Science Update Programme

Conductive Polymers: From Research to Products
Education Bureau, HKSAR 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

In 2000, The Nobel Prize in Chemistry was awarded to A. J. Heeger, A. G. MacDiarmid, and H. Shirakawa ³for the discovery and development of electrically conductive polymers´ http://www.nobel.se

³Handbook of Organic Conductive Molecules and Polymers´ Volume 2. New York. 3.. L.. New York. Macromolecules. Müllen and G. Other research articles in Nature. H. Applied Physics Letters. Chemistry of Materials. 7. .References 1. T. New York. Wiley. 5.. ³Electronic Materials: The Oligomer Approach´ K. Handbook of Conducting Polymers´ First Edition. van Hutten Eds. Marcel Dekker. Physics and Engineering´ G. Weinheim. J. M. Weinheim. WileyVCH. 1998. Kamachi Eds. Synthetic Metals etc.. R. A. 2. Wiley-VCH. Skotheim Ed. Hadziioannou and P. 1997. Marcel Dekker. Skotheim. Marcel Dekker. Ottenbrite. ³Functional Monomers and Polymers´ K. R. R. 6. Journal of Applied Physics.. Science. Advanced Materials. Elsenbaumer. West Sussex. F.. A. 2000. 1997. ³Semiconducting Polymers: Chemistry. Takemoto. 4. 1998. S. M. ³Handbook of Conducting Polymers´ Second Edition. Reynolds Eds. 1986. T. Wegner Eds. Nalwa Ed.

-1 cm-1 or S cm-1) . cm) or conductivity (.Electrical Conductivity of Materials ‡ Insulators ± W ~ 10-7 S cm-1 ‡ Semiconductors ± W ~ 10-7 to 102 S cm-1 ‡ Metals ± W > 102 S cm-1 ‡ Units are expressed as resistivity (.

onductivity ( Insulators -1 cm -1 ) etals Semiconductors 10 -20 10 -16 10 -12 10 -8 10 -4 10 0 10 4 copper nylon germanium glass silicon Quartz: W = 10-18 S cm-1 Silver/copper: W = 106 S cm-1 quartz eflon .

Interpretation of electrical conductivity in terms of simple energy band diagram 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 .

of carriers per unit volume) µn is the carrier mobility ‡ Charge transport: negative (n-type) or positive (ptype) carriers .‡ Bulk electrical conductivity W W = enµn where e is the electronic charge of the carrier n is the carrier density (no.

602 v 10-19 J ± The empty states are inaccessible by either electric field or thermal excitation ‡ Semiconductor ± Energy gaps < 2 eV ± Thermal excitation across the gap is possible ± Pure silicon: W ~ 10-5 S cm-1 .The Energy Band Gap ‡ Insulators ± Band Gap of several electron volts (eV) ± 1 eV = 8065.7 cm-1 or 1.

They produce states in the energy gap that lie close to either the conduction or the valence band ± Conduction can be either due to electrons (ntype) or holes (p-type): W ~ 10-1 S cm-1 ± Conductivity decreases at low temperature (Boltzmann distribution of states) .± Number of carriers increases rapidly as the energy gap decreases ± Dopants can also increase the conductivity.

‡ Metals ± Conductivity of materials increases as temperature decreases ± Thermal motion of the lattice and scattering processes are reduced ± True metallic behavior results when the energy gap between filled and empty states disappears What are the advantageous of using conducting polymers compared to metallic materials? .

all the valence electronic form strongly localized chemical-bonds and the energy gap is large (PE: 8 eV) .Electrical Conductivity of Polymers ‡ Typical insulator ± Polyethylene W ~ 10-15 S cm-1 ± Polytetrafluoroethylene (PTFE) W ~ 10-16 S cm-1 ± Polystyrene W ~ 10-15 S cm-1 ‡ For saturated chemical structures.

Metallic Polymers´ ‡ By pyrolysis of insulating or semiconducting polymers Precursor polymers 1000-2000 °C Product Precursor: polyesters. polyamides. phenolic resins Product: graphite type carbons (intermediate structures are not well defined) . PVC.

and are not well-characterized N N N N N N N N Ladder Polymer Doped with Br -1 2 or I 2 W = 10 S cm PAN (spin-coated film) 600-1200 °C Without doping Materials with W ~ 0.1 to 800 S cm-1 .polyacrylonitrile (PAN) CN CN CN CN CN CN CN oxidation at 200-300 °C These polymers are not soluble in any solvent.

