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c 

Miller Indices
(l,m,n) are a way of
denoting planes in
crystal lattices.

The Chemistry of Solids


rand Theory
‡ As the half-filled 4s orbitals of
an increasing number of Cu
atoms overlap, their energies
are split into a half-filled
valence band.
‡ Electrons can move from the
filled half (purple) to the
slightly higher energy upper
half (red), where they are free
to migrate from one empty
orbital to another.
Metallic ronds
‡ rand theory is an extension of molecular
orbital theory that describes bonding in
solids.
‡ rands of orbitals that are filled or partially
filled by valence electrons are called valence
bands.
‡ Higher-energy unoccupied bands in which
electrons are free to migrate are called
conduction bands.
rand Gap
‡ The energy gap between the valence and
conduction bands is called the band gap.
‡ A semiconductor is a substance whose
conductivity can be made to vary over several
orders of magnitude by altering its chemical
composition.
‡ A n-type semiconductor contains excess electrons
contributed by electron-rich dopant atoms.
‡ A p-type semiconductor contains electron-poor
dopant atoms.
rand Theory

The Fermi Energy (Level) is the energy of the highest occupied state.
rand Theory

The rand Gap influences the electrical and optical properties of the
material. Semiconductor ´dopingµ can be used to create solar cell
(PV), diodes, transistors, etc.
Some semiconducting
materials and associated
bandgaps (eV)
n-type semiconductors result
from the addition of
pentavalent impurities like
phosphorus, arsenic and
antimony. These donors
contribute ´extraµ electrons.

p-type semiconductors result


from the addition of trivalent
impurities like boron,
aluminum and gallium. These
additions create valence
´holesµ which act as additional
levels
http://britneyspears.ac/lasers.htm
The ´unit cellµ is the basic
repeating unit of the arrangement
of atoms, ions or molecules in a
crystalline solid.

The ´latticeµ refers to the 3-D array


of particles in a crystalline solid.
One type of atom occupies a
´lattice pointµ in the array.
Examples of Unit Cells
There are seven
crystal systems
also knows as
rravais Structures.

In Chapter 11 we
will cover only the
cubic systems, sc,
fcc, and bcc.
Sides:
a=b=c
Angles
|= = °
. A: rody-centered cubic (bcc) r: Simple cubic (sc)
Contributions of Atoms to Cubic Unit Cells
Position of Atoms in Contribution to Unit
Unit-Cell Type
Unit Cell Cell

Center 1 bcc

Face 1/2 Fcc

fcc, bcc, simple


Corner 1/8
cubic

How many total atoms are found in a simple cubic unit


cell? Face centered cube? rody centered cube?
Unit Cells
‡ A body-centered cubic
(bcc) unit cell has
atoms at the 8 corners
of a cube and at the
center of the cell
‡ A simple cubic unit cell
has atoms only at the 8
corners of a cube.
Vumber Atoms in a Unit Cell
‡ In the simple cubic cell
there are only the 8
atoms at the corners.
: 1/8 x 8 = 1 atom in cell
‡ In bcc, 8 atoms at the
corners and 1 in center.
: 1/8 x 8 + 1 x 1 = 2 atoms in
the cell
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Example Problem:

Polonium metal crystallizes in a simple cubic


structure. Calculate the density of the polonium
metal if the atom radius is 176 pm.

[rased on a literature density of 9.196 g cm-3,


what is the radius of Po? (167 pm)]
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Metallic Crystals
can be thought to
form via an efficient
packing scheme«
Stacking Patterns
‡ A crystalline solid is made of an ordered array of
atoms, ions, or molecules.
‡ Hexagonal closest-packed (hcp) describes a crystal
structure in which the layers of atoms or ions in
hexagonal unit cell have an a-b-a-b-a-b stacking
pattern.
‡ Cubic closest packed (ccp) describes a crystal
structure in which the layers of atoms, ions, or
molecules in face-centered cubic unit cells have an
a-b-c-a-b-c-a-b-c stacking pattern.
Fig. 10.6: Two efficient ways to pack particles together in a crystal
structure are hexagonal closest packed (A, hcp) and cubic closest
packed (r, ccp). The difference is in the third layer. In hcp the third
layer sits directly above the first layer (ababab«). In ccp the third layer
is different from the other two (abcabcabc«). The VaCl crystal
structure contains a cubic closest packed arrangement of chloride
ions.
Fig. 10.13b: Cubic closest packed structure
Hexagonal closest packed structure

