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1Solid-State Chemistry:
Structure and Properties
of Solids
2Solid-State Chemistry
Laboratory sessions (Weds)
1. ICSD and structure visualisation
(1-2 lab sessions)
2. Making a conducting polymer (2
lab sessions)
3Recommended Books
Basic Solid State Chemistry, A.R. West.
Inorganic Materials Chemistry, Shriver, Atkins
DoITPoMS Teaching and Learning Packages,
University of Cambridge,
www.msm.cam.ac.uk/doitpoms/tlplib
4Structure and bonding in
materials
REVISION SECTION:
Types of solids
Some important structure types
Basic crystallography
Read relevant sections in Inorganic Chemistry 4th ed by Shriver & Atkins (NB CHAPTER 3!)
Read DoITPoMS Teaching and Learning Packages
X-ray Diffraction Techniques (revision)
Atomic Scale Structure of Materials (do questions)
5Types of solids
Classification according to
chemical binding
and structure
6Important structure types
ccp (fcc); hcp; bcc; pc (sc)
ZnS
NaCl
CaF2
CsCl
ReO3
TiO2
BaTiO3
Covalent solids (diamond, graphite)
Molecular solids
Metals (intermetallics,
alloys,
Zintl phase)
Ionic
Covalent
networks
Molecular
7Simple Cubic Unit cells / Lattices
Metallic
Bonding and
properties
SCHEMATIC REPRESENTATION OF METALLIC SOLIDS
8Simple Cubic Unit cells / Lattices
Metallic
e.g. Po e.g. Au
e.g. Fe
9SCHEMATIC REPRESENTATION OF IONIC
SOLIDS
Ionic
Ionic
Bonding and
properties
10
STRUCTURES DERIVED FROM CUBIC
CLOSE PACKING (CCP)
Ionic
11
NiAs Nickel Arsenide
STRUCTURES DERIVED FROM
HEXAGONAL CLOSE PACKING (HCP)
ZnS Wurtzite (High T Form)
Ionic/covalent
12
CsCl Cesium Chloride
Ionic
13
ReO3 and WO3 (cubic)
(see S&A)
Ionic oxides ReO3 and WO3
14
BaTiO3(cubic or tetragonal)
(CaTiO3, SrTiO3 and mixed oxides. See S&A)
Ionic oxides BaTiO3
15
Covalent network solids
16
Molecular solidsMolecules (with intramolecular covalent bonds) and
intermolecular Van der Waals or non-covalent interactions)
Molecular solids
17
Types of solids
Classification according to
crystallinity or defects
Crystalline, polycrystalline, amorphous
Amorphous
Only short range order; no periodicity.
Powder x-ray diffraction has broad peaks
Melting point over a large range.
E.g. glasses, polymers and supercooled liquids
Crystallinecharacterized by 3-dimensional periodicity
Powder x-ray diffraction has sharp peaks
Sharp melting points
Distinct morphology
Examples of crystalline solids
Gypsum (CaSO4.H2O). A glass cannot be cleaved along particular planes
Quartz (recall that SiO2 can also exist as a glass)
Polycrystalline materials: grain structure
Iron-carbon alloy
Galvanised steel
Defects and grain structures.
Domain boundaries
Eutectoid of iron-carbon steel alloy grain boundaries
Single crystal
Polycrystalline material with grain boundaries
Liquid crystals
Liquid crystals.
characterized by 1- or 2-
dimensional order
rod- or disc-like molecules
Polymers
Polymers
only short range order; no
periodicity.
melting point over a large
range.
Quasicrystals
Quasicrystals
e.g. rapidly cooled alloys
both short- and long-range
order
but incompatible with
translational periodicity
(e.g. 5-dimensional symmetry
seen in diffraction patterns)
Nanocrystals (quantum dots)
Nano-crystals
(quantum dots)
solids of
dimensions 1-
100nm
Many electronic
and mechanical
properties of
materials change
if they are
comprised of
nano-crystalsSEM of Nanocrystal of RuS2
Semiconducting Nanocrystal
26
Structure of solids
Elementary Crystallography
27
Important concepts
Lattices & Unit Cells
Simple Cubic Unit cells / Lattices
Crystal systems
Fractional Atomic Coordinates
Basic structure types
Elementary PXRD
Crystal Planes / Miller indices
d spacings
Braggs Law
Elementary structure & bonding in solids (1st year)
28
Lattices and Unit Cell
29
Unit Cell Dimensions
a, b and c are the unit cell edge
lengths
, and are the angles (a between
b and c, etc....)