Ag. 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 . Al.Conductor-Filled Polymers ‡ A physical mixture of conducting fillers with insulating polymer matrix ‡ Fillers: carbon. Cu. metal powders (Ni.

‡ W: 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)

Pure PVK is a hole conductor with dark conductivity of ~ 10-14 S cm-1 It is a very common photoconducting materials

Polymers with Unsaturated (Conjugated) backbone structure
‡ A conjugated main chain with alternating single and double bond ‡ First example of conjugate polymer:
± Polyacetylene

Pure polyacetylene: W ~ 10-9 (cis) and 10-5 (trans) S cm-1 High electrical conductivity was observed when the polymer was ³doped´ with oxidizing or reducing agents

Synthesis of Polyacetylene
By Ziegler-Natta Catalyst

Effect of Temperature: At -78 °C or below: all-cis PA At 180 °C or higher: all-trans PA

Polymerization by Other catalysts Acetylene Catalysts: WCl6/(C6H5)4Sn WCl6/n-BuLi MoCl5/ (C6H5)4Sn PA Note: These conjugate polymers are usually insoluble in organic solvents of have very low solubility .

Durham Method Isomerization of Polybenzvalene .

counteranion ) . which abstract an electron from the polymer and forms I3.g. by iodine I2.The Conduction Process in Conjugate Polymers ‡ Soliton: a defect in which the change in bond alternation is extended over 5 to 9 repeating units The charge and spin of the defect will depend on the occupancy of the state Chemical doping will create such defects in the polymer chain (e.

Positively charged Soliton S+ Neutral soliton S0 Negatively charged Soliton S- Conduction band Valence band .

Isolated solitons are not stable in polymers. which will be strongly localized to form a polaron The polaron is mobile along the polymer chain . charge exchange will lead to the formation of S0-S+ (or S0-S-) pairs.

.Two polarons may collapse to form a bipolaron. but move as a pair. which has zero spin but with charges Q = +2e S=0 The two positive charges of bipolaron are not independent. The spins of the bipolarons sum to S = 0.

In chemical terms: .

a high concentration of counteranion is required so that the polaron can move close to the counteranion.The mobility of a polaron along the polyacetylene chain can be high and charge is carried along the backbone. I2. K. high dopant concentration is necessary. AlCl3. MoCl5 (p-type doping) Reductive: Na. Hence. Br2. However. the counteranion I3.is not very mobile. The charge can ³hop´ from one polymer molecule to another--´hopping conductivity´ Dopants: Oxidative: AsF5. lithium naphthalides (n-type doping) .

Electrical Conductivity of Some Doped Polyacetylenes Dopant I2 IBr HBr AsF5 SeF6 FeCl3 MoCl5 WCl6 Conditions Vapor Vapor Vapor Vapor Vapor CH3NO2 Toluene Anisole Toluene Toluene Anisole Conductivity (S cm-1) 360 120 7 x 10-4 560 180 897 9.0 563 356 365 8.48 Note: PA is insoluble and labile to atmospheric oxygen .

4-phenylene) or Poly(p-phenylene) (PPP) A conjugated polymer based on aromatic units on the main chain Synthesis n ~ 5-15 .Other Conjugated Polymers Poly(1.

R = C6H13 .Pure PPP is not soluble neither. The solubility can be enhanced by attaching flexible groups to the polymer chain.

polaron. and bipolaron in poly(p-phenylene) .Soliton.

Conductivity of PPP Dopant AsF5 FeCl3 SbCl5 I2 SO3 AlCl3 Napht-K+ Napht-Li+ W (S cm-1) 500 0.30 < 10-3 < 10-4 10-1 to 10-4 8.0 50 5 .

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 However. head-to-tail (HT). the coupling can be either head-to-head (HH). or tail-to-tail (TT) .

Synthesis of Regioregular Polythiophene Copolymers with aromatic compounds or vinylene group .

Conductivity of polythiophenes and polypyrroles doped under different conditions Material Polythiophene Poly(3-methylthiophene) Poly(3-ethylthiophene) Poly(3-buthylthiophene) Poly(3-hexylthiophene) Poly(3-hexylthiophene) Polypyrrole Polypyrrole Polypyrrole Polypyrrole Dopant SO3CF3PF6PF6I2 PF6I2 FeCl3 I2 Br2 Cl2 W (S cm-1) 10-20 510 270 4 30 11 3-200 2-8 5 0.5 .