The hcc (aba) structure has 6 atoms/uc which includes 6


octahedral holes and 12 tetrahedral holes.
Summary of Crystal Structures
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Fig. 10.12: Cesium chloride (CsCl) crystal structure.
Example Problem:
What is the packing efficiency in the simple
cubic cell of CsCl? What is the percentage of
empty space in the unit cell? The chloride ions
are at the corners with the cesium in the middle
of the unit cell.
rCl- = 181 pm; rCs+ = 169 pm

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Fig. 10.8: The location of the octahedral holes occupied by
sodium ions are shown by the X·s.
Fig. 10.9: The ´Xµ marks the location of the tetrahedral holes in a
face centered cubic unit cell
Fig. 10.10: The mineral
sphalerite (ZnS) is based on
a fcc arrangement of S2- ions
with four Zn2+ ions in
tetrahedral holes.

Are all the tetrahedral holes


occupied?
Fig. 10.11: The mineral fluorite (CaF2) has a fcc arrangement of Ca2+
ions with F> ions in all eight of the tetrahedral holes.
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What is the packing efficiency of VaCl? What is the


percentage of empty space in the VaCl unit cell? )
rCl- = 181 pm; rVa+ = 98 pm; edge dist.VaCl = 562.8 pm

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Atomic Size Ratios and the Location of Atoms in Unit Cells

Packing Type of Hole Radius Ratio

hcp or ccp Tetrahedral 0.22 - 0.41

hcp or ccp Octahedral 0.41 - 0.73

Simple Cubic Cubic 0.73 - 1.00


Problem
One of the expected ´productsµ of ´coldµ fusion is 3He,
radius 32 pm.
Could a 3He fit in the octahedral holes form by Pd atoms?
Table 10.2 Ion size Ratios and holes in
Closest Packed Structures
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hcp/ccp Tetrahedral 0.22-0.44

hcp/ccp Octahedral 0.44-0.73

cubic Cubic 0.73-1.00

For VaCl the radius ratio = RVa+/RCl- = 98pm/181pm =0.54


From the table data the Va+ ions are ´predictedµ to occupy
Tetrahedral hole.
Alloys
‡ An alloy is a blend of a host metal and one or
more other elements which are added to
change the properties of the host metal.
‡ In a substitutional alloy the atoms of one
metal replace atom in the crystal lattice.
‡ Interstitial alloys are formed when hetero
atoms occupy interstitial octahedral and
tetrahedral holes of the host metal lattice.
rronze is substitutional allow
Carbon Steel is an interstitial alloy
Effect of Carbon Content on the Properties of Steel

Carbon
Designation Properties Used to Make
Content (%)

0.05 - 0.19 Low Carbon Malleable, ductile Vails, cables

Construction
0.20 - 0.49 Medium Carbon High strength
girders

0.5 - 3.0 High Carbon Hard but brittle Cutting tools


Vetwork Solids
‡ Covalent network solids are made of a rigid,
three-dimensional array of covalently bonded
atoms.
‡ Crystals of molecular solids are formed by
neutral covalently bonded molecules held
together by intermolecular attractive forces.
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Crystalline Versus Amorphous
Quartz Figure 11.26 Obsidian Figure 11.27
Allotropes of Carbon
Allotropes of Phosphorus
Other Ionic Crystals
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recause of covalent linkages across unit cells, silicates are an


example of a network solid.
Other forms of Silica
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Superconductors
‡ A superconductor is a material that has zero
resistance to the flow of electric current.

‡ The critical temperature (Tc) is the temperature


below which a material becomes a superconductor.

‡ Current superconductors, like Vb3Sn, have to be


cooled to 20 K to remain superconducting.
High Temperature Superconductors

‡ Yra2Cu3O7 ceramic is
superconducting at
77K (just above liquid
nitrogen·s boiling
point).
‡ The ceramic is
structure is called a
perovskite unit cell.
Yttrium-barium-copper Oxides
‡ These and related
materials behave as
superconductors
because of the
formation of electron
pairs called Cooper
pairs.
X-ray Diffraction
‡ X-ray diffraction (XRD) is a technique for
determining the arrangement of atoms or ion in a
crystal by analyzing the pattern that results when X-
rays are scattered after bombarding the crystal.
‡ The rragg equation relates the angle of diffraction
(2s) of X-rays to the spacing (d) between the layers
of ions or atoms in a crystal: n 2dsins.
Structure Determination

X-ray Diffraction (XRD).


The rragg equation
nšȝ = 2šdšsin Ț
Can be used in conjunction with
XRD data to find the spacing
between crystal planes (d).
is the wavelength of the X-rays; n
is an integer; d is the distance
between crystal planes; Ț is the
angle of incidence.
Peaks result from h 5    
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interference for the 
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reflected X-rays
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