30
Simple Cubic Unit cells / Lattices
Metallic
e.g. Po e.g. Au
e.g. Fe
31
Fractional atomic coordinates
The position of an atom within a unit cell is normally
described using fractional coordinates (in contrast to
orthogonal coordinates).
With respect to the unit cell origin, an atom within the unit
cell displaced by x a parallel to a, y b parallel to b and
z c parallel to c is denoted by the fractional coordinates
(x, y, z).
(0.5,0.5,0.5)
Slide 3211/05/2011
Fractional atomic coordinates and projections
The position of an atom in a unit cell is
described ito fractional coordinates.
Coordinates expressed as a fraction of the
length of the side of the unit cell.
Thus the position of an atom located at xa
parallel to a, yb parallel to b and zc parallel to c
is denoted (x,y,z), with o x,y,z 1.
Projections are often a clearer / faster method
of representing 3D structures.
Typically projections are down one of the cell
axies.
(a)The structure of
metallic tungsten
(b) Its projection
representation
Slide 3311/05/2011
Example 3.1
Projection representation of
fcc unit cell
The structure of silicon sulfide
(SiS2)
Slide 3411/05/2011
NaCl Rock Salt (Halite)
35
The seven crystal systems
36
Density of a crystal
Z = number of atoms in the unit cell
M = atomic weight
NA = Avogadros number
VC = Volume of the unit cell
cAVN
ZMdensity
37
Crystal Planes &
Miller indices
Since a crystal has an ordered 3-D periodic arrangement of atoms (ions
or molecules) the atomic planes in any crystal can be related to the unit
cell.
One can label each set of planes uniquely by considering their
(fractional) intersection with the unit cell axes a,b,c and converting
these to INTEGERS h, k, and l.
e.g. the planes that intersect the b-axis at and are parallel to a and
c. ( a/ , b/2, c/) are defined by the MILLER INDiCES (0 2 0)
See: (DoITPoMS), Lattice Planes and Miller Indices
38
Expressions for d-spacings in
the different crystal systems
Cubic
Tetragonal
Orthorhombic
Hexagonal
Monoclinic
Triclinic
2
222
2
1
a
lkh
d
2
2
2
22
2
1
c
l
a
kh
d
2
2
2
2
2
2
2
1
c
l
b
k
a
h
d
2
2
2
22
2 3
41
c
l
a
khkh
d
ac
hl
c
l
b
k
a
h
d
cos2sin
sin
112
2
2
22
2
2
22
Even more complex
39
Principles of XRDX-Ray beams collide with a solid and interaction with electrons of
the particular solid takes place. Interference is possible when the
wavelength of the incoming X-ray is comparable to the separation
between the atoms. When an ordered array of scattering centres are
present, the reflected X-rays will show interference maxima and
minima. Typical wavelengths used for X-ray experiments lie
between 0.6 and 1.9. Braggs Law
sindn 2
For CUBIC structures we can show that:
2222
22
4sin lkh
a
40
Structure and properties of
materials
Bonding in solids (REVISE) See S&A
Types and structures of solids (REVISE) See Atomic
Scale Structure of Materials (and do questions)
Basic Crystallography and Diffraction methods
(REVISE) See S&A, X-ray Diffraction Techniques
(DoITPoMS), Lattice Planes and Miller Indices
(DoITPoMS)
Mechanical properties of materials (Read Introduction
to Mechanical Testing (DoITPoMS) by next week)
41
End of Revision
Crystallographic databases
42
Database Contents / Components No. of entries
ICDD
www.icdd.com
PDF-2 / PDF-4 >150,000
NIST
www.nist.gov
Unit cell, symmetry & refs >200,000
Pauling File
www.paulingfile.com
Inorg. Ordered solids
ICSD Inorg. Cryst. Structures 64,734
CSD
www.ccdc.cam.ac.uk
Org. Cryst. Structures >260,000
Crystmet ~70,000
PDB ~20,000
COD