Synthesis of Conjugate Polymers by Precursor Approach To prepare a processible/soluble precursor polymer. which can subsequently be processed into the final form .

emaraldine. pernigraniline .Polyaniline ‡ A conducting polymer that can be grown by using aqueous and non-aqueous route ‡ Can be obtained by electrochemical synthesis or oxidative coupling of aniline ‡ Doping achieved by adding protonic acid ‡ Several forms: leucoemaraldine. emaraldine salt.

.

0 1.2 .2-1.Electrical Conductivity Medium 5-Sulfosalicyclic acid Benzene sulfonic acid p-Toluene sulfonic acid Sulfamic acid Sulfuric acid W (S cm-1) 0.0 2.0 2.0 5.

1990. 1. Tech. Adv.g.Applications of Conducting Polymers ‡ Rechargeable Batteries ± Higher energy and power densities (light weight) than conventional ones using lead-acid or Ni-Cd ± e. polyaniline used in 3V coin-shaped batteries (Poly. 33) ± Rechargeable -> reversible doping .

57. Metals 1993. corrosion inhibitor (polyaniline) ‡ Antistatic materials ± Poly(ethylenedioxythiophene) doped with acid ± Also used as conducting layer in light emitting devices ± Polyaniline used as antistatic layer in computer disk by HitachiMaxwell (Synth. 3696) .‡ Electromagnetic shielding.

Other Applications Emission Properties ‡ Polymers with extended T-conjugated systems usually absorb strongly in the visible region ‡ Many of them also emit light after absorbing a photon (photoexcitation) .

Some Possible Electronic Transitions After Absorption of Photons .

LED Display ‡ Light emission resulted from the recombination of holes and electrons in a semiconductor .

When hole and electron recombine: Hole+ + ElectronExcited states Ground states Light emission .

539) ‡ Based on poly(p-phenylenevinylene) (PPV).2 eV ITO: Indium-tin-oxide -A transparent electrical conductor .Organic Light Emitting Polymer ‡ First reported in 1990 (Nature 1990. with a bandgap of 2. 347.

‡ Threshold for charge injection (turn-on voltage): 14 V (E-field = 2 x 106 V/cm ‡ Quantum efficiency = 0. It cannot be redissolved once the polymer is synthesized .05 % ‡ Emission color: Green ‡ Processible ? No!! ‡ Polymer is obtained by precursor approach.

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 .

365.Other Examples of Light Emitting Polymers Poly(p-phenylene) (PPP) Poly(9. 372.9-dialkyl fluorene) BLUE light emission CN-PPV: RED light emission Nature 1993. depending on the composition Nature 1994. 443 . 628 Polythiophene derivatives A blend of these polymers produced variable colors.

etc.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. watches. ‡ Multicolor displays can also be made by combining materials with different emitting colors. . PDA.

and the hole by the materials with lower ionization potential. Light absorption creates electron-hole pairs (excitons). and their subsequent collection at opposite electrodes.For an Electroluminescence process: Electrons Photons Can we reverse the process? Photons Electrons YES! Photodiode Production of electrons and holes in a semiconductor device under illumination of light. . The electron is accepted by the materials with larger electron affinity.

Phys.A Two-Layer Photovoltaic Devices ‡ ‡ Conversion of photos into electrons Solar cells (Science 1995. 3120) 490 nm Max. Phys. 1789. 1996. Lett. quantum efficiency: ~ 9 % Open circuit voltage Voc: 0. Lett. 3120) (Appl. 270.8 V . 1996. 68. 68. Appl.

270. ITO/MEH-PPV:C60/Ca Active materials: MEH-PPV blended with a C60 derivative light MEH-PPV h+ C60 e- ITO/MEH-PPV:C60/Ca dark light ITO/MEH-PPV/Ca dark . 1789.Another example: Science 1995.

376.04 % .A Photodiode fabricated from polymer blend (Nature 1995.15 mW/cm2) Open circuit voltage (Voc): 0.6 V Quantum yield: 0. 498) Device illuminated at 550 nm (0.

1996. 10. Mater. Lett.‡ Field Effect Transistors (FET) ± Using poly(3-hexylthiophene) as the active layer ± ³All Plastics´ integrated circuits (Appl. 4108. Phys. 69. 365) . 1998. recent review: Adv.

More Recent Development ‡ Use of self-assembled monolayer organic fieldeffect transistors ‡ Possibility of using ³single molecule´ for electronic devices (Nature 2001. 713) . 413.