CHAPTER 3:

STRUCTURE OF
CRYSTALLINE SOLIDS
MOSFET
SiO2 (amorphous)

Si (crystalline)
Materials and packing:
Types of Solids

• atoms packk iin periodic,

i di 3D arrays
• typical of: -metals
-many ceramics
-some polymers
crystalline SiO2
Si Oxygen

• atoms have no periodic packing

• occurs for: -complex structures
p cooling
-rapid g
"Amorphous" = Noncrystalline

noncrystalline SiO2
Hard sphere model and lattice:
Atomic hard sphere model is used to describe the
arrangement of atoms.

Lattice: A 3D array of
points
i i space
in
coinciding with
atom positions
(or sphere centers).
Unit cell:

Unit cell:
(Lattice cell)
Smallest structural
unit that describes
the symmetry
crystal structure.
Small repeat entities.
As an easy and simple way of representation we use
cubes or similar geometrical tools to represent a unit cell.
 Metallic Crystals

• tend to be densely packed.

• have several reasons for dense packing:

-Typically, only one element is present, so all atomic

radii are the same.
-Metallic bonding is not directional.
-Nearest neighbor distances tend to be small in
order to lower bond energy.
• have the simplest crystal structures.
structures

We will look at three such structures...

 Simple Cubic (SC)
Rare for metals due to poor packing (only Po
Poloniom has this structure)
Close-packed directions are cube edges.

• Coordination # = 6
Examples: CsCl, brass
(# nearest neighbors)
Face
ace--Centered
Cubic (FCC)

Examples: Cu, Al, Ag, Au

 Body
ody--Centered Cubic (BCC)

Examples: Fe(α), Cr, Mo

 Hexagonal Close
lose--Packed (HCP)

Examples: Mg, Ti, Zn,

6
Characteristics of Selected Elements at 20°C
At. Weight
At Density Crystal Atomic radius
Element Symbol (amu) (g/cm3) Structure (nm)
Aluminum Al 26.98 2.71 FCC 0.143
Argon Ar 39 95
39.95 ------ ------ ------
Barium Ba 137.33 3.5 BCC 0.217
Beryllium Be 9.012 1.85 HCP 0.114
Boron B 10.81 2.34 Rhomb ------ Adapted from
T bl "Charac-
Table, "Ch
Bromine Br 79.90 ------ ------ ------ teristics of
Cadmium Cd 112.41 8.65 HCP 0.149 Selected
Elements",
Calcium Ca 40.08 1.55 FCC 0.197 inside front
Carbon C 12.011 2.25 Hex 0.071 cover,
Cesium Cs 132.91 1.87 BCC 0.265 Callister 6e.
Chlorine Cl 35.45 ------ ------ ------
Ch
Chromium
i C
Cr 52 00
52.00 7 19
7.19 BCC 0 125
0.125
Cobalt Co 58.93 8.9 HCP 0.125
Copper Cu 63.55 8.94 FCC 0.128
Flourine F 19 00
19.00 ------ ------ ------
Gallium Ga 69.72 5.90 Ortho. 0.122
Germanium Ge 72.59 5.32 Dia. cubic 0.122
Gold Au 196.97 19.32 FCC 0.144
Helium He 4.003 ------ ------ ------
Hydrogen H 1.008 ------ ------ ------ 15
 DENSITIES OF MATERIAL CLASSES
Graphite/
ρmetals> ρceramics> ρpolymers Metals/
Ceramics/ Polymers
Composites/
Alloys fibers
Semicond
Why? 30
Based on data in Table B1, Callister
Metals have... 20 Platinum
Gold, W *GFRE, CFRE, & AFRE are Glass,
Tantalum Carbon, & Aramid Fiber-Reinforced
• close-packing Epoxy composites (values based on
60% volume
l ffraction
ti off aligned
li d fib
fibers
(metallic bonding) 10 Silver, Mo in an epoxy matrix).
Cu,Ni
• large atomic mass Steels

m3)
Tin, Zinc
Ceramics have... Zirconia

ρ (g/cm
5
Titanium
• less dense packing 4 Al oxide
Diamond
(covalent bonding) 3
Aluminum
Si nitride
Glass-soda Glass fibers
Concrete
• often lighter elements 2 Silicon PTFE GFRE
GFRE*
Carbon fibers
Magnesium
Polymers have... Graphite
Silicone
PVC
CFRE*
Aramid fibers
PET AFRE*
• poor packing 1 PC
HDPE, PS
(often amorphous) PP LDPE
PP,

• lighter elements (C,H,O)

0.5
Composites have... 0.4
Wood

• intermediate values 0.3

Data from Table B1, Callister 6e.
 Polymorphism
Some materials may exist in more than one crystal structure,
structure this is called
polymorphism.
If the material is an elemental solid, it is called allotropy. e.g. carbon, can exist as
diamond, graphite, fullerene, nanotubes etc.

