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Department of Chemistry
University of Hong Kong
May 2002
Course Coordinator
Dr. Wai Kin Chan, Department of Chemistry, HKU
Content
• Introduction to Electrical Conductivity
• Electrical Conductivity of Polymers
• Polyacetylene: First example of conducting
polymer
• Conduction Process in Conjugate Polymers
• Examples of other conducting polymers and
their syntheses
• Applications of Conducting Polymers
Conductive Polymers
http://www.nobel.se
References
1. “Handbook of Conducting Polymers” First Edition, T. A. Skotheim Ed.,
Marcel Dekker, New York, 1986.
2. “Functional Monomers and Polymers” K. Takemoto, R. M. Ottenbrite,
M. Kamachi Eds., Marcel Dekker, New York, 1997.
3. “Handbook of Organic Conductive Molecules and Polymers” Volume 2,
H. S. Nalwa Ed., Wiley, West Sussex, 1997.
4. “Handbook of Conducting Polymers” Second Edition, T. A. Skotheim,
R. L. Elsenbaumer, J. R. Reynolds Eds., Marcel Dekker, New York,
1998.
5. “Electronic Materials: The Oligomer Approach” K. Müllen and G.
Wegner Eds., Wiley-VCH, Weinheim, 1998.
6. “Semiconducting Polymers: Chemistry, Physics and Engineering” G.
Hadziioannou and P. F. van Hutten Eds., Wiley-VCH, Weinheim, 2000.
7. Other research articles in Nature, Science, Advanced Materials,
Applied Physics Letters, Journal of Applied Physics, Macromolecules,
Chemistry of Materials, Synthetic Metals etc.
Electrical Conductivity of Materials
• Insulators
– ~ 10-7 S cm-1
• Semiconductors
– ~ 10-7 to 102 S cm-1
• Metals
– > 102 S cm-1
• Units are expressed as resistivity ( cm)
or conductivity (-1 cm-1 or S cm-1)
Conductivity (-1 cm-1)
Insulators Semiconductors Metals
10 -20
10 -16
10 -12
10 -8
10 -4 10 0 10 4
Teflon
nylon
copper
germanium
glass
silicon
quartz
For a current to flow, an applied electric field must impart kinetic energy
to electrons by promoting them to higher energy band states
Conductivity depends on the density of available filled and empty states
• Bulk electrical conductivity
= enµn
where
e is the electronic charge of the carrier
n is the carrier density (no. of carriers per
unit volume)
µn is the carrier mobility
CN CN CN CN CN CN CN
= 10 S cm-1
600-1200 °C
PAN Materials with ~ 0.1 to 800 S cm-1
(spin-coated film) Without doping
Conductor-Filled Polymers
• A physical mixture of conducting
fillers with insulating polymer matrix
• Fillers: carbon, metal powders (Ni,
Cu, Ag, Al, Fe)
• Both the electrical and thermal
conductivity are enhanced
• The concentration of fillers has to
reach a threshold value in order to
form conductive paths
• : up to 103 S cm-1
• Example: silver-loaded epoxy
adhesives
• Applications:
– Self-regulating heaters: the
filled polymers expands as
temperature increases, leading
to a sharp decrease in
conductivity
– Antistatic components
– Resistors
Semiconducting Polymers
• Some are characterized by their
photoconductivity when exposed to light
• Example: polymer with active pendant
group
• Poly(N-vinylcarbazole) (PVK)
Effect of Temperature:
Acetylene PA
Catalysts:
WCl6/(C6H5)4Sn
WCl6/n-BuLi
MoCl5/ (C6H5)4Sn
Isomerization of Polybenzvalene
The Conduction Process in Conjugate
Polymers
• Soliton: a defect in which the change in bond
alternation is extended over 5 to 9 repeating units
Conduction band
Valence band
Isolated solitons are not stable in polymers, charge
exchange will lead to the formation of S0-S+ (or S0-S-) pairs,
which will be strongly localized to form a polaron
Q = +2e
S=0
Dopants:
Oxidative: AsF5, I2, Br2, AlCl3, MoCl5 (p-type doping)
I2 Vapor 360
IBr Vapor 120
HBr Vapor 7 x 10-4
AsF5 Vapor 560
SeF6 Vapor 180
FeCl3 CH3NO2 897
Toluene 9.0
Anisole 563
MoCl5
Toluene 356
Toluene 365
WCl6 8.48
Anisole
Note: PA is insoluble and labile to atmospheric oxygen
Other Conjugated Polymers
Poly(1,4-phenylene) or Poly(p-phenylene) (PPP)
A conjugated polymer based on aromatic units on the
main chain
Synthesis
n ~ 5-15
Pure PPP is not soluble neither. The solubility can be
enhanced by attaching flexible groups to the polymer chain.
