 2 3p6

The Silicon Atom

14 electrons occupying the 1st 3 energy levels:

1s, 2s, 2p orbitals filled by 10 electrons
3s, 3p orbitals filled by 4 electrons
To minimize the overall energy, the 3s and 3p
orbitals hybridize to form 4 tetrahedral 3sp orbitals
Each has one electron and
is capable of forming a bond
with a neighboring atom

The Si Crystal

diamond cubic lattice

Each Si atom has 4

nearest neighbors

lattice constant
= 5.431

How Many Silicon Atoms per

cm-3?
Number of atoms in a unit cell:

4 atoms completely inside cell

Each of the 8 atoms on corners are shared among cells
count as 1 atom inside cell
Each of the 6 atoms on the faces are shared among 2
cells count as 3 atoms inside cell
Total number inside the cell = 4 + 1 + 3 = 8

Cell volume:
(.543 nm)3 = 1.6 x 10-22 cm3

Density of silicon atoms

= (8 atoms) / (cell volume) = 5 x 1022 atoms/cm3

Compound Semiconductors
Ga

As

zincblende structure
III-V compound semiconductors: GaAs, GaP, GaN, etc.
important for optoelectronics and high-speed ICs