ALL CARBON;
But they all have
different
Macroscopic
Properties
 Hybridization of Carbon atom
• sp3 - Diamond • sp2 - Graphite
4 σ-electrons 1 π- and 3 σ-electrons
C σ
C π σ
109°5'
109 5 C
C 120° C C
C
σ C
C

• sp1 (No pure C solids)

2 π- and 2 σ-electrons

π1
180°
C C C

π2
σ
Parameters defining a unit cell:

Different variations for unit cells

are possible.
ibl Parameters
P describing
d ibi
the unit cells are
1 Angles
1.
2. Translation factors (Dimensions)

Lattice Parameters

CUBIC SYSTEMS (most

( t off th
the
time)
 within the content
of this course
course

Total of SEVEN
CRYSTAL STRUCTURES
Plane A

Plane A: (243)
FAMILY of PLANES:
Planes that are crystallographically
equivalent, which have the same
atomic packing.
 Area occupied by the atoms on the plane
Atomic Planar Density=
Total area of the crytallographic plane

FCC (110 plane)

BCC (110
( plane)
l )
 (FCC)
FCC) STACKING SEQUENCE
• ABCABC... Stacking Sequence
• 2D Projection
A
B B
C
A
A sites
it B B B
C C
B sites B B
C sites

A
• FCC Unit Cell B
C

11
 (HCP) STACKING SEQUENCE

• ABAB...
ABAB Stacking
St ki Sequence
S
• 3D Projection • 2D Projection

A sites Top layer

B sites Middle layer

A sites Bottom layer

 HCP FCC

Blue shaded planes correspond to the highest planar packing.

DUE TO THE DIFFERENCE IN STACKING
 Types of Crystalline
Crystalline solids
Single crystal: atoms are in a repeating or periodic array
over the entire extent of the material

Polycrystalline material:
comprised of many small crystals or grains

Grains:
G i
Orderely arrangement
within each grain,
orientation changes in
The neighbouring grain
 Amorphous/Crystalline

(c) 2003 Brooks/Cole Publishing / Thomson

Learning™

Atomic
At i arrangements t in
i crystalline
t lli silicon
ili and
d amorphous
h silicon.
ili ((a))
Amorphous silicon. (b) Crystalline silicon. Note the variation in the inter-
atomic distance for amorphous silicon.
 Single Crystalline Si Growth

(a) Czochralski growth technique for growing single crystals of

silicon (Source: From Microchip Fabrication,
silicon. Fabrication Third Edition,
Edition by P.
P
VanZant, Fig. 3-7. Copyright © 1997 The McGraw-Hill Companies.
Reprinted with permission The McGraw-Hill Companies.) (b) Overall
steps encountered in the processing of semiconductors.
semiconductors (Source:
From Fundamentals of Modern Manufacturing, by M.P. Groover, p.
849, Fig. 34-3. Copyright © 1996 Prentice Hall.)
Amorphous/Crystalline

Today’s processor
Low cost ICs

Smart cards,
displays

E-paper
Amorphous/Crystalline
 Amorphous/Crystalline

Monocrystalline Polycrystalline Amorphous

Silicon Panel Silicon Panel Silicon Panel
 SINGLE VS POLYCRYSTALS
• Single Crystals E (diagonal) = 273 GPa
Data from Table 3.3,
-Properties
p vary
y with Callister 6e.
(Source of data is
direction: anisotropic. R.W. Hertzberg,
Deformation and
-Example: the modulus Fracture Mechanics of
Engineering Materials,
off elasticity
l ti it (E) in
i BCC iron:
i 3rd ed., John Wiley
and Sons, 1989.)
E (edge) = 125 GPa
• Polycrystals
y y

-Properties may/may not 200 μm Adapted from Fig.

4.12(b), Callister 6e.
vary with direction. (Fig. 4.12(b) is
courtesy of L.C. Smith
-If grains are randomly and C. Brady, the
National Bureau of
oriented: isotropic. Standards,
Washington, DC [now
(Epoly iron = 210 GPa)
GP ) the National Institute
-If grains are textured: of Standards and
Technology,
anisotropic.
p Gaithersburg, MD].)

19
ANISOTROPY
Direction dependence in physical properties: observed in single crystals
Direction-dependence

The directional properties are related with the variance in

atomic
i and d ionic
i i spacing.
i

The degree
g of anisotropy
py increases
with decreasing structural symmetry.
 CRYSTAL STRUCTURE ANALYSIS

† Diffraction - The constructive interference, or reinforcement, of a

beam of xx-rays
rays or electrons interacting with a material
material. The
diffracted beam provides useful information concerning the
structure of the material.
† Bragg’s law - The relationship describing the angle at which a
beam of x-rays of a particular wavelength diffracts from
crystallographic
y g p p
planes of a g
given interplanar
p spacing.
p g
† In a diffractometer a moving x-ray detector records the 2y angles
at which the beam is diffracted, giving a characteristic diffraction
pattern
 XRD

(a) Destructive and

(b) reinforcing
i f i iinteractions
t ti
between x-rays and the
crystalline material.
Reinforcement occurs at
angles that satisfy Bragg’s
law.
Learning
L
( 2003 Brooks/Colee Publishing / Thomso
(c) on
 XRD
Thomson Learning
T
( 2003 Brooks/Cole Publishing /
(c)

Diagram of a diffractometer,
showing g powder sample, incident
and diffracted beams.
Example:

For BCC iron, compute (a) the interplanar spacing, and (b) the diffraction angle for
the (220) set of planes. The lattice parameter for Fe is 0.2866 nm. Also, assume
that monochromatic radiation having a wavelength of 0.1790
0 1790 nm is used
used, and the
order of reflection is 1.
 SUMMARY
• Atoms may assemble into crystalline or
amorphous structures.

• We can predict the density of a material,

material
provided we know the atomic weight, atomic
radius, and crystal geometry (e.g., FCC,
BCC HCP)
BCC, HCP).

• Material properties generally vary with single

crystal orientation (i.e., they are anisotropic),
but properties are generally non-directional
(i.e., they are isotropic) in polycrystals with
randomly oriented grains.
 Reading g Assignment:
g
CHAPTER 3: The Structure of Crystalline Solids
of Callister

• Crystal Structures
• Crystallographic Directions and Planes
• Crystalline and Non crystalline Materials