R = C6H13
Soliton, polaron, and bipolaron in poly(p-phenylene)
Conductivity of PPP
Dopant (S cm-1)
AsF5 500
FeCl3 0.30
SbCl5 < 10-3
< 10-4
I2
10-1 to 10-4
SO3
8.0
AlCl3 50
Napht-K+ 5
Napht-Li+
Polypyrrole
• A conjugated polymer based on heterocyclic
aromatic units on the main chain
• Synthesized by chemical or electrochemical
polymerization from pyrrole
• Mechanism: oxidative coupling reaction
Proposed mechanism for the electrochemical polymerization
Polythiophene
• Environmental stable and highly
resistant to heat
• Synthesized by the electrochemical
polymerization of thiophene
• Can also be obtained by various types
of metal catalyzed coupling reaction
The solubility and processibility can be enhanced by attaching
substitution groups at the 3 position
Medium (S cm-1)
• Rechargeable Batteries
– Higher energy and power densities (light
weight) than conventional ones using lead-
acid or Ni-Cd
– e.g. polyaniline used in 3V coin-shaped
batteries
(Poly. Adv. Tech. 1990, 1, 33)
– Rechargeable -> reversible doping
• Electromagnetic shielding, corrosion inhibitor
(polyaniline)
• Antistatic materials
– Poly(ethylenedioxythiophene)
doped with acid
– Also used as conducting layer in
light emitting devices
Hole+ + Electron-
Excited Ground
states states
Light emission
Organic Light Emitting Polymer
• First reported in 1990 (Nature 1990, 347, 539)
• Based on poly(p-phenylenevinylene)
(PPV), with a bandgap of 2.2 eV
ITO: Indium-tin-oxide
-A transparent electrical
conductor
• Threshold for charge injection (turn-on
voltage): 14 V (E-field = 2 x 106 V/cm
• Quantum efficiency = 0.05 %
• Emission color: Green
• Processible ? No!!
• Polymer is obtained by precursor
approach. It cannot be redissolved once
the polymer is synthesized
Other PPV Derivatives
• MEH-PPV
• More processible, can be dissolved in
common organic solvents (due to the
presence of alkoxy side chains)
• Fabrication of Flexible light-emitting diodes
(Nature 1992, 357, 477)
Substrate: poly(ethylene terephthlate) (PET)
Anode: polyaniline doped with acid-a flexible and
transparent conducting polymer
EL Quantum efficiency: 1 %
Turn-on voltage: 2-3 V
Other Examples of Light Emitting Polymers
Poly(p-phenylene) (PPP)
BLUE light
emission
Poly(9,9-dialkyl fluorene)
Polythiophene derivatives
A blend of these polymers
produced variable colors,
depending on the composition
Nature 1994, 372, 443
Applications
• Flat Panel Displays: thinner than liquid
crystals displays or plasma displays
(the display can be less than 2 mm
thick)
• Flexible Display Devices for mobile
phones, PDA, watches, etc.
• Multicolor displays can also be made by
combining materials with different
emitting colors.
For an Electroluminescence process:
Electrons Photons
Photodiode
Production of electrons and holes in a semiconductor
device under illumination of light, and their subsequent
collection at opposite electrodes.
Light absorption creates electron-hole pairs (excitons).
The electron is accepted by the materials with larger
electron affinity, and the hole by the materials with lower
ionization potential.
A Two-Layer Photovoltaic Devices
• Conversion of photos into electrons
• Solar cells (Science 1995, 270, 1789; Appl. Phys. Lett. 1996, 68, 3120)
490 nm
ITO/MEH-PPV:C60/Ca
Active materials: MEH-PPV blended with a C60 derivative
light
ITO/MEH-PPV:C60/Ca
MEH-PPV
dark
h+ e-
light
C60 ITO/MEH-PPV/Ca
dark
A Photodiode fabricated from polymer blend
(Nature 1995, 376, 498)