Solid-State

Chemistry
Unit Cells?
Unit Cells?
Unit Cells?
Unit Cells
7 types
 cubic
 orthorhombic
 tetragonal
 hexagonal
 monoclinic
 triclinic
 trigonal/rhombohedral
Space Groups
 235 discrete structural
arrangements
 some selected crystal systems
Top 6 Space Groups
 as reported in literature
 P21/c 29.2% monoclinic
 P212121 18.8 orthorhombic
P -1 11.1 triclinic
 P21 10.9 monoclinic
 C2/c 5.4 monoclinic
 Pnma 1.5 orthorhombic
 P21212 1.0 orthorhombic
Structure Determination
X-Ray Diffraction
X-ray
Tube
High Photographic
Voltage Plate
X-ray Crystal
Beam
Lead
Screen

Optical Transforms

 X Projection
Screen
35mm slide
Visible Light Laser
L
Diffraction Conditions
Diffraction Conditions
Diffraction Conditions
Fraunhofer diffraction Bragg diffraction

 

}d }d
 
d d

}
d sin d sin d sin
}

}
For constructive For constructive
interference, interference,
d sin  = n  2(d sin ) = n 
Why monochromatic radiation?
Why use the shorter wavelength?
Why use the shorter wavelength?
Reciprocal Lattice
Optical Transforms
Discovery Slide
Discovery Slide
VSEPR Slide
Powder Diffraction

Spectrum trace for

piezoelectric speaker
material from Radio Shack
Intensity

Line spectrum for

BaTi.75 Zr.25 O 3

10 20 30
 40 50 60
Single Crystal
 diffractometer
 goniometer
X-ray Diffractometer
X-ray Diffractometer with CCD Detector
Goniometer Head for Single Crystal
Miller Indices
 describe which plane of atom is
interacting with the x-rays
 used to calculate the reciprocal lattice
parameters
Miller Indices
Miller Indices
Reciprocal Lattice
Cubic
(1/dhkl) = (h2 + k2 + l2)1/2/a
Reflection Intensity
|Fo|  I

 positive or negative root

 “phase problem”
 solve using Patterson methods
when heavy atom is present
 solve using direct methods
Estimate of Error
R = | Fo - Fc| / Fo
Systematic Absences
 laser & ICE slides
Grains and Close Packing in
Metals
Grains in a polycrystalline material

Every grain
boundary is an
array of
dislocations.
Dislocations
Band Theory
Bands
Most antibonding

Intermediate orbitals
Energy ( )n

Most bonding

Avogadro's Avogadro's number of

number of isolated delocalized molecular
s atomic orbitals orbitals forming one band
Bands in Metals

3p
3p

Energy

3s
3s

Na Mg
Optical Properties of Metals
100
silver

aluminum
80

% Reflectivity
60 copper

40
gold

20

0
700 600 500 400
Some possible electronic Wavelength (nm)
transitions in a half-filled
band of a metal
Metallic Sea of Electrons

Electrons are not bonded to any particular atom

and are free to move about in the solid.
• High electrical conductivity
• High thermal conductivity
• High reflectivity of visible light
Electrical Conductivity

insulators semiconductors metals

diamond germanium copper

fused glass silicon iron
silica

10 -24 10 -20 10 -16 10 -12 10 -8 10 -4 100 10 4 10 8

Conductivity (  –1 -cm –1 )
Electrical Conductivity
conduction
band

Energy

Eg

Eg
valence
band

Insulator Semiconductor Metal

Conductivity of metals decreases with temperature as

atomic vibrations scatter free electrons.
Conductivity of semiconductors increases with temperature
as the number of carriers increases.
 Optical Properties of
Semiconductors
Absorption Emission

Eg
Eg ~30 nm

Eg

Wavelength
Energy wavelength
Band Gap Energy and Color
Color that Apparent color
corresponds to of material
band gap energy (unabsorbed light)

4
ultraviolet colorless
Bandgap energy (eV)

3 violet yellow
blue
green orange
yellow
2 red red
.

1 infrared black
Semiconductors

13 14 15 16 17
Similar shading
B C N O F indicates
complementary
11 12 Al Si P S Cl pairs that preserve
the total valence
Cu Zn Ga Ge As Se Br electron count for
AZ stoichiometry.
Ag Cd In Sn Sb Te I In the zinc blende
structure each AZ
atom is four
Au Hg Tl Pb Bi Po At coordinate.
Semiconductors
two requirements
 average number of valence shell
electrons equals four
 diamond (pure Si or Ge) crystal
structure
 or zinc blende (1:1 stoichiometry)
crystal structure
Band Gap and Periodic
Properties
Element Unit Cell , Å Do, kJ/mol Eg , eV (, nm)
C 3.57 346 5.5 (230)
Si 5.43 222 1.1 (1100)
Ge 5.66 188 0.66 (1900)
-Sn 6.49 146 < 0.1 (12,000)

Material Unit Cell, Å ² Eg, eV (, nm)

Ge 5.66 0.0 0.66 (1900)
GaAs 5.65 0.4 1.42 (890)
ZnSe 5.67 0.8 2.70 (460)
CuBr 5.69 0.9 2.91 (430)
 Solid Solutions

A 1.0 Z 0.0 A 0.8 Z 0.2 A 0.6 Z 0.4 A 0.4 Z 0.6 A 0.2 Z 0.8 A 0.0 Z 1.0
Buckminsterfullerenes
C60 & C70
 allotrope of carbon
 fcc
 lubricants, organic magnets, frequency
doubling materials, and substrates for
growing diamonds
Buckminsterfullerenes
M3C60
 high temperature superconductor
Buckminsterfullerenes
Superconductivity
 Hg was discovered to be superconducting ar
4 K in 1911
 many other metals are superconducting < 10
K (Al family, Sn, Pb, Ti, V, Zn, Cd, several
2nd & 3rd transition series)
 some alloys
Superconductivity
 1-2-3 Superconductors (MBa2Cu3O7-8)
 liquid nitrogen temperature superconductors
Superconductivity
 Loss of Resistance
 Cooper pairs

 Meissner Effect
Superconductivity
 Perovskite
 CaTiO3